CN102459693A - Pecvd coating using an organosilicon precursor - Google Patents

Pecvd coating using an organosilicon precursor Download PDF

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Publication number
CN102459693A
CN102459693A CN2010800291990A CN201080029199A CN102459693A CN 102459693 A CN102459693 A CN 102459693A CN 2010800291990 A CN2010800291990 A CN 2010800291990A CN 201080029199 A CN201080029199 A CN 201080029199A CN 102459693 A CN102459693 A CN 102459693A
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Prior art keywords
container
coating
pan straddle
plasma body
electrode
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Granted
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CN2010800291990A
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CN102459693B (en
Inventor
J·T·费尔特斯
T·E·费斯克
R·S·阿伯拉姆斯
R·J·潘格伯恩
P·J·萨高纳
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SIO2 Medical Products Inc
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CV Holdings LLC
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Priority claimed from EP10162761.0A external-priority patent/EP2251455B1/en
Priority claimed from PCT/US2010/034586 external-priority patent/WO2010132591A2/en
Publication of CN102459693A publication Critical patent/CN102459693A/en
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Abstract

A method for coating a substrate surface by PECVD is provided, the method comprising generating a plasma from a gaseous reactant comprising an organosilicon precursor and optionally O2. The lubricity, hydrophobicity and/or barrier properties of the coating are set by setting the ratio of the O2 to the organosilicon precursor in the gaseous reactant, and/or by setting the electric power used for generating the plasma. In particular, a lubricity coating made by said method is provided. Vessels coated by said method and the use of such vessels protecting a compound or composition contained or received in said coated vessel against mechanical and/or chemical effects of the surface of the uncoated vessel material are also provided.

Description

Use the PECVD coating of organosilicon precursor
Invention field
The present invention relates to store the technical field of manufacturing of the coating container of active compound biologically or blood.Especially; The present invention relates to a kind of container processing systems that container applies that is used for, be used for the container processing systems that container applies and checks, relate to a kind of carry-case support that is used for container processing systems; Relate to a kind of plasma enhanced chemical vapor deposition unit that is used for the internal surface of coating container; Relate to a kind of method that is used for the internal surface of coating container, relate to a kind of method that is used to check container coating, relate to a kind of method of processing vessel; The purposes that relates to a kind of container processing systems relates to a kind of computer-readable medium and relates to a kind of program element.
The invention provides a kind of method that is used for through PECVD coated substrate surface, this method comprises from comprising a kind of organosilicon precursor and randomly producing a kind of plasma body a kind of gaseous reactant of O2.Wherein through the ratio of O2 and this organosilicon precursor in this gaseous reactant is set, and/or through being provided for producing oilness, hydrophobicity and/or the obstacle character that the employed electric power of this plasma body is provided with this coating.Particularly, the invention provides a kind of lubricating coating of making through said method.The present invention also provides the container that applies with said method and the purposes of these containers, and this purposes is according to machinery that should uncoated container material surface and/or the chemical effect protection is included in the described coating container or by a kind of compound or the mixture of described coating container reception.
This disclosure also relates to and is used for improving one's methods of processing vessel, for example, is used for a plurality of identical container, pharmaceutical prepn storage and transportation and other purpose that venipuncture and other medical sample are collected.This container is used for these purposes in a large number, and these containers must be in the mill relatively economical and the storage and the transportation in also be very reliable.
Background of invention
For example, vacuum test tube is used for extracting the blood that is used for medical analysis from patient.These pipes are vacuumized and are sold.Be inserted in the patient's blood vessel and pierce through the closure member of this vacuum test tube at the other end of this two ends syringe needle through the end with a two ends hypodermic needle, patients'blood is communicated to the inside of a pipe.Vacuum in the vacuum test tube gets into blood draw (or saying that exactly patient's blood pressure has promoted blood) in this vacuum test tube through syringe needle, has increased the interior pressure of this pipe and so has reduced to cause the pressure reduction of blood flow.Typically to continue to remove perhaps this pressure reduction up to this pipe from syringe needle too little and can not support to flow for blood flow.
Vacuum test tube should have a substantial quality guaranteed period to help these pipes effectively and easily distributing and store before using.For example, the quality guaranteed period in 1 year makes us hoping, and the progressive in some cases longer quality guaranteed period, as 18 months, and 24 months, or 36 months also be desirable.This pipe desirably keeps perfect vacuum basically; At least reach extract enough necessary degree of the blood that is used to analyze (common standard be this pipe to keep original at least extraction volume 90%); For the whole quality guaranteed period, seldom (there is not) to provide defective pipe best.
A defective pipe might cause bleeder can not use this to manage and extract enough blood.So bleeder possibly need to obtain and use one or more other pipes to obtain enough blood sample.
Again for example, precharging type syringe normally is ready to sell, and therefore this syringe does not need to fill before use.In some instances, can be with salts solution, a kind of dyestuff that is used to inject or a kind of pharmaceutical activity preparation pre-filled syringe.
Normally, precharging type syringe is (as having a cap) that adds cap at far-end, and seals at the pulling plunger of near-end through it.Can be in a kind of sterile packed before using with prefilled injector package.In order to use this precharging type syringe; Remove packing and cap; Randomly a hypodermic needle or another delivery catheter are attached to the far-end of syringe cylinder; This delivery catheter or syringe are moved to a use location (as through hypodermic needle being inserted in the patient's blood vessel or getting in the device that content that this syringe for use is arranged washes), and this plunger advances in this to inject this content.
In making the precharging type syringe process; The content that important consideration is this syringe desirably will have a substantial quality guaranteed period; It is important that the material of filling this syringe is isolated with the barrel that contains this material, to avoid getting in these contents of filling in advance or vice versa from this leaching material.
Because these many containers are inexpensive and by a large amount of uses, using for some will be usefully, under the situation that manufacturing cost is not increased to a high untouchable level, obtain the necessary quality guaranteed period reliably.And; For some application, make us hoping be avoid Glass Containers (Glass Containers maybe damaged and be expensive) for manufacturing and prefer during normal use seldom damaged plastic containers (and if damagedly do not form sharp-pointed fragment from the residue of container yet, and the fragment as Glass tubing can form).Glass Containers has been that glass is more bubble-tight and inert for the content of pre-filled because of comparing with untreated plastics by preference.And because its tradition is used, glass is generally accepted because known when glass contacts with medical sample or pharmaceutical prepn etc., be harmless relatively.
Further consider it is to guarantee that when compressing into plunger tin it can move with constant speed and constant power about one of syringe.For this purpose, make us hoping at one of tube and plunger or a slip coating on both.
The non-exhaustive patent portfolio that possibly be correlated with comprises USP 6,068,884 and 4,844,986 and the U.S. openly apply for 20060046006 and 20040267194.
Summary of the invention
A target of the present invention provides a kind of manufacturing of improved coating container.
The device that several different methods is described below and makes according to these methods, wherein these methods can be carried out and these devices can be made through this system through the following container processing systems that further describes.
The invention provides a kind of method of coming coated surface (the for example inner surface of container) with coating (making by organosilicon precursor) through PECVD.In addition, the invention provides generation coating, be coated with the container of such coating and the purposes of this coating (for example, as slip coating, hydrophobic coating or barrier coat).And, provide to be used to carry out device of the present invention and several equipment.The present invention also provides the inspection method that is used for this coating, and the venting of volatile species (volatile species) that particularly will be through coated surface is used for a kind of method of said inspection.
The PECVD coating method
The present invention relates to a kind ofly prepare the method for coating through plasma body enhanced chemical vapor deposition process (PECVD), and a kind of method of inner surface of coating container for example.
A surface (for example inner vessels surface) is provided, as has been both a kind of reaction mixture, this mixture comprises a kind of organic silicon compound gas, randomly a kind of oxidizing gas, and randomly a kind of appropriate hydrocarbon gas.
This surface contacts with this reaction mixture.Plasma body forms in reaction mixture.Preferably, said plasma body is non-hollow cathode plasma, or in the another kind statement for same case, said plasma body is gone up basically and do not contained hollow cathode plasma.This coating is deposited at least one part (for example this container inner wall part) on this surface.
This method is following the realization.
A kind of precursor is provided.Preferably; Said precursor is a kind of silicoorganic compound (also being appointed as " organosilicon precursor " below); More preferably be a kind of silicoorganic compound that are selected from down group; This group is made up of and the following: any two kinds or more kinds of combinations of the aza analogues of linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, alkyl trimethoxysilane, any of these precursor (that is, linear silicon azane, monocycle silazane, encircle silazane more, gather the sesquialter silazane) and these precursors.Under the condition that effectively forms a kind of coating through PECVD, this precursor is applied in a kind of substrate.So this precursor is by polymerization, crosslinked, partially or even wholly oxidation or any combination among these.
In one aspect of the invention, this coating is a slip coating, and promptly it forms a surface with friction resistance lower than uncoated substrate.
In another aspect of the present invention, this coating is a kind of passivating coating, for example a kind of sedimentary hydrophobic coating still less that for example causes with the component of the contacted compsn of this coated surface.Such hydrophobic coating is characterised in that the wet tension lower than uncoated counterpart.
Slip coating of the present invention can also be a kind of passivating coating, and vice versa.
Of the present invention one further aspect, this coating is a kind of barrier coat, for example a kind of SiO xCoating.Typically, this blocking layer is anti-gas or liquid, preferably water vapor, oxygen and/or air.The vacuum of the internal tank (for example heparin tube inside) that can also use this blocking layer to set up and/or keep to be coated with this barrier coat.
In addition, method of the present invention can comprise the applying from a kind of one or more other coating of organosilicon precursor manufacturing through PECVD.Optional other step is to this SiO with that be made up of oxygen basically and a kind of process gas that be substantially free of volatile silicon compound xCoating is carried out aftertreatment.
Slip coating
One concrete aspect, the invention provides a kind of slip coating.
This coating is through the PECVD method and use aforesaid precursor and advantageously manufacturing.
For example, the invention provides a kind of method of the lubricating property that is used to be arranged on a kind of coating on the substrate surface, this method may further comprise the steps:
(a) a kind of gaseous reactant is provided near this substrate surface, this gaseous reactant comprises a kind of organosilicon precursor and O randomly 2And
(b) from a kind of plasma body of this vapor reaction deposits yields, therefore on this substrate surface, form a coating through plasma body enhanced chemical vapour deposition (PECVD), wherein the lubricating property of this coating is through O in this gaseous reactant is set 2The employed electric power of this plasma body is provided with the ratio of organosilicon precursor and/or through being provided for producing.
A preferred precursor that is used for this slip coating is the monocycle siloxanes, for example octamethylcyclotetrasiloxane (OMCTS).
Compare with untreated substrate, the coated surface that is produced has lower friction resistance.For example, when this coated surface was the inside of syringe cylinder and/or syringe plunger, this slip coating provided less than the starting force (breakout force) of needed corresponding power when this slip coating lacks or plunger sliding force or both effectively.
The article that are coated with slip coating can be to have a kind of container of slip coating at (preferably on inwall) on the wall; For example a kind of syringe cylinder or on the container surface in contact, have a kind of container parts or the container cap of said coating, for example a kind of syringe plunger or a kind of container cap.
In one aspect, this slip coating can have formula Si wO xCyH z, for example wherein w is 1, and x is 1, and x is from about 0.5 to about 2.4, and y is from about 0.6 to about 3, and z is from about 2 to about 9, and preferably wherein w is 1, and x is from about 0.5 to 1, and y is from about 2 to about 3, and z is from 6 to about 9.
Passivation, for example hydrophobic coating
Passivating coating according to the present invention is for example a kind of hydrophobic coating.
A kind of preferred precursor that is used for passivation (for example hydrophobic coating) is a kind of linear siloxane, for example SWS-F 221 (HMDSO).
A kind of passivating coating according to the present invention prevents or has reduced uncoated surface to being included in compound or the machinery and/or the chemical action of compsn in this container.For example, prevent or reduced with the deposition of a kind of compound of this contacted compsn in surface or component and/or solidify or platelet activation, for example prevented that blood coagulation or platelet activation or insulin precipitation or uncoated surface are wetting by aqueous fluids.
A concrete aspect of the present invention is the surface with a hydrophobic coating, and this coating has formula Si wO xCyH z, for example wherein w is 1, and x is from about 0.5 to about 2.4, and y is from about 0.6 to about 3, and z is from about 2 to about 9, and preferably wherein w is 1, and x is from about 0.5 to 1, and y is from about 2 to about 3, and z is from 6 to about 9.
The article that are coated with passivating coating can be to have a kind of container of this coating at (preferably on inwall) on the wall, for example a kind of pipe or on the container surface in contact, have a kind of container parts or the container cap of said coating, for example a kind of container cap.
The coating of container
When using PECVD to come coating container through above-mentioned coating method, this coating method comprises several steps.A kind of container is provided, and this container has an opening end, a closing end and an inner surface.At least a gaseous reactant is introduced in this container.Under the condition of the reaction product (i.e. a coating on the inner surface of this container) that effectively forms this reactant, within this container, form plasma body.
Preferably, this method is to be seated on the pan straddle as described herein, between the inside of this pan straddle and this container, to set up a sealing through the opening end that makes this container to be communicated with and to carry out.This preferred aspect, this gaseous reactant is introduced in this container through this pan straddle.Of the present invention one preferred especially aspect, will comprise that plasma enhanced chemical vapor deposition (PECVD) device of a pan straddle, an internal electrode, an outer electrode and a power supply is used for according to coating method of the present invention.
This pan straddle has a port, is used for handling container is received in a position of taking a seat.Thereby this internal electrode is positioned to remain to be received in and is seated within the container on the pan straddle.This outer electrode has an internal portion, and this internal portion is positioned and is seated at a container on this pan straddle with reception.Thereby this power supply is input to alternating-current and forms a kind of plasma body on these inside and/or the outer electrode in the container on being seated at this pan straddle.Typically, this power supply is input to alternating-current on this outer electrode and this internal electrode is a ground connection.In this embodiment, this container defines this plasma body reaction chamber.
Of the present invention one concrete aspect; PECVD device described in earlier paragraphs comprises an eduction pipe that must not comprise vacuum source; Be used for the gas inside from this container is perhaps transmitted in gas transfer to the inside that is landed in the container on this port, to limit a closed-chamber.
Of the present invention one further concrete aspect, this PECVD device comprises a pan straddle, first clamp, a seat on this pan straddle, a reactant feeding mechanism, a plasma generator and a container releasing device.
This pan straddle is arranged on the opening end that is seated at a container.This first clamp is arranged to and optionally keeps and discharge the closing end of container and clamp the closing end of this container simultaneously, and this container is transported near this pan straddle.This pan straddle has a seat, and this is arranged between the internal space of this pan straddle and this first container and sets up being communicated with of sealing.
This reactant feeding mechanism is operably connected to be used for through this pan straddle at least a gaseous reactant being incorporated in this first container.This plasma body producer is arranged under the condition of the reaction product that effectively forms reactant on the inner surface of this first container and in this first container, forms plasma body.
Provide this container releasing device to be used for this first container being removed from this pan straddle.A clamp (this clamp is first clamp or another clamp) is arranged to and axially transports this first container and leave this pan straddle and then discharge this first container.
Of the present invention one concrete aspect, this method is the internal surface of opening that is used for coming through PECVD a restriction of coating container, the for example container of a generally tubular.This container comprises an outer surface, defines an internal surface of an inner chamber, has a bigger opening of internal diameter and the opening of a restriction, and the opening of this restriction is limited by an internal surface and has less internal diameter than this internal diameter than big opening.A kind of processing vessel is provided, and this processing vessel has an inner chamber and a processing vessel opening.Thereby this processing vessel opening is connected with the opening of the restriction of this container and is communicated with setting up between the inner chamber that pending container is arranged and the processing vessel inner chamber via the opening of this restriction.To have within inner chamber and the processing vessel inner chamber of pending container and be pumped into partial vacuum at least.The PECVD reactant is flowed through this first opening, then through the inner chamber of pending container is arranged, then through the opening of this restriction, gets into the inner chamber of this processing vessel then.Effectively be deposited under the condition on the internal surface of opening of restriction near the generation plasma body opening of this restriction in coating with a PECVD reaction product.
The container and the container parts that apply
The present invention further provides from the coating of aforesaid method generation, the container that is coated with the surface of said coating and for example is coated with said coating.
The surface (for example a wall of container or its part) that is coated with this coating can be glass or a kind of polymkeric substance; Preferably a kind of thermoplastic polymer; More preferably be selected from down a kind of polymkeric substance of group, this group is made up of and the following: a kind of polycarbonate, a kind of olefin polymer, a kind of cyclic olefine copolymer and a kind of polyester.For example, it is a kind of cyclic olefine copolymer, a kind of polyethyleneterephthalate or a kind of Vestolen PP 7052.
Of the present invention one concrete aspect, this wall of container has an inner polymeric layer that is centered on by at least one external polymer layer.These polymkeric substance can be identical or different.For example, one of these polymer layers of cyclic olefine copolymer (COC) resin (for example, defining a water vapor barrier layer), another polymer layer is a layer of vibrin.Such container is by comprising through concentric injection nozzle a kind of method in COC and injection mold of polyester resin layer introducing to be made.
Coating container of the present invention can be empty, find time or (in advance) be filled with a kind of compound or compsn.
A concrete aspect of the present invention is the container with a kind of passivating coating (for example as above defined a kind of hydrophobic coating).
A further concrete aspect of the present invention is the surface with as above defined slip coating.It can be to have a kind of container of slip coating at (preferably on inwall) on the wall, for example a kind of syringe cylinder or on the container surface in contact, have a kind of container parts or the container cap of said coating, for example a kind of syringe plunger or a kind of container cap.
A concrete aspect of the present invention is a kind of syringe, and this syringe comprises a plunger, syringe cylinder and the as above defined slip coating of (preferably on the inwall of this syringe cylinder) at one of these syringe parts or on both.This syringe cylinder comprises a tube, and this has an inner surface that receives a plunger slidably.This slip coating can be disposed on the inner surface of this syringe cylinder or contact on this plunger surface or on said surface on both.This slip coating has effectively reduced for necessary starting force of mobile plunger in tube or plunger sliding force.
A further concrete aspect of the present invention is the syringe cylinder that is coated with like defined slip coating in the earlier paragraphs.
of the syringe cylinder of said coating concrete aspect, this syringe cylinder comprises a tube, this has defined an inner chamber and has had an inner surface that receives a plunger slidably.This syringe cylinder is advantageously processed by thermoplastic material.Through plasma body enhanced chemical vapour deposition (PECVD) slip coating is applied on this inner surface, this plunger or both.For example leaching an amount that gets in this inner chamber with this slip coating of effective minimizing, this thermoplastic material or both is applied to a kind of solute restraining mass (solute retainer) on this slip coating through surface treatment.This slip coating and solute restraining mass are to form and exist effectively to provide than a littler starting force, plunger sliding force or both relative quantities of needed corresponding power under the situation that lacks this slip coating and solute restraining mass.
Another aspect again of the present invention is a kind of syringe, and this syringe comprises plunger, syringe cylinder and an inside and exterior coating.This has an inner surface and outer surface that receives this plunger slidably.A slip coating is positioned on the inner surface, and can be with SiO xAn other barrier coat of (wherein x is from about 1.5 to about 2.9) is provided on this inner surface.For example a kind of resin or a kind of other SiO xA barrier coat of coating is provided on this outer surface.
Another aspect of the present invention is a kind of syringe, and this syringe comprises a plunger, syringe cylinder and a female luer (Luer fitting).This syringe cylinder has an inner surface that receives this plunger slidably.This female luer comprises a luer taper (Luer taper), and this luer taper has an internal passages that is limited an internal surface.This female luer is to form and to be connected on this syringe cylinder through a junctor with the form of the isolating separation member of this syringe cylinder.The internal passages of luer taper has the barrier coat of SiOx (wherein x is from about 1.5 to big about 2.9).
Another aspect of the present invention is a kind of plunger that is used for syringe, and this plunger comprises a piston and a push rod.This piston has side and rear section of a front, a substantial cylindrical, and this side is configured to be seated within the syringe cylinder movably.This plunger has one according to slip coating of the present invention on its side.This push rod engages the rear section of this plunger and is configured to make piston in syringe cylinder, to advance.This plunger can additionally comprise a SiO xCoating.
A further aspect of the present invention is the container that only has an opening, promptly is used to collect or store a kind of container of a kind of compound or compsn.One concrete aspect, such container is a kind of pipe, for example a kind of sampling tube, for example a kind of heparin tube.It is closed that said pipe can use a closure member (for example a cap or stopper).Such lid or stopper can comprise one according to of the present invention slip coating with pipe on the contacted surface it, and/or it it can comprise one according to passivating coating of the present invention on the surface of the inner chamber of this pipe.One concrete aspect, a such stopper or its part can be processed by a kind of elastomer material.
A kind of stopper like this can be made as follows: stopper is placed in the chamber of finding time basically.A kind of reaction mixture is provided, and this reaction mixture comprises a kind of organic silicon compound gas, randomly a kind of oxidizing gas and randomly a kind of appropriate hydrocarbon gas.With the contacted reaction mixture of this stopper in form plasma body.One is coated with at least a portion that is deposited upon this stopper.
A further aspect of the present invention is a kind of container that has according to barrier coat of the present invention.This container be generally tubular and can process by thermoplastic material.The inner chamber that this container has an opening and at least partly limited by a wall.This wall has an internal surface with this inner chamber boundary.One preferred aspect, by as above defined SiO xProcess one at least basically the successive barrier coat be applied on the internal surface of this wall.This barrier coat effectively keeps in this container at least 90% its initial vacuum level, and randomly 95% its initial vacuum level continues at least 24 hours quality guaranteed period.A closure member is provided, this closure member cover the opening of this container and make the inner chamber of this container and ambient air isolated.
Use coating that the PECVD of the organosilicon precursor as this specification sheets described in makes and PECVD coating method for coating conduit or cuvette to form a barrier coat, hydrophobic coating, slip coating or also to be useful more than one among these.Cuvette be a kind of have circle or square-section, end sealing, make by polymkeric substance, glass or fused quartz (being used for UV light) and be designed to hold the miniature valve that sample is used for spectrum experiment.Best cuvette is transparent as far as possible, does not have possibility to influence the impurity of spectrum reading.As a kind of test tube, thus cuvette can be to atmosphere opening or have a cap with its hermetically closing.Therefore the coating of the PECVD of applying of the present invention can be extremely thin, transparent and optics is smooth, do not disturb the optic test of this cuvette or its content.
The coating container that (in advance) fills
A concrete aspect of the present invention is aforesaid a kind of coating container, and this container is filled with a kind of compound or compsn in advance or is used for filling with a kind of compound or compsn in its inner chamber.Said compound or compsn can be
A kind of bioactive compounds or compsn, preferred a kind of medicament, more preferably Regular Insulin or comprise a kind of compsn of Regular Insulin; Or
A kind of biological fluid, preferred a kind of body fluid, more preferably blood or a kind of blood ingredient (for example, hemocyte); Or
In this container, be used for and another kind of compound or the compsn directly a kind of compound or the compsn of combination mutually, for example in heparin tube, be used to prevent a kind of compound of blood coagulation or platelet activation, as Citrate trianion or contain the compsn of Citrate trianion.
Usually; Coating container of the present invention is useful especially for machinery and/or responsive a kind of compound or the compsn of chemical action collecting or store the surface of uncoated container material, preferably to preventing or reducing with the deposition of a kind of compound of the contacted compsn of inner surface of this container or a kind of component and/or solidify or platelet activation.
For example, having wall and the cell preparation pipe that accommodate a kind of aqueous citric acid sodium reagent that is equipped with a kind of hydrophobic coating of the present invention is suitable for collecting blood and prevents or reduce blood coagulation.This aqueous citric acid sodium reagent is introduced an amount of the blood coagulation in this pipe with effective inhibition and is disposed in the inner chamber of this pipe.
A concrete aspect of the present invention is to be used to collect/receive a kind of container of blood or a kind of container of containment blood.This container has a wall; This wall has the internal surface that has defined an inner chamber.The internal surface of this wall has a part hydrophobic coating at least of the present invention.This coating can be thin like unit molecule thickness or thick as about 1000nm.Be collected or be stored in this container blood preferably with the mode that can live turn back to be disposed in the patient's blood vessel system with the contacted inner chamber of coating in.Compare with the uncoated wall of same type, this coating has effectively reduced solidifying or platelet activation of the blood that is exposed to this internal surface.
Another aspect of the present invention is a kind of container that holds Regular Insulin, and this container comprises a wall with the internal surface that has defined an inner chamber.This internal surface has a part hydrophobic coating at least of the present invention.This coating can be to approximately 1000nm is thick from unit molecule thickness on internal surface.Regular Insulin or a kind of compsn that comprises Regular Insulin be disposed in contacted this inner chamber of this coating in.Randomly, compare with the similar face that lacks this coating, this coating has effectively reduced from the Regular Insulin of contact internal surface and has formed deposition.
Therefore about the purposes of coating method, coated product and said product, the invention provides following instance:
(1) a kind of method that is used to be arranged on the lubricating property of the coating on the substrate surface, this method may further comprise the steps:
(a) near this substrate surface, provide and comprise a kind of organosilicon precursor or O randomly 2A kind of gaseous reactant; And
(b) from a kind of plasma body of this vapor reaction deposits yields, on this substrate surface, form a coating through plasma body enhanced chemical vapour deposition (PECVD) thus,
Wherein the lubricating property of this coating is through O in the gaseous reactant is set 2With the ratio of organosilicon precursor, and/or through being provided for producing the employed electric power of this plasma body is provided with.
(2) a kind of method that is used in a kind of substrate, preparing hydrophobic coating, this method may further comprise the steps:
(a) near this substrate surface, provide and comprise a kind of organosilicon precursor and O randomly 2Gaseous reactant; And
(b) from a kind of plasma body of this vapor reaction deposits yields, on this substrate surface, form a kind of coating through plasma body enhanced chemical vapour deposition (PECVD) thus,
Wherein the hydrophobic property of this coating is through O in the gaseous reactant is set 2With the ratio of this organosilicon precursor, and/or through being provided for producing the employed electric power of this plasma body is provided with.
(3) like (1) or (2) described method, this has caused a kind of coating, and this coating is characterized as being a total formula, wherein compare with total formula of organosilicon precursor, atomic ratio C: O be increase and/or atomic ratio S i: O reduces.
(4) according to each described method, wherein O in (1) to (3) 2With existing: from 0: 1 to 5: 1 with respect to gaseous reactant with lower volume-volumetric ratio; Randomly from 0: 1 to 1: 1; Randomly,, preferably wherein in this gaseous reactant, there is not oxygen at least in fact randomly from 0: 1 to 0.1: 1 from 0: 1 to 0.5: 1.
(5) according to each the described method in (1) to (4), wherein this gaseous reactant comprises the O less than 1 volume % 2,, more specifically less than the O of 0.5 volume % 2, and most preferably be not contain O 2
(6) according to each the described method in (1) to (5), wherein this plasma body is non-hollow cathode plasma.
(7) according to each the described method in (1) to (6), wherein this substrate is the inwall with container of an inner chamber, and this inner chamber has following void volume: from 0.5 to 50ml, preferably from 1 to 10ml, more preferably from 0.5 to 5ml, most preferably from 1 to 3ml.
(8) according to each the described method in (1) to (7)
(i) wherein this plasma body produces with electrode; Thereby these electrodes form a coating with enough power energy supplies on substrate surface, preferably use the electrode provide following electric power: from 0.1 to 25W, preferably from 1 to 22W; More preferably from 3 to 17W; Even more preferably from 5 to 14W, most preferably from 7 to 11W, 8W in particular; And/or
(ii) wherein the ratio of this electrode power and volume of plasma is less than 10W/ml, preferably from 5W/ml to 0.1W/ml, more preferably is from 4W/ml to 0.1W/ml, most preferably is from 2W/ml to 0.2W/ml.
(9) a kind of method that is used for a kind of coating of preparation on substrate surface, this method may further comprise the steps
(a) near this substrate surface, provide and comprise a kind of organosilicon precursor and O randomly 2A kind of gaseous reactant; And
(b) under reduced pressure from a kind of non-hollow cathode plasma of this vapor reaction deposits yields, on this substrate surface, form a coating through plasma body enhanced chemical vapour deposition (PECVD) thus,
Wherein through O in this gaseous reactant is set 2With the ratio of this organosilicon precursor, and/or through being provided for producing physics and the chemical property that the employed electric power of this plasma body is provided with this coating.
(10) a kind of method that is used for a barrier coat of preparation in substrate, this method may further comprise the steps:
(a) near this substrate surface, provide and comprise a kind of organosilicon precursor and O 2A kind of gaseous reactant; And
(b) under reduced pressure from a kind of non-hollow cathode plasma of this vapor reaction deposits yields, on this substrate surface, form a coating through plasma body enhanced chemical vapour deposition (PECVD) thus,
Wherein through O in this gaseous reactant is set 2With the ratio of this organosilicon precursor, and/or through being provided for producing the barrier properties that the employed electric power of plasma body is provided with this coating.
(11) method of basis (10)
(i) wherein this plasma body produces with electrode; Thereby these electrodes come energy supply on this substrate surface, to form a coating with enough power; Preferably use the electrode provide following electric power: from 8 to 500W, preferably from 20 to 400W, more preferably from 35 to 350W; Even more preferably from 44 to 300W, most preferably from 44 to 70W; And/or
(ii) the ratio of electrode power and volume of plasma is to be equal to or greater than 5W/ml, preferably from 6W/ml to 150W/ml, more preferably is from 7W/ml to 100W/ml, most preferably is from 7W/ml to 20W/ml.
(12) method of basis (10) or (11), wherein O 2With with respect to this gaseous reactant with lower volume: volumetric ratio exists: with respect to containing silicon precursor from 1: 1 to 100: 1; Preferably with ratio from 5: 1 to 30: 1; More preferably with from 10: 1 to 20: 1 ratio, even more preferably with 15: 1 ratio.
(13) like each the described method in (1) to (12); Wherein this organosilicon precursor is to be selected from down group; This group is made up of and the following: linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, linear silicon azane, monocycle silazane, any two kinds or the more kinds of combinations that encircle silazane more, gather sesquialter silazane, alkyl trimethoxy siloxane and these compounds, preferably linearity or monocycle siloxanes.
(14) like (1) or (2) described method, wherein this organosilicon precursor is a kind of monocycle siloxanes, preferred OMCTS.
(15) like (2) or (10) described method, wherein this organosilicon precursor is a kind of linear siloxane, preferred HMDSO.
(16) according to each the described method in (1) to (15), wherein this PECVD carries out under the flow rate of following organosilicon precursor: be equal to or less than 6sccm (" standard cubic centimeter/PM "), preferably be equal to or less than 2.5sccm, more preferably be equal to or less than 1.5sccm, most preferably be equal to or less than 1.25sccm.
(17) according to each the described method in (1) to (16); Wherein this substrate is a kind of polymkeric substance that is selected from down group; This group is made up of and the following: polycarbonate, olefin polymer, cyclic olefine copolymer and polyester, and preferably cyclic olefine copolymer, polyethyleneterephthalate or Vestolen PP 7052.
(18) according to each the described method in (1) to (17); Wherein this substrate surface be have at least one opening and an internal surface a container internal surface partly or entirely; And wherein this gaseous reactant is filled the inside inner chamber of this container, and produces this plasma body in the part of the inside of this container inner chamber or all.
(19) according to each the described method in (1) to (18); Wherein this plasma body is that the electrode that is used in energy supply under the following radio frequency produces: preferably from 10kHz to the frequency less than 300MHz; More preferably from 1 to 50MHz; Even more preferably from 10 to 15MHz, most preferably at 13.56MHz.
(20) according to each the described method in (1) to (19), wherein this plasma body be under reduced pressure produce and this decompression be less than 300mTorr, preferably less than 200mTorr even more preferably less than 100mTorr.
(21) according to each described method of (1) to (20), wherein this PECVD depositing time is from 1 to 30 second, preferably from 2 to 10 seconds, and more preferably from 3 to 9 seconds.
(22) according to each described method of (1) to (21), the coating that is wherein produced has the thickness in 1 to 100nm the scope, preferably in 20 to 50nm scope.
(23) a kind of coating, this coating can obtain through each the described method according to above claim.
(24) like (23) described coating, it is a kind of slip coating and/or hydrophobic coating.
(25) like (24) described coating, compare with organosilicon precursor, wherein the atom ratio of carbon and oxygen increases, and/or compares with organosilicon precursor, and wherein the atom ratio of oxygen and silicon reduces.
(26) like each described coating of (23) to (25), wherein this precursor is an octamethylcyclotetrasiloxane, and wherein this coating has a density, and this density is higher than under identical PECVD reaction conditions the density of the coating of making from HMDSO.
(27) each described coating of basis (24) to (26); Its floating coat (i) has the friction resistance lower than uncoated surface; Compare with uncoated surface; Wherein this friction resistance preferably is reduced by at least 25%, more preferably is reduced by at least 45%, even more preferably is reduced by at least 60%.
(28) each described coating of basis (24) to (27), this coating
(i) have the wet tension lower than uncoated surface, preferably from 20 to the wet tension of 72 dyne/cm, more preferably from 30 to the wet tension of 60 dyne/cm, more preferably from 30 wet tensions, preferred 34 dyne/cm to 40 dyne/cm; And/or
(iv) more hydrophobic than uncoated surface.
(29) a kind of container that on its at least a portion of inner surface, applies with each described coating according to (23) to (28), preferably a kind of container is:
(i) a kind of sample collection tube, a kind of specifically heparin tube; Or
(ii) a kind of bottle; Or
(iii) a kind of syringe or a kind of syringe part, a kind of specifically syringe cylinder or a kind of syringe plunger; Or
(iv) a kind of pipe; Or
(v) a kind of cuvette.
(30) according to the container of (29) described coating, additionally comprise at least one SiOx layer, wherein x is from 1.5 to 2.9, wherein
(i) this coating is between this SiOx layer and this substrate surface, or vice versa, or wherein
(ii) this coating is between two SiOx layers or vice versa, or wherein
(iii) these SiOx layers and this coating are the gradient composites of SiwOxCyHz to SiOx, or vice versa.
(31) according to each described coating container of (29) to (30), this container contains at least one other layer on its outer surface, other blocking layer that constitutes by plastics or SiOx preferably, and wherein x is from 1.5 to 2.9.
(32) each described coating container of basis (29) to (31); This container holds a kind of compound or compsn in its inner chamber; Preferably a kind of bioactive compounds or compsn or a kind of biological fluid, more preferably (i) Citrate trianion or a kind of compsn that contains Citrate trianion, (ii) a kind of medicament; Regular Insulin or a kind of compsn that contains Regular Insulin specifically, or (iii) blood or hemocyte.
(33) each described coating container of basis (29) to (32); This coating container is a kind of syringe cylinder that method according to claim 1 is made; Wherein this precursor is a kind of siloxanes; More preferably be a kind of monocycle siloxanes, even more preferably be octamethylcyclotetrasiloxane, and wherein in step (a), do not have O basically 2Gas is provided in this gaseous reactant, wherein compares with uncoated syringe cylinder, be used for mobile plunger through said coating the tube power reduced at least 25%, more preferably reduced at least 45%, even more preferably reduced at least 60%.
(34) have the coating of total formula SiwOxCyHz, wherein w is 1, and x is 0.5 to 2.4, and y is 0.6 to 3, and z is from 2 to 9, as the purposes of and the following
(i) has a kind of slip coating of the friction resistance lower than uncoated surface; And/or
(ii) more hydrophobic a kind of hydrophobic coating than uncoated surface.
(35) like (34) described purposes, wherein this coating is like defined a kind of coating in each of (24) to (28).
(36) like (34) or (35) described purposes; Wherein compare as the coated surface of the method for precursor with uncoated surface and/or with basis (1) described use HMDSO; This coating prevent or reduced with the contacted a kind of compsn of this coating in a kind of compound or the deposition of component, prevent particularly or reduced insulin precipitation or blood coagulation.
(37) purposes of basis (29) to each described coating container of (33); Be used for protecting the machinery and/or the chemical action on the surface that a kind of compound that is received or is received in said coating container or compsn avoid this uncoated container material, be preferably used for preventing or reduce with the deposition of a kind of compound of the contacted compsn of inner surface of this container or a kind of component and/or solidify.
(38) like (37) described purposes, wherein this compound or compsn are
(i) a kind of bioactive compounds or compsn, preferably a kind of medicament, Regular Insulin or comprise a kind of compsn of Regular Insulin more preferably, wherein insulin precipitation is reduced or prevents; Or
(ii) a kind of biological fluid, preferably a kind of body fluid, more preferably blood or a kind of blood ingredient, wherein blood coagulation and/or platelet activation are reduced or prevent.
(39) comprise a kind of medical science or diagnostic kit according to coating container of the present invention, this test kit can additionally comprise: a kind of medicament or diagnostic reagent, this medicine or diagnostic reagent are accommodated in the said coating container; And/or a kind of hypodermic needle, two ends syringe needle or other delivery catheters; And/or instruction book.
The present invention further provides following embodiment:
I. the container processing systems that has a plurality of treatment station and a plurality of pan straddles
According to an aspect of the present invention, provide to be used for a kind of container processing systems that container applies, this system comprises one first treatment station, second treatment station, a pan straddle and a transfer roller layout.This first treatment station is arranged to and carries out one first processing, for example the inner surface of this container is checked or is applied.This second treatment station is to be the basis with this first treatment station, and is arranged to and carries out one second processing, for example the inner surface of this container is checked or is applied.This pan straddle comprises a container port, and this port is configured to receive the opening of a container and it is taken a seat be used for via the container port that is positioned at this first treatment station and is positioned at this second treatment station the inner surface of this container of taking a seat being handled (inspection and/or apply and/or inspection).This transfer roller is arranged by adaptive being used for and after this first processing, this pan straddle and this container of taking a seat is used at this second treatment station the inner surface of this container of taking a seat being carried out second processing after this first treatment station is transported to this second treatment station.
These containers broadly are defined as the container that comprises any kind in this manual; Include but not limited to be used to collect or the sample hose of storing blood, urine or other samples; Be used to store or send the syringe of a kind of bioactive compounds or compsn; Be used to store the bottle of biomaterial or bioactive compounds or compsn; Be used to transport the conduit of biomaterial or bioactive compounds or compsn, and the cuvette that is used for containment of biological materials or bioactive compounds or compsn.
With undefined these containers all is to handle with one of the treatment system that describes below or device.In other words, with regard to a kind of device or treatment system, these characteristics that describe below can be used as also that method steps is implemented and can influence the container of processing like this.
Cuvette be have circle or square-section, end sealing, process by plastics, glass or fused quartz (being used for UV light) and be designed to hold sample be used for spectrum experiment a kind of tubule.Best cuvette is transparent as far as possible, does not have possibility to influence the impurity of spectrum reading.Like same test tube, tubule can be the top to atmosphere opening, or with a cap with its hermetically closing.
Term " inside of container " is meant and can be used for storing blood or according to the hollow space at internal tank (hollow space) of a kind of bioactive compounds or the compsn of another exemplary.
Term process can comprise a coating step and/or an inspection step or a series of coating and inspection step, for example an initial inspection step, and then a coating step, and then one second or even the 3rd or the 4th inspection then.This second, third and the 4th the inspection can carry out simultaneously.
According to an exemplary of the present invention; This pan straddle comprises a vacuum pipe that is used for from the internal space withdrawing gas of this container of taking a seat; Wherein this pan straddle is by the adaptive vacuum that is used to keep the inside of this container of taking a seat, and making does not so need other Vakuumkammer to handle this container.In other words, this pan straddle has formed a Vakuumkammer with this container of taking a seat, and this Vakuumkammer is used for providing in the internal space of this container a vacuum by adaptive.This vacuum is important for some treatment step (like plasma body enhanced chemical vapour deposition (PECVD) or other chemical vapour deposition steps).In addition, the vacuum of this internal tank possibly be important for a certain inspection of carrying out this container, and specifically for example the outgassing rate through measuring this wall or the specific conductivity of this wall come the inner surface of this wall of container is applied.
According to another exemplary of the present invention, during 30 seconds or less time, carry out this and first handle.And during 30 seconds or less time, carrying out this second handles.
Therefore, provide to be used for a kind of container processing systems that container applies, this container processing systems allows the quick manufacturing of these containers.
According to another exemplary of the present invention, this first processing and/or second processing comprise carries out an inspection to the inner surface of this container, then this inner surface is applied.
According to another exemplary of the present invention, this pan straddle comprises and being used for the gas input port of gas delivery to the inside of this container.
According to another exemplary of the present invention, this system is automatically handled this container detecting under the situation of holiday by adaptive being used for again.For example, this container processing systems and particularly this pan straddle can comprise a layout of different detectors (for example fluorescence detector, pressure probe, gas detector, be used for electrometric electrode etc.).
In addition, according to another exemplary of the present invention, this container processing systems, for example one or more treatment station comprise being used for container is transported to this pan straddle and/or is used for removing from this pan straddle one or more clamps of this container.
According to another exemplary of the present invention, this pan straddle comprises a gas input port of the inside that is used for delivering gas to this container.
According to another exemplary of the present invention, this container processing systems is automatically handled container detecting under the situation of holiday by adaptive being used for again.
Can use the gas in the internal space that is delivered to this container to come PECVD to apply the inner surface of this container.
According to another exemplary of the present invention, this first processing and/or this second processing comprise that the inner surface to this container applies.
According to another exemplary of the present invention, this first treatment station and/or second treatment station comprise and are used for the PECVD device that the inner surface to this container applies.
According to another exemplary of the present invention, this system further is included in the outer electrode on every side of top at least of this container of taking a seat.
According to another exemplary of the present invention, this pan straddle comprises a conductive probe that is used for providing at this container a counter electrode.
According to another exemplary of the present invention, this first processing and/or second is handled and is comprised that being directed against defective checks the inner surface of this container
According to another exemplary of the present invention; This system further comprises one first detector, and this first detector is adapted to be container port via this first treatment station and/or this second treatment station and is inserted into and is used in this container to defective the inner surface of this container being checked
According to another exemplary of the present invention, this container processing systems further comprises one second detector that is positioned at this container outside, and this second detector is used for to defective the inner surface of this container being checked.
According to another exemplary of the present invention, this first detector and/or this second detector are installed on this pan straddle.
According to another exemplary of the present invention, this pan straddle comprises a mould that is used to form this container.
According to another aspect of the present invention; Stated the purposes of the container processing systems of above and following description, a kind of transfer pipet that be used to make a kind of heparin tube, a kind of syringe that is used to store a kind of bioactive compounds or compsn that are used for storing blood, a kind of bottle that is used to store a kind of bioactive compounds or compsn, is used to transport a kind of conduit of multiple bioactive compounds or compsn or is used to pipette a kind of bioactive compounds or compsn.
This container processing systems can also be checked and can be carried out one first inspection to this container to defective by adaptive being used for particularly container by adaptive being used for; Inner surface to this container applies one first coating, to defective the inner surface of this coating container is carried out second inspection then.In addition, this system can be assessed the data of during the difference inspection, being obtained by adaptive being used for, and wherein this second inspection and data evaluation are consuming time less than 30 seconds.
According to another aspect of the present invention; Provide and be used for a kind of container processing systems that container is applied and checks; This system comprises a treatment station layout; This treatment station is arranged to be arranged to and is directed against defective this container is carried out one first inspection; Inner surface to this container applies one first coating, to defective the inner surface of the container of this coating is carried out one second and checks and the data of in checking process, obtaining are assessed, and wherein this second inspection and data evaluation are consuming time less than 30 seconds.
The applying of this first coating can also be called as first or second and handle and the inner surface of this coating container is carried out second inspection and can be called as second and handle.
According to another exemplary of the present invention; This treatment station is arranged and is comprised that one first treatment station being used to carry out this first inspection, the inner surface of this container of taking a seat is applied this first coating and carries out second inspection in addition; This treatment station is arranged and is comprised a pan straddle; This pan straddle comprises a container port, and this container port is arranged to an opening that receives this container and it is taken a seat and is used for the inner surface of this container of taking a seat being checked and applied first coating via the container port that is positioned at this first treatment station.
According to another exemplary of the present invention; This treatment station arranges and further comprises one second treatment station, and this second treatment station and this first treatment station are spaced apart and be arranged to and carry out second and check, apply one second coating and after applying this second coating, carry out one the 3rd inspection.In addition; This container processing systems comprises a transfer roller layout, and this transfer roller is arranged and is used for after applying this first coating, this pan straddle and this container of taking a seat being transported to the inner surface that this second treatment station is used at this second treatment station second coating being applied to this container of taking a seat from this first treatment station.Apply and check via the inner surface of the container port that is positioned at this first treatment station and is positioned at this second treatment station thereby the container port of this pan straddle is arranged to the opening that receives this container and it is taken a seat the container of taking a seat.
According to another exemplary of the present invention; This pan straddle comprises a vacuum pipe that is used for from the inside withdrawing gas of this container of taking a seat; Wherein this pan straddle is by the adaptive vacuum that is used to keep the inside of this container of taking a seat, and making does not so need other Vakuumkammer to come this container is applied and checks.
According to another exemplary of the present invention, each inspection is carried out in all during 30 seconds or less time.
According to another exemplary of the present invention, this container processing systems is automatically handled this container detecting under the situation of holiday by adaptive being used for again.
According to another exemplary of the present invention, this first treatment station and/or this second treatment station comprise a PECVD device that is used for the inner surface of this container is applied coating.
According to another exemplary of the present invention, this first coating is a barrier coat, and wherein this system is used to confirm that by adaptive a blocking layer is to exist or shortage.
According to another exemplary of the present invention, this second coating is a slip coating, and wherein this system is used to confirm that by adaptive this slip coating (i.e. this lubricant film) is to exist or shortage.
According to another exemplary of the present invention, this first coating is a barrier coat, and wherein this second coating is a slip coating, and wherein this system is used to confirm that by adaptive this blocking layer or this lubricant film are to exist or shortage.
According to another exemplary of the present invention, this system is used to confirm that by adaptive this blocking layer or this lubricant film are to exist or shortage (reaching the determinacy of at least six σ levels).
According to another exemplary of the present invention; This first inspection and/or this second inspection comprise at least one in the and the following: measure the outgassing rate from the gas of this coating container; Carry out the optical monitoring that coating applies; Measure the optical parametric of the inner surface of this coating container, and the electrical characteristic of measuring this coating container.
Can analyze corresponding take off data through treater then.
According to another exemplary of the present invention, this treatment system further comprises and is used to measure one first detector of outgassing rate and/or is used to measure one second detector of rate of diffusion and/or is used for one the 3rd detector of measuring light mathematic(al) parameter and/or is used to measure one the 4th detector of electrical parameter.
According to another exemplary of the present invention, this first coating and/or this second coating are thick less than 100nm.
According to another exemplary of the present invention, this container processing systems further comprises and is used for a treater that the data obtained during the inspection are assessed.
One aspect of the present invention is a kind of container processing systems, and this container processing systems comprises one first treatment station, second treatment station, a plurality of pan straddle and a transfer roller.This first treatment station is configured to be used to handle the container that has an opening and limit the wall of an inner surface.This second treatment station and this first treatment station separate and are configured to be used to handle the container that has an opening and limit the wall of an inner surface.
At least some, randomly all pan straddles comprise a container port, this port is configured to receive the opening of a container and it is taken a seat be used for the inner surface via handle a container of taking a seat at the container port at this first treatment station place.This transfer roller is configured to be used for that a series of pan straddle and the container of taking a seat are transported to second treatment station from this first treatment station and is used for via the inner surface of handling a container of taking a seat at the container port of this second treatment station.
The II pan straddle
II.A. the pan straddle that non-specificity sealing of quoting as proof is arranged
The carry-case support of this container processing systems can by adaptive be used to hold a container simultaneously the inner surface of this container be coated and check and simultaneously this container is transported to from one first treatment station one second treatment station of this container processing systems to defective; This pan straddle comprises a container port, and this container port is arranged to an opening that makes this container and takes a seat and be used for via being positioned at the inner surface of this container of taking a seat to first treatment station and the container port that is positioned at this second treatment station being handled.
According to another exemplary of the present invention, this carry-case support further comprises the pipeline that is used to receive second port or ventage of an extraneous gas supply and is used to make a kind of gas between vessel port and this second port that is landed on this container port, to pass through.
According to another exemplary of the present invention, this carry-case weight support frame is less than 2.25kg.
According to another exemplary of the present invention; This carry-case support further comprises a vacuum pipe and is used for via the external vacuum port of this container port from the inside withdrawing gas of this container of taking a seat; Wherein this pan straddle is by the adaptive vacuum that is used to keep the inside of this container of taking a seat, and making does not so need other Vakuumkammer to come this container is handled.
According to another exemplary of the present invention; This carry-case support further comprises a vacuum pipe and is used for via the external vacuum port of this container port from the inside withdrawing gas of this container of taking a seat; Wherein this pan straddle is by the adaptive vacuum that is used to keep the inside of this container of taking a seat, and making does not so need other Vakuumkammer to come this container is handled
According to another exemplary of the present invention, this external vacuum port has also combined a gas input port, and this gas input port is accommodated in the inside that is used for delivering the gas to this container of taking a seat in this vacuum ports.
According to another exemplary of the present invention, the processing of this container is comprised that the inner surface to this container of taking a seat applies.
According to another exemplary of the present invention, this pan straddle is processed by thermoplastic material in fact.
According to another exemplary of the present invention, this carry-case support further comprises a cylindrical form interior surface of a cylindrical wall that is used for receiving this container, at this cylindrical form interior surface and co-axial with it one first annular recesses and be disposed in one the one O shape circle that is used between this container of taking a seat and this pan straddle, providing a sealing in this first annular recesses.
According to another exemplary of the present invention, this carry-case support comprises that further one be adjacent to this cylindrical form interior surface (opening end of the container that this is taken a seat can dock above that) one is radially extended bearing (radially extending abutment).
According to another exemplary of the present invention, this carry-case support further comprise be arranged in this cylindrical form interior surface and co-axial with it and with this first annular recesses axially spaced-apart open one second annular recesses.In addition, this pan straddle comprises one the 2nd O type circle, and the 2nd O type circle is disposed in and is used to provide a sealing between this container of taking a seat and this pan straddle in this second annular recesses.
According to another exemplary of the present invention,, this carry-case support the inner surface of this container of taking a seat is checked to defective thereby further comprising one first detector that is used for inquiring after via container port the internal space of this container.
According to another exemplary of the present invention, this carry-case support comprises a mould that is used to form this container.
According to another exemplary of the present invention, the container processing systems that is used for the container coating comprises the pan straddle of above and the following stated.
According to another aspect of the present invention, this carry-case support comprises that a container port, second port, pipeline and one can carry housing.This container port is configured to make a vessel port to be seated in the relation that is interconnected.This second port is configured to receive an extraneous gas supply or ventage.This pipeline is configured to be used to make one or more gases between vessel port and this second port that is landed on this container port, to pass through.This container port, second port and pipeline are attached to this with the relation of inflexible in fact and can carry on the housing.Randomly, the weight of this carry-case support is less than five pounds.
Another aspect of the present invention is a kind of carry-case support, and this carry-case support comprises that a container port, vacuum pipe, vacuum ports and one can carry housing.This container port is configured to receive a vessel port with a relation sealing, that be interconnected.This vacuum pipe is configured to be used for from being landed in container on the container port via this container port withdrawing gas.This vacuum ports is configured between vacuum pipe and the outer vacuum source and is communicated with.This vacuum source can be to have than this vacuum pipe more pump or the reservoir or the ballast box of low pressure.This container port, vacuum pipe and vacuum ports are attached to this with the relation of inflexible in fact and can carry on the housing.Randomly, the weight of this carry-case support is less than five pounds.
II.B. comprise the pan straddle that sealing is arranged
Another aspect again of the present invention is a kind of pan straddle that is used to receive a kind of opening end of container, and this container has a columniform basically wall near its open end.This pan straddle can have a substantial cylindrical internal surface (for example cylindrical form interior surface), an annular recesses and an O type circle.Run through this specification sheets and should be understood that, it only is exemplary being indicated as being the container with circle or annular opening or cross section, and does not limit the scope of this disclosure or claims.If this container has non-circular openings or cross section (for example commonly when this container is cuvette); " circle " periphery of this pan straddle can be non-circular; And can use non-circular sealing member to seal, for example a kind of packing ring or be made into definite shape and be used to be sealed to a kind of sealing member on this noncircular cross section (except requiring especially in addition).In addition, " cylindrical " does not require the cylinder of rounded section, and comprises for example having the square of fillet by other cross-sectional shapes.
The internal surface of substantial cylindrical is made into a certain size columniform wall that is used to receive this container.
This annular recesses is disposed in this circular internal surface and is coaxial with it.This first annular recesses have one on this substantial cylindrical internal surface opening and with the isolated diapire of this substantial cylindrical inner surface radial direction.
This O type circle is disposed in this first annular recesses.With respect to this first annular recesses, this O type circle be made into a certain size be used for normally extending radially through this opening and by by the container that internal surface received of this substantial cylindrical radially to external pressure.This being arranged in forms a sealing between this container and this first annular recesses.
According to another aspect of the present invention, provide to be used for a kind of method that container is applied and checks, wherein to defective the inner surface of this container has been carried out one first inspection, the inner surface to this container applies a coating afterwards.Then, to defective the inner surface of the container of this coating is carried out one second inspection, and then the data of being obtained during this first and second inspection are assessed, wherein this second inspection and this data evaluation are consuming time less than 30 seconds.
According to another aspect of the present invention, the method that is used for processing vessel is provided, wherein this container opening is seated on the container port of a pan straddle, after this applies the inner surface of this container via this container port.Then, this coating is checked to defective via this container port.After this, this container is transported to one second treatment station from this first treatment station, wherein this container of taking a seat is held by this pan straddle during applying, check and transporting.
III is used to transport the method for the container-container that is seated on the pan straddle is handled
III.A. pan straddle is transported to treatment station
Another aspect of the present invention is a kind of method that is used for processing vessel.Provide one first treatment station and with isolated one second treatment station of this first treatment station, be used for processing vessel.A kind of container that has an opening and define a wall of an inner surface is provided.A kind of pan straddle that comprises container port is provided.The opening of this container is seated on this container port.Via the container port that is positioned at this first treatment station the inner surface of this container of taking a seat is handled.This pan straddle and the container of taking a seat are transported to this second treatment station from this first treatment station.Then, via the container port that is positioned at this second treatment station the inner surface of this container of taking a seat is handled.
III.B. treatment facility is transported to pan straddle or vice versa
Another aspect of the present invention is to be used for a kind of method that the container that comprises several parts is handled.Provide one first treatment facility and one second treatment facility, be used for processing vessel.A kind of a kind of container that has an opening and define a wall of an inner surface is provided.Provide a kind of opening of this container of pan straddle of container port that comprises to be seated on this container port.
This first treatment facility is moved into during the operability of this pan straddle engages, or vice versa.Use this first treatment facility that the inner surface of this container of taking a seat is handled via this container port
This second treatment facility is moved into during the operability of this pan straddle engages, or vice versa.Use this second treatment facility that the inner surface of this container of taking a seat is handled via this container port.
III.C. use clamp that pipe is transported and get into and leave treatment station
Another aspect again of the present invention is that one first container is carried out a kind of method that plasma body enhanced chemical vapour deposition (PECVD) is handled, and comprises following step.Provide at least one first clamp of one first container to be arranged to the closing end that optionally keeps and discharge this first container with an opening end, a closing end and an inner surface.The closing end of this first container is clamped with this first clamp, and use this first clamp with its be transported to a pan straddle near, this pan straddle is configured to make the opening end of this first container to take a seat.Use this first clamp axially to advance this first container then and its opening end is seated on this pan straddle, between the inside of this pan straddle and this first container, set up being communicated with of sealing.
At least a gaseous reactant is introduced within this first container through this pan straddle.Under the condition of the reaction product that effectively forms this reactant, on the inner surface of this first container, form plasma body.
This first container is disseated from this pan straddle, and use this first clamp or another clamp, this first container is axially transported leave this pan straddle.Then thereby this first container is discharged axially it to be transported from employed clamp and leave this pan straddle.
IV is used to make the PECVD device of container
IV.A. comprise pan straddle, internal electrode, as the PECVD device of the container of reaction chamber
According to another aspect of the present invention, provide and be used for a kind of plasma enhanced chemical vapor deposition (PECVD) device that the inner surface to container applies.This PECVD device can be the part of this container processing systems and comprise a pan straddle; Like support in above and the following stated; This support comprises a container port; This container port is arranged to one first opening that receives this container and it is taken a seat, and is used for via this container port the inner surface of this container of taking a seat being handled.In addition, this PECVD device outer electrode comprising an internal electrode within the internal space that is used to be disposed in this container of taking a seat and have an external portion that is used to receive this container of taking a seat.In addition, provide a power supply to be used in this container, producing plasma body, wherein this container of taking a seat and this pan straddle are used to limit a plasma-reaction-chamber by adaptive.
According to another exemplary of the present invention, this PECVD device further comprises and is used for a vacuum source being found time in the internal space of this container of taking a seat, and wherein this container port and this container of taking a seat are used to limit a Vakuumkammer by adaptive.
According to another exemplary of the present invention, this PECVD device further comprises and being used for the gas feed device of reactant gas from the internal space of this container of reactant gas source feeding.
According to another exemplary of the present invention, this gas feed device is positioned in the distal portions of this internal electrode.
According to another exemplary of the present invention, this internal electrode is a probe, and this probe has and is positioned to extend into a distal portions in this container of taking a seat with one heart.
According to another exemplary of the present invention, this outer electrode has a cylindrical cross-section and extends with one heart around this container of taking a seat.
According to another exemplary of the present invention; This PECVD device further comprises a clamp; This clamp is used for the closing end that selectivity keeps and discharges this container, and clamps the closing end of this container simultaneously, be used for this container be transported to this pan straddle near.
According to another exemplary of the present invention, this PECVD device is formed a kind of plasma body by adaptive being used in the internal space of this container, is substantially devoid of hollow cathode plasma.
According to another exemplary of the present invention, this PECVD device further comprises and is used for being used for to defective the inner surface of this fixed container being checked via the detector that this container port is inquired after the internal space of this container.
According to another exemplary of the present invention; This PECVD device further comprises the processing vessel with a processing vessel opening, and this processing vessel opening is used for being connected to allow reactant gas to flow into this processing vessel from the internal space of this container with one second opening that limits of this container.
According to another exemplary of the present invention, a far-end of this internal electrode is to locate to the distance of the opening of this second restriction less than the half the first big opening from this container of taking a seat.
According to another exemplary of the present invention, the far-end of this internal electrode is positioned in the outside of the first big opening of this container of taking a seat.
In addition, provide to be used for a kind of method that the inner surface to container applies, wherein this container opening is received and is seated on the container port of pan straddle and is used for the inner surface of this container of taking a seat is handled.Then, an internal electrode is arranged in the internal space of this container of taking a seat, after this a gas feed device is positioned at the distal portion office of this internal electrode.In addition, this container of taking a seat is received in the internal portion of outer electrode.The container of taking a seat in this pan straddle is used to limit a plasma-reaction-chamber by adaptive.
Specifically, can limit a Vakuumkammer and gas is extracted out from the internal space of this container of taking a seat through this container port and this container of taking a seat, making so need outer vacuum chamber to be used for applying.
In a further step, a kind of plasma body of formation and a kind of coating material are deposited on the inner surface of this container of taking a seat in the internal space of this container.
According to another exemplary of the present invention, a processing vessel opening is connected with the opening of a restriction of this container to allow reactant gas to flow into this processing vessel from the internal space of this container.
According to another aspect of the present invention; More than and the purposes of the PECVD device of following description be a kind of cuvette that be used to make a kind of heparin tube, a kind of syringe that is used to store a kind of bioactive compounds or compsn that is used for storing blood, a kind of bottle that is used to store a kind of bioactive compounds or compsn, is used to transport a kind of conduit of multiple bioactive compounds or compsn or is used to hold a kind of bioactive compounds or compsn.
Another aspect of the present invention is a kind of PECVD device that comprises a pan straddle, an internal electrode, an outer electrode and a power supply.
This pan straddle has a container is received in a port to handle in the position of taking a seat.This internal electrode is positioned and is seated to be received in that this outer electrode has an internal portion within the container on the pan straddle, thereby this internal portion is positioned and is seated at this power supply of container on this pan straddle with reception and alternating-current is input within the container that is seated on this pan straddle, forms this container of plasma body on inside and/or the outer electrode and define a plasma-reaction-chamber.
Of the present invention even another aspect is a kind of PECVD device described in earlier paragraphs; An eduction pipe that must not comprise vacuum source wherein is provided; Be used for the gas inside from this container is perhaps transmitted in gas transfer to the inside that is landed in the container on this port, to limit a closed-chamber.
IV.B. use pipe is transported the PECVD device that gets into and leave the clamp that applies the station
Another aspect of the present invention is to be used for one first container is carried out the device that PECVD handles, and this first container has an opening end, a closing end and an internal space.This device comprises a pan straddle, first clamp, a seat on this pan straddle, a reactant feeding mechanism, a plasma generator and a container releasing device.
This pan straddle is arranged to the opening end of a container is taken a seat.This first clamp is arranged to and optionally keeps and discharge the closing end of container and clamp the closing end of this container simultaneously; Near this pan straddle that this container is transported to this pan straddle has a seat, and this is configured between the internal space of this pan straddle and this first container and sets up being communicated with of sealing.
This reactant feeding mechanism is operably connected to be used for through this pan straddle at least a gaseous reactant being incorporated within this first container.This plasma body producer is configured under the condition of the reaction product that effectively forms reactant on the inner surface of this first container and in this first container, forms plasma body.
This container releasing device is provided for making this first container to disseat from this pan straddle.A clamp (this clamp is first clamp or another clamp) is arranged to and axially transports this first container and leave this pan straddle and discharge this first container then.
The V.PECVD method
A kind of method that is used for the inner surface of container is applied (and/or inspection) is provided according to another aspect of the present invention; Wherein this container opening is received and is seated to be used on the pan straddle inner surface of this container of taking a seat handled and should be noted in the discussion above that term process can be meant a coating step or several coating steps or even be meant a series of coating and inspection step.
In addition, the inner surface of this container of taking a seat is carried out one first and handle to be what a container port via the pan straddle that is positioned at one first treatment station carried out.Then; After this first treatment station place carries out first processing; The container that this pan straddle and this are taken a seat is transported to one second treatment station then, at this second treatment station place, via the container port of this pan straddle the inner surface of this container of taking a seat is carried out one second processing.
V.A. use plasma body to apply SiO xThe PECVD of barrier coat, this plasma body is substantially free of hollow cathode plasma
Another aspect of the present invention is with a kind of SiO xBarrier coat is applied to a kind of method of (preferably on the inside of a container) on the surface, and wherein x is from about 1.5 to about 2.9 in this formula, and alternately from about 1.5 to about 2.6, alternately about 2.This method comprises several steps.
A surface (like a wall of container) is provided, as has been both a kind of reaction mixture, this mixture comprises a kind of organic silicon compound gas, randomly a kind of oxidizing gas, and randomly a kind of appropriate hydrocarbon gas.
Plasma body forms in reaction mixture, is substantially free of hollow cathode plasma.This wall of container is contacted with this reaction mixture, and with SiO xBe coated with at least one part that is deposited to this wall of container.
V.B.PECVD applies the vessel port (capillary injection device) of restriction
Another aspect of the present invention is to be used for a kind of method that the internal surface to the opening of the restriction of container that the generally tubular that PECVD for use handles is arranged applies.This method comprises these steps.
Provide the container of a pending generally tubular.This container comprises an outside surface, defines an internal surface of an inner chamber, has a bigger opening of internal diameter and the opening of a restriction, the opening of this restriction limit an internal surface and the internal diameter that has less than the internal diameter of this bigger opening.
A kind of processing vessel is provided, and this processing vessel has an inner chamber and a processing vessel opening.This processing vessel opening links to each other with the opening of the restriction of this container, to set up between this inner chamber that pending container is arranged and this processing vessel inner chamber being communicated with via the opening of this restriction.
This is had in the inner chamber of inner chamber and this processing vessel of pending container be pumped into partial vacuum at least.Make a kind of PECVD reagent flow through this first opening,,, get into the inner chamber of this processing vessel then then through the opening of this restriction then through the inner chamber of pending container is arranged.Producing plasma body near the opening in this restriction under the condition on the internal surface of the opening that effectively the PECVD reaction product is deposited to this restriction.
V.C. apply the method for slip coating
Another aspect again of the present invention is that a kind of slip coating is applied to a kind of suprabasil method.This method is following the realization.
A kind of precursor is provided.Preferably a kind of silicoorganic compound of this precursor, more preferably any two kinds or the more kinds of a kind of combinations among linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane or these precursors.Also consider other precursors, for example contained the Organometallic precursor of metal of III-th family and the IV family of periodic system.Under the condition that effectively forms a kind of coating, this precursor is applied in a kind of substrate.This is coated with layers of polymer or crosslinked (or both), thereby forms a kind of lubricated surface, than untreated substrate should lubricated surface have lower like defined in this specification sheets " plunger sliding force " or " starting force ".
The VI container inspection
VI.A. comprise that precoating and back apply the container processing of inspection
Even another aspect of the present invention is a kind of container-treatment that is used to handle plastic containers, and these plastic containers have an opening and a wall that limits inner surface.This method is to carry out through following steps: to defective to as the inner surface of this container of being provided check; Inner surface to this container after checking like this container that is provided is being applied a coating; And this coating is checked to defective.
Another aspect of the present invention is a kind of container-treatment, wherein to after checking like institute's container for moulding a barrier coat is applied on this container, and the inner surface to this container of defective is checked after applying this barrier coat.
VI.B. according to the container inspection of test example like the venting of the wall of container through the blocking layer
Another aspect of the present invention is to be used for a kind of method (" venting method ") that coating is checked through measuring the volatile species of being emitted by coated article.Can use said method to come the product of coating processes is checked, wherein a kind of coating has been applied to the surface of substrate to form a kind of coated surface.Specifically, this method is used as for the online process control of a coating processes so that identify and get rid of the coated product that do not satisfy a preassigned or the coated product of damage.
Usually; " volatile species " is a kind of gas or steam under test conditions; And preferably be selected from down group; This group is made up of and the following: air, nitrogen, oxygen, water vapour, volatility coating ingredients, volatility substrate components and their a kind of combination more preferably are air, nitrogen, oxygen, water vapour or their a kind of combination.This method can be used for measuring only one or more volatile species, but preferably in step (c), has measured multiple different volatile species, and preferably in step (c), has measured all volatile species from the release of inspection object basically.
This venting method may further comprise the steps:
Provide this product as the inspection object;
Measure at least a volatile species from this inspection object to the contiguous gas space of this coated surface in release; And
The result of step (c) and result for the step (c) of at least one references object of under same test conditions, measuring are compared, thereby confirm the existence of this coating or the physics and/or the chemical property of shortage and/or this coating.
In said venting method, there are the physics of coating to be determined and/or chemical property can be selected from down group, this group is made up of and the following: its barrier effect, its wet tension and its formation and its barrier effect preferably.
Advantageously, step (c) is to carry out through the mass flow rate or the volumetric flow rate of at least a volatile species in the gas space of measurement and this coated surface vicinity.
Preferably, references object is a kind of (i) uncoated substrate; It perhaps (ii) is the substrate that a kind of usefulness applies with reference to coating.This depends on; For example, this venting method characteristic (for example comparing) of whether being used to confirm the existence or the shortage (this references object can be a kind of uncoated substrate so) of a coating or being used to confirm this coating with a kind of coating with known features.In order to confirm the consistence of this coating and a kind of specific coating, a kind of also will be typical selection with reference to coating.
This venting method can also comprise that step (b) is as in step (a) and an other step (c); This step (b) change with the contiguous gas space of coated surface in air pressure, provide like this one pass the pressure reduction of coated surface and can realize this volatile species than in the higher mass flow rate or the volumetric flow rate that do not have under the situation of pressure reduction.In this case, this volatile species will move on the direction than the low pressure differential side.If should apply, confirm that then the pressure reduction between this container intracavity and its outside is so that measure the venting from this volatile species of this coating container wall to liking a container.This pressure reduction can for example provide through the gas space of at least partly finding time in container.In this case, can measure the volatile species of being emitted this container intracavity of entering.
If application of vacuum produces a pressure reduction, can carry out this measurement through using the measuring cell between a coated surface that is inserted in substrate and the vacuum source.
On the one hand; Preferably in order to allow said volatile species to absorb on the material of this inspection object or to absorb the material that gets into this inspection object; This inspection object is contacted with a kind of volatile species; Preferably this volatile species is to be selected from down group, and this group is made up of and the following: air, nitrogen, oxygen, water vapour and a kind of their combination.Then, in step (c), measured the follow-up release of volatile species from this inspection object.Because material different (as, for example, this coating and this substrate) have different adsorption and characterization of adsorption, this can simplify the existence of a coating and confirming of characteristic.
This substrate can be a kind of polymerizable compound, randomly is a kind of combination of a kind of polyester, a kind of polyolefine, a kind of cyclic olefine copolymer, a kind of polycarbonate or these compounds.
In the context of the present invention, the coating that is characterized by this venting method typically is a kind of a kind of coating for preparing through PECVD from for example a kind of organosilicon precursor as described herein.Of the present invention concrete aspect, (i) this coating is a kind of barrier coat, preferably a kind of SiO xLayer, wherein x is from about 1.5 to about 2.9; And/or (ii) this coating is oilness and/or the capillary a kind of coating that changes this coated substrate, the layer of a kind of SiwOxCyHz preferably, and wherein w is 1, and x is from about 0.5 to 2.4, and y is from about 0.6 to about 3, and z is from 2 to about 9.
When the coating processes through its product of this venting method inspection is a kind of PECVD that under vacuum condition, carries out when applying, its venting is subsequently measured even can not have destruction to be used for carrying out under the situation of vacuum of PECVD.
The volatile species of measuring can be a kind of volatile species that discharges from this coating, a kind of volatile species that discharges from this substrate, or a kind of both combination.On the one hand, this volatile species is a kind of volatile species that discharges from this coating, a kind of volatility coating ingredients preferably, and carries out this inspection with the existing of definite this coating, characteristic and/or formation.On the other hand, this volatile species is a kind of volatile species that discharges from this substrate and carries out this inspection existing and/or the barrier effect of this coating with definite this coating.
Venting method of the present invention is particularly suitable for confirming the existence and the characteristic of a coating on wall of container.Therefore, this coated substrate can be a kind of container, and this container has one at the wall that is coated of the part at least on surface or the outside surface within it during the coating processes.For example, this coating is placed on the internal surface of this wall of container.
The condition of effectively distinguishing the existence or the shortage of this coating and/or confirming physics and/or the chemical property of this coating comprises less than one hour or less than one minute or less than 50 seconds or less than 40 seconds or less than 30 seconds or less than 20 seconds or less than 15 seconds or less than 10 seconds or less than 8 seconds or less than 6 seconds or less than 4 seconds or less than 3 seconds or less than 2 seconds or less than 1 second test time (test duration).
In order to be increased in the difference between a references object and this inspection object about the kind of rate of release and/or measured volatile species, can be through changing the rate of release that environmental stress and/or temperature and/or humidity change this volatile species.
One concrete aspect, use a kind of microcantilever beam measuring technology to measure venting.For example, this measurement can be carried out through following steps:
(i) (a) at least one microcantilever beam is provided, this microcantilever beam has mobile or changes to a difform characteristic when a kind of material of emitting exists;
(b) this microcantilever beam is exposed to the material that this is emitted causing that effectively this microcantilever beam moves or changes under the difform condition; And (c) detecting this moves or different shapes; Preferably a kind ofly come leisure that this micro-cantilever is exposed to before the venting the for example a kind of laser beam of high energy incident beam with the part of this microcantilever beam that changes shape afterwards, and measure deflection at the reflected beam that produces with this socle girder point place at interval through reflecting; Perhaps pass through
(ii) (a) provides at least one micro-cantilever, and this micro-cantilever is with a different frequency resonance when a kind of material of emitting exists;
(b) this micro-cantilever is exposed in this material of emitting effectively causing under this micro-cantilever is with the condition of a different frequency resonance; And (c) detect this different resonant frequency, for example use a resonant transducer.
Also considered to be used to carry out a kind of device of this venting method, for example a kind of device that comprises like above-mentioned micro-cantilever.
Use venting method of the present invention, for example can check a blocking layer on a kind of material of letting off steam, wherein this inspection method has several steps.Provide emit a kind of gas and have a sample of the material on part blocking layer at least.Of the present invention one concrete aspect, a pressure reduction of crossing over this blocking layer is provided, the material of at least some venting is the high-tension sides on this blocking layer like this.Measured the gas of emitting that passes this blocking layer.If there is a pressure reduction, then this measurement randomly is on the low-tension side on this blocking layer, to carry out.
The container that VII PECVD handles
VII.A.1.a.i. from the sedimentary hydrophobic coating of organosilicon precursor
Another aspect of the present invention is from the sedimentary a kind of hydrophobic coating of a kind of organosilicon precursor, for example on inner side-wall, has in the container of hydrophobic coating.This coating is the type of making through following steps.
A kind of precursor is provided; This precursor is a kind of organometallic compound; Preferably a kind of silicoorganic compound; More preferably be selected from down a kind of compound of group, this group is made up of and the following: linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, alkyl trimethoxysilane, linear silicon azane, monocycle silazane, encircle silazane more, gather any two kinds or more kinds of a kind of combinations among sesquialter silazane or these precursors.Alternately, can the organometallic compound that contain III-th family or IV family metal be thought of as precursor.
Under the condition that effectively forms a kind of coating, this precursor is applied in a kind of substrate.This coating is by polymerization or crosslinked (or both), thereby forms a hydrophobic surface that has than is untreated the higher contact angle of substrate.
The coating that generates can have total formula: Si wO xC yH z, wherein w is 1, and x is from about 0.5 to about 2.4, and y is from about 0.6 to about 3, and z is from about 2 to about 9, and preferably wherein w is 1, and x is from about 0.5 to 1, and y is from about 2 to about 3, and z is from about 6 to about 9.
These values that run through the employed w of this specification sheets, x, y and z are to be understood that and are the ratio in an empirical formula (for example, for a coating), rather than to the limited in number of the atom in the molecule.For example, has molecular formula Si 4O 4C 8H 24Octamethylcyclotetrasiloxane can describe through following empirical formula (term is changed by us), through the w in this molecular formula, x, y and z are obtained Si divided by 4 (greatest common factors) separately 1O 1C 2H 6And the value of w, x, y and z also is not limited to integer.For example, (non-annularity) octamethyltrisiloxane, molecular formula Si 3O 2C 8H 24, be Si by yojan 1O 0.67C 2.67H 8
VII.A.1.b has the Citrate trianion heparin tube that is coated with from the wall of the sedimentary hydrophobic coating of organosilicon precursor
Another aspect of the present invention is a kind of cell preparation pipe, and this pipe has a wall that is equipped with a hydrophobic coating and accommodates a kind of aqueous citric acid sodium reagent.
This wall is processed by thermoplastic material, has an internal surface that defines an inner chamber.
This hydrophobic coating is provided on the internal surface of this pipe.This hydrophobic coating is made through a kind of organometallic compound is provided; Preferably a kind of silicoorganic compound of this organometallic compound; More preferably be a kind of compound that is selected from down group, this group is made up of and the following: linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, alkyl trimethoxysilane, linear silicon azane, monocycle silazane, encircle silazane more, gather any two kinds or more kinds of a kind of combinations among sesquialter silazane or these precursors.Use PECVD on internal surface, to form a coating.The coating that generates can have following structure: Si wO xC yH z, wherein w is 1, and x is from about 0.5 to about 2.4, and y is from about 0.6 to about 3, and z is from about 2 to about 9, and preferably wherein w is 1, and x is from about 0.5 to 1, and y is from about 2 to about 3, and z is from 6 to about 9.
The amount of solidifying that the aqueous citric acid sodium reagent is introduced in the blood in this pipe with effective inhibition places the inner chamber of this pipe.
VII.A.1.c.SiO xDouble-walled plastic containers-COC, PET, SiO that the blocking layer applies xLayer
Another aspect of the present invention is to have a kind of container that at least partly centers on the wall of an inner chamber.This wall has an inner polymeric layer that is centered on by an external polymer layer.One of these polymer layers are layers that defines thick cyclic olefine copolymer (COC) resin of the 0.1mm at least of a water vapor barrier layer.Another kind in these polymer layers is a layer of the vibrin that 0.1mm is thick at least.
This wall comprises a SiO xOxygen barrier, wherein x is from about 1.5 to about 2.9 in this formula, alternately about 2 alternately from about 1.5 to about 2.6, this blocking layer has from about 10 thickness to about 500 dusts.
VII.A.Ld. make method-COC, PET, the SiO of double-walled plastic containers xLayer
Another aspect of the present invention is to make layer having a wall that an interior polymeric thing side is centered on by an external polymer layer, to be made by COC and a kind of method of the container of other parts of being made by polyester.This container is to make through a kind of technology that comprises following each item: COC and polyester resin layer are incorporated in the injection mold through the concentric injection nozzle.
An optional other step is through PECVD a kind of amorphous carbon coating to be put on this container, as a coated inside, exterior coating or as interlayer between these layers or interlayer coating.
An optional other step is with a SiO xThe blocking layer puts on the inside of this wall of container, wherein SiO xLike preceding definition.Another optional other step is to this SiO with a kind of process gas (mainly comprise oxygen and be substantially free of volatile silicon compound) xLayer carries out aftertreatment.
Randomly, can form this SiO by the silazane feed gas at least in part xCoating.
VII.A.1.e. the barrier coat of processing by glass
Another aspect of the present invention is the container that comprises a wall of container, a barrier coat and a closure member.This container roughly is piped and is processed by thermoplastic material.This container has an opening and part is by an inner chamber of a wall qualification at least, and this wall has an internal surface with this inner chamber boundary.On the internal surface of this wall, there is process by glass one successive barrier coat at least basically.Closure member covers this opening and the inner chamber of this container is isolated from ambient air.
Related fields of the present invention are a kind of containers described in earlier paragraphs, and wherein this barrier coat is to be processed by the glass of soda-lime glass, borosilicate glass or another kind of type.
The VII.A.2 stopper
VII.A.2.a. in Vakuumkammer, slip coating is applied to the method on the stopper
Another aspect of the present invention be with a kind of coating for example as a kind of slip coating of above definition be applied on a kind of elastomeric stopper a kind of method for example, a stopper is positioned in the chamber of finding time basically.A kind of reaction mixture is provided, and this reactant comprises that plasma body forms gas, promptly a kind of organic silicon compound gas, randomly a kind of oxidizing gas, and randomly a kind of appropriate hydrocarbon gas.Plasma body forms in this reaction mixture, and this reaction mixture contacts with this stopper.With a kind of slip coating (Si for example wO xC yH zA coating, preferably wherein w is 1, x is from about 0.5 to 2.4 in this formula; Y is from about 0.6 to about 3; And z is from 2 to about 9, and preferably wherein w is 1, and x is from about 0.5 to 1; Y is from about 2 to about 3, and z is from 6 to about 9) be deposited at least a portion of this stopper.
VII.A.2.b. through PECVD a coating of III-th family or IV family element and carbon is applied on the stopper
Another aspect of the present invention is that a kind of coating with the compsn of one or more elements that comprise carbon and III-th family or IV family is applied to a kind of method on the elastomeric stopper in order to realize this method, and a stopper is positioned in the sediment chamber.
A kind of reaction mixture is provided in the sediment chamber; This reaction mixture comprises that a kind of plasma body forms gas and a kind of iii group element (for example Al), the gas source of a kind of IV family's element (for example, Si, Sn) or two kinds or more kinds of a kind of combinations among these.This reaction mixture randomly comprises a kind of oxidizing gas and randomly comprises a kind of gaseous compound with one or more c h bonds.Plasma body forms in this reaction mixture, and this stopper contacts with this reaction mixture.One with iii group element or compound, a kind of IV element or compound or among these two kinds or more kinds of a kind of combination is coated with at least a portion that is deposited upon this stopper.
VII.A.3. the plastic containers with barrier coat that stopper clogs, this barrier coat effectively provide 95% vacuum to keep continuing 24 months
Another aspect of the present invention is the container that comprises a wall of container, a barrier coat and a closure member.This container be generally tubular and process by thermoplastic material.The inner chamber that this container has an opening and at least partly limited by a wall.This wall has an internal surface with this inner chamber boundary.With one at least basically the successive barrier coat be applied on the internal surface of this wall.This barrier coat effectively keeps in this container at least 90% its initial vacuum level, and randomly 95% its initial vacuum level continues at least 24 months quality guaranteed period.A closure member is provided, and this closure member covers this opening and the inner chamber of this container is isolated from ambient air.
VII.B.1.a. has the syringe that is coated with from the tube of the sedimentary slip coating of Organometallic precursor
Another aspect again of the present invention is a kind of container, and this container has a slip coating of being processed by a kind of organosilicon precursor.It is also conceivable that like a kind of different Organometallic precursor in this definition.
This coating can be the type of making through following method.
A kind of precursor is provided; This precursor is a kind of Organometallic precursor; Preferably a kind of organosilicon precursor more preferably is linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, linear silicon azane, monocycle silazane, encircle silazane, gather any two kinds or more kinds of a kind of combinations among sesquialter silazane or these precursors more.
Under the condition that effectively forms a kind of coating, this precursor is applied in a kind of substrate.This is coated with layers of polymer or crosslinked (or both), thereby forms a kind of lubricated surface, should have lower plunger sliding force or starting force in lubricated surface than untreated substrate.
Another aspect of the present invention is a kind of syringe that comprises a plunger, a syringe cylinder and a lubricant film.This syringe cylinder has an inner surface that receives this plunger slidably.This lubricant film is disposed on the inner surface of this syringe cylinder and comprises the Si that makes from like defined organosilicon precursor this specification sheets wO xC yH zA coating of lubricant film.This lubricant film has less than the thickness of 1000nm and has reduced necessary starting force of mobile plunger or plunger sliding force in tube effectively.
Another aspect of the present invention is a slip coating on the inwall of syringe cylinder.This coating is to use following material and condition to produce according to the PECVD process.Adopted a kind of cyclic precursor, this cyclic precursor is selected from monocycle siloxanes, many cyclosiloxane or two kinds or more kinds of a kind of combinations among these.At least basically there is not oxygen to join in this process.Provide enough plasma generation power inputs to form to induce coating.With respect to uncoated syringe cylinder, syringe plunger sliding force or starting force that material that is adopted and condition will move through this syringe cylinder effectively reduce at least 25%.
The coating that generates can have following formula: Si wO xC yH z, wherein w is 1, and x is from about 0.5 to about 2.4, and y is from about 0.6 to about 3, and z is from about 2 to about 9, and preferably wherein w is 1, and x is from about 0.5 to 1, and y is from about 2 to about 3,, and z is from 6 to about 9.
VII.B.1.a.i. slip coating: SiO xBlocking layer, lubricant film, surface treatment.
Another aspect of the present invention is the syringe that comprises a tube, and this defines an inner chamber and has an inner surface that receives a plunger slidably.This syringe cylinder is processed by thermoplasticity basis material.Through PECVD a slip coating for example is applied on this inner surface, this plunger or both.This slip coating be process from a kind of organosilicon precursor and be thick less than 1000nm.An amount with the leaching of this lubricant film of effective minimizing, this thermoplasticity basis material (or both) is carried out surface treatment on this slip coating.This slip coating and solute restraining mass (solute retainer) are configured and exist with the relative quantity that starting force, plunger sliding force or both (this power is less than lacking slip coating and the needed corresponding power of solute restraining mass) effectively are provided.
VII.B.1.b has the SiO of using xThe syringe of the tube of the outside that inside that applies and blocking layer apply
Another aspect again of the present invention is a kind of syringe cylinder that comprises a plunger, a tube and inside and outside barrier coat.This blocking layer is by the thermoplasticity basis made that defines an inner chamber.This has an inner surface and outer surface that receives this plunger slidably.A SiO xBarrier coat is provided on this inner surface, and wherein x is from about 1.5 to about 2.9 in this formula, and alternately from about 1.5 to about 2.6, randomly about 2.A kind of resin barrier coat is provided on this outer surface.
VII.B.1.c makes has the SiO of using xThe method of the syringe of the tube of the outside that inside that applies and blocking layer apply
Of the present invention even another aspect is to make a kind of method of syringe, and this syringe comprises a plunger, tube and inside and outer barrier coating.A kind of tube with an inner surface receiving this plunger slidably and an outer surface is provided.With a SiO xBarrier coat is provided at through PECVD on this inner surface, and wherein x is from about 1.5 to about 2.9 in this formula, and alternately from about 1.5 to about 2.6, alternately about 2.A kind of barrier coat of resin is provided on this outer surface.This plunger and tube are assembled thereby a kind of syringe is provided.
The VII.B.2 plunger
VII.B.2.a. has the piston front that the blocking layer applies
Another aspect of the present invention is a kind of plunger that is used for syringe, and this plunger comprises a piston and a push rod.This piston has side and rear section of a front, a substantial cylindrical, and this side is configured to be seated within the syringe cylinder movably.This front has a barrier coat.This push rod engages this rear section and is configured to make this piston in syringe cylinder, to advance.
VII.B.2.b. has the slip coating that has a common boundary with the side
Another aspect again of the present invention is a kind of plunger that is used for syringe, and this plunger comprises a piston, a slip coating and a push rod.This piston has a front, the side of a substantial cylindrical and a rear section.This side is configured to be seated within the syringe cylinder movably.This lubricant film and this side meet the boundary.This push rod engages the rear section of this piston and is configured to make this piston in syringe cylinder, to advance.
VII.B.3 two-piece type syringe and female luer
Another aspect of the present invention is the syringe that comprises a plunger, a syringe cylinder and a female luer.This syringe cylinder comprises an inner surface that receives this plunger slidably.This female luer comprises a luer taper, and this luer taper has an internal passages that is limited an internal surface.This female luer is to form and to be connected on this syringe cylinder through a junctor with the form of the isolating separation member of this syringe cylinder.The internal passages of this luer taper has a kind of SiO xBarrier coat, wherein x is from about 1.5 to about 2.9 in this formula, alternately from about 1.5 to about 2.6, alternately about 2.
The slip coating that VII.B.4 makes through the in-situ polymerization organosilicon precursor
VII.B.4.a. through handling and lubricated product
Another aspect again of the present invention is a kind of slip coating of processing from organosilicon precursor.This coating is the type of being processed by following method.
A kind of precursor is provided; This precursor is selected from a kind of Organometallic precursor; Preferably a kind of organosilicon precursor, encircles silazane more, gathers any two kinds or more kinds of a kind of combinations among sesquialter silazane or these precursors preferred linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, linear silicon azane, monocycle silazane.Under the condition that effectively forms a kind of coating, this precursor is applied in a kind of substrate.This is coated with layers of polymer or crosslinked (or both), thereby forms a kind of lubricated surface, should have lower plunger sliding force or starting force in lubricated surface than untreated substrate.
The coating that generates can have following structure: Si wO xC yH z, wherein w is 1, and x is from about 0.5 to about 2.4, and y is from about 0.6 to about 3, and z is from about 2 to about 9, and preferably wherein w is 1, and x is from about 0.5 to 1, and y is from about 2 to about 3, and z is from 6 to about 9.
VII.B.4.b. the product of technology and analytical characteristics
Of the present invention even another aspect is to pass through the sedimentary slip coating of PECVD from Organometallic precursor; Preferably from a kind of organosilicon precursor, more preferably from linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, linear silicon azane, monocycle silazane, encircle silazane more, gather sesquialter silazane or two kinds or more kinds of a kind of combinations among these.As having through determined this coating of X ray reflection rate (XRR) 1.25 and 1.65g/cm 3Between density.
It is also conceivable that to use and contain III-th family (promptly; Boron, aluminium, gallium, indium, thallium, scandium, yttrium or lanthanum); Or a kind of Organometallic precursor of a kind of metal of IV family (that is, silicon, germanium, tin, lead, titanium, zirconium, hafnium, thorium) or any two kinds or more kinds of combination among these.It is also conceivable that other volatile organic compoundss.Yet, preferably have organic silicon compound and carry out the present invention.
Another aspect again of the present invention is through from the sedimentary slip coating of the PECVD of feed gas; This feed gas comprises a kind of Organometallic precursor, a kind of organosilicon precursor preferably, more preferably linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, linear silicon azane, monocycle silazane, encircle silazane more, gather sesquialter silazane or two kinds or more kinds of a kind of combinations among these.It is also conceivable that the precursor that uses a kind of metal that contains III-th family or IV family.
As determined through vapor-phase chromatography/mass spectroscopy, this coating has and contains multiple-(Me) as a kind of component of exitting 2One or more oligopolymer of SiO-part.Randomly, this coating meets the qualification of any embodiment VII.B.4.a. or VII.B.4.
Another aspect again of the present invention is through from the sedimentary slip coating of the PECVD of feed gas; This feed gas comprises a kind of Organometallic precursor, a kind of organosilicon precursor preferably, more preferably linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, linear silicon azane, monocycle silazane, encircle silazane more, gather sesquialter silazane or two kinds or more kinds of a kind of combinations among these.As determined through x-ray photoelectron spectroscopy (XPS), this coating can have the atomic percent that is normalized to 100% carbon, oxygen and silicon, has less than 50% carbon and greater than 25% silicon.Randomly, this coating meets the qualification of any embodiment VII.B.4.a or VII.B.4.b..
It is also conceivable that a kind of Organometallic precursor that uses the metal that contains III-th family or IV family.
Another aspect of the present invention is from the sedimentary a kind of slip coating of a kind of feed gas through PECVD; This feed gas contains a kind of organosilicon precursor, preferably monocycle siloxanes, monocycle silazane, many cyclosiloxane, encircle silazane or two kinds or more kinds of any combinations among these more.This coating has as determined through x-ray photoelectron spectroscopy (XPS), is normalized to the atomic percent of a carbon of 100% carbon, oxygen and silicon, and this concentration is greater than the atomic percent of carbon in the atomic formula of feed gas.Randomly, this coating meets the qualification among embodiment VII.B.4.a or the VII.B.4.b.
Another aspect of the present invention is from the sedimentary a kind of slip coating of a kind of feed gas through PECVD; This feed gas comprises a kind of organosilicon precursor, preferred monocycle siloxanes, monocycle silazane, many cyclosiloxane, encircles silazane or two kinds or more kinds of any combinations among these more.This coating has as determined through x-ray photoelectron spectroscopy (XPS), is normalized to the atomic percent of a silicon of 100% carbon, oxygen and silicon, and this concentration is less than the atomic percent of silicon in the atomic formula of feed gas.Randomly, this coating meets the qualification among embodiment VII.B.4.a or the VII.B.4.b.
VII.C.1. accommodate the container that has of the blood that can live by the sedimentary coating of organosilicon precursor
Of the present invention even another aspect is a kind of container of containment blood.This container has a wall; This wall has an internal surface that defines an inner chamber.The internal surface of this wall has as above one of definition part hydrophobic coating, preferably a Si at least wO xC yH zHydrophobic coating, preferably wherein w is 1, x is from about 0.5 to 2.4 in this formula; Y is from about 0.6 to about 3, and z is from 2 to about 9, and more preferably wherein w is 1; X is from about 0.5 to 1, and y is from about 2 to about 3, and z is from 6 to about 9.This coating can be thin like unit molecule thickness, or thick 1000nm according to appointment.This container holds the blood that can live that is used to return the patient's blood vessel system, and this blood is disposed in this inner chamber and this Si wO xC yH zThe coating contact.
VII.C.2. reduced solidifying or platelet activation on wall of container from the organosilicon precursor coating deposited
Another aspect of the present invention is the container with a wall.This wall has an internal surface that defines an inner chamber and has make from a kind of organosilicon precursor through PECVD one the for example hydrophobic coating of part passivation at least, preferably a kind of Si wO xC yH zCoating, preferably wherein w is 1, x is from about 0.5 to 2.4 in this formula, y is from about 0.6 to about 3, and z is from 2 to about 9, more preferably wherein w is 1, x is from about 0.5 to 1, y is from about 2 to about 3, and z is from 6 to about 9.The thickness of this coating is thick from monatomic thickness to about 1000nm on this inner surface.Compare with the uncoated wall of same type, this coating effectively reduces the platelet activation of and blood plasma that be exposed to this internal surface that cross with the Trisodium Citrate additive treating.Compare with the uncoated wall of same type, this coating effectively reduces solidifying of the blood that is exposed to this internal surface.
VII.C.3. hold the blood that to live, container with coating of III-th family or IV family metallic element
Another aspect of the present invention is a kind of container of containment blood, and this container has a wall, and this wall has an internal surface that defines an inner chamber.This internal surface has one of a kind of formation partial coating at least, and this formation comprises one or more metals of carbon, III-th family, one or more metals of IV family or two kinds or more kinds of a kind of combinations among these.Thickness in this coating on this internal surface is between unit molecule thickness and about 1000nm thickness, comprises end value.This container holds the blood that can live that is used to return the patient's blood vessel system, this blood be disposed in contacted this inner chamber of this coating in.
VII.C.4. the coating of III-th family or IV family element has reduced solidifying or platelet activation of blood in this container
Randomly, in the container described in the above paragraph, the coating of this III-th family or IV family element effectively reduces the solidifying or platelet activation of blood of the internal surface that is exposed to this wall of container.
VII.D.1. the container that has that holds Regular Insulin by the organosilicon precursor coating deposited
Another aspect of the present invention is a kind of container that holds Regular Insulin, and this container has a wall, and this wall has an internal surface that defines an inner chamber.This inwall has process from a kind of organosilicon precursor through PECVD one coating of part passivation at least, preferably a kind of Si wO xC yH zCoating, preferably wherein w is 1, x is from about 0.5 to 2.4 in this formula, y is from about 0.6 to about 3, and z is from 2 to about 9, more preferably wherein w is 1, x is from about 0.5 to 1, y is from about 2 to about 3, and z is from 6 to about 9.This coating can be thick from unit molecule thickness to about 1000nm on this internal surface.Regular Insulin is disposed in and Si wO xC yH zIn the inner chamber of coating contact.
VII.D.2. reduced the deposition of Regular Insulin in the container by the organosilicon precursor coating deposited
Randomly, in the container of above paragraph, with shortage Si wO xC yH zThe similar face of coating compare this Si wO xC yH zCoating effectively reduce because the deposition of this internal surface of Regular Insulin contact forms.
VII.D.3. the container that holds the coating with III-th family or IV family element of Regular Insulin
Another aspect of the present invention is a kind of container that holds Regular Insulin, and this container comprises a wall, and this wall has an internal surface that defines an inner chamber.This internal surface has one of a kind of formation partial coating at least, and this formation comprises one or more metals of carbon, III-th family, one or more metals of IV family or two kinds or more kinds of a kind of combinations among these.This coating can be to about 1000nm thickness from unit molecule thickness on this internal surface.Regular Insulin be disposed in contacted this inner chamber of this coating in.
VII.D.4. the coating of III-th family or IV family element has reduced the deposition of Regular Insulin in the container
Randomly; In the container described in the above paragraph; Compare with the similar face that lacks coating, comprise that the coating of formation of one or more metals or among these two kinds or more kinds of a kind of combination of one or more metals, the IV family of carbon, III-th family effectively reduces because the deposition of Regular Insulin contact internal surface forms.
VILE. cuvette
Described in this manual PECVD coating method or the like also is useful for applying cuvette to form a barrier coat, hydrophobic coating, slip coating or among these more than one.Cuvette be have circle or square-section, an end is sealing, that processed by plastics, glass or fused quartz (being used for UV light) and be designed to hold a kind of tubule that sample is used for spectrum experiment.Best cuvette is transparent as far as possible, does not have possibility to influence the impurity of spectrum reading.As test tube or sampling tube, cuvette can be to atmosphere opening or use a cap with its hermetically closing.Therefore the coating that PECVD of the present invention applies can be extremely thin, transparent and optics is smooth, do not disturb the optic test of this cuvette or its content.
VII.F. bottle
PECVD coating method described in this specification sheets or the like, for apply bottle with form a coating, for example a combination of barrier coat or a hydrophobic coating or these coatings also is useful.Bottle is a kind of small vessels or bottle, in particular for the medicine of storage of liquids, powder or freeze dried powder type.They can also be sampling receptacles, for example are used in the automatic sampler equipment of analytical chromatography.Bottle can have tubular form or have the bottle appearance shape of a neck.Normally put down different with test tube or sampling tube (they have rounded bottom usually) this bottom.These tubules can for example be processed by plastics (for example Vestolen PP 7052, COC, COP).
Computer-readable medium and program element
In addition; A kind of computer-readable medium is provided; Storing therein is used to apply and/or check the computer program of container, when this computer program is carried out by the treater of a container processing systems, cause this treater carry out above or below the method steps mentioned.
In addition, provide to be used for a kind of program element that container is applied and/or checks, when this program element is carried out by the treater of a container processing systems, cause this treater carry out above or below the method steps mentioned.
According to this disclosure and accompanying drawing, other aspects of the present invention will be clearly.
Brief Description Of Drawings
Fig. 1 is a synoptic diagram, the figure illustrates a kind of container processing systems according to an embodiment of this disclosure.
Fig. 2 is a diagrammatic cross-sectional view that applies a pan straddle in the station according to an embodiment of this disclosure.
Fig. 3 is a view that is similar to Fig. 2 of an alternative embodiment of this disclosure.
Fig. 4 is a diagrammatic plat of an alternative embodiment of this pan straddle.
Fig. 5 is a diagrammatic plan view of another alternative embodiment of this pan straddle.
Fig. 6 is a view that is similar to Fig. 2 of container inspection device.
Fig. 7 is a view that is similar to Fig. 2 of alternative container inspection device.
Fig. 8 is a cross section along the section line A-A intercepting of Fig. 2.
Fig. 9 is an alternate embodiment of structure shown in Fig. 8.
Figure 10 is at a view that is similar to Fig. 2 (having adopted a CCD detector) that applies a pan straddle in the station according to another embodiment of this disclosure.
Figure 11 is a detailed view that is similar to Figure 10 (comparing with the corresponding section of Fig. 6, they are opposite) of light source and detector.
Figure 12 is a view that is similar to Fig. 2 (adopting microwave energy to produce plasma body) that applies a pan straddle in the station according to another embodiment again of this disclosure.
Figure 13 is a view that is similar to Fig. 2 that applies a pan straddle in the station according to another embodiment of this disclosure, wherein can this container be seated on the pan straddle that is positioned at this treatment station.
Figure 14 is that wherein this electrode can be configured to a kind of coil according to this a disclosure even view that is similar to Fig. 2 that applies a pan straddle in the station another embodiment.
Figure 15 is a view that is similar to Fig. 2 (adopting the pipe transporter container is moved into and leaves this coating station) that applies a pan straddle in the station according to another embodiment of this disclosure.
Figure 16 is that a kind of container traffic of middle operation system (system as shown in Figure 15) is to place and to keep a diagrammatical view of container at treatment station.
Figure 17 is that an aspect according to this disclosure is used to form a mould of container and a diagrammatical view of mould cavity.
Figure 18 is a diagrammatical view of the mould cavity of the Figure 17 that is equipped with a kind of container coating equipment of an aspect according to this disclosure.
Figure 19 is the view that is similar to Figure 17 that is equipped with an alternate container coating equipment according to an aspect of this disclosure.
Figure 20 be an adaptive syringe that is used as a precharging type syringe and of cap decompose the longitudinal cross-section view.
Figure 21 is that demonstration adds the syringe cylinder of cap and a view that roughly is similar to Fig. 2 of pan straddle according to one in the coating station of an embodiment of this disclosure.
Figure 22 is that figure shows that one that according to another embodiment of this disclosure one applies in the station does not add the syringe cylinder of cap and a view that roughly is similar to Figure 21 of pan straddle.
Figure 23 is a skeleton view according to the heparin tube assembly with a closure member of another embodiment again of the present invention.
Figure 24 is the heparin tube of Figure 23 and a fracture section of closing assembly.
Figure 25 is the isolating sectional view of an elastomeric insert of the closure member of Figure 23 and 24.
Figure 26 is 22 the view of being similar to that another embodiment of the invention is used to handle syringe cylinder and other containers.
Figure 27 is the partial view of an amplification of the processing vessel of Figure 26.
Figure 28 is a synoptic diagram of an alternative processing vessel.
Figure 29 be show pass coating a synoptic diagram of material outgassing.
Figure 30 is used to cause that a wall of container is deflated to a test set and a diagrammatic cross-sectional view using a venting that is inserted in the measuring cell between this container and the vacuum source to measure of the inside of this container.
Figure 31 is a graphic representation for a venting mass flow rate of on the test set of Figure 30, measuring of a plurality of containers.
Figure 32 is a bar graph that is presented at the statistical study of the end-point data shown in Figure 31.
Figure 33 is a vertical section according to the syringe cylinder of a kind of combination of another embodiment of the invention and gas reception volume.
Figure 34 is a view that is similar to Figure 34 (comprising an electrode extension) of another embodiment of the invention.
Figure 35 is a view from the section line 35-35 intercepting of Figure 34, has shown the extension electrode of far-end gas supply opening and Figure 34.
Figure 36 be according to the double-walled heparin tube assembly of another embodiment again of the present invention a skeleton view.
Figure 37 is a view that is similar to Figure 22 that shows another embodiment.
Figure 38 shows and the view that is similar to Figure 22 of another embodiment.
Figure 39 shows and the view that is similar to Figure 22 of another embodiment.
Figure 40 is a view that is similar to Figure 22 of demonstration even another embodiment.
Figure 41 is a plat of the embodiment of Figure 40.
Figure 42 be can with Fig. 1,2,3,6-10,12-16,18,19,33 and the embodiment of 37-41 being used for of using container is seated at the partial longitudinal section of the fracture that an alternative sealing on the pan straddle arranges.Figure 42 has also shown and can construct with a kind of alternative syringe cylinder that the for example embodiment of Fig. 2,3,6-10,12-22,26-28,33-34 and 37-41 is used.
Figure 43 is the partial view of an other amplification of the sealing layout shown in Figure 42.
Figure 44 is a view that is similar to Fig. 2 of the alternative gas delivery/interior electrode that can use with the for example embodiment of Fig. 1,2,3,8,9,12-16,18-19,21-22,33,37-43,46-49 and 52-54.
Figure 45 is a kind of alternative structure of the pan straddle that can use with the for example embodiment of Fig. 1,2,3,6-10,12-16,18,19,21,22,26,28,33-35 and 37-44.
Figure 46 is an array of gas delivery and is used for gas delivery is inserted a pan straddle and from a diagrammatic cross-sectional view of its mechanism that removes, shown the gas delivery that is in its complete propulsive position.
Figure 47 is a view that is similar to Figure 46 that shows a gas delivery that mediates.
Figure 48 is a view that is similar to Figure 46 that shows a gas delivery that is in complete retracted position.The array of the gas delivery of Figure 46-48 can with Fig. 1,2,3,8,9 for example, 12-16,18-19,21-22,26-28,33-35,37-45,49 and the embodiment of 52-54 use.The mechanism of Figure 46-48 can be with Fig. 2,3,8,9 for example, 12-16,18-19,21-22,26-28,33-35,37-45,49 and the gas delivery embodiment of 52-54 and use with the probe of the container inspection device of Fig. 6 and 7.
Figure 49 shows to be used for having pending container and cleaning reaction device to be delivered to a view that is similar to Figure 16 of a mechanism of a PECVD coating unit.The mechanism of Figure 49 can use with Fig. 1,9 for example, 15 and 16 container inspection device.
Figure 50 is a decomposition view of two-piece type syringe cylinder and luer lock joint.This syringe cylinder be can with Fig. 1-2 2,26-28,33-35,37-39,44 and the container of 53-54 handle and use with inspection units.
Figure 51 is an assembled view of two-piece type syringe cylinder and the luer lock joint of Figure 50.
Figure 52 is a view that is similar to Figure 42 that shows a syringe cylinder that does not have flange or finger stop that is processed.This syringe cylinder can be handled with the container of Fig. 1-19,27,33,35,44-51 and 53-54 and use with inspection units.
Figure 53 is a synoptic diagram that is used for the assembly of processing vessel.This assembly can use with the device of Fig. 1-3,8-9,12-16,18-22,26-28,33-35 and 37-49.
Figure 54 is a diagrammatical view of the embodiment of Figure 53.
Figure 55 is a diagrammatical view that is similar to Fig. 2 of one embodiment of the invention, comprises a plasma body net.
Figure 56 is the diagrammatic cross-sectional view of an array of gas delivery, has independently gas supply and is used for gas delivery is inserted pan straddle and from its mechanism that removes.
Figure 57 is a graphic representation of venting mass flow rate measured in the instance 19.
Figure 58 has shown a linear gear rack, and other are similar to Fig. 4.
Figure 59 has shown an indicative icon according to a container processing systems of an exemplary of the present invention.
Figure 60 has shown an indicative icon according to a container processing systems of another exemplary of the present invention.
Figure 61 has shown a treatment station according to a container processing systems of an exemplary of the present invention.
Figure 62 has shown a carry-case support according to an exemplary of the present invention.
Be used in these accompanying drawing figures below with reference to symbol:
Figure BDA0000126277010000551
Figure BDA0000126277010000561
Figure BDA0000126277010000581
Figure BDA0000126277010000591
Detailed description of preferred embodiments
Now will more fully describe the present invention with reference to accompanying drawing, wherein show some embodiments.Yet the present invention can be embodied in many different forms, and should not be interpreted as these embodiments that are limited in this proposition.More exactly, these embodiments are instances of the present invention, and the present invention has the indicated four corner of language by claims.Run through same numeral in full and be meant same or corresponding key element.
In context of the present invention, used to give a definition and to abridge:
RF is a radio frequency; Sccm is standard cubic centimeter/PM.
In context of the present invention, term " at least " is meant the integral body of " being equal to or greater than " follow-up said term.Word " comprises " does not get rid of other key elements or step, and except as otherwise noted, indefinite article " " or " a kind of " do not get rid of a plurality of.
" first " and " second " or similar reference example such as treatment station or treatment facility are meant the treatment station or the equipment of the minimum quantity of existence, but must not represent the order or the sum of treatment station and equipment.These terms are the quantity of limit processing station or the concrete processing carried out at the station of correspondence not.
For the purposes of the present invention, a kind of " organosilicon precursor " is to have a kind of compound that connects below at least one:
Figure BDA0000126277010000611
it be a tetravalence Siliciumatom with a Sauerstoffatom and an organic carbon atom (the organic carbon atom is the carbon atom that is connected with at least one Wasserstoffatoms) connection.A kind of volatile organosilicon precursor is defined as a kind of like this precursor, and it can be used as a steam in the PECVD device and is supplied to, and it is a kind of preferred organosilicon precursor.Preferably; This organosilicon precursor is to be selected from down group, and this group is made up of and the following: linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, alkyl trimethoxysilane, linear silicon azane, monocycle silazane, encircle silazane more, gather any two kinds or more kinds of combinations among sesquialter silazane and these precursors.
In context of the present invention, in some embodiments, " not having oxygen basically " or (same free burial ground for the destitute) " do not have oxygen in fact " and is added in this gaseous reactant.These some residual aerial oxygens of expression may reside in the reaction compartment, and feed in the step in front and do not may reside in the reaction compartment by the residual oxygen of discharging fully, they are defined as at this does not have oxygen to exist basically.Specifically, if gaseous reactant comprises less than 1 volume %O 2, more specifically less than 0.5vol%O 2, and even more specifically if it is not contain O 2If if do not have oxygen to be added in this gaseous reactant or in the PECVD process, do not have oxygen to exist at all, then do not have oxygen to be present in this gaseous reactant basically, this is also within the scope of " not having oxygen basically ".
In context of the present invention, a kind of " container " can be to have the container of any type that at least one opening and limit the wall of internal surface.In context of the present invention, term " at least " is meant the integral body of " being equal to or greater than " the following stated term.Therefore, therefore, the container in context of the present invention has one or more openings.One or two opening is just as the opening of stopple coupon (opening) or syringe cylinder (two openings) is preferred.If this container has two openings, then they can have identical or different sizes.If there is the opening more than, an opening can be used for the inlet mouth according to PECVD coating method of the present invention, and other opening or quilt are added cap or open simultaneously.Can be sampling tube (for example being used for collecting or storing biological fluid (as blood or urine)), be used for storage or the syringe (or its parts, for example a syringe cylinder) of delivery of bioactive compounds or compsn (for example medicament or pharmaceutical composition), the bottle that is used to store biomaterial or bioactive compounds or compsn, pipe (for example being used to transport the conduit of biomaterial or bioactive compounds or compsn) or be used to hold fluidic cuvette (for example being used for containment of biological materials or bioactive compounds or compsn) according to container of the present invention.
Container can have Any shape, and the container with cylindrical wall basically of contiguous at least one its opening end is preferred.Usually, the inwall of this container is columniform, and is such in stopple coupon or syringe cylinder just as for example.Stopple coupon and syringe or their parts (for example syringe cylinder) are preferred especially.
In context of the present invention, " hydrophobic layer " expression is compared with corresponding uncoated surface, this coating has reduced the wet tension on the surface that is coated with said coating.Therefore, hydrophobicity is the function of uncoated substrate and coating.Be suitable for appropriate change equally for " hydrophobic " other backgrounds that wherein use a technical term.The meaning that term " hydrophilic " expression is opposite is promptly compared with reference sample, and wet tension has increased.Concrete hydrophobic coating can be the formula of seeing service or total formula Si in the context of the present invention wO xC yH zA kind of coating, wherein w is 1, x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, and z is from 2 to about 9.
" wet tension " is for the hydrophobicity on a surface or hydrophilic a kind of specific measuring.A kind of preferred wet tension measuring method in the context of the present invention is a kind of modification of ASTM D 2578 or the method in ASTM D 2578, described.This method uses standard wet tension solution (being called dyne solution) to confirm to approach most the solution that moistening plastics film surface continued for two seconds.Here it is film wet tension.Being different from ASTM D2578 part in this employed step is; Wherein substrate is not smooth plastics film, but process according to the scheme that is used to form PET pipe and manage according to (except the contrast) that be used to use the inner scheme (referring to instance 9) of hydrophobic layer coated to apply.
" slip coating " according to the present invention is a coating with friction resistance lower than uncoated surface.In other words, compare with uncoated reference surface, it has reduced the friction resistance of coated surface." friction resistance " can be static friction resistance (static frictional resistance) and/or friction of motion resistance (kinetic frictional resistance).An optional embodiments of the present invention is the syringe part that applies with lubricant film, for example syringe cylinder or plunger.In this embodiment preferred, relevant in the context of the present invention static friction resistance is as in this defined starting force, and relevant in the context of the present invention friction of motion resistance is as at this defined plunger sliding force.For example; The existence or shortage and the lubricating property that are suitable for confirming a slip coating in the context of the present invention as at this definition and definite plunger sliding force; Whenever this coating is applied on any syringe or the syringe part, for example is applied on the inwall of a syringe cylinder.It is suitable especially that this starting force is used to be evaluated at a coating effect on the precharging type syringe; This precharging type syringe be after applying, be filled and can move (must quilt " starting ") at plunger once more and store for some time before, for example some months or even several years.
" plunger sliding force " in the context of the present invention is to keep plunger in syringe cylinder, to move (for example between suction or allotment period) needed power.This can advantageously use ISO 7886-1:1993 test said and as known in the art to confirm.The synonym of " the plunger sliding force " that often uses in this area is " plunger force " or " thrust ".
" starting force " in the context of the present invention is to be used for the needed starting force of mobile plunger in syringe (for example in precharging type syringe).
Clear in more detail " plunger sliding force " and " starting force " both and method of being used for their measurements in the further part of this specification sheets.
" slidably " be meant that this plunger is allowed in syringe cylinder, slide.
In context of the present invention; " inflexible in fact " represented these assembled components (port, pipeline and housing; Further specify following) can be used as a unit and move through this housing of operation, and can not move any assembled components about other significantly.Exactly, these parts all are not to be connected by flexible pipe or analogue that the substance that during normal use allows between the part relatively moves.The position that the regulation of the rigid relation in fact of these parts allows to be seated at the container on this pan straddle is that to be fixed to position on the housing as these parts equally be to be close to know and accurate.
Below, will at first explain to be used to carry out device of the present invention, be thereafter container and purposes according to coating method of the present invention, coating and coating.
I. the container processing systems that has a plurality of treatment station and a plurality of pan straddles
I. considered a kind of container processing systems, it comprises one first treatment station, second treatment station, a plurality of pan straddle and a transfer roller.This first treatment station is configured to be used to handle the container that has an opening and limit the wall of an internal surface.This second treatment station and this first treatment station separate and are configured to be used to handle the container that has an opening and limit the wall of an internal surface.
I. at least some, randomly all pan straddles comprise a container port, this port is configured to receive the opening of a container and it is taken a seat be used for the inner surface via handle a container of taking a seat at the container port at this first treatment station place.This transfer roller is configured to be used for that a series of pan straddle and the container of taking a seat are transported to second treatment station from this first treatment station and is used for via the inner surface of handling a container of taking a seat at the container port of this second treatment station.
I. at first referring to Fig. 1, show and be typically expressed as a container processing systems of 20.This container processing systems can comprise a plurality of treatment station, considers that more broadly these treatment station are a plurality of treatment facilities.This container processing systems 20 of the embodiment of being showed can comprise an injection moulding machine 22 (it can be considered to be a treatment station or equipment); Other treatment station or equipment 24,26,28,30,32 and 34, and output 36 (it can be considered to be a treatment station or equipment).With a minimum value, this system 20 has at least one first treatment station, and for example treatment station 28, and one second treatment station, and for example 30,32 or 34.
I. any one the treatment station 22-36 in the embodiment of being showed can be one first treatment station, and any other treatment station can be one second treatment station, or the like.
The embodiment of I. in Fig. 1, being showed can comprise eight treatment station or equipment: 22,24,26,28,30,32,34 and 36.Exemplary container processing systems 20 comprises light sources transmit station 34 and output station 36 of an injection moulding machine 22, aftershaping inspection station 24, precoating inspection station 26, light sources transmit station that applies the thickness that applies inspection station 30, a definite coating behind 28, one at the station 32, a check holiday.
I. this system 20 can comprise that a transmission mechanism 72 is used for container is moved to pan straddle 38 from injection moulding machine 22.This transmission mechanism 72 can be configured to for example robotic arm, this robotic arm with container 80 locate, move to, grasp, transmit, directed, take a seat and discharge so that they are removed and attach it to pan straddle for example on 38 from container forming machine 22.
I. system 20 can also comprise that a transmission mechanism at treatment station 74 places is used for container for example 66 is removed from one or more pan straddles, then handles for example 80 inner surface (Fig. 1) of the container of taking a seat.Therefore these containers 80 can move to packing, store or another appropriate region or process step (being typically expressed as 36) from pan straddle 66.This transmission mechanism 74 can be configured to for example robotic arm, this robotic arm with container 80 locate, move to, grasp, transmit, directed, place and discharge so that they for example 38 are removed and it is placed on other equipments at station 36 from pan straddle.
I. independent container 80 from pan straddle for example 64 remove after, it is one or more suitable to the steps that apply with check system 20 downstream randomly to carry out at the treatment station shown in Fig. 1 or equipment 32,34 and 36.Some limiting examples of the function of these stations or equipment 32,34 and 36 comprise:
The container of handling and checked 80 is placed on the transfer roller to other treatment unit;
Chemical is joined in the container;
These containers are added cap;
These containers are placed the proper process frame;
With these container packages; And
Container sterilization with packing.
I. the container processing systems of in Fig. 1, showing 20 can also comprise a plurality of pan straddles of 38 to 68 accordingly, and (or " rubber disc " (puck); As they can also a similar hockey rubber disc in some embodiments); And transfer roller; This transfer roller is typically expressed as endless belt 70, be used for one or more pan straddle 38-68 and therefore container for example 80 be transported to treatment station 22,24,26,28,30,32,34 and 36 or transport from them and to leave.
I. this treatment station or equipment 22 can be an equipment that is used for shaped container 80.The equipment 22 of a consideration can be an injection moulding machine.The equipment 22 of another consideration can be a blow molding machine.Also considered vacuum forming machine, stretch forming press (draw molding machine) but, cutting or shredder, the glass drawing machine that is used for glass or other stretch forming materials or the container forming machine of other types.Randomly, container shaping position 22 can omit, because the container that can obtain to be shaped.
The II pan straddle
II.A. provide carry-case support 38-68 to be used to hold and carry a container simultaneously container to be handled with opening.This pan straddle comprises that a container port, second port, pipeline and one can carry housing.
II.A. this container port is configured to make a vessel port to be seated in the relation that is interconnected.This second port is configured to receive an extraneous gas supply or ventage.This pipeline is configured to be used to make one or more gases between vessel port and this second port that is landed on this container port, to pass through.This container port, second port and pipeline are attached to this with the relation of inflexible in fact and can carry on the housing.Randomly, the weight of this carry-case support is less than five pounds.A kind of advantage of lightweight container support is can it more easily be transported to another station from a treatment station.
II.A. in the embodiment of some pan straddle, this pipeline more properly is that vacuum pipe and this second port more properly are vacuum ports.This vacuum pipe is configured to be used for from being landed in container on the container port via this container port withdrawing gas.This vacuum ports is configured between vacuum pipe and the outer vacuum source and is communicated with.This container port, vacuum pipe and vacuum ports can be attached to this by the relation of inflexible in fact and can carry on the housing.
II.A., the pan straddle of embodiment II.A. and II.A.1. for example has been shown in Fig. 2.Pan straddle 50 with container port 82 is configured to the opening of receiving vessel 80 and it is taken a seat.The inner surface of the container 80 of taking a seat can be handled via container port 82.Pan straddle 50 can comprise a pipeline, and for example vacuum pipe 94, is used for from being landed in container 80 withdrawing gass on the container port 92.Pan straddle can comprise one second port, for example be communicated with vacuum pipe 94 and outside vacuum ports 96 between the vacuum source (like vacuum pump 98).Container port 92 can have sealing element with vacuum ports 96; For example O shape is enclosed Butt sealing spare; Be respectively 100 and 102; Or at inside or the inside of outer cylinder wall and container 80 or the side seal between the outer cylinder wall of container port 82, be used for receiving vessel 80 or outer vacuum source 98 and form a sealing with it, allow simultaneously to be communicated with through this port.Can use (or also having used) packing ring or other sealings to arrange.
II.A. pan straddle (as 50) can be processed with any material, for example thermoplastic material and/or non-conducting material.Perhaps, pan straddle (as 50) can part or even is mainly processed by electro-conductive material and towards non-conducting material, for example in the passage that is limited container port 92, vacuum pipe 94 and vacuum ports 96.The instance of the material that is used for pan straddle 50 that is fit to is: polyacetal, ethylidene ether material of for example being sold by E.I.du Pont De Nemours and Wilmington Delaware company; Polytetrafluoroethylene (PTFE),
Figure BDA0000126277010000672
PTFE that for example sells by E.I.du Pont De Nemours and Wilmington Delaware company; Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE); High density polyethylene(HDPE) (HDPE); Known in the art or newfound other materials.
II.A. Fig. 2 has also showed this pan straddle (for example 50), when it near or be landed in 92 last times of port, can have and be used to make container 80 middle axle collars 116.
The array of pan straddle
Yet II.A. another kind ofly handle, inspection and or can be to use a kind of array of pan straddle through the method for production system moving-member.This array can comprise the entity array of independent rubber disc or these devices of loading therein.That array can allow to remain is to be tested simultaneously, carry or processing/coating more than one device (randomly many devices).This array can be (being similar to a bucket or tower tray) of unidimensional (for example being gathered to form a linear gear rack) or two dimension.
II.A. Fig. 4,5 and 58 shows three array approach.Fig. 4 shows therein the entity array 120 that (or above that) loaded these devices or container 80.In this case, these devices or container 80 can be used as a solid array and move through production process, though they can be removed and be passed on the independent pan straddle in this production process.An one pan straddle 120 has a plurality of container ports (as 122) that are used to carry an array of the container (as 80) of taking a seat, and this array moves as a unit.In this embodiment, can provide a plurality of independent vacuum ports (as 96) to receive the array of a vacuum source 98.Perhaps, an one vacuum ports that is connected to all container ports (as 96) can be provided.A plurality of inlet mouth probes (as 108) can also be provided in an array.The array that can be installed into gas port probe or vacuum source to be moving as a unit, thereby handles many containers (as 80) simultaneously.Perhaps, in a treatment station, can once or one by one a plurality of container ports (as 122) addressing (addressed) be become a row or many rows.The quantity of the device in array can be relevant, perhaps relevant with other tests or the step that can consider efficient during operation with the quantity of the device of moulding in single step.Under the situation of an array of processing/coating, electrode can or combine (to form a large electrode), or can be independent electrode (each has its power supply).All above methods can be applicable (from the viewpoints of geometric electrode, frequency etc.).
II.A. in Fig. 5, independent rubber disc or pan straddle (as above discussing) gathered together becomes an array (as coming around them through an external frame 130).When this when being desirable, this layout provides the advantage of the solid array of Fig. 4, and allows this array to be used for container 80 is therein become different arrays or single array by addressing other treatment steps by dismission.
II.A. Figure 58 has shown a linear gear rack, and other are similar to Fig. 4.If use a linear gear rack, except those of above explanation, another option is to transport this tooth bar through a treatment station with single-row mode, thereby handles these containers continuously.
II.B. comprise the pan straddle that O shape circle is arranged
II.B. Figure 42 and 43 is equipped with an alternative sealing to arrange, the partial longitudinal cross-section view and the partial view that are used for container is seated at a fracture of a pan straddle 450 on the pan straddle that can use with Fig. 2,3,6,7,19,12,13,16,18,19 for example, 30 and 43 pan straddle embodiment.With reference to Figure 42, this container (for example being seated at a syringe cylinder 438 on the pan straddle 450) have by a general toroidal (and normally chamfering or sphering) aft opening 442 limiting of the sidewall 454 of antelabium 452 and a substantial cylindrical.A medical fluid collection tube has the antelabium 452 of same type usually, but does not have flange 440, and therefore alternatively can be seated on the pan straddle 450.
II.B comprises the internal surface 456 of a substantial cylindrical like pan straddle 450 in the embodiment of being showed, in illustrated embodiment this cylindrical form interior surface as guiding surface to receive the substantial cylindrical sidewall 454 of syringe cylinder 438.This wall is defined by the bearing 458 of a general toroidal further, and when syringe cylinder 438 is seated at 450 last times of pan straddle, this annular lip 452 is resisted against on the bearing of this general toroidal.Provide the dimple or the groove 460 of a general toroidal that in internal surface 456, forms to be used to keep the sealing element, for example an O shape circle 462.The radial depth of this dimple 460 is less than the radial section of sealing element (for example an O shape circle 462 (as shown in Figure 42)), and preferably the internal diameter of this O shape circle 462 preferably is slightly less than the external diameter of this annular lip 452.
When II.B is taken a seat (as shown in Figure 42) when container (for example 438), the radial section that these relative dimensions cause O shape circle 462 compression flatly (shown in scheming 42) between the substantial cylindrical sidewall 454 of the outer wall 464 of dimple 460 at least and syringe cylinder 438.This compression flattens the area supported of O shape circle 462, between the substantial cylindrical sidewall 454 of the outer wall 464 of this dimple 460 at least and syringe cylinder 438, has formed a sealing.
II.B. randomly, thus can construct dimple 460 with respect to the size of O shape circle 462 forms plural sealing (through approximately at a distance of enclose 462 radial section diameter as far as corresponding O shape that roof 468 and diapire 466 is spaced apart) between diapire 466 and roof 468 and sidewall 454.When between the sidewall 454 of outer wall 464 that O shape circle 462 is compressed in this dimple 460 and substantial cylindrical, its elasticity will cause it upwards with expansion (as shown in Figure 43) downwards, so also engaged roof 468 and diapire 466 and made their flattened.Therefore O shape circle 462 randomly will vertically and flatly be out of shape on both direction, tends to its common rounded section is become square.Additionally, be seated at annular lip 452 on this bearing 458 with PECVD process reaction thing and other gases that are introduced into and the flow rate of material of restricted passage or contiguous this aft opening 442.
II.B is as the result of this optional structure, and only the gap (as shown in Figure 43) at the following right corner place of O shape circle 462 is outsides of O shape circle and therefore is exposed to the process gas that in the inside of container 438, is introduced into or produces, plasma body or the like.This establishing protective O shape circle 462 and neighbouring surface (like the neighbouring surface of the outer surface of sidewall 438) are avoided the sedimental accumulation of unwanted PECVD and are attacked by activatory chemical species in the plasma body.Additionally, like opposite with elastic surface (this elastic surface will through directly against docking of the annular lip 452 of this O shape circle take a seat and represent (like institute's displayings in some of other figure)), container 438 be corrected by the hard surface of bearing 458 and is located to ground.In addition, when container 438 was limited to prevent any substantial shaking, the power around the main circumference of this O shape circle 462 on the obverse was distributed more equably.
II.B. perhaps, its diapire 466 that can be on the bearing shown in Figure 43 458 forms dimple 460.In another embodiment, when container 438 is seated at 458 last times of this bearing, thereby can provide the dimple of opening more than one axially spaced-apart 460 a dual seal or higher levels of sealing to be provided and further to limit container 438 and avoid shaking.
II.B. Figure 45 is an alternative structure that is used for pan straddle 482, and this structure can use with the for example embodiment of Fig. 1,2,3,6-10,12-16,18,19,21,22,26,28,33-35 and 37-44.Pan straddle 482 is included in a top 484 and base 486 that connecting joint 488 places connect.Between top 484 at connecting joint 488 places and base 486, a sealing element (a for example O shape circle 490 (its right side is excised to allow this dimple that its is kept with to be described)) is hunted down.In the embodiment of this displaying, when top 484 is connected to 486 last times of base, this O shape circle 490 is received in the annular concave seat 492 with this O shape delineation position.
II.B. in this embodiment; When top 484 was connected (being connected with 500 through screw 498 in this case) with base 486, O shape circle 490 was hunted down and leans abutment surface 494 of radially extending and the wall 496 that radially extends that partly limits dimple 492.So O shape circle 490 is seated between top 484 and the base 486.The O shape of between top 484 and base 486, catching circle 490 has also received container 80 (being removed for the characteristic that clearly demonstrates other in this drawing) and has formed one first seal with O ring spare about the container port 502 of the opening of container 80, and the seal with O ring around container aft opening 442 that is similar among Figure 42 is arranged.
II.B. in this embodiment (though not requiring); Container port 502 has O shape that an O shape encloses 490 sealing members and second axially spaced-apart and encloses 504 sealing members this two; Have the external diameter (be similar to sidewall 454 in Figure 43) of an internal diameter (as being sized to 506) separately, be used between container port 502 and container (as 80), sealing with receiving vessel (as 80).Spacing between O shape circle 490 and 504 is that container (as 80) provides support (at the some place of two axially spaced-aparts), has stoped this container (as 80) to enclose 490 and 504 or container port 502 and tilting with respect to O shape.In this embodiment (though not requiring), the abutment surface 494 of radially extending is positioned at the nearside of O shape circle 490 and 506 sealing members and centers on vacuum pipe 508.
III. be used to transport the method that container-processing is landed in the container on the pan straddle
III.A. pan straddle is transported to treatment station
III.A. Fig. 1,2 and 10 shows a kind of method that is used for processing vessel 80.This method can be carried out as follows.
III.A., container 80 with opening 82 and the wall 86 that limits internal surface 88 can be provided.As an embodiment, can be in mould (as 22) shaped container 80 and therefrom it being removed then.Randomly; In case in 60 seconds that from this mould, remove after this container, or in 30 seconds, or in 25 seconds, or in 20 seconds, or in 15 seconds, or in 10 seconds, or in 5 seconds, or in 3 seconds, or in 1 second, or handling during container 80 can be moved and can not twist it the time (suppose that it is under the temperature of a rising, to process, its is by cooling gradually hereafter) vessel port 82 is landed on the container port 92.Container 80 has reduced the dust that possibly arrive surface 88 or other impurity and prevention or has prevented the adhesion of the coating 90 of barrier coat or other types from moving rapidly of mould 22 to container port 92.And the vacuum of after it is made into, on container 80, being pumped into is fast more, and the chance that then any granulometric impurity adheres on the internal surface 88 is just more little.
III.A., the pan straddle that comprises container port 92 (as 50) can be provided.The opening 82 of container 80 can be landed on the container port 92.Before the opening 82 of container 80 is seated in container port 92, during or after, pan straddle like 40 (for example in Fig. 6) thus can be transported and get into and the engaging with respect to treatment facility or treatment station (as 24) and positioning vessel support 40 of one or more area supporteds 220 to 240.
III.A. when processing is positioned at the inner surface 88 of the container of taking a seat 80 of treatment station or equipment (as 24); In these treatment station (like 24-34) one, can comprise an area supported that is used for supporting one or more pan straddles (as 40) more than one or all treatment station (like what showed), one or more as in area supported 220,222,224,226,228,230,232,234,236,238 or 240 in the predetermined position through the station shown in Fig. 6 24.These area supporteds can be the structures of the static or piecemeal activity of part, for example are handling track or the guiding piece that this container guided and located this pan straddle (as 40) simultaneously.For example, when probe 108 was inserted in the pan straddle 40, the area supported 222 and 224 of these faces downwards was positioned on the pan straddle 40 and serves as the reaction surface that stops pan straddle 40 to move up.Reaction surface 236 is positioned on the pan straddle and stops pan straddle 40 to be moved to the left, and vacuum source 98 (according to Fig. 2) is seated on the vacuum ports 96 simultaneously.These area supporteds 220,226,228,232,238 and 240 are positioned on the pan straddle 40 similarly and during handling, stop and move horizontally.Area supported 230 and 234 is positioned on the pan straddle (as 40) similarly and stops the displacement of its vertical shifting.Therefore, at each treatment station one first area supported, second area supported, the 3rd area supported, or more a plurality of area supporteds can be provided.
III.A. can handle the inner surface 88 of the container 80 of taking a seat via container port 92 at first treatment station then, this first treatment station can be that as an instance, the blocking layer applies the coating station 28 that applies station or other types shown in figure 2.Pan straddle 50 and the container 80 of taking a seat are transported to second treatment station (for example treatment station 32) from first treatment station 28.Can handle the inner surface 88 of the container 80 of taking a seat at second treatment station (as 32) via container port 92.
III.A. any above method can comprise the step of further removing container 80 from pan straddle (as 66), the inner surface 88 of the container 80 of taking a seat in second treatment station or device processes afterwards.
III.A. any above method can comprise after removing step further provides the step with opening 82 and second container 80 of the wall 86 that limits inner surface 88.The opening 82 of second container (as 80) can be landed on the container port 92 of another pan straddle (as 38).Can handle the inner surface of second container 80 of taking a seat via container port 92 at first treatment station or equipment (as 24).Can pan straddle (as 38) and second container 80 of taking a seat be transported to second treatment station or equipment (as 26) from first treatment station or equipment 24.Can handle second container 80 of taking a seat via container port 92 through second treatment station or equipment 26.
III.B. transport treatment facility to pan straddle or vice versa
III.B. perhaps; These treatment station can more broadly be treatment facilities; And or these pan straddles can be transferred with respect to these treatment facilities; These treatment facilities can be transferred with respect to pan straddle, perhaps can some of each layout be provided in the given system.Still in another is arranged, can these pan straddles be delivered to one or more stations, and can adopt treatment facility more than one at least one or near the station of at least one.Therefore, corresponding one to one between treatment facility and treatment station is not essential.
III.B. a method that comprises several portions is considered for handling a kind of container.Provide one first treatment facility (like 108 (Fig. 2) that pop one's head in) and one second treatment facility (, Figure 10) to be used for processing vessel (as 80) like light source 170.The container 80 that provides has an opening 82 and the wall 86 that limits inner surface 88.A pan straddle 50 that comprises a container port 92 is provided.The opening 82 of container 80 is landed on the container port 92.
First treatment facility (as popping one's head in 108) is moved into during the operability of pan straddle 50 engages, and perhaps vice versa.Use first treatment facility or pop one's head in and 108 handle the inner surface 88 of the container 80 of taking a seat via container port 92.
III.B. (as 170, Figure 10) move into during the operability of pan straddle 50 engages, perhaps vice versa to make second treatment facility then.Use second treatment facility (like light source 170) to handle the inner surface 88 of the container 80 of taking a seat via container port 92.
III.B. randomly, any amount of other treatment step can be provided.For example, can provide one the 3rd treatment facility 34 to be used for processing vessel 80.The 3rd treatment facility 34 is moved into during the operability of pan straddle 50 engages, and perhaps vice versa.Can use the 3rd treatment facility 34 to handle the inner surface of the container 80 of taking a seat via container port 92.
III.B. be used for the another kind of method of processing vessel, the container 80 with opening 82 and the wall 86 that limits inner surface 88 can be provided.A pan straddle (as 50) that comprises container port 92 can be provided.The opening 82 of container 80 is landed on the container port 92.Can handle the inner surface 88 of the container 80 of taking a seat via container port 92 at first treatment facility, this first treatment facility can be, as an instance, and the coating unit 28 of blocking layer coating unit or other types shown in figure 2.Pan straddle 50 and the container 80 of taking a seat are transported to second treatment facility (the for example treatment facility shown in Fig. 1 and 10 34) from first treatment facility 28.Can handle the inner surface 88 of the container 80 of taking a seat then through second treatment facility (as 34) via container port 92.
III.C. use clamp to be used for pipe is transported entering and leaves the coating station
III.C. another embodiment is a kind of method of the PECVD processing of one first container again, and this method comprises several steps.One first container is provided, and this container has an opening end, a closing end and an inner surface.At least one first clamp is arranged to the closing end that optionally keeps and discharge this first container.Clamp the closing end of first container with this first clamp, and use this first clamp with its be transported to pan straddle near, this pan straddle is configured to make the opening end of this first container to take a seat.Use this first clamp axially to advance this first container then and its opening end is seated on this pan straddle, between the inside of this pan straddle and this first container, set up being communicated with of sealing.
III.C. at least a gaseous reactant is introduced within this first container through this pan straddle.Under the condition of the reaction product that effectively forms this reactant, on the inner surface of this first container, form plasma body.
This first container is disseated from this pan straddle, and use this first clamp or another clamp, this first container is axially transported leave this pan straddle.Then thereby this first container is discharged axially it to be transported from employed clamp and leave this pan straddle.
III.C. refer again to Figure 16 and 49, can use a placed in-line transfer roller 538 support and transport a plurality of clamps (as 204) through this device and as said the processing.With clamp 204 be operably connected on this placed in-line transfer roller 538 and be arranged to a series with at least two containers 80 in turn be transported to this pan straddle 48 near, and carry out other steps of purging method as described herein.
IV is used to make the PECVD device of container
IV.A. comprise pan straddle, interior electrode, as the PECVD device of the container of reaction chamber
IV.A. another embodiment is a kind of PECVD device, and this device comprises pan straddle, interior electrode, outer electrode and power supply.The container that is landed on the pan straddle defines a plasma-reaction-chamber, and it randomly can be a Vakuumkammer.Randomly, can supply with vacuum source, reacting gas source, gas feed or two kinds or more kinds of combinations among these.Randomly, the eduction pipe that must not comprise vacuum source is provided, has been used for the internal gas from this container is perhaps transmitted in gas transfer to the inside that is landed in the container on this port, to limit a closed-chamber.
IV.A. this PECVD device can be used for normal atmosphere PECVD, and plasma-reaction-chamber need not work as Vakuumkammer in this case.
In the embodiment of IV.A. in Fig. 2, showing, pan straddle 50 comprises gas input port 104, is used for delivering gas to a container that is landed on the container port.Gas input port 104 has one by at least one O shape circle 106, or the O shape circle of two serial connections, or the sliding seal that provides of the O shape circle of three serial connections; When probe 108 is inserted into through gas input port 104, can leans on cylindrical probe 108 and take a seat.Probe 108 can be an air inlet conduit, and this air inlet conduit extends to the gas delivery port at its far-end 110 places.The far-end 110 of the embodiment of showing can be inserted into deeply is used to provide one or more PECVD reactants and other process gass in the container 80.
In the embodiment of IV.A. randomly in Fig. 2, showing; Perhaps more generally in the embodiment of any disclosure; For example in the embodiment of Fig. 1-5,8,9,12-16,18,19,21,22,26-28,33-35,37-49 or 52-55; And as among Figure 55 special the disclosure, can provide the plasma body net 610 to be used for that the plasma bodys that are formed on usually in the container 80 are limited in the volume of plasma body net more than 610.Plasma body net 610 is a kind of electroconductibility porous materials, and its some instances are Steel Wool, porous sintered metal or the stupalith that is coated with conductive material or porous plate or the dish processed by metal (for example brass) or other conductive materials.An instance is a pair of salver that has centre hole (its size is confirmed as through inlet mouth 108) and have the hole (spaced apart with 0.04 inch (1mm)) of 0.02 inch (0.5mm), and the hole of these center hearts (center-to-center) provides 22% open area in the ratio of the surface-area of this dish.
IV.A. in particular for wherein popping one's head in 108 also as the acting embodiment of counter electrode, opening 82 places of pipe, syringe cylinder or other containers 80 that is being processed in (or approaching), plasma body net 610 can closely electrically contact with inlet mouth 108.Alternately, plasma body net 610 can ground connection, randomly has common potential with inlet mouth 108.Plasma body net 610 reduced or eliminated in pan straddle 50 and its internal passages and be connected (for example vacuum pipe 94, gas input port 104, O shape circle 106 near, other devices of vacuum ports 96,0 shape circle 102 and contiguous inlet mouth 108) in plasma body.Simultaneously, the porosity of plasma body net allows process gas, air and analogue to flow out from container 80 and gets into vacuum ports 96 and downstream unit.
IV.A. in the coating station of in Fig. 3, being showed 28; Pan straddle 112 comprises compound gas input port and the vacuum ports 96 that is communicated with vacuum ports 92, and these two ports are used for gas delivery is got into withdrawing gas (via vacuum source 98) the container 80 (via probe 108) that is seated on the container port 92 and the container on being seated at container port 92 accordingly.In this embodiment, gas inlet probe 108 and vacuum source 98 can provide with the form of combined probe.Such as hope ground, can be with these two probes with a unitary form or advance dividually.This layout has been eliminated for the needs of one the 3rd sealing member 106 and has been allowed to use throughout Butt sealing spare.Thereby Butt sealing spare for example allows through extracting vacuum in the container 80 being applied an axial force through making O shape annular strain take a seat container 80 and vacuum source 98 with coming forward, and this tends to the closed any gap that stays through the existence of any irregularity in the sealing face on one of two sides enclosing O shape.In the embodiment of Fig. 3, the axial force that is applied on the pan straddle 112 by container 80 and vacuum source 98 is opposite, and this tends to container 80 and pan straddle 112 are kept together and keep corresponding Butt sealing spare.
IV.A. Figure 13 is that wherein this container 80 can be landed on the pan straddle 48 that is positioned at this treatment station according to a view that is similar to Fig. 2 that applies a pan straddle 48 in the station of another embodiment again of this disclosure.This can be used for processing vessel 80; This container for example 48 does not move with pan straddle; Or it can be used for the coating station 28 that the blocking layer applies station or other types; Before the container of taking a seat 80 being delivered to other devices through system 20, the coating station that this blocking layer applies station or other types at first makes container 80 be seated in the pan straddle (as 48).
IV.A. as a replacement scheme of the U-shaped electrode of Fig. 2 and 9, Figure 13 has shown a cylindrical electrode 160 that is suitable for from 50Hz to 1GHz frequency.Or through before electrode being moved down or pan straddle being moved up, can move this pan straddle (or this electrode) in place.Perhaps; Can avoid this pan straddle and electrode moving in vertical surface through setting up an electrode 160; This electrode is configured to similar clam shell (two semicylinders; When pan straddle was gone up in position and prepared to be used for processing/coating, these semicylinders can combine from opposite side).IV.A. randomly; If this process be a successive process (wherein pipe be moved through this coatings station (for example 28) simultaneously through pop one's head in 108 extracting vacuum and with the gas introducing); Applying 28 places, station, vacuum source 98 constitutes a sealing (can during moving this pan straddle, be kept) with rubber disc or pan straddle 50.Perhaps; Can adopt a static process; Wherein this rubber disc or pan straddle 50 are moved and get into a static position, 108 upwards push in this equipment and at vacuum ports 96 places pump or vacuum source 98 are connected then and activate the generation vacuum thereby will pop one's head in this moment.108 in position and produced vacuum in case pop one's head in; Can set up plasma body in the inside of pipe or container 80 with an external stability electrode 160, this external stability electrode is independent of this rubber disc or pan straddle 50 and pipe or other containers 80.
IV.A. Figure 53 has shown the other optional details at the coating station 28 that can use with the embodiment of Fig. 1,2,3 for example, 6-10,12-16,18,19,21,22,26-28,30,33-35,37-44 and 52.In leading in the vacuum pipeline 576 of pressure transmitter 152 of it, apply station 28 and can also have a main vacuum valve 574.A manual bypass valve 578 is provided in by-pass line 580.Vent valve 582 is controlled at the flow rate at ventage 404 places.
The outflow of IV.A.PECVD gas source 144 is to be controlled through the main reaction gas trap 584 of the flow rate of main reaction thing feeding line 586 by adjusting.An assembly of gas source 144 is organosilicon liquid reservoir 588.Content through organosilicon capillary line 590 extraction reservoirs 588 provides pipeline 590 so that desirable flow rate to be provided with suitable length.Flow rate by organosilicon stopping valve 592 control organosilicon steams.Liquid reservoir 588 headspaces 614 are exerted pressure; For example one from the scope of pressure source 616 (as be connected to the forced air of headspace 614 through the pressure line 618) pressure at 0-15psi (0 to 78cm.Hg), and the repeatably organosilicon liquid that does not rely on normal atmosphere (and fluctuation wherein) with foundation is sent.Reservoir 588 be sealing and kapillary to connect 620 be in the bottom of reservoir 588, (not being the gas under pressure from headspace 614) flow through kapillary 590 to guarantee having only purified organosilicon liquid.If be necessary or hope, randomly can heat this organosilicon liquid to being higher than envrionment temperature so that this organosilicon liquid evaporation forms a kind of organosilicon steam.Via the oxygen feed pipeline oxygen is provided from oxygen canister 594, this oxygen feed pipeline is by 598 controls of mass flow rate unit and be equipped with an oxygen stopping valve 600.
IV.A. in the embodiment of Fig. 7, this station or equipment 26 can comprise and adaptively be used to be seated at a vacuum source 98 on the vacuum ports 96, be connected to wing passage 134 or both on the probe 108 (as shown in).In the embodiment of this displaying, this wing passage 134 comprises a stopping valve 136, and this stopping valve is adjusted in the flow rate between probe port 138 and the vacuum ports 140.In the embodiment of this displaying; This selector valve 136 has two states at least: a vacuum state; Port one 38 is connected with 140 therein; This provides two parallel paths that are used for gas flow (therefore increased pumping rate and reduced pumping force), and an off-state, and port one 38 separates with 140 therein.Randomly, selector valve 136 can have one the 3rd port, as is used for introducing from gas source 144 a PECVD gas input port 142 of PECVD reactant gas and process gas.This stopgap measure allow same vacuum supply and pop one's head in 108 be used to leak or penetration testing and being used to apply this barrier coat or other types coating both.
IV.A. in the embodiment of this displaying, the vacuum pipeline (as 146) that leads to vacuum source 98 can also comprise a stopping valve 148.When being connected to pan straddle example (as 44) last time, probe 108 and vacuum source 98 can stopping valve 136 and 148 not closed; Make like this when container 80 when a pan straddle 44 moves on another, the wing passage that leaves container 80 134 and the vacuum pipeline 146 that do not need to be positioned on valve 136 and 148 sides are found time.108 axially to remove in order promoting to pop one's head in, can to provide a flexible pipe line 150 to move axially with respect to the position of port 96 to allow probe 108 to be independent of vacuum pipeline 146 from gas input port 104.
IV.A. Fig. 7 has also shown another the optional characteristic that can use with any embodiment-by the ventage 404 that leads to ambient air of valve 406 controls.After processing vessel 80, no matter whether from pan straddle 44, discharge container 80, from vacuum source 98, be released in the pan straddle 44 of vacuum ports 96 or randomly both, can valve 406 is open to break vacuum apace.
IV.A. in the embodiment of this displaying (still with reference to figure 7) can also be connected to probe 108 on the pressure warning unit 152 and can be communicated with the inside 154 of container 80, to allow the interior pressure of container to be measured 80.
IV.A. in the device of Fig. 1, it can be a PECVD device that for example further describes hereinafter that container applies station 28, its under appropriate condition by operation with SiO xThe coating 90 of blocking layer or other types deposits on the inner surface 88 of container 80, and is as it be shown in fig. 2.
IV.A. particularly with reference to Fig. 1 and 2, treatment station 28 can comprise an electrode 160 through radio-frequency power supply 162 power supplies, is used for during handling, providing an electric field in container 80, to produce plasma body.In this embodiment, probe 108 also is conduction and ground connection, and therefore counter electrode is provided in container 80.Alternately, in another embodiment, can make outer electrode 160 ground connection and probe 108 is directly connected on the power supply 162.
IV.A. in the embodiment of Fig. 2, this outer electrode 160 can be or the substantial cylindrical shown in Fig. 2 and 8 or the gallery that is a roughly U-shaped shown in Fig. 2 and 9 (Fig. 8 and 9 is the alternative embodiments along the cross section of the section line A-A intercepting of Fig. 2).The embodiment of each displaying has one or more sidewalls, as 164 and 166 and optional top 168, very around container 80 configurations with pressing close to.
IV.A., IV.B. Figure 12 to 19 has shown that container applies other variants (as noted earlier) of station or equipment 28.In these variants any one or a plurality of container shown in can alternate figures 1-5 apply station or equipment 28.
IV.A. Figure 12 has shown an alternative electrode system, this electrode system can under the frequency more than the 1GHz, use (with the same way as of top discussion, use identical pan straddle and inlet mouth).Under these frequencies, can be with being passed to the inside of pipe through one or more guide wave devices from the electric energy of power supply, these guide wave devices are connected on the cavity, this cavity or absorb energy or makes this energy resonance.Make this energy resonance allow it to be attached on the gas.Can provide different cavitys to be used for using, and because container 80 will interact with this cavity, container (as 80) has changed its resonance point, produced and be used to the plasma body that applies and/or handle with different frequency.
IV.A. Figure 12 has shown that applying station 28 can comprise a microwave power supply 190, and with the microwave microwave cavity 194 that leads, this microwave cavity is at least in part around the container 80 that will produce plasma body within it through guide wave device 192 for this microwave power supply.This microwave cavity 194 can be regulated with selecting with respect to the frequency of microwave and the dividing potential drop of gas, to absorb microwave and to be attached on the gas that produces plasma body.In any one of the Figure 13 and the embodiment of being showed, at container 80 and cavity 194 (or electrode, detector or other surrounding structures) thus between can leave a little gap 196 and avoid scuffing or other infringements container 80.Also in Figure 13, microwave cavity 194 has a flush end wall 198, makes that like this gap 196 is uneven with respect to the circular edge place of end wall 198 on width in particular.Randomly, can make terminal 198 bendings so that a uniform basically gap 196 to be provided.Figure 44 is a view that is similar to Fig. 2 of an alternative gas delivery/interior electrode 470, and this alternative gas delivery/interior electrode can for example use with the embodiment of Fig. 1,2,3,8,9,12-16,18-19,21-22,33,37-43,46-49 and 52-54.As shown in Figure 44, the distal portions 472 of interior electrode 470 comprises a long and narrow porous sidewall 474, and this sidewall is centered around an internal passages 476 within the electrode in this.The proximal part 478 of the interior electrode 470 of internal passages 476 through extending to container 80 outsides is connected on the gas feed device 144.The far-end 480 of interior electrode 470 can also randomly be a porous.Porous sidewall 474 and; If exist, thereby the porosity of porous distal 480 allows laterally to select from least a portion of the reactant gas of gas feed device 144 feedings from passage 476 reactant gas is provided to the neighbouring part of inner surface 88 of container 80.In this embodiment, the porous part of this porous sidewall 474 extends the whole length of the interior electrode 470 in the container 80, though this porous part possibly be more not widely, has only extended the part of the length of interior electrode 470.As other places in this manual are pointed, and interior electrode 470 can also be longer or shorter with respect to the length of container 80 and than shown in Figure 44, and this porous part can be continuous or discontinuous.
The external diameter of IV.A. interior electrode 470 can be at least 50% or at least 60% or at least 70% or at least 80% or at least 90% or at least 95% of the contiguous internal diameter of the side direction of container.Employing is with respect to the interior electrode 470 of the larger diameter of the internal diameter of container 80; If particularly electrode 470 is concentric with container 80; Then reduced the distance between the contiguous inner surface 88 of the outside of interior electrode 470 and container 80; Plasma body is limited to a littler zone, and it can be more uniform in this zone.When being incorporated in plasma body at a plurality of somes place that closely separates live gas along the length of inner surface 88 position of initial reaction (very near); Adopt the interior electrode 470 of larger diameter also provide reactant gas and/or carrier gas along the distributing more uniformly of inner surface 80, and from flowing opposite with respect to a single point of the inner surface that is used to form 88.
IV.A. in a layout of being considered, represent with solid line that power supply 162 has towards power supply of electrode 200 and connects, it can be at any one point along electrode 200 that this power supply connects, and pops one's head in and 108 can be grounded.In this configuration, can use a capacitive load within container 80, to produce plasma body.In the layout of another consideration; Represent (and having eliminated the connection that shows with solid line) with imaginary line; The lead of the correspondence of power supply 162 is connected on the corresponding end of coil 200, and this coil can be called as " electrode " once more in this manual for convenience's sake.In this configuration, can use an inductive load within container 80, to produce plasma body.In an alternative embodiment, can also use a combination of inductance and capacitive load.
IV.A. Figure 46-48 has shown an array of two or more gas delivery (like 108 (also being shown among Fig. 2), 510 and 512), and they also are interior electrodes.This array can be linear or a carousel (carousel).Carousel shape array allows these electrodes periodically to be re-used.
IV.A. Figure 46-48 also shows an interior electrode extender and retractor 514, be used for gas delivery/interior electrode 108,510 and 512 be inserted into one or more pan straddles for example 50 or 48 the neutralization remove from it.These characteristics are the optional stopgap measures to the using gas delivery tube.
IV.A. in the embodiment of this displaying; With reference to figure 46-48 and 53, interior electrode 108,510 and 512 is connected to accordingly on the common gas supply device 144 by flexible pipe 516,518 and 520 via stopping valve 522,524 and 526 and (in Figure 46-48, through omitting slack these flexible pipes is pressed far and near reduced scale).With reference to topic Figure 56, flexible pipe 516,518 and 520 can alternately be connected to independently on the gas source 144 briefly.Provide a mechanism 514 to prolong and the interior electrode (as 108) of withdrawing.Electrode moved between with respect to the position of propelling fully, mid-way and the retracted position of pan straddle in electrode extender and retractor were configured to be used to make in being somebody's turn to do.
IV.A. in Figure 46 and 56, interior electrode 108 is extended on its work point that extends within this pan straddle 50 and the container 80, and its stopping valve 522 is open.And in Figure 46, idle interior electrode 510 and 512 is contracted and their stopping valve 524 and 526 is closed.In the embodiment of this displaying, idle in one or more in the electrode 510 and 512 be disposed in an electrode cleaning equipment or stand within 528.Randomly, can clean being replaced of at the station one or more electrodes within 528 and other.These cleaning operations can relate to chemical reaction or container to be handled to remove settling, grind physically removing settling, or plasma treatment is with the cumulative settling (as limiting examples) that burnouts in fact.
IV.A. in Figure 47, idle interior electrode 510 and 512 is as the front, and electrode 108 leaves container 80 withdrawals in the work and made, and wherein its far-end is retained within the pan straddle 50, and its valve 522 has been closed.In this case, can remove and make a new container to be seated on the pan straddle 50 in container 80, make electrode 108 and the container 80 contacted danger of being removed or replacing and have no.After container 80 is replaced, can interior electrode 108 be advanced on the position of Figure 46 and 56, and can stopping valve 522 be opened again, begin to apply new container 80 to use the interior electrode 108 identical with the front.Therefore; A series of therein containers 80 are seated on the pan straddle 50 and from a layout of wherein removing; At the place, station of the interior electrode 108 that is in use, when container 80 is mounted or from pan straddle 50, removes, can be with interior electrode 108 prolongations and repeatedly partially retracted.
IV.A. in Figure 48, pan straddle 50 and its container 80 are with a new pan straddle 48 and 80 replacements of another container.With reference to figure 1, in the embodiment of this type, when its pan straddle reaches when applying the station, the pan straddle (as 50 or 48) that each container 80 remains on it goes up and an interior electrode (as 108) is inserted in each container.
IV.A. additionally; In Figure 48; Interior electrode 108,510 and 512 is all by withdrawal fully; And compare with separately position among Figure 47, interior electrode 108,510 and 512 array have been moved to the right side with respect to pan straddle 48 and electrode cleaning station 528, make so to be moved displacement and interior electrode 510 has been moved to suitable position with respect to electrodes 108 in the pan straddle 48.
IV.A. moving of the array of electrode can be independent of moving of pan straddle in should be understood that.They can be that move together or independent moving, thereby side by side or independently are transformed into a new pan straddle and/or a new interior electrode.
IV.A. Figure 46-48 has shown an array of two or more gas delivery (like 108 (also being shown among Fig. 2), 510 and 512), and they also are interior electrodes.This array can be linear or a carousel.The carousel array allows these electrodes periodically to be reused.
IV.A. Figure 46-48 has also shown an interior electrode extender and retractor 514, is used for that gas delivery/interior electrode 108,510 and 512 is inserted into one or more pan straddles (as 50 or 48) neutralization and removes from it.These characteristics are the optional stopgap measures to the using gas delivery tube.
IV.A. in the embodiment of this displaying; With reference to figure 46-48 and 53, interior electrode 108,510 and 512 is connected to accordingly on the common gas supply device 144 by flexible pipe 516,518 and 520 via stopping valve 522,524 and 526 and (in Figure 46-48, through omitting slack flexible pipe is pressed far and near reduced scale).Provide a mechanism 514 to be used for prolonging and the interior electrode (as 108) of withdrawing.Should in electrode extender and retractor be configured to be used for an interior electrode is moved advancing fully between position, a mid-way and a retracted position with respect to of this pan straddle.
IV.A. in Figure 46 and 56, interior electrode 108 is lengthened on its work point within this pan straddle 50 and the container 80, and its stopping valve 522 is open.And in Figure 46 and 56, idle interior electrode 510 and 512 is contracted and their stopping valve 524 and 526 is closed.In the embodiment of this displaying, idle interior electrode 510 and 512 is disposed in an electrode cleaning or stands within 528.Randomly, can clean being replaced of at the station some electrodes within 528 and other.These cleaning operations can relate to chemical reaction or solvent treatment to remove settling, to grind physically to remove settling or plasma treatment with the cumulative settling (as limiting examples) that burnouts in fact.
IV.A. in Figure 47, idle interior electrode 510 and 512 is as the front, and electrode 108 leaves container 80 withdrawals in the work and made, and wherein its far-end is retained within the pan straddle 50, and its valve 522 has been closed.In this case, can remove and make a new container to be seated on the pan straddle 50 in container 80, make electrode 108 and the container 80 contacted danger of being removed or replacing and have no.After container 80 was replaced, interior electrode 108 can be advanced on the position of Figure 46 and 56, and stopping valve 522 can be open to use the interior electrode 108 identical with the front to begin to apply new container 80 by once more.Therefore; A series of therein containers 80 are seated on the pan straddle 50 and from a layout of wherein removing; At the place, station of the interior electrode 108 that is in use, when container 80 is mounted or from pan straddle 50, removes, can be with interior electrode 108 prolongations and repeatedly partially retracted.
IV.A. in Figure 48, pan straddle 50 and its container 80 are with a new pan straddle 48 and 80 replacements of another container.With reference to figure 1, in the embodiment of this type, when its pan straddle reaches when applying the station, the pan straddle (as 50 or 48) that each container 80 remains on it goes up and an interior electrode (as 108) is inserted in each container.
IV.A. additionally; In Figure 48; Interior electrode 108,510 and 512 is all by withdrawal fully; And compare with separately position among Figure 47, interior electrode 108,510 and 512 array have been moved to the right side with respect to pan straddle 48 and electrode cleaning station 528, make so to be moved displacement and interior electrode 510 has been moved to suitable position with respect to electrodes 108 in the pan straddle 48.
IV.A. moving of the array of electrode can be independent of moving of pan straddle in should be understood that.They can be that move together or independent moving, thereby side by side or independently are transformed into a new pan straddle and/or a new interior electrode.
IV.A. electrodes 108,510 and an array of 512 are useful in two or more because in some cases when they are used to apply a series of containers (for example 80) single combined gas delivery/interior electrode 108,510 and 512 will tend to accumulate the settling of polymeric reactant gas or some other types.These settlings can be accumulated to inhomogeneity this point that their impairments apply speed or generation, and this possibly be undesirable.In order to keep a uniform process, electrode can be stopped periodically operation, replacement or cleaning in these, and can electrode new or that cleaned be put into operation.For example; From Figure 46 to Figure 48; Interior electrode 108 is replaced with interior electrode 510 up-to-date or that repaired, thereby this interior electrode up-to-date or that repaired has been ready to be extended get in pan straddle 48 and the container 80 coated inside is applied on the new container.
IV.A. therefore; An interior electrode driver 530 operationally is connected with retractor 514 with interior electrode stretcher; Be used for one first interior electrode 108 is removed the retracted position that arrives it from its extended position; Replace this first interior electrode 108 with a second inner electrode 510, and this second inner electrode 510 is advanced into its extended position (being similar to Figure 46 and 56, except the replacement of electrode).
IV.A. the array of the gas delivery of Figure 46-48 and interior electrode driver 530 be can be for example with Fig. 1,2,3,8,9,12-16,18-19,21-22,26-28,33-35,37-45,49 and the embodiment of 52-54 use.The extension of Figure 46-48 and retraction mechanism 514 be can be for example with Fig. 2,3,8,9,12-16,18-19,21-22,26-28,33-35,37-45,49 and the gas delivery embodiment of 52-54 connects and use with the probe of the container inspection device of Fig. 6 and 7.
Electrode 160 shown in IV.A Fig. 2 can be shaped as similar " U " shape passage, and its length gets into the page, and this rubber disc or pan straddle 50 can pass through activated (energy supply) electrode and move during processing/coating processes.Be noted that because used outside and internal electrode, this device can be employed between 50Hz and the 1GHz, be applied to the frequency on this U-shaped channel electrode 160 from power supply 162.Probe 108 can ground connection to improve circuit, allow electric current to flow to the inside of container 80 through one or more low-pressure gases.This electric current produces plasma body and handles and/or apply with the selectivity of the inner surface 88 that allows this device.
The electrode of IV.A in Fig. 2 can also be by pulse power energy supply.Pulse allows the consumption of reactant gases, and then removes by product in activation with before consuming (once more) reactant gases.Typically pulse power system is characterised in that their work period, and this work period has determined the time quantum of the electric field that exists (and being plasma body therefore).Conduction time is relative with power-off time.For example 10% work period can be corresponding to the conduction time in 10% cycle, and wherein 90% time power supply is closed.As a concrete instance, can switch on 0.1 second and cut off the power supply 1 second.Pulse power system has reduced the active power input for given power supply 162, because power-off time has caused the treatment time that increases.When this system was pulse system, the coating of generation can be very pure (not having by product or pollutent).Another result of pulse system possibly realize ald (ALD).In this case, can adjust the work period, cause the deposition of the desirable material of individual layer like this conduction time.By this way, considered monoatomic layer of deposition in each cycle.This method can cause the coating (though under the temperature of deposition needs on the polymer surfaces, randomly keeping low temperature (＜100 ℃) and low temperature coating can be amorphous phase) of high purity and highly structural.
IV.A. an alternative coating station is disclosed among Figure 12, and it adopts microwave cavity to replace outer electrode.The energy that applies can be a kind of microwave frequency, for example 2.45GHz.
IV.B. use pipe is transported the PECVD device that gets into and leave the clamp that applies the station
IV.B. another embodiment is to be used for container is carried out the device that PECVD handles, and this device adopts foregoing clamp.Figure 15 and 16 shown usually with 202 indications be used for first container 80 is carried out the device that PECVD handles, the internal space that this first container has an opening end 82, a closing end 84 and limited on surface 88.This embodiment comprises that a pan straddle 48, at least one first clamp 204 are (in this embodiment; For example; A suction cup), the seat that limits container port 92 on this pan straddle 48, reactant feeding mechanism 144, a plasma generator, a container releasing device (it can be that a vent valve is as 534) and an or identical clamp 204 or one second clamp (in fact, randomly one second clamp 204) by electrode 108 and 160 representatives.
IV.B. this first clamp 204, and as the clamp of being showed 204 in any, be configured to be used for optionally keeping and discharging the closing end 84 of container 80.When clamping the closing end 84 of container, this first clamp 204 can with this container be transported to pan straddle 48 near.In the embodiment of this displaying, this delivery functions is promoted through a serial transfer roller 538, wherein clamp 204 with a series of mode by attached on it.
IV.B. pan straddle 48 has combined with other embodiments in front and has been illustrated, and is configured to be used to be seated in the opening end 82 of container 80.The seat that is limited container port 92 has combined with other embodiments in front and has been illustrated, and is configured in to set up to seal between the internal space 88 of pan straddle 48 and this first container (and be in this case container 80 any one) and is communicated with.Reactant feeding mechanism 144 has combined with other embodiments in front and has been illustrated, and is operably connected and is used at least a gas reactant is introduced within these first containers 80 through pan straddle 48.The plasma generator that is limited electrode 108 and 160 has combined with other embodiments in front and has been illustrated, and is configured on the inner surface of this first container and under the condition of the reaction product that effectively forms reactant, within this first container, forms plasma body.
IV.B. can use container releasing device 534 or other stopgap measures; As a kind of reactant gas, a kind of carrier gas or a kind of cheap gas (like compressed nitrogen or air) are introduced within the container 80 of taking a seat, so that this first container 80 disseats from this pan straddle 48.
IV.B. clamp 204 is configured to be used for axially this first container 80 is transported leave pan straddle 48, and discharges this first container 80 then, as through discharging the suction that comes between comfortable clamp 48 and the container ends 84.
IV.B. Figure 15 and 16 has also shown a kind of method of one first container being carried out the PECVD processing, and this method comprises following step.One first container 80 is provided, and this container has an opening end 82, a closing end 84 and an inner surface 88.At least one first clamp 204 is provided, and this first clamp is configured to be used for the closing end 84 that optionally keeps and discharge this first container 80.Clamp the closing end 84 of first container 80 with this first clamp 204, and thus with its be transported to pan straddle 48 near, this pan straddle is configured to make the opening end of this first container to take a seat.In the embodiment of Figure 16, two pan straddles 48 are provided, this allows once to accomplish container 80 is advanced and is seated on the pan straddle 48, therefore useful efficiency is doubled.Then, use this first clamp 204 to be used for axially advancing and make its opening end 82 to be seated at this pan straddle 48 in this first container 80, between the inside of this pan straddle 48 and this first container, set up being communicated with of sealing.Then, pass through this pan straddle to a kind of gas reactant of major general and introduce within this first container, randomly illustrated like the front embodiment.
IV.B. next, under the condition of a kind of reaction product that effectively forms this reactant, in this first container, having formed plasma body on the inner surface of this first container, randomly illustrated like the front embodiment.This first container is disseated from this pan straddle, randomly illustrated like the front embodiment.Randomly illustrated like the front embodiment, use this first clamp or another clamp that this first container is axially transported and leave this pan straddle.Can this first container be discharged from clamp then, be used for axially it being transported leaving this pan straddle, randomly illustrated like the front embodiment.
IV.B. another optional step that can carry out according to this method comprises a reaction vessel that provides different with this first container; This reaction vessel has an opening end and an internal space; And the opening end that makes this reaction vessel is seated on this pan straddle, between the internal space of this pan straddle and this reaction vessel, sets up being communicated with of sealing.A PECVD reactant conduit can be provided within this internal space.Form plasma body within the internal space at reaction vessel under the condition of sedimental at least a portion of effectively from reactant conduit, removing the PECVD reaction product.These reaction conditionss have combined with embodiment noted earlier and have been illustrated.Can make reaction vessel disseat and it is transported then and leave this pan straddle from pan straddle.
IV.B. can carry out other optional step according to any one embodiment of this method, comprise:
At least one second clamp is provided;
Operationally at least the first and second clamps are connected on the placed in-line transfer roller;
One second container is provided, and this second container has an opening end, a closing end and an inner surface;
A clamp is provided, and this clamp is configured to be used for the closing end that optionally keeps and discharge this second container;
Clamp the closing end of this second container with this clamp;
Use this clamp with this second container be transported to a pan straddle near, this pan straddle is configured to make the opening end of this second container to take a seat;
Use this clamp axially to advance and make its opening end to be seated on this pan straddle in this second container, between the inside of this pan straddle and this second container, set up being communicated with of sealing;
Through this pan straddle at least a gas reactant is introduced within this second container;
Under the condition of a kind of reaction product that effectively forms reactant, in this second container, forming plasma body on the inner surface of this second container;
This second container is disseated from this pan straddle; And
Use this second clamp or another clamp that this second container is axially transported and leave this pan straddle; And
Discharge this second container from this clamp, be used for axially transporting it and leave this pan straddle.
IV.B. Figure 16 is to use a suction cup type equipment to keep an instance of the end of sampling tube (in this instance), and this sampling tube can move through a production line/system.Specific examples in this demonstration is a possible step (like one of above and following a plurality of possibility steps of summarizing) of coating/processing.This pipe can move in this coating step/zone, and can be with reducing in this pan straddle of entering and (at this instance) cylindrical electrode by pipe.This pan straddle, sampling tube and suction cup can move to next procedure together then, and this electrode is by energy supply and handle/apply there.In this instance, can use any in the above kind of electrodes.
IV.B. therefore, Figure 15 and 16 has shown a pan straddle 48 in the coating station 28 that is similar to Figure 13, and this pan straddle adopts to be often referred to and is shown 202 conveyor system of container and container 80 is moved into and leaves applies station 28.Conveyor system of container 202 can be equipped with anchor clamps 204, and these anchor clamps can be suction cups in illustrated transporter 202.Can also use an adhesive pad, active vacuum source (use pump extracting air from these anchor clamps, produce vacuum actively) or other stopgap measures as anchor clamps.For example, thus can use conveyor system of container 202 to reduce in the seated position that container 80 gets into container ports 92 container 80 location to apply.After the processing that is positioned at 28 places, station can be done, can also use conveyor system of container 202 container 80 that raises to leave container port 92.Before container 80 and conveyor system of container 48 are elevated to a station together, can also use conveyor system of container 202 that container 80 is taken a seat.Can also use this conveyor system of container drive container 80 be resisted against it on the seat on the container port 92.And, container 80 is vertically raise from top though Figure 15 can be directed to show, can consider a kind of invert orientation, therein conveyor system of container 202 be under container 80 and from following support it.
IV.B. Figure 16 has shown the embodiment of a method, conveyor system of container 202 (like suction cup 204) transport box 80 flatly wherein, for example from a station to next station, and (or alternatively) vertically get into and leave a station (for example 28).Container 80 can be raised and in any direction on transport.Figure 16 therefore representative carries out a kind of method that PECVD handles to one first container 80, and this method comprises several steps.
IV.B. in the embodiment of Figure 13, outer electrode 160 can be a substantial cylindrical, and it has a plurality of opening ends, and can be immobilized.Container 80 can be raised through outer electrode 160 and be seated on the container port 96 until opening 82.In this embodiment, probe 108 randomly can be permanent shaped or additionally be fixed in the gas input port 104, and allow on the contrary in the wiping that the relatively moves sealing (wiping seal) between port one 04 and the probe 108.
IV.B. Figure 14 has shown an other replacement scheme that is used for electric energy is attached to plasma body under 50Hz to 1GHz.This can be made up of a coil, and this coil perhaps can be lowered in place or this pan straddle (having device) can be pushed upwardly in place.The round electrode is called as inductive coupled device, and can a magnet assembly be given to the inside that can produce the equipment of plasma body therein.
IV.B. can also use the probe of being discussed as among Fig. 2 and Figure 13 108.Other aspects of the pan straddle 48 of this pan straddle or top discussion can keep identical.
IV.B. for example shown in figure 49, a reaction vessel 532 different with this first container 80 can be provided, the internal space that this container also has an opening end 540 and limited this inner surface 542.Be similar to container 80, this reaction vessel 532 can make its opening end 540 on pan straddle 48, and between the internal space 542 of pan straddle 48 and this reaction vessel, sets up being communicated with of sealing.
IV.B. Figure 49 is a view that is similar to Figure 16, has shown to be used for having pending container 80 and cleaning reaction device 532 to be delivered to a mechanism of a PECVD coating unit.In this embodiment, interior electrode 108 randomly can be cleaned and need not it is removed from pan straddle 48.
IV.B. Figure 49 has shown when reaction vessel is seated at alternate container 80 on the pan straddle 48 (being provided for coating like this container noted earlier), thereby is placed within the internal space 542 that is positioned in reaction vessel 532 like foregoing PECVD reactant conduit 108.Figure 49 is presented at the reactant conduit 108 in this configuration, though conduit 108 has an external portion and an interior distal end.If reactant conduit 108 extends in container 80 or 532 at least in part, it satisfies this purpose and these claims.
IV.B. for example, be to use with the embodiment of Fig. 1 and 15-16 at least like the mechanism of Figure 49 of being showed.In an alternative embodiment, cleaning reaction device 532 can also be provided as being seated at a kind of simple receptacle that pan straddle (as 48) is gone up and transported above that.In this configuration, cleaning reaction device 532 can with for example at least the device of Fig. 1-3,8,9,12-15,18,19,21,22,26-28,33-35,37-48 and 52-54 use.
IV.B. the plasma generator that is limited at electrode 108 and 160 is can be configured to be used under the condition of sedimental at least a portion of effectively removing the PECVD reaction product from reactant conduit 108, in the internal space of reaction vessel 532, forming plasma body.What more than consider is; Interior electrode and gas source 108 can be a kind of contact tubes; For example a kind of metal tube; And reaction vessel 532 can be to be processed by any suitable preferably heat-stable material (maybe can stand the more other materials of high calorie than thermoplastic container like, pottery, quartzy, glass).The material of reaction vessel 532 can also desirably be chemical or plasma body, and this chemical or plasma body are resistances for the sedimental condition that employed usefulness in this reaction vessel removes reaction product.Randomly, reaction vessel 532 can be processed by electro-conductive material, and it self serves as the special purpose outer electrode of from reactant conduit 108, removing for settling.As another replacement scheme again, reaction vessel 532 can be configured to a cap, and this cap is seated on the outer electrode 160, and in this case, thereby outer electrode 160 preferably is seated at the cleaning reaction chamber that defines a closure on the pan straddle 48.
What IV.B. considered is, the reaction conditions of from reactant conduit 108, effectively removing sedimental at least a portion of PECVD reaction product comprises: introduce major portion oxidation reactant such as oxygen or ozone (perhaps produce respectively or through the plasma device generation), than be used for the higher power level of deposited coatings, than being used for longer cycling time of deposited coatings or known sedimental other stopgap measures that are used to remove the undesired type that runs in reactant conduit 108.For another instance, can also use mechanical mill to remove unwanted deposits.Perhaps, can force solvent or other reagent to pass through reactant conduit 108 with rid.These conditions can be than 80 strictnesses that can withstand of container to be coated are arranged more, because reaction vessel 532 need not be suitable for the normal use of container 80.Yet randomly, container 80 can be used as reaction vessel, and in an alternative embodiment, too strict if settling is removed condition, can the container 80 as reaction vessel be discarded.
V. be used to make the PECVD method of container
V.1PECVD coating precursor
The precursor that is used for PECVD coating of the present invention broadly is defined as a kind of Organometallic precursor.Be defined as have organic residue the metallic element compound of being understood of (for example hydrocarbon, aminocarbonyl or oxygen carbon (oxycarbon) residue) from all a kind of Organometallic precursors of purpose in this manual from III-th family in the periodic table of elements and/or IV family.Any precursor that comprises (or randomly carrying out bonding) organic moiety on silicon or other III/IV family atoms metals that has Direct Bonding like present defined organometallic compound through oxygen or nitrogen-atoms.The relevant element of periodic table of elements III-th family is boron, aluminium, gallium, indium, thallium, scandium, yttrium and lanthanum, and aluminium and boron are preferred.The relevant element of periodic table of elements IV family is silicon, germanium, tin, lead, titanium, zirconium, hafnium and thorium, and wherein silicon and tin are preferred.It is also conceivable that other volatile organic compoundss.Yet silicoorganic compound are preferred for carrying out the present invention.
Preferred a kind of organosilicon precursor, wherein a kind of " organosilicon precursor " run through this specification sheets and the most broadly are defined as the compound with connection below at least one:
Figure BDA0000126277010000931
Or
Be the tetravalence Siliciumatom that is connected on a Sauerstoffatom and the organic carbon atom (an organic carbon atom is the carbon atom that is bonded at least one Wasserstoffatoms) just in the first above structure.Be the tetravalence Siliciumatom that is connected on a NH-connection and the organic carbon atom (an organic carbon atom is the carbon atom that is bonded at least one Wasserstoffatoms) just in the second above structure.Preferably; This organosilicon precursor is to be selected from down group, and this group is made up of and the following: linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, linear silicon azane, monocycle silazane, encircle silazane more, gather any two kinds or more kinds of combinations among sesquialter silazane and these precursors.What also be considered as precursor is a kind of alkyl trimethoxysilane (although not in above two formulas).
If use a kind of oxygen containing precursor (for example a kind of siloxanes), the empirical formula of the representational prediction that then under the condition that forms a kind of hydrophobic or slip coating, generates from PECVD will be Si wO xC yH z, wherein w is 1, is from about 0.5 to about 1 for this formula x, y is from about 2 to about 3, and z is from 6 to about 9, and the empirical combination thing of the representational prediction that under the condition that forms a barrier coat, generates from PECVD is SiO x, wherein x is from about 1.5 to about 2.9 in this formula.If use a kind of nitrogen precursor (for example a kind of silazane) that contains, then the compsn of prediction will be Si W*N X*C Y*H Z*, promptly at Si according to the present invention wO xC yH zMiddle O is replaced by N and these subscripts are compared the N (3 rather than 2) that is adapted to higher valency with O.For corresponding subscript in its azepine counterpart (aza counterpart), the latter's adaptation will be followed the ratio of w, x, y and z in siloxanes usually.At a particular aspects of the present invention, Si W*N X*C Y*H Z*, wherein the definition of w*, x*, y* and z* is with identical for the w in the siloxanes counterpart, x, y and z, except the deviation of the quantitative aspects of optional Wasserstoffatoms.
One type precursor parent material with above empirical formula is a kind of linear siloxane, for example has a kind of material of following formula:
Figure BDA0000126277010000941
Wherein, R is selected from alkyl independently of one another, for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, vinyl, alkynes or other, and n is 1,2,3,4 or bigger, randomly is 2 or bigger.Several instances of the linear siloxane of considering are
SWS-F 221 (HMDSO),
Octamethyltrisiloxane,
Decamethyl tetrasiloxane,
Ten dimethyl-, five siloxanes,
Or two kinds or more kinds of combinations among these.For making similar coating, similarly silazane also is useful, wherein-and NH-replaced the Sauerstoffatom in above structure.Several instances of the linear silicon azane of considering are prestox three silazane, decamethyl four silazane or two kinds or more kinds of combinations among these.
V.C. the precursor parent material of another kind of type is a kind of monocycle siloxanes, for example has a kind of material of following structural formula:
Figure BDA0000126277010000942
Wherein R be as defined for this linear structure and " a " be from 3 to about 10, perhaps similar monocycle silazane.The assorted substituted and unsubstituted monocycle siloxanes of considering and several instances of silazane comprise:
1,3,5-trimethylammonium-1,3,5-three (3,3, the 3-trifluoro propyl) methyl] cyclotrisiloxane
2,4,6,8-tetramethyl--2,4,6,8-tetrem thiazolinyl cyclotetrasiloxane,
Pentamethyl-ring penta siloxanes,
Five vinyl pentamethyl-rings, penta siloxanes,
Hexamethyl cyclotrisiloxane,
The hexaphenyl cyclotrisiloxane,
Octamethylcyclotetrasiloxane (OMCTS),
The octaphenyl cyclotetrasiloxane,
Decamethylcyclopentasiloxane
Ten diformazan basic rings, six siloxanes,
Methyl (3,3, the 3-trifluoro propyl) cyclosiloxane,
Also considered the epoxy/organosilicon azane, as
The prestox cyclotetrasilazane,
1,3,5,7-tetrem thiazolinyl-1,3,5,7-tetramethyl cyclotetrasiloxane silazane pregnancy basic ring three silazane,
The prestox cyclotetrasilazane,
Decamethyl ring penta silazane,
Ten dimethyl-hexamethylene silazane, or
Any two kinds or more kinds of combinations among these.
V.C. the precursor parent material of another kind of type is a kind of many cyclosiloxane, for example has a kind of material of one of following structural formula:
Figure BDA0000126277010000951
Wherein Y can be oxygen or nitrogen, and E is a silicon, and Z is a Wasserstoffatoms or an organic substituent, and alkyl for example is like methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, vinyl, alkynes or other.When Y each naturally during oxygen, from left to right these corresponding structures are hetero nitrogen silicon tricyclic (silatrane), accurate hetero nitrogen silicon tricyclic (silquasilatrane) and preceding hetero nitrogen silicon tricyclic (silproatrane).When Y was nitrogen, then these corresponding structures were hetero nitrogen silicon tricyclics (azasilproatrane) before azepine hetero nitrogen silicon tricyclic (azasilatrane), the accurate hetero nitrogen silicon tricyclic of azepine (azasilquasiatrane) and the azepine.
V.C. many cyclosiloxane of another kind of type precursor parent material is a kind of polysilsesquioxane, the formula that sees service RSiO 1.5And following structural formula:
Figure BDA0000126277010000961
Wherein R is a Wasserstoffatoms or an organic substituent, and alkyl for example is like methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, vinyl, alkynes or other.The material of such two kinds of commerce is that SST-eM01 gathers (methyl silsesquioxane), wherein each methyl naturally of R; And SST-3MH1.1 gathers (methyl-hydrogen silsesquioxanes), and wherein 90% R group is a methyl, the 10%th, and Wasserstoffatoms.This material is operational in a kind of 10% tetrahydrofuran solution for example.Two kinds or more kinds of combinations among these have also been considered.Other instances of the precursor of considering are that methyl hetero nitrogen silicon tricyclic (CAS 2288-13-3) (wherein Y each Sauerstoffatom and Z are methyl naturally), methyl azepine hetero nitrogen silicon tricyclic (methylazasilatrane), SST-eM01 gather (methyl silsesquioxane) (wherein R randomly can be methyl separately), SST-3MH1.1 gathers (methyl-hydrogen silsesquioxanes) (wherein 90% R group is that methyl and 10% is a Wasserstoffatoms), or any two kinds or more kinds of combinations among these.
V.C. for making similar coating, it also is useful similarly gathering the sesquialter silazane, wherein-and NH-replaced the Sauerstoffatom in above structure.The instance of being considered that gathers the sesquialter silazane is to gather (methyl sesquialter silazane) (wherein R each methyl) naturally and gather (methyl-hydrogenation sesquialter silazane) (wherein 90% R group is a methyl, the 10%th, Wasserstoffatoms).Two kinds or more kinds of combinations among these have also been considered.
V.C. the precursor that is used for according to a kind of special consideration of lubricant film of the present invention is a kind of monocycle siloxanes, for example is octamethylcyclotetrasiloxane.
The precursor that is used for according to a kind of special consideration of hydrophobic layer of the present invention is a kind of monocycle siloxanes, for example is octamethylcyclotetrasiloxane.
The precursor that is used for according to a kind of special consideration of barrier coat of the present invention is a kind of linear siloxane, for example is HMDSO.
V.C. in any coating method according to the present invention, this apply step randomly can through evacuator body before will being somebody's turn to do and with its be provided to this substrate near carry out.For example, OMCTS is heated about 50 ℃ and evaporate before this PECVD device in that it is applied to usually.
V.2 common PECVD method
In the context of the present invention, use following PECVD method usually, this method may further comprise the steps:
(a) a kind of gas reactant is provided near this substrate surface, this gas reactant comprises one as at the precursor of this definition, preferably a kind of organosilicon precursor and O randomly 2And
(b), on this substrate surface, form a coating through plasma body enhanced chemical vapour deposition (PECVD) thus from a kind of plasma body of this gas reaction deposits yields.
In said method, these coating characteristics are advantageously set through one or more following conditions: O in plasma characteristics, the pressure that applies plasma body, the generation power that plasma body applied, the gas reactant 2Existence and relative quantity, volume of plasma and organosilicon precursor.Preferably, these coating characteristics are through O in the gas reactant 2Existence and relative quantity and/or produce that power that plasma body applied sets.
In all embodiments of the present invention, this plasma body is a kind of non-hollow cathode plasma (non-hollow-cathode plasma) at one aspect preferred.
Another preferred aspect, this plasma body produces down in decompression (comparing with environment or normal atmosphere).Preferably, this decompression is less than 300 millitorrs, more preferably less than 200 millitorrs, even more preferably less than 100 millitorrs.
PECVD preferably carries out through this gas reactant that contains this precursor with electrode excitation, and these electrodes come energy supply with microwave frequency or radio frequency (and preferably with radio frequency).The radio frequency that is preferred for carrying out embodiment of the present invention can also be called as " RF frequency ".Be used to carry out typical radio-frequency region of the present invention and be from 10kHz to less than 300MHz, more preferably from 1 to 50MHz, even more preferably from 10 to 15MHz frequency.13.56MHz frequency be most preferred, this is the frequency that is used to carry out PECVD work of government permission.
With respect to using a kind of microwave source, use the RF power supply to have several advantages:, to have the heating of substrate/container still less under a lower power because RF moves.Because focus of the present invention is that plasma coating is placed on the plastic-substrates, so lower treatment temp is desirable, to prevent the fusing/distortion of this substrate.Overheated in order to prevent the substrate when using microwave PECVD, produce with the pulse of short pulse through power and to apply microwave PECVD.The pulse of power produces and has prolonged the cycling time that is used to apply, and this is undesirable in the present invention.The microwave of upper frequency has also caused volatile matter in this plastic-substrates, as the exhaust (offgassing) of residuary water, oligopolymer and other materials.This exhaust meeting disturbs PECVD to apply.A main worry using microwave to be used for PECVD is the leafing of coating from substrate.Because before this coat of deposition, microwave has changed the surface of substrate, can leave by genetic horizon.In order to reduce the possibility of leafing, developed a plurality of interfaces coat and be used for microwave PECVD to be implemented in the good combination between this coating and the substrate.Use RF PECVD not need such interface coat, because there is not the risk of leafing.At last, advantageously use lower power to apply according to slip coating of the present invention and hydrophobic coating.Than microwave power, RF power has moved and provides more control for the PECVD process under lower power.However, though microwave power is less preferred, under proper technical conditions, be available.
In addition, for all PECVD methods described herein, between the volume of the inner chamber that the power that is used for producing plasma body (with wattmeter) and plasma body produce therein, there is a kind of special dependency.Typically, said inner chamber is the inner chamber of a kind of container of coating according to the present invention.If adopt identical electrode system, then RF power should be proportional with this volume of a container.In case set composition (for example this precursor and the O of gas reactant 2Between ratio) and the parameter (except that power) of every other PECVD coating method, when the geometrical shape of a container remains unchanged and only during its stereomutation, typically they will can not change.In this case, this power will be directly proportional with this volume.Therefore but, the power that provides from this specification sheets and the ratio of volume begin, and can find at an easy rate in order to have same geometry to accomplish identical in the container of different sizes or similarly coating and the power that must apply at one.Geometrical shape through for the instance of syringe cylinder and the result who compares for the instance of pipe container being described is to there being the influence of power to be applied.
For any coating of the present invention, plasma body is to produce with having the electrode that is enough to the power energy supply of a coating of formation on this substrate surface.For a slip coating or hydrophobic coating; In the method according to one embodiment of the invention, plasma body preferably produces through and the following: (i) use the electrode that provides following electric power: from 0.1 to 25W, preferably from 1 to 22W, more preferably from 3 to 17W in addition more preferably from 5 to 14W, most preferably from 7 to 11W 8W for example; And/or (ii) wherein the ratio of electrode power and volume of plasma be less than 10W/ml, preferably from 5W/ml to 0.1W/ml, more preferably be from 4W/ml to 0.1W/ml, most preferably be from 2W/ml to 0.2W/ml.For a barrier coat or SiO xCoating; This plasma body preferably uses the electrode that provides following electric power through (i) that and the following produces: from 8 to 500W, preferably from 20 to 400W, more preferably from 35 to 350W; Even more preferably from 44 to 300W, most preferably from 44 to 70W; And/or (ii) the ratio of electrode power and volume of plasma is to be equal to or greater than 5W/ml, preferably from 6W/ml to 150W/ml, more preferably is from 7W/ml to 100W/ml, most preferably is from 7W/ml to 20W/m.
The geometrical shape of container can also influence the selection of the inlet mouth that is used for the PECVD coating.One specific aspect, can apply a syringe with the tube inlet of an opening, and can apply a pipe with a inlet mouth with a plurality of apertures, it is inner that this inlet mouth extends to this pipe.
The power (with wattmeter) that is used for PECVD can also influence coating characteristic.Typically, the increase of power will increase the barrier properties of coating, and the oilness and the hydrophobicity that reduce to increase this coating of power.For example, for the coating on the inwall of a syringe cylinder of the volume with about 3ml, will cause less than the power of 30W mainly is a kind of coating of barrier coat, and will to cause greater than the power of 30W mainly be a kind of coating (referring to instance) of slip coating.
Another parameter of decision coating characteristic is the O that is used for producing the gas reactant of plasma body 2The ratio of (or another kind of oxygenant) and this precursor (for example, organosilicon precursor).Typically, O in the gas reactant 2The increase of content will increase the barrier properties of coating, and O 2The oilness and the hydrophobicity that reduce to increase coating of content.Therefore, PECVD coating method of the present invention can be used to be provided with coating lubricating property, coating hydrophobic characteristics and by the barrier properties of the coating of said method preparation.
If a slip coating is desirable, O preferably then 2Be with the volume-volumetric ratio of gas reactant for from 0: 1 to 5: 1, more preferably from 0: 1 to 1: 1 even more preferably from 0: 1 to 0.5: 1 or even existed from 0: 1 to 0.1: 1.The most advantageously, in this gas reactant, there is not oxygen in fact.Therefore, this gaseous reactant comprises the O less than 1 volume % 2,, more specifically less than the O of 0.5 volume % 2, and most preferably be not contain O 2This is used for hydrophobic layer equally.
If barrier coat or SiO on the other hand, xCoating is desirable, then contains silicon precursor with respect to this, O 2Preferably with the volume of gas reactant from 1: 1 to 100: 1: volumetric ratio and existing, preferably from 5: 1 to 30: 1 ratio, more preferably from 10: 1 to 20: 1 ratio, even 15: 1 ratio more preferably.
V.A. use plasma body to apply SiO xThe PECVD of barrier coat, this plasma body is substantially free of hollow cathode plasma
V.A. a concrete embodiment is a kind of SiO that applies xThe method of barrier coat; This coating is defined as a coating that contains silicon, oxygen and optional other elements in this specification sheets (only if under concrete situation explanation) in addition, x wherein, and the ratio of oxygen and Siliciumatom is from about 1.5 to about 2.9; Or 1.5 to about 2.6, or about 2.These alternate definition of x are applicable to the term SiO of any use in this manual xBarrier coat is applied to the inside of a container (the for example container of a sampling tube, a syringe cylinder or another kind of type).This method comprises several steps.
V.A., a wall of container is provided, as is both a kind of reaction mixture, this mixture comprises the gas that forms plasma body, that is, and and a kind of organic silicon compound gas, randomly a kind of oxidizing gas, and randomly a kind of appropriate hydrocarbon gas.
V.A. plasma body forms in reaction mixture, is substantially free of hollow cathode plasma.This wall of container is contacted with this reaction mixture, and with SiO xBe coated with at least one part that is deposited to this wall of container.
V.A. in certain embodiments, to produce a kind of uniform plasma body be preferred spreading all on this part that container to be coated is arranged, because have been found that in some cases to have produced the SiO that better stops oxygen is provided xCoating.Uniformly plasma body representes not comprise the plasma body of rule of the hollow cathode plasma (this plasma body has than the higher emissive porwer of the plasma body of rule and is shown as a more high-intensity regional area of intensity more uniformly that has interrupted regular plasma body) of real mass.
V.A. hollow cathode effect is produced by pair of conductive property surface, and this to the surface with respect to a common anode with identical negative potential against each other.If leaving at interval, (depending on pressure and gas type) makes that like this space charge layer (space charge sheath) is overlapping; Then electronics begins vibration between the reflectivity electromotive force (reflecting potential) at opposite parietal layer; Cause multiple collision, quickened because these electronics stride across the potential gradient of layer region.These electronics are limited in the space charge ply, and this has caused the very high ionizing event and the plasma body of macroion density.This phenomenon is described to hollow cathode effect.Those of ordinary skill in the art can change treatment condition, and for example the pressure of power level and input speed or gas perhaps forms the plasma body that comprises hollow cathode plasma in various degree thereby form uniform plasma body throughout.
V.A. in an alternative method, use the for example device of foregoing Figure 12, thereby can use micro-wave energy in pecvd process, to produce plasma body.Yet treatment condition can be different, will excite (vibration) water molecules because be applied to a micro-wave energy on the thermoplastic container.Because on all plastic materials, there is a spot of water, microwave will heat these plastics.When plastics are heated; The big motivating force that produces by the vacuum in the device with respect to the outer normal atmosphere of device will attractive material dissociate out or easily with its desorption to internal surface 88, these materials will become volatile or will faintly be attached on this surface there.These faintly the bonded material will produce an interface then, this interface will stop coating (from plasma-deposited) subsequently to adhere on the plastic interior surfaces 88 of this device.
V.A. as a kind of method of eliminating this coating inhibition, can adhere to the cap on it thereby produced a coating subsequently in above instance with coating of low-down power deposition (being to be higher than 5 to 20 watts) with 2.45GHz.This has caused the coating processes (and two coats) of one two step.In above instance, can initial air-flow (adding the cap layer for this) be changed into the oxygen of 2sccm (" standard cubic centimeter/PM ") HMDSO and 20sccm, wherein processing power is 5 to 20 watts and continues about 2-10 second.Can flow rate and the power level that be increased to 20-50 watt of these gas regulation in the above instance be made to deposit a SiO then xCoating, wherein x is from about 1.5 to about 2.9 in this formula, alternately is from about 1.5 to about 2.6, alternately is about 2.It should be noted that in certain embodiments, adding the cap layer can provide seldom (even not having) functionality, only if at the SiO of higher-wattage xBe coated with and stop material transition in the layer deposition process to inner surface of container 88.Should also be noted that the migration that in the device wall, is easy to the material of desorption typically is not a problem, because lower frequency can not excite (vibration) molecular species under lower frequency (for example most RF scopes).
V.A. the another kind of method of the above coating inhibition of describing is eliminated in conduct, can be with container 80 dryings before applying micro-wave energy, to remove the water that includes.Container 80 dewater or drying can for example be passed through thermic heating container 80, as using the heating of electric heater or force air and accomplishing.The dewatering or dry can also be exposed to accomplishing of in a kind of siccative or the inside of gas contacting container 80 of container 80 through inside with container 80.Can also use other methods easily, come dry this container like vacuum-drying.These easily method can in the one or more stations showed or equipment or through an independent station or equipment, carry out.
V.A. in addition, the coating inhibition of more than describing can be through selecting or processing vessel 80 minimizes from the resin of its moulding and with the water cut of this resin and solves.
V.B.PECVD applies the vessel port (capillary injection device) of restriction
V.B. Figure 26 and 27 shows and roughly is expressed as 290 method and device, is used for applying through PECVD the internal surface 292 of opening 294 (opened front 294 of the for example restriction of a syringe cylinder 250) of restriction of the container 250 of a pending generally tubular.Be connected to through the opening 294 that will limit and revise the above method of describing on the processing vessel 296 and randomly to carry out some other modification.
The container 250 of V.B. pending generally tubular comprises an outside surface 298, the internal surface that defines an inner chamber 300 or inner surface 254, has the bigger opening 302 of an internal diameter and the opening 294 of a restriction, the opening of this restriction limit internal surface 292 and the internal diameter that has less than the internal diameter of this bigger opening 302.
V.B. this processing vessel 296 has an inner chamber 304 and a processing vessel opening 306, and this opening randomly is unique opening, although randomly pent one second opening in treating processes can be provided in other embodiments.This processing vessel opening 306 has the opening 294 of the restriction of pending container 250 to link to each other with this, to set up between this inner chamber that pending container 250 is arranged 300 and this processing vessel inner chamber being communicated with via the opening 294 of this restriction.
V.B. be pumped into partial vacuum at least in the inner chamber 304 with this inner chamber 300 that pending container 250 arranged and this processing vessel 296.A kind of PECVD reactant is flowed through this first opening 302 from gas source 144 (referring to Fig. 7), and the inner chamber 300 through pending container 250 is arranged then through the opening 294 of restriction, gets into the inner chamber 304 of this processing vessel 296 then then.
V.B. the interior electrode 308 that this PECVD reactant can be through providing a generally tubular is introduced into through the bigger opening 302 of container 250; Should in electrode have an interior passageway 310, near-end 312, a far-end 314 and a distal openings 316; In alternative embodiment, a plurality of distal openings may be provided near this far-end 314 and with internal passages 310 and are communicated with.The far-end of electrode 308 can place near the bigger opening 302 of pending container 250 or within.A kind of reactant gas can be fed in the inner chamber 300 of pending container 250 through the distal openings 316 of electrode 308.This reactant will flow through the opening 294 of this restriction, get into inner chamber 304 then, and its degree is under the higher pressure of the vacuum of initially being pumped into before than this PECVD reactant of introducing, to be provided for this PECVD reactant.
V.B. near the opening 294 in this restriction under the condition on the internal surface 292 of the opening 294 that effectively the PECVD reaction product is deposited to this restriction, produce plasma body 318.In the embodiment shown in Figure 26, through producing plasma body on the outer electrode 160 that RF can be input to U type roughly and with interior electrode 308 ground connection.Charging for these electrodes can also be opposite with ground connection connection, though pending if container 250 has, and electrode 308 is moving through this U-shaped outer electrode in therefore also having when plasma body is generated, and this counter-rotating possibly introduced complicacy.
V.B. the plasma body 318 that in the treating processes of at least a portion, in container 250, produces can be included in the hollow cathode plasma of generation in opening 294 and/or the processing vessel inner chamber 304 of restriction.The generation of hollow cathode plasma 318 can be facilitated the ability that successfully applies a barrier coat at opening 294 places of this restriction, although the present invention does not limit according to the accuracy or the suitability of this theory of operation.Therefore; In the operator scheme of a consideration; This processing can be partly produces under the condition of uniform plasma body and carries out spreading all over container 250 and this inlet mouth, and for example partly under near the condition that produces a kind of hollow cathode plasma the opening 294 of this restriction, carries out.
V.B. desirable is that this method is carried out under such condition, and as illustrated and illustrated in the accompanying drawings at this, plasma body 318 fills the air the opening 294 that spreads all over this syringe inner chamber 300 and this restriction basically.What also hope is that plasma body 318 fills the air the opening 294 that spreads all over this syringe inner chamber 300, this restriction and the inner chamber 304 of this processing vessel 296.This uniform coating of having supposed the inside 254 of container 250 is desirable.In other embodiments, inhomogeneous plasma can be desirable.
V.B. usually desirablely be; Plasma body 318 has one of the opening 294 basic color uniformly that spreads all over this syringe inner chamber 300 and restriction in treating processes, and preferably spreads all over the basic color uniformly of inner chamber 304 of opening 294 and this processing vessel 296 of this syringe inner chamber 300, this restriction basically.Desirable is that this plasma body spreads all over the opening 294 of this syringe inner chamber 300 and restriction and the inner chamber 304 that preferably spreads all over this processing vessel 296 in addition is stable.
V.B. the order of not considering step in this method is crucial.
V.B. in the embodiment of Figure 26 and 27; The opening 294 of restriction has one first joint 332; And processing vessel opening 306 has one second joint 334, and this second joint is adapted to be and is seated on this first joint 332 with being communicated with between the inner chamber 304 that is based upon this processing vessel 296 and the inner chamber that pending container 250 is arranged 300.
V.B. in the embodiment of Figure 26 and 27, this first and second joint is respectively outer Rule and interior luer lock joint 332 and 334, and they are one with the structure of opening that defines restriction 294 and processing vessel opening 306 accordingly.Outside under the situation of luer lock joint 332; One of these joints comprise a lock collar 336; This lock collar have a threaded internal surface and define an axial plane to first bearing 338 of general toroidal, and another joint 334 comprise one towards the axial plane of this first bearing 338 to second bearing 340 (when joint 332 and 334 engages) of general toroidal.
V.B. in the embodiment of this displaying, can with a sealing member for example O type circle 342 be positioned at this first and this second joint 332 and 334 between.For example, lip ring can be bonded on this first and this second bearing 338 and 340 between.Should in female luer 334 can also comprise a claw 344, this claw engage with the threaded internal surface of this lock collar 336 with this first and this second joint 332 and 334 between extracting O type circle 342.Randomly, via being leakproof at least basically being communicated with of between the inner chamber 304 of this inner chamber 300 that pending container 250 arranged and processing vessel 296, setting up of the opening 294 of this restriction.
V.B. select as another kind of, any in the luer lock joint 332 and 334 or both can be processed by conducting fibre material (for example stainless steel).The formation that the opening 294 of this formation restriction or building material adjacent thereto can be facilitated plasma body in the opening 294 of this restriction.
It is compromise between a little volume and big volume that the volume of the inner chamber 304 of V.B. desirable processing vessel 296 is considered; This little volume can not make to leave in a large number desirablely has the reactant flow on product to be coated surface to turn to, this big volume fully fill support a large amount of openings that passes through this restriction 294 before this inner chamber 304 the reactant gas flow rate this flow rate is reduced to a more undesirable value (striding across the pressure reduction of the opening 294 of restriction through reduction).The volume of the inner chamber of being considered in one embodiment 304 is three times less than the volume of the inner chamber that pending container 250 is arranged 300; Or this has the twice of volume of the inner chamber 300 of pending container 250 less than this; Or the volume of the inner chamber 300 of pending container 250 is arranged less than this; Or less than this have pending container 250 inner chamber 300 volume 50%, or less than this have pending container 250 inner chamber 300 volume 25%.Other effectively relations of the volume of corresponding inner chamber have also been considered.
V.B. ladies and gentlemen contriver has found that also the homogeneity of coating can be improved through the far-end of reorientating electrode 308 with respect to container 250 in certain embodiments, like this it does not penetrate container 250 inner chamber 300 inside as far as as in the position of the interior electrode shown in the above accompanying drawing.For example; Although in certain embodiments; Distal openings 316 can be close to the opening 294 of this restriction and be located; This distal openings 316 can be located less than 7/8 (randomly less than this distance 3/4, randomly less than half of this distance) of the distance of the bigger opening 302 that pending container is arranged from this to the opening 294 of restriction in other embodiments, feeds reactant gas simultaneously.Perhaps, this distal openings 316 can by less than 40%, less than 30%, less than 20%, less than 15%,, less than 10%, less than 8%, less than 6%, less than 4%, less than 2% or less than 1% from this have pending container bigger opening to the opening 294 of restriction distance and locate and feed reactant gas simultaneously.
V.B. perhaps, the far-end of this electrode 308 can this have pending container 250 bigger opening 302 slightly in or slightly outside or concordant with it and location simultaneously with the internal communication of this container 250, and the inside of feeding reactant gas to this container 250.With respect to this pending container 250 is arranged, the location of distal openings 316 can owing to concrete size and other treatment condition through it being tested and optimizing in different positions.A particular location for handling the electrode 308 that syringe cylinder 250 considered is that far-end 314 penetrates into about 1/4th inches (the about 6mm) that container intracavity 300 is higher than bigger opening 302.
V.B. ladies and gentlemen contriver considers at present advantageously to place to the far-end 314 of major general's electrode 308 that it will suitably work as an electrode like this in the container 250, although this is not must be a prerequisite.Unexpectedly, can get into processing vessel inner chamber 304 thereby fill the air the opening 294 that passes restriction so that the plasma body 318 that in container 250, produces is more even, wherein electrode 308 less penetrates in the previous already used inner chamber 300.Arrange through other, as handle the container of a closing end that the far-end 314 of electrode 308 is placed in than its inlet more near the closing end of this container usually.
V.B. perhaps, the far-end 314 of electrode 308 can be positioned in opening 294 places of restriction or surpass the opening 294 of restriction, for example in processing vessel inner chamber 304, like what in Figure 33, showed.Different stopgap measures can randomly be provided, as this processing vessel 296 is shaped to improve the air-flow through the opening 294 of this restriction.
V.B. as another replacement scheme; Like what showed among Figure 34-35; Electrode and feed tube 398 can have near for example 400 (randomly being positioned at this bigger opening 302) and extension electrodes 402 of a plurality of far-end gas supply openings in this was compound; This extension electrode extends to the far-end of these far-end gas supply openings 400, a far-end of opening 294 vicinities that randomly extend to and limit, and randomly further extend in this processing vessel 324.This structure is considered to promote in the internal surface 292 that the opening 294 with restriction is close to, forming plasma body.
V.B. in the embodiment of another consideration again, can in treating processes, move, for example at first extend in this processing vessel inner chamber 304, then along with the carrying out of process progressively withdrawn from near-end like the interior electrode 308 in Figure 26.If container 250 is longer under selected treatment condition, and interior electrode mobile help handling more equably internal surface 254, and this stopgap measure is to consider especially.Use this stopgap measure; Treatment condition (like gas feed speed, vacuum take-off rate, be applied to electric energy on the outer electrode 160, withdraw from speed or other factors of electrode 308) can change along with the carrying out of process, thereby for the different process of different parts customizations that pending container is arranged.
V.B. easily; In other processes of describing in this manual; Can the bigger opening of the container that pending generally tubular is arranged 250 be placed on the container support 320, as being landed on the port 322 of this pan straddle 320 through the bigger opening 302 that makes pending container 250.Then, before being pumped into a part of vacuum in the inner chamber 300 that pending container 250 is arranged at least, can interior electrode 308 be positioned in the container 250 that is seated on the pan straddle.
V.B. in an alternative embodiment (in displaying) like Figure 28; One first opening 306 (as shown in Figure 26) that can provide processing vessel 324, this conduit to have with the form of conduit to be fixed on the pending container 250 and one second opening 328 that is communicated with vacuum ports 330 in the pan straddle 320.In this embodiment, pecvd process gas can flow into container 250, and the opening 294 via restriction gets in the processing vessel 324 then, returns through vacuum ports 330 then.Randomly, apply before the PECVD reactant can through opening 294 and 302 both container 250 is found time.
V.B. perhaps; Through 144 introducing the opening of the rear end 256 of reactants through being positioned at tube 250 and use the opening extracting vacuum at front end 260 places of vacuum source 98 through being positioned at tube from originating, a syringe cylinder 250 (as shown in Figure 22) that adds cap can be equipped with a kind of SiO xThe PECVD coating of coated inside, barrier coat or the other types of (wherein x is from about 1.5 to about 2.9 in this formula, alternately from about 1.5 to about 2.6, alternately about 2).For example, can connect vacuum source 98 through one second joint 266 on the front end 260 that is seated at syringe cylinder 250.Use this stopgap measure; These reactants can be at a folk prescription to (making progress; As shown in Figure 22; Though this direction is not critical) flow through tube 250, and need reactant not carried through a probe that within syringe cylinder 250, feed gas and vent gas is separated.In an alternative layout, can also the front end 260 of syringe cylinder 250 be reversed with respect to this coating unit with rear end 256.Probe 108 can work as an electrode simply, and can be a tubular rod or solid spar in this embodiment.As preceding, on most of at least length of syringe cylinder 250, inner surface 254 can be uniform with the separating between 108 of popping one's head in.
V.B. Figure 37 is a view that is similar to Figure 22 that shows another embodiment, and joint 266 is independently and not to be attached on plate electrode 414 and 416 in this embodiment.Joint 266 can have one by adaptive with the luer lock joint on the corresponding joint of waiting to be fixed to syringe cylinder 250.This embodiment allows vacuum piping 418 to pass through from electrode 416 tops, and during coating step, pan straddle 420 and attached container 250 move between electrode 414 and 416 simultaneously.
V.B. Figure 38 has shown and the view that is similar to Figure 22 of another embodiment, and the front end 260 of syringe cylinder 250 is open and Vakuumkammer 422 that syringe cylinder 250 is seated on the pan straddle 424 centers in this embodiment.In this embodiment, the pressure P 1 in the syringe cylinder 250 and in the Vakuumkammer 422 is roughly the same, and randomly the front end 260 through syringe cylinder 250 comes the vacuum in the extracting vacuum chamber 422.When these flow of process gases got into syringe cylinders 250, they flowed front end 260 through syringe cylinder 250 until a stable formation is provided in syringe cylinder 250, at electrode 160 at this moment by energy supply to form coating.What consider is, because the location with respect to the bigger volume and the counter electrode 426 within the syringe cylinder 250 of syringe 250 of Vakuumkammer 422, the process gas through this front end 260 will not form significant settling on the wall of Vakuumkammer 422.
V.B. Figure 39 be show and another embodiment be similar to a view of 22; The back flange of this syringe cylinder 250 is clamped between pan straddle 428 and the electrode assemblie 430 in this embodiment, wherein is designated as 160 cylindrical electrode or pair of plates electrode and a vacuum source 98 and is fixed on this electrode assemblie.Thereby in this embodiment, being shown 432 volume around outside being often referred to of syringe cylinder 250 is less relatively the minimum PECVD of operation process to be reduced in needs be used to the to find time pumping of inside of volume 432 and syringe cylinder 250.
V.B. Figure 40 is that view and the Figure 41 that is similar to Figure 22 is a plan view; This plan view shown as the replacement scheme of Figure 38 in addition another embodiment; Wherein through a pressure proportioning valve 434 is provided, pressure ratio P1/P2 is maintained at a desired horizontal.What considered is during PECVD handles, to compare with P2, and P1 can be a lower vacuum, and promptly higher pressure makes the front end 260 that process gas and by product will be through syringe cylinder 250 and being excluded of giving up like this.And the providing of the Vakuumkammer conduit 436 that separates that is used for Vakuumkammer 422 allows to use vacuum pump separately to come the bigger closed volume 432 of finding time quickly.
V.B. Figure 41 is a plan view of the embodiment of Figure 40, has also shown the electrode of from Figure 40, removing 160.
V.C. apply the method for slip coating
V.C. another embodiment is the method that applies slip coating, and this slip coating obtains from organosilicon precursor.A kind of " lubricant film " or any other similar term are generally defined as the coating that has reduced the friction resistance of coated surface with respect to uncoated surface.If this coated article is a kind of syringe (or syringe part; Syringe cylinder for example) or any other generally include a plunger or be in the movable part in the sliding contact with this coated surface, then this friction resistance has two main aspect-starting forces and plunger sliding force.
Plunger sliding force test is the test of testing the coefficient of sliding friction of the plunger in a syringe specially, has explained a fact: solve through the matching standardization between other containers that make plunger or other sliding members and pipe or it and slide therein in the relevant normal force of the coefficient of sliding friction of measuring on the flat surface with common.The parallel force relevant with the coefficient of sliding friction of common measurement with as the measured plunger sliding force described in this manual be comparable.The plunger sliding force can for example provide like institute in ISO 7886-1:1993 test and measure.
Plunger sliding force test can also be adapted to be the friction resistance of measuring other types through suitably modifier and step, for example a stopper is remained on the frictional force in the pipe.In one embodiment, this plunger can replace and the power of withdrawing from that shifts out or insert this closure member can be used as the counterpart of plunger sliding force and measures with closure member.
And can measure this starting force (or replacing this plunger sliding force).This starting force is immobilized plunger of starting needed power of in a syringe cylinder, moving, or a static closure member of taking a seat is disseated (unseat) and makes the needed power of its setting in motion.Measure this starting force on this plunger through a power is applied to, this power is from zero or till low value begins and increase when this plunger setting in motion.After this precharging type syringe plunger is pushed the lubricant of intervention open or adhered on the tube (because this plunger and the lubricant between this decompose), this starting force is tended to increase with the storage of injector.Starting force is to overcome the needed power of " adhesion " (" sticktion "), is the industry slang of adhesion to start this plunger and to allow it to begin to move between plunger and tube that is used for overcoming.
V.C. some practical applications that are coated with lubricant film in all or part of (as optionally in the surface that contacts with sliding relation with miscellaneous part) of container make inserts or shifts out stopper or be easy through a sliding members (like piston in syringe or the stopper in a sample hose).This container can be to be processed by glass or a kind of polymer materials such as polyester (for example polyethyleneterephthalate (PET)), cyclic olefine copolymer (COC), alkene (like Vestolen PP 7052) or other materials.Applying a slip coating through PECVD can avoid or reduce through spraying, immersion coating wall of container or closure member or additionally apply organosilicon or the needs of other lubricants (normally with than using through the much bigger amount of PECVD process deposition).
V.C. in office how going up among the embodiment V.C., a kind of plasma body, randomly a kind of non-hollow cathode plasma randomly can form near substrate.
V.C. in any embodiment V.C., this precursor can be randomly exist basically under the oxygen and is providing.V.C. in any embodiment V.C., this precursor can be randomly provide not existing under the carrier gas basically.V.C. in any embodiment V.C., wherein this precursor can be randomly exist basically under the nitrogen and is providing.V.C. in any embodiment V.C., wherein this precursor randomly can be by providing less than the absolute pressure of 1 holder.
V.C. in any embodiment V.C., this precursor randomly can be provided to a plasma emission thing near.
V.C. in any embodiment V.C., randomly can by 1 to 5000nm 10 to 1000nm or the thickness of 10-200nm or 20 to 100nm this coating is applied in the substrate.Can for example pass through transmission electron microscopy (TEM) and measure the thickness of this and other coatings.
V.C. for example TEM can carry out as follows.Can prepare by two kinds of methods and be used for the sample that focused ion beam (FIB) section is analyzed.Perhaps can use a K575X Emitech application system at first to use a carbon thin layer (50-100nm is thick) to apply and then apply these samples, or can use protectiveness sputter Pt layer directly to apply these samples with a sputter platinum layer (50-100nm is thick).Can the sample of these coatings be placed a FEI FIB200FIB system.Can carry out other platinum layer of FIB-deposition through injecting a kind of organic metal gas while gallium ion beam of raster scanning 30kV on interesting areas.Can each sample interesting areas be chosen as one along the position of this syringe cylinder down to half length.The original position FIB extrusion technique (in-situ FIB lift-out technique) that can use a kind of special use takes out from die surface and is measured as that about 15 μ m (" micron ") grow, 2 μ m are wide and the dark thin section of 15 μ m.Can use the sedimentary platinum of FIB-that these sections are attached to one 200 purpose copper TEM carries on the net.Can use the gallium ion beam of FEI FIB to make in each section, to be measured as wide one or two window (window) of about 8 μ m and be thinned to the electron lucent degree.
V.C. can use transmission electron microscope (TEM) or scanning transmission electron microscope (STEM) or the two sample to carry out the cross-sectional image analysis to these preparations.All view data can be used digital recording.For the STEM image, can the net that carry of the paillon foil with attenuation be transferred on the special-purpose STEM of a Hitachi HD2300.Can obtain to be in the scanning transmission electronic image at suitable enlargement ratio of ordination number contrastive pattern (ZC) and transmitted electron pattern (TE).Can use following instrument setting.
Figure BDA0000126277010001121
V.C. for tem analysis, can the sample grid be transferred to a HitachiHF2000 transmission electron microscope and can obtain the transmitted electron image under suitable enlargement ratio.The relevant instrument setting of in image acquisition process, using can be following those that provide.
V.C. in any embodiment V.C.; This substrate can comprise glass or a kind of polymkeric substance, for example carbonate polymer, olefin polymer, cyclic olefine copolymer, polyacrylic polymer, polyester polymers, polyethylene terephthalate polymer or any two kinds or more kinds of combinations among these.
V.C. in any embodiment V.C.; Randomly can carry out this PECVD through the gas reactant that uses as the electrode excitation of the RF frequency power energy supply of above definition contains this precursor, this frequency be for example one from 10kHz to less than the frequency of 300MHz, more preferably from 1 to 50MHz in addition more preferably from 10 to 15MHz, the frequency of 13.56MHz most preferably.
V.C. in any embodiment V.C., the gas reactant that can contain this precursor through the electrode excitation that use provides the electric power that is enough to form a slip coating produces this plasma body.Randomly; The gas reactant that can contain this precursor through the electrode excitation that provides following electric power produces this plasma body, and this power is: from 0.1 to 25W, preferably from 1 to 22W; More preferably from 3 to 17W; Even more preferably from 5 to 14W, most preferably from 7 to 11W, 8W particularly.The ratio of electrode power and volume of plasma can be less than 10W/ml, preferably from 5W/ml to 0.1W/ml, more preferably be from 4W/ml to 0.1W/ml, most preferably be from 2W/ml to 0.2W/ml.These power levels are suitable for being used for applying slip coating to the syringe and the stopple coupon of the void volume with 1 to 3mL (wherein having produced the PECVD plasma body) and container with similar geometric.Be determine this process in proportion, the power that correspondingly increases or reduce to be applied according to the size of this substrate for what bigger or less object was considered.
V.C. the product of a consideration randomly can be the syringe with tube of handling through any one or a plurality of methods of embodiment V.C..
V.D. the coating that applies of liquid
V.D. another example of the coating of suitable barrier coat or other types can be the coating 90 of the other types on a kind of liquid obscures coating, lubricant coating, surface energy customization coating or the internal surface that is applied to a container, and it can directly use, or the coating that can apply with PECVD or other PECVD disclosed here handle or the Si that applies with the PECVD of one or more interventions wO xC yH z(SiO x) coating, slip coating or the two be used in combination.
V.D. can be randomly for example through on the internal surface that a kind of liquid monomer or other polymerizable or curable materials is applied to container 80 and curing, polymerization or crosslinked this liquid monomer apply the suitable liquid obscures coating or the coating 90 of other types to form a kind of solid polymer.Can also be applied on the surface 88 through polymkeric substance and remove and change solvent the suitable liquid obscures coating or the coating 90 of other types are provided a kind of solvent dispersion.
V.D. any in the above method can be included on the inside 88 of a container 80 via a step that forms coatings 90 at the container port 92 at a treatment station or equipment 28 places.Example is for example the liquid coating of a kind of curable monomer, prepolymer or polymeric dispersions to be applied on the internal surface 88 of container 80 and with it to solidify to form a film, and this film is isolated from its internal surface 88 content of container 80 with physics mode.Description of the Prior Art be suitable for the polymer-coated technology of coating plastic heparin tube.For example, can randomly use at USP 6,165, acrylic acid and polyvinylidene dichloride (PVdC) coating material and the coating method described in 566 combine this patent hereby by reference.
V.D. each in the above method can also comprise or comprise as a step that on the outside outer wall of a container 80, forms coating.This coating randomly can be a barrier coat, oxygen barrier coat randomly, or water resistance barrier coating randomly.The instance of a suitable coating is a polyvinylidene dichloride, and it is as a water blocking layer and an oxygen barrier layers and work.Randomly, this barrier coat can be used as a coating based on water and applies.This coating randomly can be ejected into it on this container through with this tank immersion therein, perhaps other stopgap measure and applying.Also considered to have a kind of container of the outer barrier coating of above description.
VI. container inspection
Shown in V1 Fig. 1 one stands or equipment is treatment station or equipment 30; It can be configured to check the defective of the inner surface of a container 80, as through measuring through the atmospheric pressure lost of a wall of container or the venting of mass flow rate or a volumetric flow rate or a wall of container.Equipment 30 can work with equipment 26 similarly; Except the better properties (in leakage less under the given processing condition or infiltration) that possibly require this container with the inspection that is provided through equipment 30; Because in the embodiment of being showed; Before station or equipment 30 arrive, applied the coating of a barrier coat or other types through station or equipment 28.In one embodiment, this inspection of coating container 80 can compare with the inspection at the identical container 80 at the equipment or 26 places of standing.At the station or the less leakage at equipment 30 places and infiltration shown that this barrier coating is to play to a certain degree effect at least.
VI. that measure at place, two different stations or by the personal characteristics of the container 80 of two different device measurings can each pan straddle 38-68 goes up and near the personal characteristics of the container of two or more difference places measurements of the coupling pool conveyer shown in Fig. 1 is confirmed through individual recognition characteristic (like a barcode, other marks or a kind of RF identification (RFID) equipment or mark) is placed on.Because these pan straddles can be utilized again; When they arrive the position of the pan straddle 40 among Fig. 1 (only after a new container 80 is landed on the pan straddle 40); They can be registered in a Computer Database or other data store organisations; And near the destination county of this process or its, from data register, remove, when the container 80 of position and processing that for example arrives the pan straddle 66 of Fig. 1 when them is removed by transmission mechanism 74 or afterwards.
VI. this treatment station or equipment 32 can be configured to container of inspection, for example the defective of the coating of barrier coat that puts on this container or other types.In the embodiment of this displaying, stand or equipment 32 has been confirmed the light sources transmit of coating, as measuring of the thickness of coating.If suitably apply, the coating of this barrier coat or other types can make container 80 more transparent (though having applied other material), because it provides a surface more uniformly.
VI. other that also considered coat-thickness are measured; For example difference through using the miles of relative movement between the interferometry energy waves of confirming to rebound in the inboard (and the atmosphere the internal tank 154 meets the boundary) from coating 90 and the energy waves of rebounding from the inner surface 88 (and outer side joint circle of coating 90) of container 80 is as being known, with respect to test condition directly (as through measure the time of arrival of corresponding ripple with pinpoint accuracy) or indirect (like a wavelength) through definite projectile energy that strengthens or eliminate confirm the difference of miles of relative movement.
VI. can be used for checking the coating integrity another kind of measuring technology be the ellipsometry (ellipsometric measurement) of relevant device.In this case, can perhaps throw polarized laser beam from the inside of container 80 or from the outside.Under the situation of projecting laser bundle internally, this laser beam can by quadrature point to from the teeth outwards and then can to or transmitted beam or reflected beam measure.Can measure the change aspect light beam polarity.Because coating on device surface or processing will influence the polarization of (change) laser beam, it can be desirable result that polar changes.It is to exist the amount of coating or direct result of handling and change relevant with the amount of processing or coating from the teeth outwards that polar changes.
If VI. this polarized beam is to throw from the outside of device, can a detector be positioned at the inner component (and as above definite polarity) that goes up with the transmission of measuring bundle.Perhaps, can a detector be placed on a position of the outside of device, this position corresponding is in the reflection spot (on the inside at this device) of the bundle that comes the interface between the comfortable processing/coating.Can confirm one or more reversings like above detailed description then.
VI. except measuring the optical characteristics and/or the leakage rate of as above explanation, other probes and/or device can be inserted into this equipment and the inside of the measuring apparatus processed by detector means.This device does not receive the restriction of measuring technology or method.Can utilize other testing method, these testing method adopt machinery, electricity or magnetic properties, or any other physics, optics or chemical property.
VI. during plasma treatment is set up, randomly can use an optical detection system to write down plasma emission spectroscopy (wavelength and intensity curve), this spectrum is corresponding to unique chemical feature of plasma environment.The confirmation that this characteristic emission spectrum provides this coating to be applied in and to have handled.To each part of handling, this system also provides a kind of and has accurately measured in real time and the data filing instrument.
VI. any above method can comprise a step of the inner surface 88 of container 80 being checked to defective like 24,26,30,32 or 34 places as at treatment station.As at 24,32 and 34 places, station, can be through inserting in containers 80 via container port 92 detection probe 172 and using the situation of the coating 90 of probe 172 detection receptacle inner surface 88 or barrier coat or other types to check.As shown in Figure 11, can 172 detect this energy and check through wall of container 86 and internal tank surface 88 and with popping one's head in through inside quantity of radiant energy.Perhaps, can come detected energy inspection through reflecting from the radiation on internal tank surface 88 and with being positioned at container 80 inner detectors.Perhaps, can check through the situation of detection receptacle inner surface 88 in the lip-deep a plurality of tight spacings of internal tank position.
VI. any above method can be carried out in the position of the enough numbers that spread all over internal tank surface 88, will effectively prevent to be increased to greater than 20% of ambient atmosphere pressure during the quality guaranteed period in 1 year at the pressure of (when it initially is evacuated and its wall is exposed to ambient atmosphere following time) within this container with the coating 90 of confirming a barrier coat or other types.
VI. any above method can be included in 30 seconds or carry out this inspection step within elapsed time of shorter/every container or 25 seconds or shorter/every container or 20 seconds or shorter/every container or 15 seconds or shorter/every container or 10 seconds or shorter/every container or 5 seconds or shorter/every container or 4 seconds or shorter/every container or 3 seconds or shorter/every container or 2 seconds or shorter/every container or 1 second or shorter/every container.The effectiveness (as shown in Figure 7) of the wall of container that for example applies through the coating of measuring this barrier coat or other types; This possibly relate to a measurement for entire container 80; Or through check a plurality of abreast or even all the point of examine is arranged; As through using charge coupled device, can make it to become possibility as detector 172 (like Fig. 6, shown in 10 and 11 or replacedly).The situation of the coating of barrier coat or other types is detected in the position that latter's step can be used for a plurality of tight spacings on internal tank surface 88 in very short total time.
VI. in any embodiment of this method; Can come further to accelerate the multiple spot container to detect (if desired) through following steps: use charge coupled device 172 to collect data; Transport and remove just checked container 80; And shortly after that the data of collecting are handled, container 80 moves in downstream simultaneously.If, can make defective container 80 for example leave circuit in a some place in the downstream of 34 (Figure 10) at measuring station because data processing has been confirmed the defective in the container 80 subsequently.
VI. in officely how go up in the embodiment; This inspection step can be carried out in the position of enough numbers of the inner surface that spreads all over container 80 88, with the coating 90 of confirming a barrier coat or other types will effectively prevent during the initial vacuum level (promptly the original pressure with respect to environment reduces) of (when it initially is evacuated and its wall 86 is exposed to ambient atmosphere following time) within the container 80 quality guaranteed period, to reduce more than 20% at least 12 months or at least 18 months or at least two years, randomly more than 15%, randomly more than 10%, randomly more than 5%, randomly more than 2%.
VI. the initial vacuum level can be a high vacuum; Be that surplus pressure is less than 10 holders; Or a littler vacuum, as less than the malleation excess pressure of vacuum (promptly surpass) of 20 holders or less than 50 holders or less than 100 holders or less than 150 holders or less than 200 holders or less than 250 holders or less than 300 holders or less than 350 holders or less than the malleation of 380 holders.In many cases, the initial vacuum level of vacuum test tube for example is to be decided by the type that test tube to be used is arranged and the type of the reagent that is added into during fabrication therefore and suitable amount.Thereby this initial vacuum level is set usually with the blood of inspiration appropriate amount and combines with reagent in charging into this pipe.
VI. in officely how go up in the embodiment; Can carry out the inspection step of the coating 90 of this barrier coat or other types in the position of the enough numbers that spread all over internal tank surface 88, with the coating 90 of confirming this barrier coat or other types will effectively prevent during the quality guaranteed period of pressure at least one year of (when it initially is evacuated and its wall is exposed to ambient atmosphere following time) within this container 80, to be increased to more than ambient atmosphere pressure 15% or more than 10% of ambient atmosphere pressure.
VI.A. comprise that precoating and back apply the container processing of inspection
VI.A. in addition another embodiment be a kind of container-treatment that is used to handle the plastic containers of a moulding, the plastic containers of this moulding have an opening and a wall that limits inner surface.This method is carried out through following steps: by moulding or just in time before applying, check the defective of the inner surface of container; Arrived the inner surface of this container by the after-applied coating of container for moulding in inspection; And the defective of inspection coating.
VI.A. another embodiment is a kind of container-treatment, wherein after inspection is by container for moulding, a barrier coat is applied on this container, and the inner surface to this container of defective is checked after applying this barrier coat.
VI.A. in one embodiment, can use station or equipment 26 (it can also work as station or equipment 28 and be used to apply a coating) to be used for barochamber inspection as follows.Under one of valve 136 and 148 or both openings, can container 80 be evacuated to a desirable degree, preferably to a low-down pressure (like 10 holders, randomly less than 1 holder).Whichever is open at first in the valve 136 and 148, can then it be closed, and the inside 154 and the pressure warning unit 152 of the container of finding time 80 separated with envrionment conditions and with vacuum source 98.The change of pressure in the Measuring Time process; No matter whether be because gas gets into through wall of container or from the material of this wall and/or in the coating on this wall of container, exits, can and be used for the speed (when being installed in 44 last times of pan straddle) of computing environment air admission container 80 by sensing then.For this purpose, venting is defined as randomly under partial vacuum at least from the absorption of wall of container or the release of occluded gas or water vapour.
VI.A. another optional modification can be environmental gas to be provided being higher than under the barometric point.This can increase gas again and shift the speed through the layer of blocking layer or other types, in such as the time shorter under really providing than low environment pressure, a measurable difference is provided.Perhaps, can under being higher than environmental stress, gas be introduced in the container 80, this has increased the transfer rate through wall 86 again.
VI.A. can be randomly, at this station the place or the container inspection through equipment 26 can through a kind of inspection gas such as helium are provided with respect to a upstream side of substrate (within container 80 or outside) and in the downstream side detection it make amendment.A kind of low-molecular-weight gas (like hydrogen) or a kind of gas more not expensive or that more can get (like oxygen or nitrogen) also can be used as a kind of inspection gas.
VI.A. considered that helium is as a kind of inspection gas; It can increase leaks or speed that infiltration detects, and this is because it is much faster as to pass the coating of a defective barrier coat or other types or pass one leakage sealed than common surrounding gas such as the nitrogen in the normal air and oxygen.Helium has through many solid substrates or closely spaced high pass speed, and this is owing to it: (1) is inert, thereby it is not adsorbed with any big degree by substrate; (2) be not easy by ionization; Thereby its molecule is very closely, and this is owing to its electronics and the high-caliber attraction between the nucleus, and the molecular weight that (3) have is 4; Relative with nitrogen (molecular weight 28) and oxygen (molecular weight 32), make molecule more closely and easily through a kind of porous substrate or gap once more.Because these factors, helium will be much faster as to pass and have a given infiltrative blocking layer than many other gases.Equally, atmosphere contains the very helium of small proportion natively, thereby the existence of extra helium can relatively easily detect, if particularly helium is introduced within the container 80 and outside container 80, detects measure to leak and during infiltration.Therefore, the pressure drop upper reaches (pressure drop upstream) through this substrate or detect helium through additive method (like the spectroscopic analysis of the gas downstream through this substrate).
VI.A. through to from O 2An instance of the barochamber inspection that the oxygen concentration of fluoroscopic examination is confirmed is followed as follows.
VI.A. a kind of vacuum of having used a driving source (Ocean Optics USB-LS-450 blue pulse LED), optical fiber component (Ocean Optics QBIF6000-VIS-NIR), spectrometer (USB4000-FL spectrofluorometer), oxygen sensor probe (Ocean Optics FOXY-R) and being connected on the vacuum source connects adapter (as VFT-1000-VIS-275).Can apply a vacuum and remove ambient air; And when this container is in defined pressure following time, thereby can use this detection system to confirm that the pipe that from ambient air, leaks or penetrate into a coating of any oxygen content that is full of this container again substitutes uncoated pipe and can carry out O 2Measurement of concetration.Because (SiO on the pipe that applies xThe surface is with respect to uncoated PET or glass surface) otherness O 2The surface absorbs and/or from the O on surface 2The change of rate of diffusion is compared with uncoated sample, and the pipe of coating will prove and reappear the different atmosphericoxygen content in ground.Can be less than a second detection time.
VI.A. these gas pressure means should not be considered a kind of specific gas (can consider that helium detects or gas gas) or a kind of specific device or the layout that is limited to institute's sensing.
VI.A. this treatment station or equipment 34 can also be configured to defective the coating of barrier coat or other types is checked.In the embodiment of Fig. 1 and 10; Treatment station or equipment 34 can be another kind of optical checks; At this moment be intended to the position of a plurality of tight spacings on the coating 90 of barrier coat or other types at least a portion, or the characteristic of the coating 90 of whole basically barrier coat or other types scans or separately measurement to the coating 90 of barrier coat or other types.In each case or average on this surperficial at least a portion; The position of these a plurality of tight spacings can be for example to separate about 1 micron or separate about 2 microns or separate about 3 microns or separate about 4 microns or separate about 5 microns or separate about 6 microns or separate about 7 microns, therefore dividually the some or all of small portions of the coating 90 of barrier coat or other types is measured.In one embodiment; Each zonule of coating is separated scanning for finding independent pin hole or other defect, and possibly be useful for the local influence (as big zone) of from more common defective, distinguishing needle pore defect with too thin or porous coating.
VI.A. can carry out according to the following steps through the station or the inspection of equipment 34: for example through inserting in the containers 80 via container port 92 source of radiation or light source 170 or any other radio frequency, microwave, infrared rays, visible light, ultraviolet ray, X ray or electron beam source that is fit to and using detector to detect and come the for example situation of barrier coat 90 of detection receptacle inner surface from the radiation of source of radiation transmission.
VI.A. can also use above pan straddle system to be used to test this device.For example, the probe 108 that has Fig. 2 of a gas delivery port one 10 can be replaced by a light source 170 (Figure 10).Light source 170 can shine the inside of this pipe and can accomplish test subsequently in the outside of this pipe then, measures transmission or other characteristics.Can make light source 170 extend into the inside of this pipe in an identical manner, promptly popping one's head in 108 is pushed in rubber disc or the pan straddle 62, though vacuum is not essential with sealing.Light source 170 can be a kind of optical fiber source, a kind of laser, a kind of pointolite (for example LED) or any other source of radiation.Radiation can be carried out with one or more frequencies of (100 microns) and all frequencies between them from dark UV (100nm) to far infrared in this source.To the not restriction of operable light source.
VI.A. as a specific examples, referring to Figure 10.In Figure 10, pipe or container 80 are positioned in rubber disc or the pan straddle 62, and the light source 170 that is arranged in probe 108 end has been inserted into this pipe.Light source 170 can be a blue led light source of the sufficient intensity that remains to be received by the detector 172 around the outside of container 80 in this case.Light source 170 can be three-dimensional charge-coupled device (CCD) for example, and this charge coupled device is included in an array (for example 174) of a plurality of pixels on the interior surface thereof 176.These pixels receive and detect radiation through barrier coat or the coating 90 of other types and the illumination of wall of container 86 as 174.In this embodiment, have electrode 164 and separating of container 80 of bigger internal diameter with respect to container 80 detectors 172, and have cylinder-shaped top part rather than dome end parts near closing end 84 than Fig. 2.This external detector 172 can have the littler radius clearance of leaving container 80, and near its one of the top office gap of uniform-dimension more closing end 84.When container 80 is taken a seat, this can be for example through providing a common centre of curvature to realize for the top of closing end 84 and detector 172.This change possibly provide the more consistent inspection of the crooked closing end 84 of container 80, is fit to though any one of two kinds of changes all is considered.
VI.A. before light source is opened, CCD is measured, and the value that will obtain storage (can deduct it from observed value subsequently) as a setting.Obtain observed value with light source 170 unlatchings and with CCD then.Can use then the observed value that obtains calculate total light transmission rate (thereby and compare confirm average coat-thickness with uncoated pipe) and defect concentration (if compare through the independent photon counting on each element of obtaining CCD and with them and threshold value-photon counting is lower, then this corresponding to do not have enough light by through).Low light transmission rate possibly be do not have or too the result of shallow layer-the pipe on coating in defective.Through the quantity of the contiguous element with low photon counting is measured, can estimate the size of defective.Size and quantity through to defective gather, and can evaluate the quality of pipe, or confirm other characteristics, and these characteristics possibly be specific for the radiating frequency from light source 170.
VI.A. in the embodiment of Figure 10, energy can be to external irradiation through the internal tank surface, as through coating 90 and wall of container 86, and uses the detector 172 that is positioned at this external container to detect.Can use dissimilar detector 172.
VI.A. can be bigger (with comparing) because of the coating of passing through this barrier coat or other types 90 of 170 emissions and the incident radiation of wall of container 80 for less incident angle at the reference line of any given angle perpendicular to wall of container 80 from the source; Be positioned at through the pixel on the normal of wall of container 86 (as 174) and will receive than near the more radiation of pixel; Though can receive some light of giving certain portions more than one pixel, and will be received by a specific pixel (as 174) through the coating 90 of this barrier coat or other types and the light of giving certain portions more than one of wall of container 80 through the coating of this barrier coat or other types.
Make its pel array (as 174) be very approaching with the profile of wall of container 86 and be tight consistent the resolution of the pixel (as 174) that VI.A. can detect through the radiation of settling CCD to increase to be used for to specific part coating 90 and wall of container 86 through this barrier coat or other types.Can also be through selecting littler or substantial pointolite (like expression diagrammatically among Fig. 6) increase resolution to illuminate the inside of container 80.Use less pixel also will improve the resolution of the pel array among the CCD.
VI.A. a pointolite 132 (laser or LED) is positioned in the end of bar or probe in Fig. 6.(" pointolite " be meant or from the light of the small volume light emitted that is similar to mathematics point (diffusion tip produces in all directions as can be through little LED or on an optical fiber radiation light) or be meant light (coherent light that for example transmits) by laser apparatus with the form emission of small cross-section bundle).Pointolite 132 can be or immobilized or movably, for example can axially move, and simultaneously the coating 90 of barrier coat or other types and the characteristic of wall of container 80 measured.If removable, can pointolite 132 be moved up and down in device (pipe) 80 inside.Can scan the inner surface 88 of container 80 and carry out subsequently measurement to confirm the coating integrity with above-mentioned similar mode through an external detection apparatus 134.An advantage of this method is to use linearly polarized or the similar coherent source with specificity directivity.
VI.A. can (indexed) pixel (for example 174) be pointed in the position of pointolite 132 and make the illumination that when detector is positioned at normal angle with respect to a Special Areas of coating 90, can confirm detector like this.In the embodiment of Figure 10, can use a cylindrical detector 172 (randomly having the bent ends that the curve (if any) with the closing end 84 of container 80 is complementary) to detect the characteristic of cylindrical vessel 80.
VI.A. through should be understood that, make light from the inside of external radiation through wall of container 86 to container 80 thereby can change inspection station or equipment 24 or 34 through the position of counter-rotating light source or other source of radiation 170 and detector 172 with reference to Figure 10.If select this stopgap measure, in one embodiment, can a uniform incident light or other source of radiation be provided through the wall 184 of container 80 through an integrating sphere light source 186 inserted in an opening 182.The integrating sphere light source is 170 outside and this integrating sphere is inner to container 80 from the source with dispersed light or radiation, and the light of the point of the correspondence of the feasible like this wall 86 through container 80 will be uniform relatively.This will tend to reduce and the distortion that is caused by the illusion of a plurality of part correlations with difform wall 86.
VI.A. in the embodiment of Figure 11, can show that the inner surface 88 of coating 90 or container 80 of detector 172 and barrier coat or other types is closely consistent.Because detector 172 can be positioned on the side of the wall of container 86 identical with the coating of barrier coat or other types 80; This near the resolution that will tend to increase pixel (as 174); Though in this embodiment; Detector 172 preferably will be with respect to the coating 90 of barrier coat or other types and accurate location, to avoid damaging the scraping each other of one of coating or ccd array.Place near the of coating 90 can also reduce the refraction effect that causes by wall of container 86 detector 172 immediately; In the embodiment of Figure 10; This refraction effect takes place after light or other radiation are through the coating 90 of this barrier coat or other types, make like this have signal to be detected by difference reflect (local shape and light or other radiating incident angles that depend on container 80).
VI.A. and, perhaps, can use the coating inspection technology and the equipment of other barrier coats or other types.For example, can use fluorescence measurement to characterize the processing/coating of relevant this device.Use Figure 10 and the identical device described in 6, can select a light source 132 or 170 (or other source of radiation), this light source can interact with the doping agent in the polymer materials of the polymer materials of wall 86 and/or wall 86.Combine with detection system, the characteristic that this can be used to characterize certain limit comprises defective, thickness and other performance factors.
VI.A. another instance again of inspection is to use X ray to characterize this processing/coating and/or this polymkeric substance self.In Figure 10 or 6, light source can be replaced with the X-radiation source, and external detector can be to be used for a type of measured X gamma intensity.Can use this technology to carry out the ultimate analysis of the coating of barrier coat or other types.
V1.A. as in station 22 after device 80 of moulding, some potential problems possibly occur, these problems will make that any subsequent disposal or coating are imperfect, and maybe be invalid.If before applying, checked these problems for these devices, these devices can be coated up to the process of 6-δ control with a kind of height optimization, optional, and it can guarantee desirable result (or a plurality of result).
VI.A. but some potential problems of interfere processing and coating comprise (character that depends on the coated article that remains to be produced):
VI.A.1. the particle contamination defective of big density (for example at its longest dimension place separately greater than 10 microns), or the big particle contamination of less density (for example at its longest dimension place separately greater than 10 microns).
VI.A.2. chemistry or other surface contaminations (for example silicone molds discharges or oil).
VI.A.3. high surfaceness is characterized in that the cliffy summit and/or the paddy of height/big quantity.This can also characterize through quantizing mean roughness (Ra), and this mean roughness should be less than 100nm.
VI.A.4. do not allow any defective (like a hole) in vacuum this device.
VI.A.5. be used to produce any defective on this device surface (the for example opening end of a sampling tube) of a sealing.
VI.A.6. big wall thickness heterogeneity, this possibly hinder or change the power coupling through the thickness in processing or coating procedure.
VI.A.7. will make the invalid other defect of coating of this barrier coat or other types.
VI.A. it is successful operating for this processings/coating that guarantees to use the parameter in processing/coating operation, one or more above potential problems or other problems that can this device of preliminary examination.Disclosed in the past and be used to hold a device (rubber disc or pan straddle such as 38-68) and it is moved through a kind of device of a production process, this production process comprises different tests and a kind of processing/coating operation.Can carry out some possible tests and have the surface that suitable being used to handled/applied to guarantee a device.These comprise:
VI.A.1. optical check, the radiative transfer through this device for example from the inside of this device or from the radiation reflection of outside, absorbs or for the radiation interference of this device for the radiation of this device.
VI.A.2. digit check-for example, use can measure length-specific and geometrical shape digital camera (for example, with respect to a reference, the opening end of sampling tube be how " circle " or otherwise how to be shaped equably or correctly).
VI.A.3. vacuum leak inspection or pressure test.
VI.A.4. the acoustics of device (ultrasonic) test.
The VI.A.5.X X-ray analysis X.
VI.A.6. the specific conductivity of device (plastics tubing material and SiO with different resistance x-for example at the quartz (as bulk material) of the grade of 1020Ohm-cm and for polyethyleneterephthalate) in the grade of 1014Ohm-cm.
VI.A.7. the thermal conductivity of device (for example, the thermal conductivity of quartzy (as bulk material) is about 1.3W-° K/m, and the thermal conductivity of polyethyleneterephthalate is 0.24W-K/m).
VI.A.8. the venting of wall of container, this randomly can measure to confirm a venting baseline under following back coating inspection.
VI.A. above test can be carried out in a station 24 as shown in Figure 6.In this drawing, this device (for example sampling tube 80) can be received in position and with a suitable light source (or other source) 132 insert in these devices and the outside that suitable detector 134 is positioned at this device to measure desirable result.
VI.A. under the situation that vacuum leak detects, this pan straddle and device can be incorporated on a vacuum pump and the metering facility that is inserted in this pipe.This test can also be carried out like the detailed description in the other places of this specification sheets.
VI.A. treatment station or equipment 24 can be visually inspect stations, and can be configured to be used for to defective to the inner surface 88 of container, its outer surface 118 or one or multinomial inspection of inside between its surface 88 and 118 of its wall of container 86.If particularly this container is transparent or translucent for the type of radiation that is used to check and wavelength, can carry out from the outside of container 80 inspection of outer surface 118, inner surface 88 or wall of container 86.To the inspection of inner surface 88, if desired, can promote through a fibre-optical probe that is inserted in the container 80 is provided via container port 92, can obtain the view of the inside of container 80 like this from the outside of container 80.For example, in this environment, can use an endoscope or borescope.
VI.A. can be that a light source 132 is inserted within the container 80 at another stopgap measure shown in Fig. 6.Light through wall of container 86 transmission and become clearly through light that the illusion of container 80 can detect from the outside of container 80 (as through using detector measures device 134).For example can use this station or equipment 24 to detect and proofread and correct or remove unjustified container 80 that correctly is not seated on the container port 96 or the container 80 that in wall 86, has visible distortion, impurity or other defect.Substitute or except machinery survey, also can observe container 80 and visually inspect container 80 through the workman.
VI.A. treatment station or equipment 26 (being illustrated in greater detail among Fig. 7) can randomly be configured to be used for to defective the inner surface 88 of container 80 is checked; And for example be used for measuring the gaseous tension loss through wall of container 86, this can accomplish before the coating that a barrier coat or other types are provided.This test can be through producing a pressure difference between two sides of barrier coat 90; For example through being pressurizeed in the inside of container 80 or finding time; Thereby inside 154 isolation of container 80 are made that this pressure will keep constant nothing to leak or not have gas-permeable through this wall of container around the sealing part, and measure time per unit and carry out from the pressure change that these problems accumulate.This measurement not only can disclose any gas through wall of container 86; But also leakage sealed between detection receptacle outlet 82 and O shape circle or other sealing members 100, this is leakage sealed possibly indicate perhaps about the aligning of container 80 or about the problem of the function of sealing member 100.In one of two kinds of situation down, the pipe of can error recovery taking a seat maybe can take out this pipe from handle line, attempting to realize or keep the proper process vacuum level and prevent that the process gas quilt from being saved time aspect the air dilution of inefficacy sealing member extraction.
VI.A. can said system be incorporated in a manufacturing and the inspection method, this method comprises a plurality of steps.
VI.A. foregoing Fig. 1 has shown a kind of synoptic diagram (though the invention is not restricted to a kind of single notion or method) of step of possible method.At first carry out visual inspection at this place, station or by 24 pairs of these containers 80 of equipment, this can comprise the dimensional measurement of container 80.If found any defective, then this device or container 80 are rejected and check this rubber disc or pan straddle like 38 defective, recycling or remove this disk or pan straddle.
VI.A. next step leakage rate or other characteristic as having tested a pan straddle 38 and the assembly of the container 80 of taking a seat at 26 places, station, and its storage is used for after applying, comparing.Then this rubber disc or pan straddle 38 are for example moved on in the coating step 28.With the line frequency of for example 13.56MHz, use a kind of SiO xOr the coating of other barrier coats or other types applies this device or container 80.In case be coated, test once more this pan straddle leakage rate or other characteristics (this can as in the testing station 26 or dual or similar station carry out like second test at 30 places, the use at a dual station can increase throughput of system).
VI.A. can measurement that apply and uncoated measurement be compared.If the ratio of these values has surpassed preset desired level, shown a kind of acceptable overall coating performance, this pan straddle and device continue to move.For example, a blue-light source and an outside integrating sphere detector are followed to measure total light that passes through this pipe transmission in optic test station 32.It is to surpass a preestablished limit that this value can be asked to, and is rejected or is recycled and be used for other coating at this this device of limit place.Then (for there not being unaccepted device), can use one second optic test station 34.In this case, it is inner and slowly pull out a pointolite to be inserted into pipe or container 80, and the tubulose CCD detector array with this tube outside obtains measuring result simultaneously.Then data being carried out computational analysis distributes to confirm defect concentration.Based on these measuring results, this device perhaps is approved for last packing or is rejected.
VI.A. use statistical process control technology can above data randomly write down or map the mode of electronics (for example with) thus guarantee 6 σ quality.
VI.B is according to the container inspection of the venting that detects the wall of container that passes through the blocking layer
VI.B. another embodiment is a kind of method that is used to check the layer of blocking layer or other types on the material of letting off steam, has some steps.A specimen material is provided, and this material is emitted a kind of gas and is had part blocking layer at least.Randomly, a pressure reduction that strides across this blocking layer can be provided, make that like this material of venting of at least a portion is the high-tension side on this blocking layer.In another option, the gas that can allow to emit spreads not providing under the pressure reduction.Measured the gas of emitting.If a pressure reduction that strides across this blocking layer is provided, can measure venting in the high pressure or the low-tension side on this blocking layer.
VI.B. in addition, the effectiveness of measuring coated inside (above applying) can be carried out through measuring the rate of diffusion of material particular types or absorption in the wall (before coating) of device.When comparing with uncoated (untreated) pipe, such measurement can provide the characteristic of stopping of this coating or processing or other types or the existence that applies or handle or the direct measurement of shortage.Coating that is detected or processing (except being the blocking layer or replacing a blocking layer) can be a lubricant film, hydrophobic layer, decorative coveringn or other types change the layer (through increasing or reduce it) of venting of this substrate.
VI.B. as a concrete instance; Use is from the pan straddle of Fig. 2 and refer again to Fig. 7, can a device or container 80 be inserted in rubber discs or the pan straddle 44 and (can also carry out this test from the mobile container of taking a seat 80 that is written into rubber disc or the pan straddle (as 44) of another operation (like coatings/processings)).In case this pan straddle moves in the test zone of blocking layer, can with measuring tube or pop one's head in 108 insert inner (with the similar mode of the gas-filled valve that is used to apply, although this measuring tube needn't extend in this pipe). Valve 136 and 148 both can be open and inside this pipe can be evacuated (producing a vacuum).
VI.B. in case reach desirable measuring stress, can valve 136 and 148 cut out and pressure warning unit 152 can begin to measure this pressure.Reach the time of specified pressure (being higher than initial pressure) or through measuring the pressure the time of specified rate after, reached through measurement, can measuring tube, pan straddle, pump channel and be connected on this internal volume still by the rate of rise (or leakage rate) of valve 1 and 2 isolated every other parts.If this value compares with uncoated pipe then, the ratio of two observed values (value of coated is divided by the value of uncoated pipe) can produce an observed value through the leakage rate of the coated surface of this pipe.This measuring technology possibly need with this pan straddle, pump channel and be connected on this internal volume but be reduced to by the internal volume of the isolated every other part of valve 1 and 2 (except this pipe/device) minimum, thereby with gas-permeable or reduce to minimum from these surperficial exhausts influences.
VI.B. in this disclosure, between " infiltration ", " leakage " and " surface diffusion " or " venting ", made differentiation.
Like " infiltration " at a container of this employed reference is a kind of material through the crossing an of wall 346 or other obstacles, as the path in Figure 29 350 or this path oppositely from the external-to-internal of container or vice versa.
Venting is meant for example outwards moves through coating 348 (if existence) and gets into container 358 (arriving the right side among Figure 29) within material such as gas molecule 354 or 357 or 359 a kind of absorption or absorption wall 346 or the coating 348 from Figure 29.Venting can also be meant that a kind of material shifts out from wall 346 (left side shown in Figure 29) as 354 or 357, thereby arrives the outside like the container of being showed 357.Venting can also be meant from the material of the surface removal of article absorption, for example from the gas molecule 355 on the surface of the exposure of barrier coat 90.
Leakage is meant that a kind of material moves rather than move through or leave the surface of this obstacle around the obstacle by wall 346 and coating 348 expressions, as through passing through between a closure member and the wall of a container with the closure member closure.
VI.B. infiltration has shown that gas moves through a kind of speed of material, and very close to each other/defective and not relating to is leaked or venting.With reference to Figure 29, shown a wall of container or had other substrates 346 of a barrier coat 348, infiltration be a kind of gas along the path 350 fully through the crossing of this substrate 346 and coating 348, this path is through these two layers.Infiltration is considered to a kind of thermodynamic (al), therefore process relatively slowly.
VI.B. the infiltration measurement is very slow, and this is because infiltration gas must pass completely through a complete wall of this plastic article.Under the situation of vacuum test tube; Gas is used as this container along with the time direct indication of the tendency of loss of vacuum in the past routinely through the measurement of the infiltration of its wall; But normally a utmost point is measured slowly; Usually need 6 days test time, thereby therefore be not enough to support online coating inspection fast.Such test is generally used for the off-line test container sample.
VI.B. for the effectiveness that stops at a kind of thick suprabasil a kind of shallow layer, penetration testing is not that a kind of very sensitive is measured equally.Because all gas flow are through this coating and this substrate, will introduce the variation that effectiveness causes that stops that is not owing to coating itself in the variation of flowing aspect this thick substrate.
VI.B. gas or other gasiform or the venting that volatile constituent is passed through this coating of the sharp separation of method-measurements in this wall of container that ladies and gentlemen contriver has found faster and potential more sensitive is measured the barrier properties of a coating.These gasiform or volatile constituent can be any materials of in fact exitting, and maybe can be to be selected from one or more concrete materials to be detected.These components can be including, but not limited to: the by product of the by product of oxygen, nitrogen, air, carbonic acid gas, water vapour, helium, volatility organic materials (like alcohol, ketone, hydrocarbon), coating precursor, substrate components, coating prepn such as volatility organosilicon, coated substrate preparation, other components that occur by chance or that introduce through the admixture substrate or the mixture or the combination of any of these.
Surface diffusion and venting are synonyms.Each term be meant be adsorbed at first on the wall 346 (like a wall of a container) or be absorbed in the fluid in this wall; And cause that through certain power this fluid penetrates contiguous space, as vacuumize (having produced the air movement shown in the arrow 352 of Figure 29) in the container with a wall thus force fluid to flow out the inside that this wall enters into this container.Venting or diffusion are considered to dynamic (dynamical) a, process relatively fast.What considered is, for a wall 346 that has the substantive resistance of 350 the infiltration along the path, venting will be shifted out the molecule as 354 apace, and these molecules approach the interface 356 between wall 346 and blocking layer 348 most.Molecule through big quantity (as show as venting interface 356 near 354), and other molecules through big quantity (as with interface 356 far away and not as the demonstration of exitting 358), shown the difference venting.
VI.B. therefore, consider to be used to check the another kind of again method on the blocking layer on the material of letting off steam, comprised some steps.A specimen material is provided, and this material is emitted a kind of gas and is had part blocking layer at least.A pressure reduction that strides across this blocking layer is provided, has made that like this material of initial venting of at least a portion is the high-tension side on this blocking layer.Whether measurement is transported to the gas of emitting of the low-tension side on this blocking layer in a test process, confirming such information, exist or how effective it is as the blocking layer like this blocking layer.
VI.B. in this method, the material of emitting a kind of gas can comprise a kind of polymer compound, a kind of thermoplastics mixing material or one or more compounds with both characteristics.The material of emitting a kind of gas can comprise polyester, for example polyethyleneterephthalate.The material of emitting a kind of gas can comprise a kind of polyolefine, like Vestolen PP 7052, these two examples of a kind of cyclic olefine copolymer, or these combination.The material of emitting a kind of gas can be two kinds of composite of different materials, and this two kinds of materials at least a emitted a kind of steam.An example is the bilayer structure of Vestolen PP 7052 and polyethyleneterephthalate.Another example is the bilayer structure of cyclic olefine copolymer and polyethyleneterephthalate.These materials and matrix material are exemplary; Can use any suitable material or the combination of material.
VI.B. randomly, the material of emitting a kind of gas is that the form with the container with wall (having an outside surface and an internal surface) provides, and this internal surface is around an inner chamber.In this embodiment, this blocking layer randomly is placed on this wall of container, randomly places on the internal surface of this wall of container.This blocking layer can or also be placed on the outside surface of this wall of container.The material of randomly, emitting a kind of gas can provide with a kind of form of film.
VI.B. this blocking layer can be the coating wholly or in part on any present described blocking layer.This blocking layer can be thick or thick or thick or thick or thick or thick or thick or thick or thick or thick or thick less than 5nm less than 10nm less than 20nm less than 30nm less than 40nm less than 50nm less than 60nm less than 80nm less than 100nm less than 300nm less than 500nm.
VI.B. under the situation that applies wall, ladies and gentlemen contriver finds that diffusion/venting can be used for confirming the coating integrity.Randomly, through the inner chamber or the internal space of this container of finding time at least in part, a pressure reduction that strides across this blocking layer can be provided.Thereby this can be for example through accomplishing this inner chamber via this inner chamber of finding time at least in part on pipe connection to a vacuum source.For example, after vacuumizing, a uncoated PET wall 346 that has been exposed to a container of ambient air will be emitted a certain amount of oxygen and other gas molecules from its inner surface and continued the regular hours as 354.If identical PET wall is had a kind of barrier coat 348 in internal coat, then this barrier coat will stop, slowing down or reduce this venting.SiO for example xBarrier coat 348 is like this really, and the venting of this coating is less than a frosting.Through measuring this venting difference that applies between PET wall and the uncoated PET wall, can confirm the barrier effect of coating 348 with regard to the material of emitting apace.
If VI.B. the zone owing to known or theoretical hole, crack, gap or not enough thickness or density or composition causes that barrier coat 348 is defective, then this PET wall will preferentially be exitted through the defective part, increase the total amount of venting thus.The primary source of collected gas is dissolved gases or the transpirable component (descended) in the surface from the plastic article that approaches this coating, rather than from the outside of these article.Can measure in a different manner the venting that surpasses a basic horizontal amount (for example do not have defective by one or a standard coated having the defective of minimum accessible degree or have average and a defective acceptable degree through or the amount that discharges) to confirm the integrity of this coating.
VI.B. this measurement can be for example through providing the venting measuring cell of a connection between this inner chamber and this vacuum source to carry out.
VI.B. this measuring cell can be realized any multiple different measuring technology.An a kind of instance of suitable measuring technology is the micrometeor technology.For example, can measure the mass flow rate of the material of emitting.Can carry out this measurement by the mobile operation scheme of molecule.A kind of exemplary measurement is the mensuration of amount of per pitch time of the gas that section is emitted through this blocking layer.
VI.B. can under the condition of the existence of effectively distinguishing the blocking layer or shortage, measure the gas of emitting in the low-tension side on this blocking layer.Randomly, the condition of effectively distinguishing existence or the shortage on this blocking layer comprises less than one minute or less than 50 seconds or less than 40 seconds or less than 30 seconds or less than 20 seconds or less than 15 seconds or less than 10 seconds or less than 8 seconds or less than 6 seconds or less than 4 seconds or less than 3 seconds or less than 2 seconds or less than 1 second test time.
VI.B. randomly, in above any time interval of identifying, can be proved the determinacy of 6-δ level at least for the existence on this blocking layer or the measurement of shortage.
VI.B. randomly, the gas of emitting in the low-tension side on blocking layer is barrier improvement factor (barrier improvement factor, (the comparing with the same material that does not have the blocking layer) of measuring under condition BIF) of effectively confirming this blocking layer.Can for example measure BIF through following steps: through two groups of identical containers are provided, with the barrier properties on the container that the blocking layer joins in one group of container, test has the blocking layer (as in PM micrograms or the another kind of outgassing rate of measuring that is fit to), on the container that lacks the blocking layer, carry out identical test and obtain material with blocking layer and the ratio that does not have the properties of materials on blocking layer.For example, if the outgassing rate through the blocking layer is not have 1/3rd of outgassing rate under the blocking layer, then the BIF that has of this blocking layer is 3.
VI.B. randomly, there is venting therein more than (as being under the situation of nitrogen and oxygen at the gas of emitting) can be measured multiple gas with various under the situation of one type gas.Randomly, can measure the venting of all in fact or all gases of emitting.Randomly, as through using physics to measure (as the mass flow rate of the merging of all gas), the venting that can measure all in fact gas of emitting simultaneously.
VI.B. compare with air pressure test and can accomplish quickly, but test rate is reduced to the degree that this deflated part only is measured kind for the quantity of the independent gaseous species (for example oxygen or helium) of discharging or the measurement of dividing potential drop from sample.For example; Test than the same sensitivity of having measured all kinds of emitting from wall of container; If nitrogen and oxygen discharge from the PET wall with about 4: 1 atmosphere ratio; But only measured the oxygen venting, then this test will move the time (in order to obtain the result of enough statistical quality, with regard to molecule number to be detected) of five double-lengths.
VI.B. for the sensitivity of a given level, what considered is a kind of like this method, and this method has explained that the volume of all kinds of emitting from the surface will provide desirable confidence level quickly than the test of the venting of measuring a particular types (like Sauerstoffatom).Therefore, can produce the venting data that are used for on-line measurement with actual utility.This type of on-line measurement can randomly be carried out on the container of each manufacturing, thereby has reduced number speciality or isolating defective and eliminated their (at least when measuring) potentially.
VI.B. in the measurement of a reality, a factor that changes the apparent amount of venting is the leakage of when in venting is being tested, vacuumizing, crossing the defective sealing member sealing member of a container on the vacuum received block (as be landed in).Leak a detour solid walls of these article of a kind of fluid of expression, for example fluid passes between a heparin tube and its closure member, between syringe plunger and the syringe cylinder, between a container and its cap or vessel port and one fix above that between the sealing member of this vessel port (owing to defective or wrong fixed sealing member).Word " leakage " typically refers to the motion/gas of gas through an opening in the plastic article.
VI.B. can be thought of as the factor of venting basic horizontal with leaking with (under a given situation if necessary) infiltration; Acceptable like this test result has guaranteed that this container suitably is landed in (so its surface of taking a seat is complete and suitably is shaped also localized) on the vacuum received block; This wall of container is not supported the infiltration (so this wall of container is complete and suitably is shaped) of unacceptable level, and this coating has enough integrities that stops.
VI.B. can measure venting in a different manner, as through barometric surveying (after being pumped into initial vacuum, measure in a given time quantum pressure change in this container) or through measuring the flow rate or the dividing potential drop of the gas of emitting from sample.The equipment of measuring mass flow rate with the mobile operation scheme of molecule can get.Adopting an instance of such commercially available equipment of micrometeor technology is from ATC, Inc., and Indianapolis, IN can get.Referring to U.S. Patent number 5861546,6308556,6584828 and EP1356260, they are combined in this by reference, be used to further describe this known equipment.Also referring to the instance in this specification sheets 8, shown to be used for distinguishing very apace and reliably the instance that polyethyleneterephthalate (PET) pipe that the blocking layer applies and the venting of uncoated pipe are measured.
VI.B. for the container of processing by polyethyleneterephthalate (PET), SiO xThe surface that applies is very different with respect to the miniflow rate on uncoated surface.For example, in the operational instances 8 in this specification sheets, after test run 30 seconds, be 8 micrograms or more for the miniflow rate of PET, as shown in Figure 31.Than for SiO xThe measured speed of the PET that applies (after test has moved 30 seconds less than 6 micrograms), this speed for uncoated PET is much higher, still as shown in Figure 31.
VI.B. a possible explanation for this species diversity of flow rate is that uncoated PET comprises roughly 0.7% equilibrium moisture; This high moisture content has been considered to cause observed high miniflow rate.For a kind of SiO xThe PET plastics that apply, this SiO xCoating has higher levels of surface moisture than uncoated pet sheet mask.Yet under test condition, this barrier coat is considered to stop from body PET plastics desorb moisture additionally, has caused lower miniflow rate.From uncoated PET plastics with respect to SiO xThe oxygen of the PET that applies or the miniflow rate of nitrogen will be diacritic by expection equally.
VI.B. when using other materials, the test that is used for the PET pipe more than the modification possibly be suitable.For example, polyolefin plastics tends to have very little moisture content.A kind of polyolefinic instance with low moisture content is
Figure BDA0000126277010001351
cyclic olefine copolymer (COC), has equilibrium moisture content more much lower than PET (0.01%) and moisture vapor transmission speed.Under the situation of COC, uncoated COC plastics can have and SiO xSimilar or even the littler miniflow rate of the COC plastics that apply.This is most likely because SiO xThe lower balance body moisture content of the higher surperficial moisture content of coating and uncoated COC frosting and lower infiltration rate.This makes uncoated more difficult with the differences COC article that apply.
What the present invention showed is, has the surface of COC article to be tested (uncoated with apply) to be exposed to moisture and has caused at uncoated and SiO xImproved and consistent miniflow between the COC plastics that apply separates.This is shown in the instance 19 and Figure 57 of this specification sheets.This humidity exposure can just be exposed to the relative humidity of scope from 35%-100%, and is perhaps indoor a controlled relative humidity, or directly is exposed to (humidifier) or cold (vaporizer) moisture source of heating, and wherein the latter is preferred.
Though not being the accuracy according to this theory, validity VI.B. of the present invention and scope be not restricted, with respect to saturated SiO xMix in the COC surface that applies, moisture or the admixture of uncoated COC plastics seems has increased its humidity or other deflatable contents.This can also be exposed to other gases or their mixture (for example air) that comprise oxygen, nitrogen with uncoated pipe and accomplish through that will apply.
VI.B. therefore, before the gas that measurement is emitted, can make blocking layer and water for example water vapour contact.Can water vapour be provided through the blocking layer is contacted under 35% to 100%, alternately 40% to 100%, alternately 40% to 50% relative humidity with air.Replace water or except water, the blocking layer is contacted with oxygen, nitrogen or oxygen with the mixture (for example ambient air) of nitrogen.Duration of contact can be from 10 seconds to one hour, alternately from one minute to 30 minutes, alternately from 5 minutes to 25 minutes, alternately from 10 minutes to 20 minutes.
Alternately; The wall 346 that will exit can be from the opposite side on a blocking layer 348 by admixture or replenish; For example be exposed to a kind of material of air inlet (ingas) in the wall 346, then in the left side shown in Figure 29 or the right side venting through left side with the wall shown in Figure 11 346.Through air inlet from the left side wall of admixture or other materials as 346; The venting of (or vice versa) is different from infiltration and measures the material of admixture then from the right side; Because when measuring venting; This material by admixture within wall 346, opposite with the material in the whole paths 350 that move through this wall (when measuring the gas that occurs through coating).Air inlet can occur in the long time period, as an embodiment that applies before the coating 348, and as applying after the coating 348 and to another embodiment before its test venting.
VI.B. be increased in uncoated plastics and SiO xThe possible method of isolating another kind of the miniflow response between the coating plastic is to change measuring stress and/or temperature.Pressure boost or reduction temperature can cause water molecules at SiO when measuring venting xThe bigger relative combination of ratio in uncoated COC among the COC that applies.The gas of therefore, emitting can from 0.1 hold in the palm 100 the holder, alternately from 0.2 hold in the palm 50 the holder, alternately from 0.5 hold in the palm 40 the holder, alternately from 1 hold in the palm 30 the holder, alternately from 5 hold in the palm 100 the holder, alternately from 10 hold in the palm 80 the holder, alternately from 15 hold in the palm 50 the holder pressure under measure.The gas of emitting can be from 0 ℃ to 50 ℃, alternately from 0 ℃ to 21 ℃, alternately under 5 ℃ to 20 ℃ temperature, measure.
VI.B. in any embodiment of this disclosure, be to adopt a kind of micro-cantilever measuring technology for measuring a kind of method considered of exitting.A kind of like this technology is considered and is used for allowing to measure littler of poor quality in the venting, might be 10 -12G (pik) is to 10 -15On the order of magnitude of g (flying gram).This littler quality examination allows in less than 1 second, randomly less than in 0.1 second, randomly about microsecond, carry out coated surface with respect to of the differentiation of uncoated surface together with different coating.
VLB in some cases, through because molecular absorption causes bending or additionally moves or change shape that micro-cantilever (MCL) transmitter can be in response to a kind of existence of that emit or the material that provides in addition.In some cases, micro-cantilever (MCL) transmitter can be through responding in the change aspect the resonant frequency.In other cases, these MCL transmitters can or otherwise change with this dual mode.They can be operated under varying environment, like atmosphere surrounding, liquid or vacuum.In gas, micro-cantilever beam sensor can be used as an artificial nose and operates, and the beam mode of the silicon cantilever of eight kinds of polymer-coated little manufacturing array is characterized by the different steam from solvent, seasonings and beverage thus.It is also conceivable that the Electronic Nose of passing through any technological operation of using any other type.
Used and considered that some MCL Electronic Design (method that comprises voltage dependent resistor, piezoelectricity and electric capacity) measure MCL moving after being exposed to chemical, change in shape or change of frequency.
VI.B. a specific examples measuring venting can carry out as follows.At least one micro-cantilever is provided, and this micro-cantilever has and when a kind of material of emitting exists, moves or change over difform characteristic.Causing that effectively this micro-cantilever moves or changes under the difform condition, is exposed to the material that this is emitted with this micro-cantilever.Detect then and should move or different shapes.
VI.B. as an instance, this move or different shapes can detect through reflecting from high energy incident beam of a part (before or after this micro-cantilever is exposed to venting) and the deflection of measuring at the reflected beam that produces with this micro-cantilever point place at interval of moving or change the micro-cantilever of shape.This shape is preferably to measure with this socle girder point place at interval at one, this be because the amount of deflection of restrainting under the given condition be and the reflection spot of this MP and bundle between distance proportional.
VI.B. the several suitable instance of a high energy incident beam is a kind of photon beam, a kind of electron beam or these two kinds or more kinds of combinations.Alternately, two kinds or more kinds of different bundle can be from MCL along different incident and/or reflection paths and reflecting, and move or alteration of form confirming from more than one visual angle.The type of a concrete high energy incident beam of considering is a kind of coherent photons bundle, like a kind of laser beam." photon " discussed in this manual defines to comprise that wave energy is together with particle or photon energy itself involvedly.
VI.B. an alternate practical measuring examples has utilized some MCL when running into a kind of environmentally conscious materials, to change the characteristic of resonant frequency, and this environmentally conscious materials is in one and effectively accomplishes the amount that resonant frequency changes.Such measurement can be carried out as follows.At least one micro-cantilever is provided, and this micro-cantilever is with a different frequency resonance when a kind of material of emitting exists.Effectively causing under the condition of this micro-cantilever with a different frequency resonance, can this micro-cantilever be exposed in this material of emitting.Detect this different resonant frequency through any suitable method then.
VI.B. as an instance, can be through energy input be detected this different resonant frequency to induce it to resonate in micro-cantilever before or after this micro-cantilever is exposed to venting.Measured poor before being exposed to venting and between the resonant frequency of afterwards MCL.Alternately, replace to measure the poor of resonant frequency, when the material of a kind of venting that has enough concentration or amount, a kind of known MCL with a certain resonant frequency can be provided.Use a resonant transducer to detect this different resonant frequency or show the resonant frequency of the material of emitting that has capacity.
As using the MCL technology to measure an instance of venting, can a MCL equipment be merged in the silica valve, this silica valve is connected on a container and the vacuum pump.Can make up a kind of resonant transducer, this transmitter use a commercially available pressure drag socle girder, a plurality of Wheatstone bridge circuit, positive regeeration unit, one excite piezo-activator and a phase-locked loop (PLL) detuner.Referring to, for example,
·Hayato?Sone，Yoshinori?Fujinuma?and?Sumio?Hosaka?Picogram?Mass?Sensor?Using?Resonance?Frequency?Shift?of?Cantilever，Jpn.J.Appl.Phys.43(2004)3648；
·Hayato?Sone，Ayumi?Ikeuchi，Takashi?IzumM，Haruki?Okano2and?Sumio?Hosaka?Femtogram?Mass?Biosensor?Using?Self-SensingCantilever?for?Allergy?Check，Jpn.J.Appl.Phys.43(2006)2301)。
In order to prepare the MCL that is used to detect, can apply a side of micro-cantilever with gelatin.Referring to, Hans Peter Lang for example, Christoph Gerber, STM and AFM Studies on (Bio) molecular Systems:Unravelling the Nanoworld, Topics in Current Chemistry, Volume 285/2008.Combine with gelatin from the water vapour of vacuum coat vessel surface desorption, cause crooked and its change of resonant frequency of this socle girder, as measured through laser deflection from a surface of this socle girder.Be distinguishable in the decimal place that uncoated container is taken into account in second with respect to the variation of the quality of coating container and be highly reproducible.The article of more than quoting together with the socle girder technology for they can be used to detect and disclosure that the specific MCL of the kind that quantizes to exit and equipment are arranged is combined in this by reference.
Replace above-described gelatin coating or except above-described gelatin coating, can the alternative coating that be used for detection of moisture (phosphoric acid) or oxygen detection be applied to MCL.
What VI.B. further consider is, any venting test set of being considered at present can with a SiO xApplying the station combines.In a kind of like this layout, measuring cell 362 can use the main vacuum tunnel that is used for PECVD as bypass 386 like above displaying.In one embodiment, usually can with as Figure 30 362 shown in measuring cell be combined in a pan straddle as in 50, wherein this by-pass channel 386 is configured to main vacuum manifold 94 and this measuring cell 362 is wing passages.
VI.B. this combination of measuring cell 362 and pan straddle 50 measurements that will randomly allow to exit, and do not have destruction to be used for the vacuum of PECVD.Randomly; The vacuum pump that is used for PECVD will be operated a time weak point, the preferred standard amount to pump some or all of remaining residual reactants gas after coating step (vacuumize less than a holder, another option is before vacuumizing, to allow a spot of air, nitrogen, oxygen or other gas blow-washings (flush out) or dilute these process gass).This will promote the anabolic process of test of existence and barrier level of coating and this coating of this container.
VI.B. after this specification sheets of summary, what those of ordinary skill in the art will be further understood that is, venting is measured and every other described blocking layer measuring technology can be used for multiple purpose (be different from the effectiveness of confirming a blocking layer or in addition).Give one example, this test can be used on uncoated container or the coating container to confirm the venting degree of wall of container.For example this test can be with needing a kind of uncoated polymkeric substance with under the situation of emitting the gas that is less than a specified quantitative therein.
VI.B. another example; These venting are measured and every other described blocking layer measuring technology can be used on blocking layer coated film or the uncoated film, perhaps as a kind of static test or as a kind of on-line testing with measure a film when it crosses measuring cell in the variation aspect the venting.This test can be used for confirming the coutinuity of coating of other types or stopping effectiveness, these coatings such as aluminum coating or EVOH barrier coat or packaging film layer.
VI.B. these venting are measured and every other described blocking layer measuring technology can also be used to confirming being applied to the effectiveness of (relative with measuring cell) such as a blocking layer on the side of a wall of container, films, as are applied to a blocking layer of the venting of on the outside of a wall of container and inside that be used to inquire after wall of container.In this case, this mobile difference will be used for infiltration through this barrier coat, and infiltration is through this substrate film or wall subsequently.Be under the situation of infiltration quite easily (like extremely thin or a porous film or a wall) at substrate film or wall, this measurement will be useful especially.
VI.B. these venting measurements and every other described blocking layer measuring technology can also be used to confirming the effectiveness on a blocking layer; This blocking layer is an interior layer, film of a wall of container etc., in this case any venting that will detect the layer through contiguous measuring cell of this measuring cell add through one or more layers (with the distance of measuring cell than farther with the distance on blocking layer) the venting on blocking layer.
VI.B. the blocking material that these venting are measured and every other described blocking layer measuring technology can also be used to confirming a kind of pattern is to the percentage of coverage of a kind of material of emitting, like the ratio (if on the material of any part, not having the blocking layer existence) of the venting degree through confirming the material that the part blocking layer applies as the discharge quantity of expection.
A kind of measuring technology of speed that VI.B. can be used to increase the venting of a container of test with any venting test implementation scheme available in this specification sheets is to reduce the void volume of container, as through insert a plunger or closure member in this container to reduce the void volume of container portions to be tested.Reduce void volume and allow container to be evacuated down to a given vacuum level quickly, therefore reduced test interval.
VI.B. after this specification sheets of summary, present described venting is measured and multiple other application of every other described blocking layer measuring technology will be tangible for those of ordinary skill.
The container that VII.PECVD handles
VII. the container of being considered has a barrier coat 90 (for example shown in Fig. 2), and it can be a SiO who applies xCoating, the thickness that applies is 2nm or 4nm or 7nm or 10nm or 20nm or 30nm or 40nm or 50nm or 100nm or 150nm or 200nm or 300nm or 400nm or 500nm or 600nm or 700nm or 800nm or 900nm at least at least at least at least at least at least at least at least at least at least at least at least at least at least at least at least at least at least.This coating can be to reach 1000nm, or at most 900nm or 800nm or 700nm or 600nm or 500nm or 400nm or 300nm or 200nm or 100nm or 90nm or 80nm or 70nm or 60nm or 50nm or 40nm or 30nm or 20nm or 10nm or 5nm is thick at most at most at most at most at most at most at most at most at most at most at most at most at most at most at most at most at most at most.Clearly consider specific thickness range by above-mentioned any one minimum thickness, add that the thickness of any equal or bigger above-mentioned maximum ga(u)ge is formed.Can measure this SiO xOr the thickness of other coatings, for example pass through transmission electron microscopy (TEM), and can measure its formation through x-ray photoelectron spectroscopy (XPS).
That is VII. considered is the material chosen and the SiO that applies of this coating of infiltration that is under an embargo xThe character of coating can influence its effect that stops.For example, the instance that is intended to forbidden two kinds of materials usually is oxygen and water/water vapor.Material is normally for a kind of better blocking layer of another kind that is compared to.This is considered to so at least in part, because the oxygen transmission is passed through the machine-processed different of coating through the mechanism of coating with the water transmission.
VII. the oxygen transmission is influenced by the physical features of this coating, for example other physical details of its thickness, fissured existence and this coating.On the other hand, usually the transmission of phase menstruation to receive the influence of chemical factor (promptly processing the material of coating) bigger than the influence that receives physical factor.Ladies and gentlemen contriver thinks that also at least a these chemical factors are the essence concentration of the OH part in the coating, and it has caused the transmission rate of higher water through this blocking layer.A kind of SiO xTherefore coating contains the OH part usually, and to contain at high proportion physically firm (physically sound) coating of OH part be to be better blocking layer (than for water) for oxygen.A kind of physically firm coating based on carbon is considered to for the better blocking layer of water (than SiO like decolorizing carbon or diamond-like carbon (DLC) usually xCoating), because this barrier coat based on carbon more generally has the OH part of lower concentration.
VII. yet other factors have caused for a kind of SiO xCoating preferred, as its oxygen stop render a service and it to glass and quartzy approaching chemical similarity.Glass and quartz (when the time) as the base mateiral of a container be known for a long time demonstrate for the very high barrier properties of oxygen G&W transmission and have container in two kinds of materials of substantive inert of many materials of carrying usually.What therefore, hope usually is to optimize water resistance retaining characteristic such as a kind of SiO xThe water vapor transmission rate of coating (WVTR), rather than select a kind of coating different or other type to serve as a water transmission blocking layer.
VII. some modes below having considered are used to improve SiO xThe WVTR of coating.
VII. can increase organic moiety (compound of carbon and hydrogen) and OH concentration ratio partly in the coating deposited.This can for example accomplish (like the feeding rate through increasing the oxygen feeding rate or reducing one or more other components) through the ratio that increases the oxygen in the feed gas.What the increase of oxygen charging and the level of response of hydrogen in the silicone source produced more volatile water and lower concentration in the PECVD exhaust thereby the influence mode of the OH that reduces part is considered to holds back or is combined in the OH part in the coating.
VII. can in the PECVD process, use higher energy, perhaps continue long time period through rising plasma body generation power level or through applying power (or both).When being used for applying a plastics tubing or other devices, the increase aspect the energy that is applied is adopted with taking every caution against error, and this is because it also has the tendency (reaching the degree that this pipe bears this plasma body generation power) that makes the container deformation that is being processed.Here it is is preferred RF power under the application's where the background.The distortion of medical device can be to reduce or eliminate through and the following: through the energy of employing by the pulse of two or more series of separating cooling time; Through when applying energy, cooling off these containers; Through in the shorter time, applying coating (therefore making that usually it is thinner); Through the frequency (this coating is that the selecteed base mateiral that is coated of minimally absorbs) of selecting to apply coating; And/or through applying more than one coating (applying the time between the step) in corresponding energy.As, can use high power pulse by 1 millisecond of operation, work period of stopping 99 milliseconds, continue this process gas of feeding simultaneously.This process gas is refrigerant then, and it keeps flowing between pulse equally.Another replacement scheme is to reconfigure power to apply device, thus as through add magnet with the plasma confinement body increase active power apply (power of the coating that in fact causes increasing, with cause heating or the wasted power of undesired coating opposite).This rights and interests measure causes applying more coating and forms energy (every total watt-hour of the energy that is applied).Referring to for example USP 5,904,952.
VII. oxygen aftertreatment that can application of coatings, so as from before remove the OH part the coating deposited.Considered that also this processing is to remove residual volatility silicoorganic compound or silicone or this coating of oxidation to form other SiO x
VII. can be with this plastic basis material preheating.
VII. a different volatility silicon source can be used as a part or all silicone chargings like hexamethyldisilazane (HMDZ).What considered is feed gas to be changed over HMDZ will solve the problem that is provided, because in this compound, do not have the oxygen part.What considered is, a source of the OH part in the coating in HMDSO source is the hydrogenation of at least some Sauerstoffatoms of in unreacted HMDSO, existing.
VII. can use a kind of compound coating, as with SiO xA kind of coating of bonded based on carbon.This can be for example through change reaction conditions or through to feed gas together with a kind of based on organosilyl compound in a kind of substituted or unsubstituted hydrocarbon of adding (like a kind of alkane, alkene or alkynes) accomplish.Referring to for example USP 5; 904,952, it relevant portion " for example; being mingled with of a kind of lower hydrocarbon such as propylene carbon part is provided and improved most of characteristic (except light transmission) of sedimentary film, and binding analysis has shown that this film is silicon-dioxide in itself.Yet it is the film of silicone in itself that the use of methane, methyl alcohol or acetylene has produced.A small amount of gaseous nitrogen is mingled with the nitrogen part that provides in sedimentary film and has increased deposition, improved in transmission on glass and reflective optics characteristic and in response to the N that changes in air-flow 2Amount has changed specific refractory power.In air-flow, adding Nitrous Oxide has increased sedimentation rate and has improved optical characteristics, but is tending towards reducing film hardness " middle statement.
VII. a diamond-like carbon (DLC) coating can be used as main or unique deposited coatings and forms.This can for example not have oxygen through changing reaction conditions or accomplishing these reaction feed through feeding methyl alcohol, hydrogen and helium to one a PECVD process, thereby does not have the OH part to be formed.Give one example, can be with a SiO xCoating is applied on the inside of a pipe or a syringe cylinder, and can an outside DLC coating be applied on the outside surface of a pipe or syringe cylinder.Perhaps, this SiO xA single or multiple lift that can be used as an inner tube or syringe cylinder coating with the DLC coating is applied in.
VII. with reference to Fig. 2, the coating 90 of this barrier coat or other types has reduced the transmission that atmospheric gas gets into container 80 through inner surface of container 88.Perhaps, the coating 90 of this barrier coat or other types has reduced the content of container 80 and contacting of internal surface 88.The coating of this barrier coat or other types can comprise for example SiO x, amorphous (for example quasi-diamond) carbon or these combination.
VII. said any coating can be used to apply a surface, for example a frosting.It can be by further as a blocking layer, for example as an a kind of gas of antagonism or liquid, preferably resist the blocking layer of water vapour, oxygen and/or air.If the surface is uncoated, it can also be used to stop or reduce machinery and/or the chemical action for a kind of compound or compsn that the surface that applies possibly have.For example, it can stop or reduce the deposition of a kind of compound or compsn, for example insulin precipitation or blood coagulation or platelet activation.
The blood collection container of VII.A. finding time
VII.A.1. manage
VII.A.I. with reference to Fig. 2, shown that container is like 80 more details.The container of being showed 80 can be a generally tubular, has an opening 82 at an end of container, and is relative with a closed end 84.This container 80 also has a wall 86, and this wall defines an internal surface 88.An instance of container 80 is medical science stopple coupons, like a vacuum test tube, as usually being used in the heparin tube of venipuncture sample that being used in the medical laboratory receives a patient's blood by bleeder is employed.
VII.A.1. this container 80 can for example be processed by thermoplastic material.Some instances of suitable thermoplastic material are polyethyleneterephthalate or a kind of polyolefine (like Vestolen PP 7052) or a kind of cyclopolyolefin multipolymer.
VII.A.1. container 80 can be processed by any suitable method, as through injection moulding, through blow molding, through cut, through from pipe material assembling or through other methods that is fit to.PECVD can be used for forming one at SiO xCoating on the internal surface.
If VII.A.1. be intended to as a vacuum test tube; When being exposed to external pressure 760 holders or barometric point and other coating processing conditions, desirably this container 80 can be the sufficiently solid not distortion in fact to stand a kind of inner vacuum in fact completely.Can in a thermoplastic container 80, this specific character be provided; Through the container 80 that provides to process with suitable size and a second-order transition temperature higher than the treatment temp of coating processes by the material that is fit to; Cylindrical wall 86 for example, it has the enough diameters that is suitable for it and the wall thickness of material.
VII.A.1. medical container or vessel (as sampling tube and syringe) are less and the type that is injection moulded into has thicker wall, and this makes them to be evacuated and is not crushed by ambient atmosphere pressure.Therefore they are firmer than aerated soft drink bottle or other plastic wares bigger or that wall is thinner.Because be designed as the sampling tube of vacuum vessel and typically constructed to stand perfect vacuum during preservation, they can be used as Vakuumkammer.
VII.A.1. so adaptive (these containers are they self Vakuumkammers) possibly got rid of these containers are put into and be used for PECVD handles (this typically carries out) under low-down pressure necessity in the Vakuumkammer.Container as the application of himself Vakuumkammer can cause treatment time faster (because an isolated Vakuumkammer load and from time of its these parts of unloading be unnecessary) and the equipment configurations that can cause simplifying.In addition; Considered a kind of pan straddle is used for some embodiment, this support will hold this device (being used to be registered to gas-filled valve and other devices), seal this device (thereby can produce vacuum through this pan straddle is connected on the vacuum pump) and between moulding and subsequent processing steps, move this device.
VII.A.1. a container 80 that is used as a vacuum test tube should stand external pressure; Simultaneously at inner pumping under for a useful decompression of the application of expection, and do not have air or other atmospheric gases of essence volume to leak in this pipe (as through the closure member that detours) or in its quality guaranteed period infiltration pass through wall 86.If just container for moulding 80 can not meet this requirement, it can apply this internal surface 88 through the coating 90 with a barrier coat or other types and handle.Desirable is to handle and/or apply the internal surface of these devices (like sampling tube and syringe cylinder) to give different characteristic, and these characteristics will provide the advantage of the existing glasswork that surpasses existing polymer device and/or imitation.What also make us hoping is at the different qualities of handling or apply before and/or measure afterwards these devices.
VII.A.1.a. from a kind of organosilicon precursor coating deposited through the manufacturing of in-situ polymerization organosilicon precursor
Considered that a kind of being used for is applied to the method in a kind of substrate (the for example inside of a syringe cylinder) with a slip coating; Comprise that the thickness with 1nm to 5000nm or 10nm to 1000nm, optional 10-200nm, optional 20nm to 100nm applies a kind of described precursor to a kind of substrate or near a kind of substrate, and the randomly crosslinked or polymerization with this coating in a PECVD process (or both) so that a lubricated surface to be provided.The coating that applies through this process is considered to new equally.
VII.A.1.a. one kind meets Si wO xC yH zCoating, wherein w is 1, x is that y is from about 0.6 to about 3 from about 0.5 to 2.4 in this chemical formula; And z is from 2 to about 9, and preferably wherein w is 1, and x is that y is from about 2 to about 3 from about 0.5 to 1; And z is from 6 to about 9, applies through PECVD, further has the application as hydrophobic coating.Whether it is hydrophobic that such coating is considered, do not rely on them and work as slip coating.Compare with corresponding uncoated surface or untreatment surface, if a kind of coating or processing have reduced the wet tension on a surface, then it is defined as " hydrophobic ".Therefore hydrophobicity is be untreated substrate and a kind of function of handling both.
Through formation, characteristic or the deposition method that changes a coating, can change its a hydrophobicity degree.For example, the SiOx coating that has seldom or do not have the hydrocarbon composition is than the Si that has like defined substitution value in the specification sheets wO xC yH zCoating is more hydrophilic.Generally speaking, with respect to its silicone content, the C-H of coating x(for example CH, CH 2Or CH 3) part content (perhaps by weight, volume or molar concentration meter) is high more, then this coating is hydrophilic.
A hydrophobic coating can be extremely thin, and the thickness that has is 4nm or 7nm or 10nm or 20nm or 30nm or 40nm or 50nm or 100nm or 150nm or 200nm or 300nm or 400nm or 500nm or 600nm or 700nm or 800nm or 900nm at least at least at least at least at least at least at least at least at least at least at least at least at least at least at least at least at least.This coating can be up to 1000nm or 900nm or 800nm or 700nm or 600nm or 500nm or 400nm or 300nm or 200nm or 100nm or 90nm or 80nm or 70nm or 60nm or 50nm or 40nm or 30nm or 20nm or 10nm or 5nm is thick at the most at the most at the most at the most at the most at the most at the most at the most at the most at the most at the most at the most at the most at the most at the most at the most at the most at the most at the most.Clearly consider specific thickness range by above-mentioned any one minimum thickness, add that the thickness of any equal or bigger above-mentioned maximum ga(u)ge is formed.
VII.A.1.a. be to make collected blood isolation in a kind of thermoplasticity tube wall (for example processing) and this pipe for a kind of application of such hydrophobic coating by polyethyleneterephthalate (PET).This hydrophobic coating can be applied in a hydrophilic SiO on the internal surface of this pipe xOn the coating.This SiO xCoating has increased the barrier properties of this thermoplastic pipe and the surface energy that this hydrophobic coating has changed blood surface in contact and this tube wall.This hydrophobic coating can be processed through a kind of precursor is provided, and this precursor is those that are selected from this specification sheets to be identified.For example, this hydrophobic coating precursor can comprise SWS-F 221 (HMDSO) or octamethylcyclotetrasiloxane (OMCTS).
VII.A.1.a. another purposes of a hydrophobic coating is that a preparation glass cell preparation pipe (glass cell preparation tube) this pipe has one and defines the wall of an inner chamber, the hydrophobic coating in the internal surface of this glass wall, and comprises a kind of Citrate trianion reagent.This hydrophobic coating can be processed through a kind of precursor is provided, and this precursor is to be selected from those that other places in this manual identify.Another example, this hydrophobic coating precursor can comprise SWS-F 221 (HMDSO) or octamethylcyclotetrasiloxane (OMCTS).The another kind of source material that is used for hydrophobic layer is a kind of alkyl trimethoxysilane with following formula:
R-Si(OCH 3) 3
Wherein R is a Wasserstoffatoms or an organic substituent, for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, vinyl, alkynes, epoxide or other.It is also conceivable that two kinds or more kinds of combinations among these.
VII.A.1.a. the combination of acid or base catalysis and heating (using aforesaid a kind of alkyl trimethoxysilane precursor) can be with this precursor condensation (removing the ROH by product) to form crosslinked polymkeric substance, and it can be through a kind of alternative method by randomly further crosslinked.A concrete instance is like Shimojima et.al.J.Mater.Chem., 2007,17,658-663.
VII.A.1.a. applying a SiO xBarrier coat to the internal surface 88 of container 80 after, can apply a Si wO xC yH zCoating as a follow-up coating so that a lubricated surface to be provided, if when particularly this top coat is a kind of liquid silicone siloxane compound when coating processes finishes.
VII.A.1.a. randomly, applying this Si wO xC yH zAfter the coating, it can be by after fixing after the PECVD process.Can use radiation-curing method; Comprise (radical or positively charged ion), electron beam (E bundle) and thermopair that UV causes; As described in the Development Of Novel Cycloaliphatic Siloxanes For Thermal and UV-Curable Applications (Ruby Chakraborty Dissertation, 2008).
VII.A.1.a. the another kind of method that is used to provide a slip coating is when the thermoplastic container that injection moulding remains to be lubricated, to use a kind of silicone release agent.What for example, considered is to use any releasing agent and recessive monomer (latent monomer) that in moulding process, forms original position thermopair slip coating that cause.Perhaps, can above-mentioned monomer be doped in traditional releasing agent to realize identical effect.
VII.A.1.a. considered to be used for a kind of lubricated surface especially like the internal surface of a following syringe cylinder that further describes.A lubricated internal surface of a syringe cylinder can reduce plunger sliding force (in the operating process of a syringe, in this, advancing a plunger to need) or (for example because this plunger and the decomposition of the lubricant between this) starting force that plunger moves of starting after this precharging type syringe plunger has been pushed the lubricant of intervention open or adhered on the tube.As explaining in the other places of this specification sheets, a Si wO xC yH zCoating, wherein w is 1, and x is from about 0.5 to about 2.4 in this chemical formula, and y is from about 0.6 to about 3, and z is from 2 to about 9, and the internal surface 88 that can also put on container 80 is to improve SiO afterwards xCoating bonding.
VII.A.1.a. therefore, coating 90 can comprise a SiO xLayer and a Si wO xC yH zLayer, wherein w is 1, and x is from about 0.5 to 2.4 in this chemical formula, and y is from about 0.6 to about 3, and z is from 2 to about 9, and preferably wherein w is 1, and x is from about 0.5 to 1, and y is from about 2 to about 3, and z is from 6 to about 9.This Si wO xC yH zLayer can be deposited on this SiO xBetween the internal surface of layer and this container.Perhaps, this SiO xLayer can be deposited on Si wO xC yH zBetween the internal surface of layer and this container.Perhaps, can in these two kinds of coating compositions, replace or use progressively three or more layer equally.Can be with this SiO xBe deposited upon Si wO xC yH zNear the layer or away from them, wherein has at least one intervening layer of another kind of material.This SiO xLayer can be deposited near the internal surface of this container.Perhaps, this Si wO xC yH zLayer can be deposited near the internal surface of this container.
VII.A.1.a. in another rights and interests measure of this consideration, for the SiO of adjacent layers xAnd Si wO xC yH z, be Si wO xC yH zA kind of gradient composites, wherein w is 1, x is from about 0.5 to 2.4 in this chemical formula, y is from about 0.6 to about 3, and z is from 2 to about 9, preferably wherein w is 1, x is from about 0.5 to 1, y is from about 2 to about 3, and z is from 6 to about 9.A kind of gradient composites can be Si wO xC yH zLayer and SiO xA plurality of isolating layer (transition or the interface that wherein between them, have intermediate composition) or Si wO xC yH zAnd SiO xA plurality of isolating layer (middle the different layers that wherein between them, has intermediate composition) or an individual layer, this individual layer is by as follows continuously or progressively variation: from Si wO xC yH zA kind of compsn to similar SiO xA kind of compsn (with conventional direction through this coating).
VII.A.1.a. the gradient in gradient composites can be by arbitrary direction process.For example, Si wO xC yH zCompsn can be applied directly in this substrate and along with apart from SiO xThe distance on surface crossfades into a kind of compsn.Perhaps, SiO xCompsn can be applied directly in this substrate and along with apart from Si wO xC yH zThe distance on surface crossfade into a kind of compsn.If an a kind of coating of compsn is attached to other layers and goes up when better for adhering in this substrate specific viscosity, special what consider is a kind of gradient cladding, and this in this case better adherent compsn can for example be applied directly in this substrate.What considered is; Gradient cladding further from part can be more inconsistent than the neighbouring part of gradient cladding; Because this coating gradually changes on characteristic at any some place; Thereby the neighbouring part at the place of the degree of depth much at one of this coating has formation much at one, and substantially the part of the physical sepn to a greater extent at different depths place can have more various characteristic.What also consider is; The coating layer portion that forms a better blocking layer (this blocking layer antagonism material transfer is to this substrate or from this substrate transfer) can be directly against this substrate, receives with the coating layer portion (forming a relatively poor blocking layer) that prevents farther end and is intended to forbidden or the pollution of the material that stops by this blocking layer.
VII.A.1.a. this coating (rather than gradient) can randomly have the abrupt change transition between layer and another layer, and does not have substantial formation gradient.Such coating can for example be processed through following steps: through providing gas to produce as a kind of layer that is in the steady state flow of non-plasma state, then this system is encouraged in this substrate, to form a coating with an of short duration plasma discharge.If a follow-up coating to be applied is arranged; Then remove the gas of the coating that is used for the front and before this plasma body of excitation, apply the gas that is used for next coating with steady state way; And on the surperficial of this substrate or its top coating, form a different layer again, at the gradient transition that has seldom (if any) at the interface.
VII.A.1.b. have with the Citrate trianion heparin tube of deposition from the wall of the hydrophobic coating coating of organic silicon precursor
VII.A.1.b. another embodiment is the cell product pipe, and this pipe has the wall that on its internal surface, provides hydrophobic coating, and this pipe contains a kind of sodium citrate aqueous solution reagent.This hydrophobic coating can also put on the hydrophilic SiO on the internal surface that is positioned at pipe xThe top of coating.This SiO xCoating has increased the barrier properties of thermoplastic pipe, and this hydrophobic coating has changed the surface energy with the blood surface in contact of tube wall.
VII.A.1.b. this wall is processed by thermoplastic material, has the internal surface that limits an inner chamber.
VII.A.1.b. the heparin tube according to embodiment VII.A.1.b can have the SiO on this pipe internal surface xLayer applies as explanation in this manual, to have the effect that oxygen stops and to prolong quality guaranteed period of the vacuum test tube of being processed by thermoplastic material.Then can be with one the 2nd Si wO xC yH zLayer is applied on the blocking layer on the internal surface of this pipe so that a hydrophobic surface to be provided, and wherein w is 1, and x is from about 0.5 to 2.4 in this chemical formula; Y is from about 0.6 to about 3; And z is from 2 to about 9, and preferably wherein w is 1, and x is from about 0.5 to 1; Y is from about 2 to about 3, and z is from 6 to about 9.Compare with the uncoated wall of same type, this coating has reduced the platelet activation of and blood plasma that be exposed to this internal surface that cross with the Trisodium Citrate additive treating effectively.
VII.A.1.b.PECVD is used on internal surface, forming coating, has following structure: Si wO xC yH zDifferent with the Citrate trianion heparin tube of routine, have a Si wO xC yH zThe surface of the feasible pipe that the heparin tube of hydrophobic layer does not need to apply like routine has hydrophobicity and smokes a coating on the silicone on the wall of container.
VII.A.1.b. can use same precursor (for example HMDSO or OMCTS) and different PECVD reaction conditionss to apply this two layers.
Thereby VII.A.1.b. then Trisodium Citrate anti-freezing reagent is placed in this pipe and it is vacuumized and seal with a closure member and produce a vacuum test tube.The component of this reagent and prescription are known for those of ordinary skills.The amount of solidifying that the aqueous citric acid sodium reagent is introduced in the blood in this pipe with effective inhibition places the inner chamber of this pipe.
VII.A.1.c.SiO xDouble-walled plastic containers-COC, PET, SiO that the blocking layer applies xLayer
VII.A.1.c. another embodiment is to have a kind of container that at least partly centers on the wall of inner chamber.This wall has an inner polymeric layer that is centered on by an external polymer layer.One of these polymer layers are layers that defines thick cyclic olefine copolymer (COC) resin of the 0.1mm at least of a water vapor barrier layer.Another kind is a layer of the vibrin that 0.1mm is thick at least in these polymer layers.
VII.A.1.c. this wall comprises the SiO that has from the thickness of about 10 dusts to about 500 dusts xAn oxygen barrier layers.
VII.A.1.c. in one embodiment, like what showed among Figure 36, container 80 can be (being processed by identical or the material different accordingly) double-walled container with an inwall 408 and an outer wall 410.Can use by wall of cyclic olefine copolymer (COC) moulding and by another wall of a kind of polyester (for example polyethyleneterephthalate (PET)) moulding and make specific embodiments, wherein a SiO of this type xCoating is as previously mentioned on inner surface 412.When needing, can a connection coating or layer be inserted between the inner and outer wall to promote the adhesion between them.An advantage of this wall structure is a kind of matrix material that can thereby the wall with different qualities be combined to form the corresponding characteristics with each wall.
VII.A.1.c. as an instance, inwall 408 can be by on internal surface 412, being coated with a SiO xThe PET on blocking layer processes, and outer wall 410 can be processed by COC.As other places showed in this manual, be coated with SiO xPET be a kind of outstanding oxygen barrier layers, and COC is a kind of outstanding blocking layer for water vapour, it provides low water vapor transmission rate (WVTR).For oxygen and water vapour, this composite material vessel can have excellent barrier properties.For example; Considered this medical sampling tube of vacuum that is configured to; The medical sampling tube of this vacuum comprises a kind of aqueous reagent that promptly has during fabrication; And have the substantial quality guaranteed period, so it should have the outside transmission of water vapour or oxygen or the inside a kind of blocking layer of transmitting of other gas that during its quality guaranteed period, prevents through its composite walls.
VII.A.1.c. as another instance, inwall 408 can be by being coated with a SiO on the inner surface 412 xThe COC on blocking layer processes, and outer wall 410 can be processed by PET.For example, consider that with this precharging type syringe that is configured to, this syringe contains a kind of sterile aqueous fluid that has when making.This SiO xThe blocking layer will prevent that the wall that oxygen passes through it from getting in this syringe.This COC inwall will prevent the entering or the outflow of other materials (for example water), prevent that therefore the water in the sterile aqueous fluid from will leach from the material of wall material in the entering syringe.Consider also that this COC inwall prevents to come from this sterile aqueous fluidic water and flows out syringe (therefore undesirably having concentrated this sterile aqueous fluid), and will prevent having bacterium water or other fluids to get into and causing that these contents become bacterium is arranged of syringe exterior through this injector wall.Consider that also this COC inwall is useful for reducing the starting force or the frictional force of plunger on the inwall of syringe.
VII.A.1.d. make double-walled plastic containers-COC, PET, SiO xThe method of layer
VII.A.1.d. another embodiment is to make the method for the container with a wall, and this wall has an inner polymeric layer that is centered on by an external polymer layer, and layer is processed by COC and another is processed by polyester.This container is by comprising through concentric injection nozzle a kind of method in COC and injection mold of polyester resin layer introducing to be made.
VII.A.1.d. an optional other step is through PECVD a kind of amorphous carbon coating to be put on this container, as a coated inside, exterior coating or as an interlayer coating between these layers.
VII.A.1.d. an optional other step is with a SiO xThe blocking layer puts on the inside of this wall of container, wherein SiO xLike preceding definition.Another optional other step is to this SiO with a kind of process gas (mainly consist of oxygen and be substantially free of volatile silicon compound) xLayer carries out aftertreatment.
VII.A.1.d. randomly, can form this SiO by the silazane feed gas at least in part xCoating.
VII.A.1.d. as shown in Figure 36 container 80 can be made from inside to outside; For example; Through inwall being injected and molded in one first mould cavity; Then with the inwall of core and moulding from this first mould cavity moves to one second, bigger mould cavity, then in this second mould cavity on inwall the injection moulding outer wall.Randomly, with outer wall Overmolded to the articulamentum before, can an articulamentum be provided on the outside surface of inwall of this moulding.
VII.A.1.d. or; Container 80 shown in Figure 36 can be made from outside to inside; For example, through one first core being inserted in the mould cavity injection moulding outer wall in this mould cavity; Then one second, littler core, injection moulding inwall on the outer wall in still being present in this mould cavity are then removed and inserted to this first core from the first wall of this moulding.Randomly, with this inwall Overmolded to the articulamentum before, can an articulamentum be provided on the internal surface of outer wall of this moulding.
VII.A.1.d. or, container 80 as shown in Figure 36 can be made in a double-color mold.For example, this can be used for the material of inwall and accomplish from the material that concentric external nozzles injection moulding is used for outer wall through nozzle injection moulding internally.Randomly, can an articulamentum be provided from being disposed between this inwardly projecting orifice and the external nozzles one the 3rd, concentric nozzle.These nozzles can feed corresponding wall material simultaneously.A useful stopgap measure is to begin to feed outer wall materials through external nozzles slightly before through inwardly projecting orifice feeding inner-wall material.If there is an intermediary concentric nozzle, the mobile order can begin from external nozzles, and continues from this intermediate noxzzle and then from this inwardly projecting orifice according to priority.Perhaps, the order of beginning charging nozzle internally begins, and outwards moves with comparing with opposite order of front description.
VII.A.1.T. the barrier coat of processing by glass
VII.A.1.e. another embodiment is the container that comprises a wall of container, a barrier coat and a closure member.This container roughly is piped and is processed by thermoplastic material.。This container has an opening and part is by an inner chamber of a wall qualification at least, and this wall has an internal surface with this inner chamber boundary.On the internal surface of this wall, there is process by glass one successive barrier coat at least basically.Closure member covers this opening and the inner chamber of this container is isolated from ambient air.
VII.A.1.e. container 80 can also for example be processed by the glass (for example soda-lime glass, borosilicate glass or other glass preparations) of any kind that is used for medical science or laboratory applications.Also considered and to be used for system 20 by other containers that any material is processed with any proterties or size.An effect of coating glass containers can be to reduce the ion in the glass or enter into the content (the for example reagent of vacuum test tube or blood) of this container from this glass wittingly or as impurity (for example, sodium, calcium or other materials).Another effect of all or part of (for example optionally with respect to the surface of other parts) coating glass containers with sliding relation contact be to coating provide oilness (for example, be used for being easy to inserting take out stopper or make a sliding members for example plunger syringe through).The Another reason again of coating glass containers be prevent that the reagent of container or the sample of expection (for example blood) from adhering on the wall of a container or with the increase of the solidification rate of the contacted blood of this wall of a container.
VII.A.1.e.i. a relevant embodiment is a kind of container described in earlier paragraphs, and wherein this barrier coat is to be processed by the glass of soda-lime glass, borosilicate glass or another kind of type.
VII.A.2. stopper
VII.A.2. Figure 23-25 has explained container 268, and it can be a kind of heparin tube of finding time, and has closure member 270 so that inner chamber 274 is isolated with surrounding environment.Closure member 270 comprise an inner chamber 274 that is exposed to container 268 towards interior surface 272 and the wall surface in contact 276 that contacts with the internal surface 278 of a wall of container 280.In illustrated embodiment, closure member 270 is the assemblies with stopper 282 and shield [support 284.
VII.A.2.a. apply the method for the stopper in slip coating to the Vakuumkammer
VII.A.2.a. another embodiment is the method that on elastomeric stopper (for example 282), applies coating.To place the chamber of finding time basically with container 268 isolating stoppers 282.The reaction mixture that provides comprises the gas that forms plasma body, i.e. organic silicon compound gas, randomly oxidizing gas and appropriate hydrocarbon gas randomly.In reaction mixture, form plasma body, this plasma body is contacted with stopper.Si of deposition at least a portion stopper wO xC yH zCoating, wherein w is 1, and x is from about 0.5 to 2.4 in this chemical formula, and y is from about 0.6 to about 3, and z is from 2 to about 9, and preferably wherein w is 1, and x is from about 0.5 to 1, and y is from about 2 to about 3, and z is from 6 to about 9.
VII.A.2.a. in illustrated embodiment, apply the wall surface in contact 276 of closure member 270 with slip coating 286.
VII.A.2.a. in some embodiments, this Si wO xC yH zCoating is effectively to penetrate container intracavity with the component (the for example metals ion component of this stopper) or the component of this wall of container that reduces one or more these stoppers.One or more metals ions that contain trace for the elastic composition of making some useful type of stopper 282.These ions can not migrate to the amount that perhaps becomes in the inner chamber 274 with reality sometimes and contact with container contents, if particularly sampling receptacle 268 is used to collect the sample that is used for trace metal analysis.Consider that for example these coatings contain less organic composition, promptly wherein y and z are very low or be zero, are useful especially as the metals ion barrier so in this application.Take silica as the metals ion barrier, referring to for example Anupama Mallikarjunan, Jasbir Juneja; Guangrong Yang, Shyam P.Murarka, and Ton-Ming Lu; The Effect of lnterfacial Chemistry on Metal Ion Penetration into Polymeric Films, Mat.Res.Soc.Symp.Proc, Vol.734; Pp.B9.60.1t o B9.60.6 (Materials Research Society, 2003); USP 5578103 and 6200658 and European application EP0697378A2 is combined in this with it by reference in full.Yet, consider for providing to have more elastic coating and for the surface of elastomer that adheres to this coating to stopper 282, some organic compositions can be useful.
VII.A.2.a. in some embodiments, this Si wO xC yH zCoating can be the matrix material with material of the first layer and the second layer, wherein first or internal layer 288 join with elastomeric stopper 282, and one or more components that effectively reduce stopper 282 penetrate container intracavity.The second layer 286 can join with the inwall 280 of container and on stopper 282 is positioned at container 268 or among the time, effectively reduce the friction between the inwall 280 of stopper 282 and container.In the other places of this specification sheets, it is relevant with the syringe coating that this matrix material is described to.
VII.A.2.a. perhaps, limit the first layer and the second layer 288 and 286 with coating with gradient characteristic, wherein in the first layer the value of y and z greater than the value in the second layer.
VII.A.2.a. can apply Si wO xC yH zCoating is for example through aforesaid basically PECVD.This Si wO xC yH zCoating can be for example 0.5 and 5000nm (5 to 50,000 dust) thick between, perhaps 1 and 5000nm thick between; Perhaps 5 and 5000nm thick between, perhaps 10 and 5000nm thick between, perhaps 20 and 5000nm thick between; Perhaps 50 and 5000nm thick between, perhaps 100 and 5000nm thick between, perhaps 200 and 5000nm thick between; Perhaps 500 and 5000nm thick between, perhaps 1000 and 5000nm thick between, perhaps 2000 and 5000nm thick between; Perhaps 3000 and 5000nm thick between, perhaps 4000 and 10, between 000nm is thick.
VII.A.2.a. compare with the organo-silicic oil that the routine spraying of thicker (thick a micron or more) far away applies, considered some advantage for the oilness layer of plasma coated.Compare with silicone resin spray or that micron applies; Plasma coating has the lower migration potentiality in the blood that move to far away, and this all is because the amount of plasma coated material still less and because of it can more closely be applied to coated surface and combine on the throne better far away.
VII.A.2.a. consider with micron coating and compare that the slip for the stream of adjacently situated surfaces or adjacent fluid provides lower resistance like the nano coating that applies through PECVD, because plasma coating tends to the surface that provides more level and smooth.
VII.A.2.a. still another embodiment is on elastomeric stopper, to apply Si wO xC yH zThe method of coating.For example this stopper can be used to seal said vesse.This method comprises several portions.Stopper is placed the chamber of finding time basically.The reaction mixture that comprises the gas that forms plasma body is provided, promptly a kind of organic silicon compound gas, randomly a kind of oxidizing gas and randomly a kind of appropriate hydrocarbon gas.In reaction mixture, form plasma body.Stopper contacts with reaction mixture, at least a portion stopper, deposits Si wO xC yH zCoating.
VII.A.2.a. in putting into practice this method,, consider that reaction mixture can comprise appropriate hydrocarbon gas for y and the z that obtains higher value, as above and below further describe.Randomly, if the value of considering to reduce the value of y and z or improving x, reaction mixture can contain aerobic so.Perhaps, particularly in order to reduce the value of oxidation and increase y and z, reaction mixture can not contain oxidizing gas basically.
VII.A.2.a. in putting into practice this method some embodiment (for example stopper 282), consider in the depression of essential injection reaction mixture to stopper with the coating stopper.For example, a large amount of stoppers (for example 282) wherein can located and handle to the wall of stopper 282 contact and be protruding basically towards interior surface 276 and 272, and therefore easily through the batch process processing in one reaction chamber of finding time basically.Further contemplate in some embodiments; Coating 286 and 288 need not show as for oxygen and water the barrier with the same difficulty of barrier coat on the internal surface 280 of container 268, because the material of stopper 282 can be brought into play this function to a great extent.
VII.A.2.a. consider a lot of variations of stopper and stopper coating method.Stopper 282 can contact with plasma body.Perhaps can form plasma body at the upper reaches of stopper 282, the production plasma products, and plasma products can contact with stopper 282.Can be through forming plasma body with electromagnetic energy and/or micro-wave energy provocative reaction mixture.
VII.A.2.a. consider the variation of reaction mixture.The gas that forms plasma body can comprise a kind of rare gas element.For example, this rare gas element can be argon or helium or other gases of in this disclosure, describing.Organic silicon compound gas can be or comprise HMDSO, OMCTS, any other silicoorganic compound of in this disclosure, mentioning, perhaps two kinds in these or more kinds of combinations.Oxidizing gas can be other gases mentioned in oxygen or this disclosure or two kinds or more kinds of combinations in these.For example appropriate hydrocarbon gas can be methane, methyl alcohol, ethane, ethene, ethanol, propane, propylene, propyl alcohol, acetylene or two kinds or more kinds of combinations in these.
VII.A.2.b. on stopper, apply III or IV family element and carbon coating through PECVD
VII.A.2.b. another embodiment is the method that on elastomeric stopper, applies a kind of composition coating, and said composition comprises carbon and one or more III or IV family element.In order to carry out this method, a stopper is positioned in the sediment chamber.
VII.A.2.b., a kind of reaction mixture is provided in the sediment chamber, comprise have iii group element, the gas of the formation plasma body of the gaseous source of IV family element or in these two kinds or more kinds of combination.Reaction mixture randomly contains a kind of oxidizing gas and randomly contains the gaseous compound with one or more c h bonds.In reaction mixture, form plasma body, and stopper contacts with reaction mixture.An iii group element or compound, IV family element or compound or in these two kinds or more kinds of being coated with of combination are deposited upon at least a portion stopper.
VII.A.3. having effectively provides 95% vacuum to keep the stopper plastic containers of 24 months barrier coat
VII.A.3. another embodiment is a container, comprises container, barrier coat and closure member.This container generally is piped and is processed by thermoplastic material.This container has mouth and the inner chamber that at least partly receives the wall restriction.This wall has an internal surface that joins with inner chamber.On the internal surface of this wall, apply a basic at least successive barrier coat.This barrier coat is effectively so that a basic quality guaranteed period to be provided.The closure member of covering container mouth is provided, and the inner chamber of container and ambient air are isolated.
VII.A.3. with reference to figure 23-25, show container 268 (for example a kind of heparin tube of finding time or other containers).
VII.A.3. in this embodiment, this container generally is a tubular vessel, has a basic at least successive barrier coat and closure member.This container is processed by thermoplastic material, has mouth and the inner chamber that at least partly receives the wall restriction, and this wall has the internal surface that joins with inner chamber.This barrier coat is deposited on the internal surface of this wall, and effectively keeps the initial vacuum level of at least 95% or at least 90% container to continue at least 24 months, randomly at least 30 months, quality guaranteed period of at least 36 months randomly.The mouth of this closure member covering container and the inner chamber that makes container and ambient air isolation.
VII.A.3., this closure member is provided, for example at the closure member of closure member 270 or another type shown in these figure with the retaining part vacuum, and/or contain a kind of sample and limit or stop it to be exposed to oxygen or pollutent.Figure 23-25 is based on U.S. Patent number 6,602, the figure that sets up in 206, but this discovery is not limited to the closure member of it or any other particular type.
VII.A.3. closure member 270 comprise container 268 be exposed to inner chamber 274 towards interior surface 272, and the wall surface in contact 276 that contacts with the internal surface 278 of wall of container 280.In illustrated embodiment, closure member 270 is the assemblies with stopper 282 and shield [support 284.
VII.A.3. in illustrated embodiment; Stopper 282 defines wall surface in contact 276 and internal surface 278; This shield [support is most of or fully outside the container 268 of stopper simultaneously, and keep and the handle that is used for stopper 282 is provided, and in mobile closure member 270; Prevent that the people is exposed to from container 268 and emits any content of (for example when opening container 268 and air and pour or go out with the equilibrium pressure difference, because the external and internal pressure of container 268 is poor).
VII.A.3. further contemplate, can be incorporated into these coatings and the wall surface in contact 276 of stopper on the wall of container 280.Can use the oilness silicone layer to apply this stopper, and can use harder SiO xLayer or with below SiO xLayer and oilness overcoat apply the wall of container of for example being processed by PET or glass 280.
VII.B. syringe
VII.B. the description of front has solved largely a kind of barrier coat is applied to and has had on the terminal pipe of closed permanent, for example heparin tube or, more generally, a sample reception pipe 80.This device is not limited to a kind of like this device.
VII.B. another instance (shown in Figure 20-22) of the container that is fit to is a syringe cylinder 250 that is used for injector for medical purpose 252.This type syringe 252 is equipped with preparatory filling salt brine solution, a kind of pharmaceutical prepn or analogue to be used for medical technology sometimes.Also considered the SiO of precharging type syringe 252 from the internal surface 254 xBenefit in the coating of barrier coat or other types, do not contact with the plastics (the for example syringe cylinder between the shelf lives 250) of this syringe with the content that keeps this precharging type syringe 252.Can use the coating of this barrier coat or other types to avoid the component of these plastics is leached in this content through internal surface 254.
VII.B. as the syringe cylinder 250 of usually moulding at the rear end 256 that is used for receiving plunger 258 and the front end that is used to receive hypodermic needle 260 both, a nozzle or to be used for the content of dispense syringe 252 or to be used for material is received the tubing place that gets into syringe 252 can be open.But front end 260 can randomly add cap and before using precharging type syringe 252 plunger 258 randomly can assemble in position, two ends with tube 250 sealings.Perhaps a cap 262 can be installed, until cap 262 is removed and till (randomly) be installed on the front end 260 hypodermic needle or other delivery catheters when preparing to use syringe 252 from the syringe purpose of handling syringe cylinder 250 or assembling or in order between the shelf lives of precharging type syringe 252, to remain on the appropriate location.
VII.B.1. assembly
VII.B.1. Figure 42 also shows available as alternate syringe cylinder structure, for example uses by Figure 21,26,28,30 and 34 embodiment and the pan straddle 450 that is adjusted into those figure.
VII.B.1. Figure 50 is that syringe decomposition view and Figure 51 are the views of the assembling of syringe.Can with container handle and Fig. 1-2 2,26-28,33-35,37-39,44 and the inspection units of 53-54 handle this syringe cylinder.
VII.B.1. mounting cover 262 makes tube 250 become a closed end container in the device of describing in the past, and this closed end container can be provided SiO on its internal surface 254 xStop or the coating of other types, also randomly on the inside 264 of lid, coating is provided, and the interface of bridge joint between the front end 260 of the inside 264 of lid and tube.Show the suitable device that is adjusted into this purposes, for example in Figure 21, the similar Fig. 2 of Figure 21, except alternate figures 2VII.B be used for container 80 add a cover syringe cylinder 250.
VII.B.1 Figure 52 is the view that is similar to Figure 42, does not have flange or finger stop 440 but show the syringe cylinder that is processed.Container with Fig. 1-19,27,33,35,44-51 and 53-54 is handled and inspection units, and this syringe cylinder is an available.
VII.B.1.a. have with the syringe of deposition from the tube of the slip coating coating of organic silicon precursor
VII.B.1.a. still another embodiment is to have SiwO xC yH zSlip coating meets the container of the type of processing through following method.
VII.B.1.a., a kind of as above defined precursor is provided
VII.B.1.a. under the condition that effectively forms a kind of coating, this precursor is applied in a kind of substrate.This is coated with layers of polymer or crosslinked (or both), thereby forms a kind of lubricated surface, should have lower plunger sliding force or starting force in lubricated surface than untreated substrate.
VII.B.1.a. about any one and subdivision among the instance VII, randomly through evacuator body before will being somebody's turn to do and with it be provided to this substrate near carry out this and apply step.
VII.B.1.a. about any embodiment VII.A.1.a.i, near substrate, randomly form a kind of plasma body, randomly form a kind of non-hollow cathode plasma.Randomly, under basic anoxybiotic condition, this precursor is provided.Randomly, under the condition of basic shortage vector gas, this precursor is provided.Randomly, under the condition of basic shortage nitrogen, this precursor is provided.Randomly, under absolute pressure, this precursor is provided less than 1 holder.Randomly, provide this precursor near plasma emission.Randomly, with 1 to 5000nm thick or 10 to 1000nm thick or 10-200nm is thick or 20 to 100nm thick thickness, apply its reaction product of this precursor to substrate.Randomly, substrate comprises glass.Randomly; Substrate comprises a kind of polymkeric substance, randomly a kind of carbonate polymer, randomly a kind of olefin polymer, randomly a kind of cyclic olefine copolymer, randomly a kind of polyacrylic polymer, randomly a kind of polyester polymers, a kind of polyethylene terephthalate polymer randomly.
Randomly; The vapor reaction deposits yields plasma body that contains precursor through electrode excitation with energy supply; For example with the RF frequency that is defined as above, for example with from 10kHz to frequency, more preferably with from 1 to 50MHz frequency less than 300MHz; Even more preferably with 10 to 15MHz frequency, most preferably with the frequency of 13.66MHz.
Randomly, through with provide from 0.1 to 25W, preferably from 1 to 22W, more preferably from 3 to 17W in addition more preferably from 5 to 14W, most preferably from 7 to 11W, particularly the electrode excitation of the power of 8W contains the vapor reaction deposits yields plasma body of precursor.The ratio of this electrode power and volume of plasma can preferably from 5W/ml to 0.1W/ml, more preferably be from 4W/ml to 0.1W/ml less than 10W/ml, most preferably is from 2W/ml to 0.2W/ml.These power levels are the containers that are fit to apply slip coating to syringe and stopple coupon and meet the similar geometric with 1 to 3mL void volume, produce the PECVD plasma body therein.Be determine this process in proportion, the power that correspondingly increases or reduce to be applied according to the size of this substrate for what greater or lesser object was considered.
Another embodiment of VII.B.1.a is the slip coating on the syringe cylinder inwall.This coating produces from the PECVD method of using following material and condition.Preferred adopt a kind of cyclic precursor, be selected from monocycle siloxanes, many cyclosiloxane or these two kinds or more kinds of combinations, as for this slip coating the other places in the specification sheets limit.The instance of a suitable cyclic precursor comprises octamethylcyclotetrasiloxane (OMCTS), randomly mixes with other precursor materials in any ratio.Randomly; This cyclic precursor is made up of octamethylcyclotetrasiloxane (OMCTS) basically; Mean that other precursors can exist by the amount of basic and characteristic novelty of the slip coating that does not change generation, i.e. the plunger sliding force or the starting force on its surface of having reduced to apply.
VII.B.1.a does not add oxygen to this process at least basically.In this syringe cylinder, can have the oxygen in some remaining atmosphere, and charging and remaining oxygen that do not exhaust fully may reside in this syringe cylinder in the former step, this is defined as at this and does not have oxygen basically.If do not add oxygen to this process, this is also in the scope of " not having oxygen basically ".
VII.B.1.a imports competent plasma generation power, for example provides any power level one or more operational instances or that describe in this manual that is successfully used to this specification sheets to form to impel coating.
VII.B.1.a is with respect to uncoated syringe cylinder, the material of employing and condition be effectively with the syringe plunger sliding force that reduces to move or starting force at least 25% through this syringe cylinder, alternately at least 45%, alternately at least 60%, alternately greater than 60%.The scope of considering to reduce plunger sliding force or starting force is from 20% to 95%, alternately from 30% to 80%, alternately from 40% to 75%, alternately from 60% as for 70%.
VII.B.1.a. another embodiment is the container that has hydrophobic coating on the inwall of following structure having: Si wO xC yH z, wherein w, x, y and z are as former definition.As explaining, make this coating, but effectively forming under the condition of the hydrophobic surface that has higher contact angle than untreated substrate for slip coating with analogous composition.
VII.B.1.a. about any embodiment VII.A.1.a.ii, this substrate randomly comprises glass or a kind of polymkeric substance.This glass randomly is borosilicate glass.This polymkeric substance randomly is a kind of carbonate polymer, randomly a kind of olefin polymer, randomly a kind of cyclic olefine copolymer, randomly a kind of polyacrylic polymer, randomly a kind of polyester polymers, a kind of polyethylene terephthalate polymer randomly.
VII.B.1.a. another embodiment is the syringe that comprises a plunger, a syringe cylinder and a lubricant film.This syringe cylinder comprises internal surface of plunger that reception is used to slide.This lubricant film is arranged on the internal surface of syringe cylinder, and comprises a kind of Si wO xC yH zThe lubricant film coating.This lubricant film is thick and effective the minimizing for necessary starting force of mobile plunger in tube or plunger sliding force less than 1000nm.Reduce the plunger sliding force and alternately be expressed as the coefficient of sliding friction that is reduced in the plunger in the tube or reduce plunger force, these terms are regarded as and have identical implication in this manual.
VII.B.1.a. the syringe 544 of Figure 50-51 comprises plunger 546 and syringe cylinder 548.Syringe cylinder 548 has the internal surface 552 that receives plunger 546 slidably.The internal surface 552 of syringe cylinder 548 further comprises Si wO xC yH zSlip coating 554.This lubricant film is thick less than 1000nm, randomly thick less than 500nm, randomly thick less than 200nm, randomly thick less than 100nm, randomly thick less than 50nm, and for reduce to be used to overcome the necessary starting force of adhesion of plunger after storing or after plunger breaks away from tube mobile its necessary plunger sliding force be effective.This lubricant film is characterised in that to compare with uncoated surface to have littler plunger sliding force or starting force.
VII.B.1.a. can be individually or use any in the precursor of above any kind with two kinds among them or more kinds of combinations so that a slip coating to be provided.
VII.B.1.a. except utilizing vacuum technology, can also use low-temperature atmosphere-pressure (antivacuum) plasma process preferably in nonoxidizing atmosphere (for example helium or argon) come inducing molecule ionization and deposition through the precursor monomer delivery of vapor.Dividually, can consider hot CVD (through the fast pyrogenation deposition).
VII.B.1.a. aforesaid method is similar to vacuum PECVD, is that surface-coated and crosslinked mechanism can take place simultaneously.
VII.B.1.a. another stopgap measure again of considering for said any or multiple coating be applied to unevenly container whole inner 88 on coating.For example, compare, can a different or other coating optionally be applied on the barrel portion of this internal tank, or vice versa with the hemisphere portion of this internal tank that is positioned at closing end 84.Syringe cylinder or sampling tube for like the following stated have been considered this stopgap measure especially; Wherein can with lubricated surface be provided to this barrel portion partly or entirely on, this plunger or piston or closure member can slide (but not being elsewhere) herein.
VII.B.1.a. randomly; Can there be oxygen, do not having oxygen or do not exist under the condition of oxygen basically; There is nitrogen, do not having nitrogen or do not exist under the condition of nitrogen basically, perhaps having vector gas, do not having a vector gas or do not exist under the condition of vector gas this precursor is provided basically.In the embodiment of a consideration, this precursor is delivered in this substrate individually and stands PECVD and applies and solidify this coating.
VII.B.1.a. randomly, this precursor can be provided under the absolute pressure less than 1Torr.
VII.B.1.a. randomly, this precursor can be provided in the emission of this plasma body near.
VII.B.1.a. randomly, can by 1 to 5000nm 10 to 1000nm or the thickness of 10-200nm or 20-100nm apply its reaction product of this precursor to substrate.
VII.B.1.a. in any above-mentioned embodiment; This substrate can comprise glass or a kind of polymkeric substance; Polymkeric substance is one or more of carbonate polymer, polyolefin polymer (for example a kind of cyclic olefine copolymer or a kind of polyacrylic polymer) or polyester polymers (for example, a kind of polyethylene terephthalate polymer) for example.
VII.B.1.a. in any above-mentioned embodiment, produce plasma body through the gaseous reactant that contains this precursor with electrode excitation, this electrode is to come energy supply like defined RF frequency in this specification sheets.
VII.B.1.a. in any above-mentioned embodiment, produce plasma body through the gaseous reactant that contains this precursor with electrode excitation, this electrode is provided with the electric power that enough being used to produces lubricant film.Randomly; Gaseous reactant through contain this precursor with electrode excitation produces plasma body, this electrode provides from 0.1 to 25W, preferably from 1 to 22W, more preferably from 3 to 17W in addition more preferably from 5 to 14W, most preferably from 7 to 11W, the electric power of 8W particularly.The ratio of this electrode power and volume of plasma can preferably from 5W/ml to 0.1W/ml, be more preferably from 4W/ml to 0.1W/ml less than 10W/ml, most preferably is from 2W/ml to 0.2W/ml.These power levels are suitable for being used for applying slip coating to the syringe and the stopple coupon of the void volume with 1 to 3mL (wherein having produced the PECVD plasma body) and container with similar geometric.Be determine this process in proportion, the power that correspondingly increases or reduce to be applied according to the size of this substrate for what bigger or less object was considered.
VII.B.1.a. this coating can be cured, and as through polymerization or crosslinked (or both) this coating, thereby forms a kind of lubricated surface, should have lower plunger sliding force or starting force in lubricated surface than untreated substrate.Curing can occur in this and apply during the process (like PECVD), maybe can carry out or part completion at least through separate treatment.
Though VII.B.1.a. used the plasma-deposited coating characteristic that proves at this, can use the alternate deposition method, quilt keeps as much as possible and the while still adheres to a kind of solid film on this base substrate as long as the chemistry of parent material constitutes.
VII.B.1.a. for example; Can form this coating or substrate is impregnated in this coated material and this coated material (from liquid state) is applied on this syringe cylinder through spraying, wherein this coating or pure precursor or be a kind of precursor (allowing mechanical setting) of solvent cut than shallow layer.Randomly can use heat energy, UV ability, electron beam ability, plasma physical efficiency or these any combination to come crosslinked this coating
VII.B.1.a. also considered aforesaid silicone precursor is applied on the surface, carried out an independent curing schedule then.Apply the atmospheric plasma that can be similar to precoating Polyfluoroalkyl ether and solidify employed those (a kind of technologies of under trade mark , carrying out) with the solidified condition.The more details of this technology can find at http://www.triboglide.com/process.htm.
VII.B.1.a. in a kind of like this technology, there is the zone of part to be coated randomly to carry out pre-treatment with atmospheric plasma.This pre-treatment cleaning and activated should the surface makes it be easy to accept for the lubricant that in next step, sprays like this.
VII.B.1.a. then this lubricating fluid (being one of above multiple precursor or a kind of polymeric precursor in this case) is sprayed on the pending surface.For example, can use the accurate distribution technique of IVEK come to atomize exactly this fluid and produce uniform coating.
VII.B.1.a. and then use the atmospheric plasma field that this coating is combined or be linked on these parts.The two has been fixed coating and has improved lubricity.
VII.B.1.a. randomly, can be in this container produce this atmospheric plasma from ambient air, in this case, gas feed and to vacuumize equipment be unwanted.Yet, preferably, when producing plasma body this container be at least basically sealing power demand is minimized and prevents plasma body from contacting with the surface or the material of this external container.
VII.B.1.a.i. slip coating: SiO xBlocking layer, lubricant film, surface treatment
Surface treatment
Another embodiment of VII.B.1.a.i is the syringe that comprises a tube, and this has defined an inner chamber and has had an inner surface that receives a plunger slidably, promptly receives a plunger that is used for this inner surface sliding contact.
VII.B.1.a.i. this syringe cylinder is processed by thermoplasticity basis material.
VII.B.1.a.i. randomly, this inner surface is coated with like a described elsewhere in this manual SiO xThe blocking layer.
VII.B.1.a.i. a lubricant film is applied on this inner surface, this plunger (or both), or is applied to the SiO that the front applies xOn the blocking layer.As in embodiment VII.B.1.a or proposed elsewhere in this manual can provide, apply and solidify this lubricant film or coating.
VII.B.1.a.i. for example, in any one embodiment, can apply this lubricant film through PECVD.This lubricant film is sedimentary from a kind of organosilicon precursor, and is thick less than 1000nm.
VII.B.1.a.i. on this lubricant film, carry out surface treatment with a leaching of this lubricant film of effective minimizing, this thermoplasticity basis material (or both) or an amount of extractable content.Therefore a kind of solute restraining mass (solute retainer) can be served as in the surface of this processing.This surface treatment can cause a skin coat, and is for example thick and thick or thick or thick or thick or thick or thick or thick or thick or thick or thick or less than a thick skin coat of 0.5nm less than 1nm less than 2nm less than 3nm less than 5nm less than 10nm less than 20nm less than 30nm less than 40nm less than 50nm less than 100nm less than 1nm.
As in this use, " leaching " is meant that material is transferred out of and gets in the content of container (for example syringe) from substrate (for example wall of container).Normally, but extract is measured through following steps: the container that will be filled with the expection content stores, thereby then what material these content analyses are defined is leached into the content of these expections from this wall of container." extraction " is meant through introducing a kind of solvent or the dispersion medium different with the expection content of this container material shifted out from substrate, enter into to confirm under test condition, to have what material from this substrate, to be shifted out and extract medium.
VII.B.1.a.i. surface treatment causes a kind of solute restraining mass, randomly can be a SiO xOr Si wO xC yH zLayer, each is above freely to define in specification sheets.In one embodiment, can pass through SiO xOr Si wO xC yH zPECVD deposit and apply surface treatment.Randomly, can use than be used to produce the higher power of this lubricant film or stronger oxidizing condition (or both) and apply this surface treatment, therefore a kind of harder, thinner, successive solute restraining mass 539 is provided.In slip coating surface treatment can be less than 100nm deeply, randomly less than 50nm deeply, randomly less than 40nm deeply, randomly less than 30nm deeply, randomly less than 20nm deeply, randomly less than 10nm deeply, randomly less than 5nm deeply, randomly less than 3nm deeply, randomly less than 1nm deeply, randomly less than 0.5nm deeply, randomly 0.1 to 50nm dark between.
VII.B.1.a.i. this solute restraining mass is considered provides low solute leaching performance to below lubricant film and other layers (comprising this substrate (as required)).This restraining mass will be only needs be a kind of to big solute molecule and oligopolymer (for example; Siloxanyl monomers for example HMDSO, OMCTS, they fragment and from the movable oligopolymer of lubricant deutero-, for example a kind of " but extract restraining mass ") a kind of solute restraining mass rather than a kind of gas (O 2/ N 2/ CO 2/ water vapour) blocking layer.Yet a kind of solute restraining mass can also be a kind of barrier layer for gases (for example, according to a SiOx coating of the present invention).But people can produce a kind of good extract restraining mass that does not have capacity for air resistance through vacuum or based on non-pressurized PECVD process.What make us hoping is that this " but extract restraining mass " will be enough thin; Promptly when syringe plunger moves; This plunger will easily penetrate this " solute restraining mass "; Thereby the lubricant film that the stopper head that slides just is exposed to below forms a lubricated surface, should have lower plunger sliding force or starting force in lubricated surface than untreated substrate.
This surface treatment is carried out on the surface (as through this surface is exposed to the oxygen in the plasma environment) of the lubricant film that can apply through the oxidation front VII.B.1.a.i. in another embodiment.Can use the plasma environment described in this specification sheets to form SiO xCoating.Perhaps, can the atmospheric plasma concrete conditions in the establishment of a specific crime be applied in the oxygen-enriched environment.
Yet VII.B.1.a.i., can randomly solidify formed lubricant film and solute restraining mass simultaneously.In another embodiment, this lubricant film can after this, can be provided, apply surface treatment and can solidify this solute restraining mass by partly solidified at least, completely solidified randomly.
VII.B.1.a.i. lubricant film and solute restraining mass are configured and exist with the relative quantity that starting force, plunger sliding force or both (this power is less than lacking needed corresponding power under lubricant film and the surface treatment) effectively are provided.In other words, thereby the thickness of this solute restraining mass is that such material that reduced leaches into the content of syringe from lubricant film with constituting, and allows lubricant film below to lubricate this plunger simultaneously.To such an extent as to that is considered is that this solute restraining mass will be easy to break away from and is that enough thin this lubricant film when it is moved will still work to lubricate this plunger.
VII.B.1.a.i. in the embodiment of a consideration, can swabbing and surface treatment be applied on the tube inner surface.In the embodiment of another consideration, can swabbing and surface treatment be applied on the plunger.In the embodiment of another consideration again, can swabbing and surface treatment be applied on tube inner surface and the plunger.In any of these embodiment, the optional SiO on the inside of this syringe cylinder xThe blocking layer can be to exist or shortage.
VII.B.1.a.i. an embodiment of being considered is a multilayer (the for example 3 layers) configuration that is applied on the internal surface of syringe cylinder.。Layer 1 can be a SiO who under oxidizing atmosphere, is processed by the PECVD of HMDSO, OMCTS (or both) xBarrier layer for gases.As described in this specification sheets, for example can a kind of like this atmosphere be provided in the PECVD coating unit through HMDSO and oxygen are fed into.Layer 2 can be to use a kind of lubricant film of the OMCTS that puts in the nonoxidizing atmosphere.As described in this specification sheets, for example can a kind of like this nonoxidizing atmosphere (randomly lacking oxygen basically or fully) be provided in the PECVD coating unit through OMCTS is fed into.(this processing forms a thin SiO through a processing can to use OMCTS and/or HMDSO to use higher power and oxygen xOr SiwO xC yH zEpidermal area, as the solute restraining mass) form solute restraining mass subsequently.
VII.B.1.a.i. some in these laminated coatings is considered and has one or more following optional advantages at least to a certain extent.They can solve the organosilyl difficulty of the processing of being reported; Because this solute restraining mass can the restricted internal silicone and prevented that it from moving in the content of syringe or other places, this has caused silicone particles less in the content of sending of syringe and the interactional chance between the content of slip coating and syringe still less.They can also solve lubricant film or coating is moved the problem of leaving from oiling point, have improved the oilness at the interface between syringe cylinder and plunger.For example, can reduce breakaway force (break-free force), can reduce the towing force (drag) on mobile plunger, or randomly both.
What VII.B.1.a.i. considered is when the solute restraining mass is destroyed, and this solute restraining mass is with continuing to adhere on this slip coating and the syringe cylinder, and this can forbid any particle entrainment in the content of sending of this syringe.
VII.B.1.a.i. certain in these coatings some also the manufacturing advantage will be provided, if when this barrier coat, slip coating and surface treatment are applied in the same device (for example described PECVD device) especially.Randomly, this SiO xBarrier coat, slip coating and surface treatment can be applied in the PECVD device, have therefore greatly reduced essential treatment capacity.
Can obtain further advantage through using identical precursor and changing this this barrier coat of technology formation, slip coating and solute restraining mass.For example, can apply a SiO through following steps xBarrier layer for gases: at superpower/high O 2Use a kind of OMCTS precursor under the condition, through using a kind of OMCTS precursor to apply a lubricant film under the oxygen, use a kind of OMCTS precursor under middle power and oxygen, to carry out surface treatment at last then in low power and/or lacking basically or fully.
VII.B.1.b has SiO xThe syringe of the tube of the outside that inside that applies and blocking layer apply
VII.B.1.b. shown in Figure 50, still another embodiment is the syringe 544 that comprises plunger 546, tube 548 and inside and outside barrier coat 554 and 602.An inner chamber 604 processed and limited to tube 548 can the thermoplastic based material.Tube 548 can have the internal surface 552 and outside surface 606 that receives plunger 546 slidably.Can be with a kind of SiO xBarrier coat 554 be provided on tube 548 the internal surface 552, wherein x is from 1.5 to about 2.9.Can a kind of barrier coat 602 of resin be provided on the outside surface 606 of tube 548.
VII.B.1.b. in any embodiment, this thermoplasticity basis material typically can comprise a kind of polyolefine for example Vestolen PP 7052 or a kind of cyclic olefine copolymer (material of for example selling down at trade mark
Figure BDA0000126277010001691
), a kind of polyester (for example polyethyleneterephthalate), a kind of polycarbonate (for example a kind of bisphenol-a polycarbonate thermoplastics) or other materials.Considered the matrix material syringe cylinder, they have identical or different a kind of as internal layer as in outer and these materials of any in these materials.Can also use any combination of materials of described matrix material syringe cylinder in other places in this manual or stopple coupon.
VII.B.1.b. in any embodiment, this resin randomly can comprise the polyvinylidene dichloride that is in homopolymer or multipolymer form.Saran) or multipolymer for example, can adopt USP 6,165, (the popular name: of the PvDC homopolymer described in 566 (being combined in this by reference).This resin randomly can be applied on this outer surface with the form of latex or other dispersion-ss.
VII.B.1.b. in any embodiment, this syringe cylinder 548 randomly can comprise a slip coating, and this slip coating is placed in this plunger and SiO xBarrier coat between.Suitable slip coating has been described in other places in this manual.
VII.B.1.b. in any embodiment, this slip coating preferably can apply through PECVD, and randomly can comprise having composition Si wO xC yH zMaterial.
VII.B.1.b. in any embodiment, this syringe cylinder 548 can comprise that randomly a component with this slip coating of effective minimizing, this thermoplasticity basis material that covers this slip coating (or both) leaches into a surface treatment that amount is carried out in the inner chamber 604.
VII.B.1.c makes has SiO xThe method of the syringe of the tube of the outside that inside that applies and blocking layer apply
VII.B.1.c. in addition another embodiment be make a kind of syringe as any embodiment of part of V II.B.1.b described in method, this syringe comprises a plunger, tube, reaches inside and outside barrier coat.A kind of tube is provided, and this has and is used to receive inner surface of plunger and outer surface that is used to slide.Through PECVD with a SiO xBarrier coat be provided on this inner surface.A kind of barrier coat of resin is provided on this outer surface.This plunger and tube are assembled thereby a kind of syringe is provided.
VII.B.1.c. for use latex effectively applies (moistening equably) this plastic article, what considered is that surface tension and this plastic-substrates of this latex are complementary is useful.This can for example, reduce the surface tension (with tensio-active agent or solvent) of this latex, and/or this plastic article is carried out corona pre-treatment, and/or this plastic article is carried out Chemical Pretreatment (priming) through independently or combine the ground several methods to realize.
VII.B.1.c. this resin randomly can pass through the latex dip-coating to this outer surface; With this latex spray (or both) and be applied in to this outer surface; Article based on plastics are provided thus, improved gas and steam barrier properties are provided.Can make polyvinylidene chloride plastic and laminate article, compare with the no lamination plastic article, these article provide significantly improved capacity for air resistance.
VII.B.1.c. in any embodiment, randomly can this resin thermofixation.Randomly solidify this resin through removing to anhydrate.Can be through with the resin thermofixation, resin be exposed to partial vacuum or low-humidity environment, catalytically solidifies this resin or other stopgap measures and remove and anhydrate.
VII.B.1.c. considered an effective thermofixation scheme so that final drying to be provided, thereby allowed the PvDC crystallization, this provides barrier properties.At high temperature (for example between 180 ° of F to 310 ° of F (82 ℃ to 154 ℃)) carry out primary curing reaction, and this depends on the thermotolerance of this thermoplasticity basis material certainly.Randomly the barrier properties after the primary curing reaction can be about 85% of the final barrier properties realized after the final curing.
VII.B.1.c. can under the TR of the time (as four hours) that continues the lasting weak point of a long time (for example 2 weeks) to high temperature (like 122 ° of F (50 ℃)) from envrionment temperature (like about 65 ° of F to 75 ° of F (18 ℃ to 24 ℃)), carry out final curing.
VII.B.1.c. the PvDC plastic lamination article of randomly considering (except excellent barrier properties) are with performance that one or more hope are provided (for example water white transparency, good gloss, wear resistance, impressionability and mechanical strain resistance).
VII.B.2. plunger
VII.B.2.a. has the piston front that the blocking layer applies
VII.B.2.a. another embodiment is a kind of plunger that is used for syringe, comprises a piston and a push rod.This piston has side and rear section of a front, a substantial cylindrical, and this side is configured to be seated within the syringe cylinder movably.This front has a barrier coat.This push rod engages this rear section and is configured to make piston in syringe cylinder, to advance.
VII.B.2.b. has the slip coating that meets the boundary with the side
VII.B.2.b. another embodiment is a kind of plunger that is used for syringe again, comprises a piston, a slip coating and a push rod.This plunger has a front, the side of a substantial cylindrical and a rear section.This side is configured to be seated in the syringe cylinder movably.This slip coating and side meet the boundary.This push rod engages the rear section of this plunger and is configured to make piston in syringe cylinder, to advance.
VII.B.3. two-piece type syringe and female luer
VII.B.3. another embodiment is the syringe that comprises a plunger, a syringe cylinder and a female luer.This syringe comprises the tube with the internal surface that receives plunger slidably.Female luer comprises a luer taper, and this luer taper has an internal passages that is limited an internal surface.This female luer is to form and to be connected on this syringe cylinder through a junctor with the form of the isolating separation member of this syringe cylinder.The internal passages of this luer taper has a SiO xBarrier coat.
VII.B.3. with reference to figure 50-51, syringe 544 can randomly comprise a female luer 556, and it comprises that a luer taper 558 is to receive an intubate (not shown, routine) that is contained on the attached luer taper.Luer taper 558 has an internal passages 560 that is limited internal surface 562.Female luer 556 randomly conduct forms and is connected on the syringe cylinder 548 through a junctor 564 with these syringe cylinder 548 isolating separation members.Shown in Figure 50 and 51, junctor 564 in this example has a convex part 566 and a female component 568, and the female luer that will exist with the mode of basic at least sealing is fixed to tube 548 thereby they are fastened togather.The internal surface 562 of this luer taper comprises a SiO xBarrier coat 570.This barrier coat is can be less than 100nm thick and effectively reduce the internal passages that oxygen gets into this female luer.Can, this female luer apply barrier coat before being connected to syringe cylinder.The syringe of Figure 50-51 also has the locking collar 572 that has IT arbitrarily, is used in the attached luer taper of boring this intubate of locking on 558 on the throne.
VII.B.4. lubricating composition-deposition is from the slip coating of the organosilicon precursor of processing through the in-situ polymerization organosilicon precursor
VII.B.4.a. the product of handling and lubricating
VII.B.4.a. another embodiment is a kind of slip coating again.This coating can be the type of processing through following processing.
VII.B.4.a. any of these precursor of mentioning elsewhere in this manual can individually or make up and use.Under the condition that effectively forms a kind of coating, precursor is applied in the substrate.This is coated with layers of polymer or crosslinked (or both), thereby forms a kind of lubricated surface, should have lower plunger sliding force or starting force in lubricated surface than untreated substrate.
VII.B.4.a. another embodiment is a kind of method that applies lubricant film.Under the condition that effectively forms a kind of coating, a kind of organosilicon precursor is applied in the substrate.This is coated with layers of polymer or crosslinked (or both), thereby forms a kind of lubricated surface, should have lower plunger sliding force or starting force in lubricated surface than untreated substrate.
VII.B.4.b. the product of technology and analytical characteristics
VII.B.4.b. of the present invention even another aspect is through from the sedimentary slip coating of the PECVD of feed gas; This feed gas comprises a kind of Organometallic precursor, a kind of organosilicon precursor preferably, preferably a kind of linear siloxane, a kind of linear silicon azane, a kind of monocycle siloxanes, a kind of monocycle silazane, a kind of many cyclosiloxane, a kind of many ring silazane or two kinds or more kinds of any combinations among these.As have 1.25 and 1.65g/cm through determined this coating of X ray reflection rate (XRR) 3Between, randomly 1.35 and 1.55g/cm 3Between, randomly 1.4 and 1.5g/cm 3Between, randomly 1.44 and 1.48g/cm 3Between density.
VII.B.4.b. another aspect again of the present invention is through from the sedimentary slip coating of the PECVD of feed gas; This feed gas comprises a kind of Organometallic precursor, a kind of organosilicon precursor preferably, preferably a kind of linear siloxane, a kind of linear silicon azane, a kind of monocycle siloxanes, a kind of monocycle silazane, a kind of many cyclosiloxane, a kind of many ring silazane or two kinds or more kinds of any combinations among these.As determined through vapor-phase chromatography/mass spectroscopy, this coating has and contains multiple-(Me) as a kind of component of exitting 2One or more oligopolymer of SiO-part.Randomly, this coating meets the qualification of any embodiment VII.B.4.a or VII.B.4.b.Randomly, be not contain trimethyl silanol basically like the component of exitting through determined this coating of vapor-phase chromatography/mass spectroscopy.
VII.B.4.b. as determined, through vapor-phase chromatography/mass spectroscopy this coating venting component can be the every test of 10ng/ at least contain multiple-(Me) 2The oligopolymer of SiO-part, this vapor-phase chromatography/mass spectroscopy is used following test condition:
GC post: 30mX0.25mm DB-5MS (J&W Scientific), 0.25 micron film thickness
Flow velocity: 1.0ml/ minute, constant current mode
Detector: mass selective detector (MSD)
Injection way: split stream sampling (10: 1 splitting ratios)
Venting condition: 1 1/ 2" (37mm) chamber was cleaned flow rate 60ml/min three hours at 85 ℃
Oven temperature: 40 ℃ (5 minutes) rise to 300 ℃ with 10 ℃/minute speed; Kept 5 minutes at 300 ℃.
What VII.B.4.b. randomly, this venting component can comprise the every test of 20ng/ at least contains multiple-(Me) 2The oligopolymer of SiO-part.
VII.B.4.b. randomly; This feed gas comprises a kind of monocycle siloxanes, a kind of monocycle silazane, a kind of many cyclosiloxane, a kind of many ring silazane or two or more any combination among these; For example a kind of monocycle siloxanes, a kind of monocycle silazane or two kinds or more kinds of any combinations, for example octamethylcyclotetrasiloxane among these.
VII.B.4.b. the slip coating of any embodiment can have through transmission electron microscopy (TEM) measure 1 and 500nm between a thickness; Randomly 20 and 200nm between; Randomly 20 and 100nm between, randomly 30 and 100nm between.
VII.B.4.b. another aspect of the present invention is through from the sedimentary slip coating of the PECVD of feed gas, and this feed gas comprises a kind of monocycle siloxanes, a kind of monocycle silazane, a kind of many cyclosiloxane, a kind of many ring silazane or two kinds or more kinds of any combinations among these.As determined through x-ray photoelectron spectroscopy (XPS), this coating can have an atomic percent of the carbon that is normalized to 100% carbon, oxygen and silicon, and this concentration is greater than the atomic percent of carbon in the atomic formula of feed gas.Randomly, this coating meets the qualification of embodiment VII.B.4.a or VII.B.4.b.A.
VII.B.4.b. randomly; The atomic percent of carbon from 1 atom % be increased to 80 atom % (as calculated and based on the XPS condition the instance 15); Alternately from 10 atom % to 70 atom %; Alternately from 20 atom % to 60 atom %, alternately from 30 atom % to 50 atom %, alternately from 35 atom % to 45 atom %, alternately from 37 atom % to 41 atom %.
VII.B.4.b. an other aspect of the present invention is through from sedimentary lubricant film of the PECVD of feed gas or coating, and this feed gas comprises a kind of monocycle siloxanes, a kind of monocycle silazane, a kind of many cyclosiloxane, a kind of many ring silazane or two kinds or more kinds of any combinations among these.This coating has as determined through x-ray photoelectron spectroscopy (XPS), is normalized to the atomic percent of a silicon of 100% carbon, oxygen and silicon, and this concentration is less than the atomic percent of silicon in the atomic formula of feed gas.Randomly, this coating meets the restriction of embodiment VII.B.4.a or VII.B.4.b.
VII.B.4.b. randomly; The atomic percent of silicon from 1 atom % be increased to 80 atom % (as calculated and based on the XPS condition the instance 15); Alternately from 10 atom % to 70 atom %; Alternately from 20 atom % to 60 atom %, alternately from 30 atom % to 55 atom %, alternately from 40 atom % to 50 atom %, alternately from 42 atom % to 46 atom %.
VIIB.4.b. also considered to have the slip coating of the combination of any two kinds or the more kinds of characteristics in part of V II.B.4, quoted as proof especially.
VII.C. container is summarized
VII.C. as described herein and/or can be used to receive and/or store and/or send a kind of compound or compsn according to the container or the vessel of the coating of said method preparation.This compound or compsn can be responsive, and be for example air-sensitive, oxygen sensitive, to humidity sensitive and/or responsive to mechanical influence.It can be a kind of bioactive compound or compsn, and for example a kind of medicament is as Regular Insulin or comprise the compsn of Regular Insulin.In yet another aspect, it can be a kind of biological fluid, preferably a kind of body fluid, for example blood or a kind of blood ingredient.Of the present invention aspect some in; This compound or compsn are to remain to be administered to it is had the intravital a kind of product of experimenter that needs; For example a kind of have a product to be injected; For example blood (as from donor to the process of acceptor blood transfusion, or blood introduced from the patient again turn back in this patient's body) or Regular Insulin.
VII.C.A is as described herein and/or can be further used in machinery and/or the chemical action that protection is included in the surface that a kind of compound or compsn in its internal space avoid this uncoated container material according to the container of the coating of said method preparation or vessel.For example, it can be used to prevent or reduce said composition compound or a kind of component deposition and/or solidify or platelet activation for example insulin precipitation or blood coagulation or platelet activation.
VII.C. it can be further used for protecting the external environment influence that a kind of compound or compsn in the inside that is included in it are avoided this container, for example through preventing or reduce one or more compounds to enter into the internal space of this container from the environment around this container.This type environmental compound can be a kind of gas or solution, for example a kind of atmospheric gas or liquid that contains oxygen, air and/or water vapour.
VII.C. the container of coating as described herein can also be vacuumized and stored with vacuum state.For example, this coating of comparing with corresponding uncoated container allows better vacuum to keep.Aspect of this embodiment, the container of this coating is a kind of heparin tube.Said pipe can also contain and is useful on a kind of reagent that prevents blood coagulation or platelet activation, for example EDTA or heparin.
VII.C. for example as container through provide from about 1cm to about 200cm, randomly from about 1cm to about 150cm, randomly from about 1cm to about 120cm, randomly from about 1cm to about 100cm, randomly from about 1cm to about 80cm, randomly from about 1cm to about 60cm, randomly from about 1cm to about 40cm, randomly from about 1cm to the about long pipe length of 30cm; And be described below and come it is handled, can process any above-mentioned embodiment with a probe electrode.Particularly for the long length in the above-mentioned scope, what should consider is that relatively moving between probe and the container possibly be useful during forming coating.For example, this can be through coming mobile containers or coming mobile probe to accomplish with respect to container with respect to probe.
VII.C. in these embodiments, what considered is that this coating of comparing with preferred barrier coat can be thin or more incomplete, because this container high blocking layer integrity that will not need vacuum test tube and had in some embodiments.
VII.C. as one of any above-mentioned embodiment optional characteristic, this container has a central axis.
VII.C. as one of any above-mentioned embodiment optional characteristic, this wall of container is enough flexible at least once bending (stride across from straight at least basically and do not destroy wall to being not more than 100 times scope of the external diameter that equals this container in the central axis bending radius) under 20 ℃.
VII.C. as one of any above-mentioned embodiment optional characteristic; Bending radius at the central axis place be not more than 90 times of the external diameter that equals this container (be not more than equal 80 times or be not more than equal 70 times be not more than equal 60 times or be not more than equal 50 times be not more than equal 40 times or be not more than equal 30 times be not more than equal 20 times or be not more than equal 10 times be not more than equal 9 times or be not more than equal 8 times be not more than equal 7 times or be not more than equal 6 times be not more than equal 5 times or be not more than equal 4 times be not more than equal 3 times or be not more than equal 2 times), or be not more than the external diameter of this container.
VII.C. as one of any above-mentioned embodiment optional characteristic, this wall of container can be the surface of a kind of contacting with fluid of being processed by flexible material.
VII.C. as one of any above-mentioned embodiment optional characteristic, this container intracavity can be a kind of fluid flowing passage of pump.
VII.C. as one of any above-mentioned embodiment optional characteristic, this container can be a kind of by the adaptive blood bag that is in the good condition that is used for medical use with maintenance blood.
VII.C, VII.D. be as one of any above-mentioned embodiment optional characteristic, this macromolecular material can be a kind of silicone elastomer or a kind of thermoplastic polyurethane (as two instances) or be suitable for blood or with the contacted any material of Regular Insulin.
VII.C, VII.D. are in an optional embodiments, and this container has 2mm or the internal diameter of 4mm at least at least.
VII.C. as one of any above-mentioned embodiment optional characteristic, this container is a kind of pipe.
VII.C. as one of any above-mentioned embodiment optional characteristic, this inner chamber has at least two open end.
VII.C.1. contain active blood, have the container of a deposition from the coating of organic silicon precursor
VII.C.1. in addition another embodiment be a kind of container that contains blood.A kind of so some limiting examples of container are transfusion bags, have wherein collected the blood collection bag of the blood sample collection container of sample, the pipeline of cardiopulmonary machine, flexible wall or the orthopaedic surgical operations intra-operative is used to collect blood samples of patients and the pipeline of blood being introduced again patient's vascular system.If this container comprises a pump that is used for pump blood, a specially suitable pump is impeller pump or peristaltic pump so.This container has a wall; This wall has an internal surface that limits inner chamber.The internal surface of this wall has a Si of part at least wO xC yH zCoating, wherein preferred w is 1, and x is from about 0.5 to 2.4, and y is from about 0.6 to about 3, and z is from 2 to about 9, and more preferably wherein w is 1, and x is from about 0.5 to 1, and y is from about 2 to about 3, and z is from 6 to about 9.This coating can be as thin as unit molecule thickness or thick to this container of about 1000nm. contain activated for the vascular system that returns the patient, be arranged in the inner chamber and Si wO xC yH zThe blood of coating contact.
VII.C.1. an embodiment is the Sheng blood container that comprises a wall and have the internal surface that limits inner chamber.This internal surface has a Si of part at least wO xC yH zCoating.This coating can also comprise or basically by SiO xForm, wherein define in x such as this specification sheets.On internal surface, the thickness of this coating is in the scope thick to about 1000nm from unit molecule thickness.That this container contains is activated for the vascular system that returns the patient, be arranged in the inner chamber and Si wO xC yH zThe blood of coating contact.
VII.C.2. deposit from a kind of coating of organosilicon precursor and reduce solidifying or platelet activation of blood in this container
VII.C.2. another embodiment is the container with a wall.This wall has one and limits the internal surface of inner chamber and have a Si of part at least wO xC yH zCoating, wherein preferably w, x, y and z such as above definition: W are 1, and x is from about 0.5 to about 2.4, and y is from about 0.6 to about 3, and z is from 2 to about 9, and more preferably wherein w is 1, and x is from about 0.5 to 1, and y is from about 2 to about 3, and z is from 6 to about 9.On internal surface, the thickness of this coating is thick from unit molecule thickness to about 1000nm.The Si that do not use with same type wO xC yH zThe wall that applies is compared, and this coating effectively reduces solidifying or platelet activation of the blood that is exposed to internal surface.
VII.C.2. as with it with unmodified polymkeric substance or SiO xThe characteristic of surface contact compare, consider to combine Si wO xC yH zCoating will reduce adhering to of blood or solidify formation trend.Consider that this characteristic maybe possibly eliminate for the needs with the heparin processing blood to reduce; As during cardiac operation; Such when using the cardiopulmonary machine, standing one type of needs will shift out blood and return heparin patient's the operating patient then from the patient essential haemoconcentration through reducing.Consider that this relates to minimizing in the operating complication through the blood channel of such container, through reducing by the hemorrhage complication that uses heparin to cause.
VII.C.2. another embodiment is to comprise a wall and have a container that limits the internal surface of inner chamber.This internal surface has the Si of part at least wO xC yH zCoating, on this internal surface, the thickness of this coating is thick from unit molecule thickness to about 1000nm, this coating effectively reduces blood coagulation or the platelet activation that is exposed to this internal surface.
VII.C.3. the container that contains active blood, has the coating of an III or IV family element
VII.C.3. another embodiment is the Sheng blood container with a wall, and this wall has an internal surface that limits inner chamber.This internal surface has at least the coating of the compsn of part, and said composition comprises one or more iii group elements, one or more IV family elements or two or more the combination in these.On this internal surface, the thickness of this coating is between unit molecule thickness and about 1000nm thick (being included).This container contain for the vascular system that returns the patient activity is arranged, be arranged in inner chamber that coating contacts in blood.
VII.C.4. the coating of III or IV family element has reduced solidifying or platelet activation of blood in this container
VII.C.4. randomly, in front in the container in the paragraph, the coating of III or IV family element effectively reduces the solidifying or platelet activation of blood of the internal surface that is exposed to this wall of container.
VII.D. medicine delivery container
VII.D. as said, the container of a coating or vessel can be used for stoping or reduce the compound that is included in said container or compsn and escape and get into the environment that centers on this container.
Consider also as said this coating of further use and container that they are clearly from any part of these explanations and claim.
VII.D.1. the container that contains Regular Insulin has the coating of deposition from organic silicon precursor
VII.D.1. another embodiment is the Sheng insulin reservoir that comprises a wall, and this wall has the internal surface that limits inner chamber.This internal surface has a Si of part at least wO xC yH zCoating, preferably wherein w, x, y and z such as above definition: w are 1, and x is from about 0.5 to 2.4, and y is from about 0.6 to about 3, and z is from 2 to about 9, and more preferably wherein w is 1, and x is from about 0.5 to 1, and y is from about 2 to about 3, and z is from 6 to about 9.On this internal surface, this coating can be thick from unit molecule thickness to about 1000nm, and Regular Insulin is disposed in the inner chamber and Si wO xC yH zThe coating contact.
VII.D.1. still another embodiment is the Sheng insulin reservoir that comprises a wall and have the internal surface that limits inner chamber.This internal surface has a Si of part at least wO xC yH zCoating, the thickness of coating is thick from unit molecule thickness to about 1000nm on this internal surface.Regular Insulin, for example the FDA approval is used for people's medicine Regular Insulin, is disposed in the inner chamber and Si wO xC yH zThe coating contact.
VII.D.1. consider a Si wO xC yH zThe combination of coating will be reduced in adhering to of Regular Insulin in the delivery tube of insulin pump or precipitate formation trend (with its characteristic that contacts with unmodified polymer surfaces relatively the time).Thereby considering that this characteristic reduces maybe possibly eliminate for the Regular Insulin that will pass delivery tube filters the needs remove solid precipitation.
VII.D.2. deposit the deposition that reduces Regular Insulin in container from the coating of organic silicon precursor
VII.D.2. randomly, in front in the container of paragraph, and lack Si wO xC yH zThe similar face of coating is compared, this Si wO xC yH zCoating effectively reduces from Regular Insulin contact internal surface and forms deposition.
VII.D.2. in addition another embodiment be the container that comprises a wall once more and have the internal surface that limits inner chamber.This internal surface comprises a Si of part at least wO xC yH zCoating.On this internal surface, the thickness of coating is in the scope thick to about 1000nm from unit molecule thickness.This coating effectively reduces from Regular Insulin contact internal surface and forms deposition.
VII.D.3. the container that contains Regular Insulin has unit of III or IV family element coating
VII.D.3. another embodiment is the Sheng insulin reservoir that comprises a wall, and this wall has an internal surface that limits inner chamber.This internal surface has the composition coating of part at least, and said composition comprises carbon, one or more iii group elements, one or more IV family elements or two kinds or more kinds of combinations in these.On this internal surface, this coating can be thick from unit molecule thickness to about 1000nm.Regular Insulin is disposed in the inner chamber and contacts with coating.
VII.D.4. unit of III or IV family element coating reduces the deposition of Regular Insulin in the container
VII.D.4. randomly; In front in the container described in the paragraph; Compare with the similar face that lacks coating, comprise carbon, III-th family one or more elements, IV family one or more elements or in these coating of the compsn of two or multinomial a kind of combination effectively reduce from Regular Insulin contact internal surface and form deposition.
Operational instances
Instance 0: be used to form and the basic experiment scheme of coated and syringe cylinder
Form and be coated in the container of testing in the operational instances subsequently according to following exemplary experiment scheme (except in addition indicated in independent instance).The concrete parameter value that in following basic experiment scheme, provides (for example electric power and process gas flow rate) is a representative value.Compare with these representative values, when parameter value changes, this will indicate in operational instances subsequently.Same principle is applied to the type and the formation of process gas.
Be used to form the experimental program of COC pipe (for example in instance 1,19, using)
Have usually cyclic olefine copolymer (COC) pipe (" COC pipe ") as the shape and size of vacuum test tube and be from
Figure BDA0000126277010001821
8007-04 cyclic olefine copolymer (COC) resin comes injection moulding; This resin can obtain from the Hoechst AG company in Frankfurt, Germany city, and these COC pipes have following these sizes: the length of 75mm, the external diameter of 13mm; And the wall thickness of 0.85mm, have about 7.25cm separately 3End volume and a closure, circular.
Be used to form the experimental program of PET pipe (for example in instance 2,4,8,9,10, using)
It is injection moulding in the equal dies of the experimental program that is used to form the COC pipe that the common polyethyleneterephthalate (PET) that is used as the type of the heparin tube (" PET pipe ") of finding time is managed; Length with these sizes: 75mm; The external diameter of 13mm; And the wall thickness of 0.85mm, have about 7.25cm separately 3End volume and a closure, circular.
Be used to SiO xThe experimental program of the inside of (for example in instance 1,2,4,8,9,10,18,19, using) coated
Use has the device shown in Fig. 2 of the sealing mechanism of Figure 45, and this is the embodiment of a special consideration.Pan straddle 50 is to process (can E.I.du Pont de Nemours and Co company obtains from Delaware, USA Wilmington city) by
Figure BDA0000126277010001822
Derlin, has the external diameter of 1.75 inches (44mm) and the height of 1.75 inches (44mm).Pan straddle 50 is accommodated in
Figure BDA0000126277010001823
structure, allows device to move into and shift out electrode (160).
Electrode 160 is that the copper by the shielding that has becomes.
Figure BDA0000126277010001825
shielding is to come conformal around the outside of copper electrode 160.Electrode 160 measured about 3 inches (76mm) high (the inside) and be that about 0.75 inch (19mm) is wide.
To insert the bottom seals (
Figure BDA0000126277010001827
is U.S. Dupont Performance Elastomers LLC, the trade mark of Wilmington Delaware) of the pan straddle 50 of
Figure BDA0000126277010001826
O shape circle 490,504 of using outside (Figure 45) as the pipe of container 80 around this pipe.To manage 80 and carefully move to sealing station, this position and is pushed a copper plasma body net on (static) 1/8-inch (3-mm) diameter brass probe that extends or counter electrode 108.
Copper plasma body net 610 is foraminous, cut the copper foil material (U.S. K and S Engineering with the external diameter that is fit to this pipe; Chicago Illinois; And abutment surface 494 clampings (referring to Figure 45) on the throne the Part#LXMUW5 copper mesh), through radially extending, serve as the stopper that is used for this pipe insertion.With two copper mesh fit snugly in this brass probe or counter electrode 108 around, to guarantee good electrical contact.
Brass probe or counter electrode 108 extend the inside of about this pipe of 70mm entering and have the array of a #80 wire (diameter=0.0135 inch or 0.343mm).Brass probe or counter electrode 108 extend through joint that is positioned at pan straddle 50 bottoms (from U.S. Swagelok Co.; Solon Ohio can get), extend through the bottom construction of pan straddle 50.This brass probe or counter electrode 108 are grounding on the shell of this RF matching network.
Gas delivery port one 10 is along two holes in the probe of the length of this pipe or 12 holes in the counter electrode 108 (three on each limit on four limits of directed 90 degree mutually) and the aluminium lid in the end of jam-pack gas delivery port one 10.Gas delivery port one 10 is connected to the stainless steel assembly, and this assembly comprises
Figure BDA0000126277010001832
joint, a thermopair pressure warning unit and by-pass valve that is connected to the vacuum exhaust pipeline of the manual manipulation ball valve that combination is used to exit.In addition, this gas system is connected to gas delivery port one 10, allows mobile the entering through gas delivery port one 10 (under processing pressure) of process gas, oxygen and SWS-F 221 (HMDSO) to be somebody's turn to do pipe inside.
This gas system comprises
Figure BDA0000126277010001833
GFC17 mass flowmeter (U.S. Part#EW-32661-34; Cole-Parmer Instrument Co.; Barrington Illinois) polyetheretherketone (" the PEEK ") kapillary of (it is used to make oxygen to get into this process with the 90sccm specific flow rates of specific examples (or be used for report) controllable flow) and a length 49.5 inches (1.26m) (1/16 inch of external diameter " OD " (1.5mm), internal diameter " ID " 0.004 inch (0.1mm)).This PEEK capillary end is inserted liquid SWS-F 221 (" HMDSO "; Alfa parts number L16970; The NMR level; From Johnson Matthey PLC, London can get) within.Because the pressure during handling in the pipe is lower, this liquid HMDSO is attracted through this kapillary.Then in this exit capillaceous when HMDSO gets into the area of low pressure HMDSO be evaporated into and be steam.
In order to ensure not having liquid HMDSO through this point after; When it does not flow into this pipe inside and is used for through
Figure BDA0000126277010001841
3 logical valves and handles, this gas stream (comprising oxygen) is diverted to pumping line.In case this pipe is mounted, the vacuum pump valve is opened to the inside of pan straddle 50 and this pipe.
Alcatel rotary vane vacuum pump and gas blower are formed this vacuum pump system.When process gas flowed with specified speed, this pump system allowed the inside of this pipe to be reduced to the pressure less than 200mTorr.
In case arrive the base vacuum level, pan straddle 50 assemblies moved in electrode 160 assemblies.This gas stream (oxygen and HMDSO steam) flows into the gas delivery port one 10 (through regulating 3 logical valves from pumping line to gas delivery port one 10) of this brass.As measured through near the capacitance manometer (MKS) the valve of control vacuum that is installed on this pumping line, this pipe pressure inside is about 300mTorr.Except pipe pressure, use the thermocouple gauge that is connected on this gas system also to measure the internal pressure of this gas delivery port one 10 and gas system.This pressure typically is less than 8Torr.
In case this gas stream is inner to this pipe, the RF power supply is opened into its constant power level.Use 600 watts of RF power supplys of ENI ACG-6 (with 13.56MHz) with about 50 watts constant power level.In the operating period of this coating unit, use the model 43RF of the Bird company watt meter in the RF output be connected to power supply in this and whole following experimental programs and a plurality of instance, to calibrate output rating.Relation below finding between dial card setting on the power supply and output rating: RF power output=55x dial card is provided with.The application in first to file, usage factor 100, this is incorrect.This RF power supply is connected on the automatic adaptation of COMDEL CPMX1000, and this adaptation is complementary the complex impedance of plasma body (remaining in this pipe, to be produced) and 50 ohm of output impedance of ENI ACG-6RF power supply.Forward power is that 50 watts (or to specific amounts that specific examples is reported) and reflective power are 0 watt, makes the power that is applied be delivered to the inside of pipe like this.This RF power supply be control through a laboratory timing register and will be set at 5 seconds conduction time (or certain period of time of reporting to specific examples).When starting the RF power supply, among the inside of this pipe, set up uniform plasma body.This plasma body is kept and is stopped by timing register until this RF power supply whole 5 seconds.Plasma body has produced the thick silica coating (or specific thickness of in specific examples, being reported) of about 20nm on this pipe inner surface.
After applying, this gas stream is gone back to this vacuum pipeline and is closed this vacuum valve.Then purging valve is opened, made the inside of pipe turn back to normal atmosphere (about 760Torr).Should manage carefully then and from pan straddle 50 assemblies, remove (after pan straddle 50 assemblies are shifted out electrode 160 assemblies).
Be used for hydrophobic coating (for example using) the inner experimental program of coated at instance 9
Use has the device shown in Fig. 2 of the sealing mechanism of Figure 45, and this is the embodiment of a special consideration.Pan straddle 50 is processed (can E.I.du Pont de Nemours and Co company obtains from Delaware, USA Wilmington city) by
Figure BDA0000126277010001851
Derlin, has the external diameter of 1.75 inches (44mm) and the height of 1.75 inches (44mm).Pan straddle 50 is accommodated in
Figure BDA0000126277010001852
structure, allows device to move into and shift out electrode (160).
Electrode 160 is that the copper by the shielding that has
Figure BDA0000126277010001853
becomes.
Figure BDA0000126277010001854
shielding is to come conformal around the outside of copper electrode 160.Electrode 160 measured about 3 inches (76mm) high (the inside) and be that about 0.75 inch (19mm) is wide
To insert pan straddle 50 bottom seals (
Figure BDA0000126277010001856
is U.S. Dupont Performance Elastomers LLC, the trade mark of Wilmington Delaware) of
Figure BDA0000126277010001855
O shape circle 490,504 of using outside (Figure 45) as the pipe of container 80 around this pipe.To manage 80 and carefully move to sealing station, this position and is pushed a copper plasma body net on (static) 1/8-inch (3-mm) diameter brass probe that extends or counter electrode 108.
Copper plasma body net 610 is foraminous, cut the copper foil material (U.S. K and S Engineering with the external diameter that is fit to this pipe; Chicago Illinois; And abutment surface 494 clampings (referring to Figure 45) on the throne the Part#LXMUW5 copper mesh), through radially extending, serve as the stopper that is used for this pipe embedding.With two copper mesh fit snugly in this brass probe or counter electrode 108 around, to guarantee good electrical contact.
Brass probe or counter electrode 108 extend the inside of about this pipe of 70mm entering and have the array of a #80 wire (diameter=0.0135 inch or 0.343mm).Brass probe or counter electrode 108 extend through joint that is positioned at the pan straddle bottom (from U.S. Swagelok Co.; Solon Ohio can get), extend through the bottom construction of pan straddle 50.This brass probe or counter electrode 108 are grounding on the shell of this RF matching network.
Gas delivery port one 10 is along two holes in the probe of the length of this pipe or 12 holes in the counter electrode 108 (three on each limit on four limits of directed 90 degree mutually) and the aluminium lid in the end of jam-pack gas delivery port one 10.Gas delivery port one 10 is connected to the stainless steel assembly, and this assembly comprises
Figure BDA0000126277010001862
joint, a thermopair pressure warning unit and by-pass valve that is connected to the vacuum exhaust pipeline of the manual manipulation ball valve that combination is used to discharge.In addition, this gas system is connected to gas delivery port one 10, allows mobile the entering through gas delivery port one 10 (under processing pressure) of process gas, oxygen and SWS-F 221 (HMDSO) to be somebody's turn to do pipe inside.
This gas system comprises
Figure BDA0000126277010001863
GFC17 mass flowmeter (U.S. Part#EW-32661-34; Cole-Parmer Instrument Co.; Barrington Illinois) (be used for controllably making oxygen to flow into this process) and polyetheretherketone (" the PEEK ") kapillary of a kind of length 49.5 inches (1.26m) (1/16 inch of external diameter " OD " (1.5mm), internal diameter " ID " " 0.004 inch (0.1mm)) with the 60sccm specific flow rates of specific examples (or be used for) with report.With this PEEK capillary end insert liquid SWS-F 221 (" HMDSO " Alfa
Figure BDA0000126277010001864
parts number L16970; The NMR level; From JohnsonMatthey PLC, London can get).Because the pressure during handling in the pipe is lower, this liquid HMDSO is attracted through this kapillary.Then in this exit capillaceous when HMDSO gets into the area of low pressure HMDSO be evaporated into and be steam.
In order to ensure not having liquid HMDSO through this point after; When it did not flow into this pipe inside and is used for through
Figure BDA0000126277010001865
3 logical valves and handles, this gas stream (comprising oxygen) was turned into pumping line.In case this pipe is mounted, the vacuum pump valve is opened to the inside of pan straddle 50 and this pipe.
Alcatel rotary vane vacuum pump and gas blower are formed this vacuum pump system.When process gas flowed with specified speed, this pump system allowed the inside of this pipe to be reduced to the pressure less than 200mTorr.
In case arrive the base vacuum level, pan straddle 50 assemblies just move into electrode 160 assemblies.This gas stream (oxygen and HMDSO steam) flows into the brass gas delivery port one 10 (through adjusting 3 logical valves from pumping line to gas delivery port one 10).As measured through near the capacitance manometer (MKS) the valve of control vacuum that is installed on this pumping line, this pipe pressure inside is about 270mTorr.Except pipe pressure, use the thermocouple gauge that is connected on this gas system also to measure the internal pressure of this gas delivery port one 10 and gas system.This pressure typically is less than 8Torr.
In case this gas stream is inner to this pipe, the RF power supply is opened to its fixed power level.About 39 watts constant power level is used 600 watts of RF power supplys of ENI ACG-6 (with 13.56MHz).This RF power supply is connected on the automatic adaptation of COMDEL CPMX1000, and this adaptation is complementary the complex impedance of plasma body (remaining in this pipe, to be produced) and 50 ohm of output impedance of ENI ACG-6RF power supply.Forward power is that 39 watts (or to specific amounts that specific examples is reported) and reflective power are 0 watt, makes the power that is applied be delivered to the inside of pipe like this.This RF power supply be control through a laboratory timing register and will be set at 7 seconds conduction time (or certain period of time of reporting to specific examples).When starting the RF power supply, among the inside of this pipe, set up uniform plasma body.This plasma body is kept and is stopped by timing register until this RF power supply whole 7 seconds.Plasma body has produced the thick silica coating (or specific thickness of in specific examples, being reported) of about 20nm on this pipe inner surface.
After applying, this gas stream is gone back to this vacuum pipeline and is closed this vacuum valve.Then purging valve is opened, made the inside of pipe turn back to normal atmosphere (about 760Torr).Should manage carefully then and from pan straddle 50 assemblies, remove (after pan straddle 50 assemblies are shifted out electrode 160 assemblies).
Be used to form the experimental program of COC syringe cylinder (for example in instance 3,5,11-18,20, using)
From
Figure BDA0000126277010001871
8007-04 cyclic olefine copolymer (COC) resin injection molding syringe cylinder (" COC syringe cylinder "), CV hold assembly 11447 (each have the TV (not comprising female luer) of 2.8ml and delivery volume or the plunger free air delivery of 1ml), female luer type; From German Hoechst AG; Frankfurt am Main can get; Have these sizes: at the total length of about 51mm of cylindrical part; 8.6mm inner injectors tube diameter and the wall thickness of 1.27mm; Have the needle-like hair tubule female luer of moulding integral body 9.5 millimeters long at one end, and be molded near two finger-type flanges the other end.
Be used to SiO x(for example in instance 3,5,18, using) applies the inner experimental program of COC syringe cylinder
Use SiO xApply the inside of the COC syringe cylinder of injection moulding.Modification has the device shown in Fig. 2 of the sealing mechanism of Figure 45, and the bottom that is used for being clamped in the COC syringe cylinder has the COC syringe cylinder of joint packing.In addition, make a lid (shown in Figure 26), the inside of this COC syringe cylinder that allows to find time by the stainless steel female luer and the polypropylene cap of end of this COC syringe cylinder of sealing.
Pan straddle 50 is processed by , has the external diameter of 1.75 inches (44mm) and the height of 1.75 inches (44mm).Pan straddle 50 is incorporated in
Figure BDA0000126277010001882
structure, and this structure allows device to move into and shift out electrode 160.
Electrode 160 is that the copper by the shielding that has
Figure BDA0000126277010001883
becomes.
Figure BDA0000126277010001884
shielding is to come conformal around the outside of copper electrode 160.Electrode 160 measured about 3 inches (76mm) high (the inside) and be that about 0.75 inch (19mm) is wide.The COC syringe cylinder is inserted pan straddle 50, and the bottom is with seal with O ring.
COC syringe bucket is carefully moved to sealing station, and this position and is pushed a copper plasma body net on (static) 1/8-inch (3-mm) diameter brass probe that extends or counter electrode 108.Copper plasma body net is foraminous, cut the copper foil material (K and S Engineering Part #LXMUW5 copper mesh) with the external diameter that is fit to this COC syringe cylinder, and on the throne through serving as abutment surface 494 clampings that are used for the stopper that this COC syringe cylinder inserts.With two copper mesh fit snugly in this brass probe or counter electrode 108 around, to guarantee good electrical contact.
This probe or counter electrode 108 extends the inside of about this COC syringe cylinder of 20mm entering and in its open-ended.Brass probe or counter electrode 108 extend through joint that is positioned at pan straddle 50 bottoms, extend through the bottom construction of pan straddle 50.This brass probe or counter electrode 108 are grounding on the shell of this RF matching network.
Gas delivery port one 10 is connected to the stainless steel assembly, and this assembly comprises
Figure BDA0000126277010001891
joint, a thermopair pressure warning unit and by-pass valve that is connected to the vacuum exhaust pipeline of the manual manipulation ball valve that combination is used to exit.In addition, this gas system is connected to gas delivery port one 10, allows process gas, oxygen and SWS-F 221 (HMDSO) to flow and gets into this COC syringe cylinder inside through gas delivery port one 10 (under processing pressure).
This gas system comprises
Figure BDA0000126277010001892
GFC17 mass flowmeter (U.S. Part#EW-32661-34; Cole-Parmer Instrument Co.; Barrington Illinois) polyetheretherketone (" the PEEK ") kapillary of (it is used for controllably making oxygen to flow into this process with the 90sccm specific flow rates of specific examples (or be used for report)) and a kind of length 49.5 inches (1.26m) (OD1/16 inch (3mm), ID 0.004 inch (0.1mm)).This PEEK capillary end is inserted liquid SWS-F 221 (Alfa
Figure BDA0000126277010001893
parts number L16970, NMR level).Because the pressure in this COC syringe cylinder is lower during handling, this liquid HMDSO is attracted through this kapillary.Then in this exit capillaceous when HMDSO gets into the area of low pressure HMDSO be evaporated into and be steam.
In order to ensure not having liquid HMDSO through this point after; When it did not flow into this COC syringe cylinder inside and is used for through
Figure BDA0000126277010001894
3 logical valves and handles, this gas stream (comprising oxygen) was turned into pumping line.
In case this COC syringe cylinder is mounted, the vacuum pump valve is opened to the inside of pan straddle 50 and this COC syringe cylinder.Alcatel rotary vane vacuum pump and gas blower are formed this vacuum pump system.When process gas flowed with specified speed, this pump system allowed the inside of this COC syringe cylinder to be reduced to the pressure less than 150mTorr.Opposite with this pipe, can reach a lower pumping pressure with the COC syringe cylinder, because this COC syringe cylinder has littler internal volume far away.
Arrive after the base vacuum level, pan straddle 50 assemblies just move in electrode 160 assemblies.This gas stream (oxygen and HMDSO steam) flows into brass gas delivery port one 10 (through adjusting 3 logical valves from pumping line to gas delivery port one 10).Near the capacitance manometer (MKS) the valve of control vacuum through being installed on this pumping line is measured, and this COC syringe cylinder pressure inside is about 200mTorr.Except COC syringe cylinder pressure, use the thermocouple gauge that is connected on this gas system also to measure the internal pressure of this gas delivery port one 10 and gas system.This pressure typically is less than 8Torr.
Inner to this COC syringe cylinder when this gas stream, the RF power supply is opened to its constant power level.Use 600 watts of RF power supplys of ENI ACG-6 (with 13.56MHz) with about 30 watts constant power level.This RF power supply is connected on the automatic adaptation of COMDEL CPMX1000, and this adaptation is complementary the complex impedance of plasma body (remaining in this COC syringe cylinder, to be produced) and 50 ohm of output impedance of ENI ACG-6RF power supply.Forward power is that 30 watts (or to any values that operational instances is reported) and reflective power are 0 watt, makes this power be delivered to the inside of this COC syringe cylinder like this.This RF power supply be control through a laboratory timing register and will be set at 5 seconds conduction time (or certain period of time of reporting to specific examples).
When starting the RF power supply, among the inside of this COC syringe cylinder, set up uniform plasma body.This plasma body is kept whole 5 seconds (perhaps indicated other coating times in particular instance) and is stopped by timing register until this RF power supply.Plasma body has produced the thick silica coating (or thickness of in particular instance, being reported) of about 20nm on this COC syringe cylinder inner surface.
After applying, this gas stream is gone back to this vacuum pipeline and is closed this vacuum valve.Then purging valve is opened, made the inside of this COC syringe cylinder turn back to normal atmosphere (about 760Torr).Then this COC syringe cylinder is removed carefully (after pan straddle 50 assemblies are shifted out electrode 160 assemblies) from pan straddle 50 assemblies.
Be used for applying the inner experimental program of COC syringe cylinder with OMCTS slip coating (for example using) at instance 11,12,15-18,20
With slip coating apply inner, like the COC syringe cylinder of former discriminating.The device modification shown in Fig. 2 that will have the sealing mechanism of Figure 45, the bottom that is used for being clamped in the COC syringe cylinder has the COC syringe cylinder of joint packing.In addition, make a lid (shown in Figure 26) by the stainless steel female luer and the polypropylene cap of the end of this COC syringe cylinder of sealing.The Buna-N O shape circle that is mounted on this female luer allows a vacuum-packed sealing, allows the inside of this COC syringe cylinder to be evacuated.
Pan straddle 50 is processed by
Figure BDA0000126277010001901
, has the external diameter of 1.75 inches (44mm) and the height of 1.75 inches (44mm).Pan straddle 50 is incorporated in
Figure BDA0000126277010001911
structure, and this structure allows device to move into and shift out electrode 160.
Electrode 160 is that the copper by the shielding that has
Figure BDA0000126277010001912
becomes. shielding is to come conformal around the outside of copper electrode 160.Electrode 160 measured about 3 inches (76mm) high (the inside) and be that about 0.75 inch (19mm) is wide.This COC syringe cylinder is inserted pan straddle 50, and the bottom is with
Figure BDA0000126277010001914
seal with O ring of the bottom of the antelabium that centers on these finger-type flanges and this COC syringe cylinder.
COC syringe bucket is carefully moved to sealing station, and this position and is pushed a copper plasma body net on (static) 1/8-inch (3-mm) diameter brass probe that extends or counter electrode 108.Copper plasma body net 610 is foraminous, cut the copper foil material (K and S Engineering Part#LXMUW5 copper mesh) with the external diameter that is fit to this COC syringe cylinder, and on the throne through serving as abutment surface 494 clampings that are used for the stopper that this COC syringe cylinder inserts.With two copper mesh fit snugly in this brass probe or counter electrode 108 around, to guarantee good electrical contact.
This probe or counter electrode 108 extends that about 20mm (except as otherwise noted) get into the inside of this COC syringe cylinder and in its open-ended.Brass probe or counter electrode 108 extend through
Figure BDA0000126277010001915
joint that is positioned at the pan straddle bottom, extend through the bottom construction of pan straddle 50.This brass probe or counter electrode 108 are grounding on the shell of this RF matching network.
Gas delivery port one 10 is connected to the stainless steel assembly, and this assembly comprises
Figure BDA0000126277010001916
joint, a thermopair pressure warning unit and by-pass valve that is connected to the vacuum exhaust pipeline of the manual manipulation ball valve that combination is used to exit.In addition; This gas system is connected to gas delivery port one 10, allows process gas, oxygen and octamethylcyclotetrasiloxane (OMCTS) (or report is used for the special process gas of specific examples) to flow and gets into this COC syringe cylinder inside through gas delivery port one 10 (under processing pressure).
This gas system comprises the mass flow vapo(u)rization system of the Horiba VC1310/SEF8240OMCTS 10SC4CR heating that commerce can get, and heating OMCTS is to about 100 ℃ in this system.PFA pipe coupling to liquid octamethylcyclotetrasiloxane internal diameter, 1/8 inch (3mm) external diameter (Alfa
Figure BDA0000126277010001917
parts number A12540,98%) of this Horiba system through having 1/16 inch (1.5mm).The OMCTS flow velocity is set to 1.25sccm (or report is used for the particular silicone precursor flow rate of specific examples).In order to ensure the OMCTS process this point after that does not have evaporation; When being used in the inside that it does not flow into this COC syringe cylinder through
Figure BDA0000126277010001921
that 3 logical valves are handled, this gas stream (comprising oxygen) is turned into pumping line.
In case this COC syringe cylinder is mounted, the vacuum pump valve is opened to the inside of pan straddle 50 and this COC syringe cylinder.Alcatel rotary vane vacuum pump and gas blower are formed this vacuum pump system.When process gas flowed with specified speed, this pump system allowed the inside of this COC syringe cylinder to be reduced to the pressure less than 100mTorr.Compare with above COC syringe cylinder instance with this pipe, under this situation, can obtain lower pressure, because the overall process gas flow rate is lower in this case.
In case arrive the base vacuum level, pan straddle 50 assemblies just move into electrode 160 assemblies.This gas stream (OMCTS steam) flows into brass gas delivery port one 10 (through adjusting 3 logical valves from pumping line to gas delivery port one 10).As measured through near the capacitance manometer (MKS) the valve of control vacuum that is installed on this pumping line, this COC syringe cylinder pressure inside is about 140mTorr.Except COC syringe cylinder pressure, use the thermocouple gauge that is connected on this gas system also to measure the internal pressure of this gas delivery port one 10 and gas system.This pressure typically is less than 6Torr.
In case this gas stream is inner to this COC syringe cylinder, the RF power supply is opened to its constant power level.Constant power level with about 7.5 watts (perhaps other indicated power levels in particular instance) is used 600 watts of RF power supplys of ENI ACG-6 (with 13.56MHz).This RF power supply is connected on the automatic adaptation of COMDEL CPMX1000, and this adaptation is complementary the complex impedance of plasma body (remaining in this COC syringe cylinder, to be produced) and 50 ohm of output impedance of ENI ACG-6RF power supply.Forward power is that 7.5 watts and reflective power are 0 watt, and such 7.5 watts power (the different power level of perhaps in the instance that provides, sending) is delivered to the inside of this COC syringe cylinder.This RF power supply be control through a laboratory timing register and will be set at 10 seconds conduction time (different time of perhaps in the instance that provides, stating).
When starting the RF power supply, among the inside of this COC syringe cylinder, set up uniform plasma body.This plasma body is kept the whole coating time, is stopped by timing register until this RF power supply.Plasma body produces a slip coating on this COC syringe cylinder inner surface.
After applying, this gas stream is gone back to this vacuum pipeline and is closed this vacuum valve.Then purging valve is opened, made the inside of this COC syringe cylinder turn back to normal atmosphere (about 760Torr).Then this COC syringe cylinder is removed carefully (after pan straddle 50 assemblies are shifted out electrode 160 assemblies) from pan straddle 50 assemblies.
Be used for applying the inner experimental program of COC syringe cylinder with HMDSO coating (for example using) at instance 12,15,16,17
Except replacing OMCTS, be used for applying the inner experimental program of COC syringe cylinder and also be used to apply a HMDSO coating with the OMCTS slip coating with HMDSO.
Instance 1
V. as be used to form described in the experimental program of COC pipe, in following test, SWS-F 221 (HMDSO) is used as the organosilicon (" O-Si ") of the PECVD device that is fed to Fig. 2 to apply a SiO xCoating is to the internal surface of cyclic olefine copolymer (COC) pipe.Be used to SiO xSummarized mode of deposition in experimental program that coated is inner and the table 1.Contrast is the pipe that does not apply the same type of barrier coat.Then test that apply with uncoated pipe, penetrate speed (WVTR) about their oxygen transfer rate (OTR) and their water vapor.
V. reference table 1, and uncoated COC pipe has the OTR in a 0.215cc/ pipe/sky.The average OTR that the pipe A of experience PECVD14 second and B have a 0.0235cc/ pipe/sky.These results illustrate SiO xCoating provides an oxygen transmission BIF who surpasses 9.1 times of uncoated pipes.In other words, SiO xBarrier coat will be reduced to through the oxygen transmission of this pipe less than 1/9th of its value that does not have coating.
V. experience the OTR that 7 seconds pipe C of PECVD has 0.026.This result illustrates SiO xCoating provides an OTR BIF who surpasses 8.3 times of uncoated pipes.In other words, the SiO that in 7 seconds, applies xBarrier coat will be reduced to through the oxygen transmission of this pipe less than 1/8th of its value that does not have coating.
V. also measured a plurality of relevant WVTR of the identical barrier coat that is coated on the COC pipe.Uncoated COC pipe has the WVTR in a 0.27mg/ pipe/sky.Experience 14 seconds pipe A of PECVD and B have a 0.10mg/ pipe/sky or average WVTR still less.7 seconds pipe C of experience PECVD has the WVTR in a 0.10mg/ pipe/sky.This result illustrates SiO xCoating provides above the uncoated about 2.7 times water vapor of pipe and has penetrated barrier improvement factor (WVTR BIF).This is a surprising result, because uncoated COC pipe has had a low-down WVTR.
Instance 2
V. a series of PET pipes are processed according to the experimental program that is used to form the PET pipe, under the condition of table 2 report, according to being used to SiO xThe inner experimental program of coated is used SiO xApply.Contrast is to process according to the experimental program that is used to form the PET pipe, but uncoated.The OTR and the WVTR sample that prepare these pipes through open end to an aluminium adapter of each pipe of epoxy sealing.
In a test that separates, use the PET pipe of the coating of same type, the mechanical scraper that has different lengths with a draw point guiding passes through coated inside, and test OTR BIF.The pipe of the coating of the same type of contrast or scraper uncoated or that do not have guiding.When reducing, this OTR BIF still is modified above uncoated pipe (table 2A).
V. according to the OTR of following testing tube.Each sample/adapter assembly is installed on
Figure BDA0000126277010001941
Oxtran 2/21 oxygen permeability instrument.Under following test condition, allow sample to keep balance to transfer rate steady state (1-3 days):
Test gas: oxygen
Testing gas concentration: 100%
Test gas humidity: 0% relative humidity
Test gas pressure: 760mmHg
Probe temperature: 23.0 ℃ (73.4 ° of F)
Vector gas: 98% nitrogen, 2% hydrogen
Vector gas humidity: 0% relative humidity
V. this OTR is reported as the average of two measured values in the table 2.
V. according to the WVTR of following testing tube.Sample/adapter assembly is installed to Permatran-W 3/31 water vapor permeability instrument.Under following test condition, allow sample to keep balance to transfer rate steady state (1-3 days):
Test gas: water vapour
Testing gas concentration: NA
Test gas humidity: 100% relative humidity
The test gas temperature: 37.8 (℃) 100.0 (° F)
Vector gas: exsiccant nitrogen
Vector gas humidity: 0% relative humidity
This WVTR is reported as the average of two measured values in the table 2.
Instance 3
According to the experimental program that is used to form the COC syringe cylinder, process a series of syringe cylinders.Perhaps use SiO xStop to apply these syringe cylinders, perhaps be not used to SiO xApply under the condition of reporting in the inner experimental program of COC syringe cylinder modification as indicated in table 3.
The OTR and the WVTR sample that prepare these syringe cylinders through open end to an aluminium adapter of each syringe cylinder of epoxy sealing.In addition, with the capillary pipe end of this syringe cylinder of epoxy sealing.To manage OTR or the WVTR that the identical mode of sample is tested these syringe adapter assemblies, reuse
Figure BDA0000126277010001951
Oxtran 2/21 oxygen permeability instrument and Permatran-W 3/31 water vapor permeability instrument with PET.In table 3, reported the result.
Instance 4
Use is used for the plasma-coated formation of x-ray photoelectron spectroscopy (the XPS)/electron spectroscopy of chemical analysis (ESCA), surface analysis and measures
V.A. that will process according to the experimental program that is used to form PET pipe and according to being used to SiO xThe PET pipe that the inner experimental program of coated applies cuts in half to expose the internal surface of pipe, and using x-ray photoelectron spectroscopy (XPS) to analyze then should the surface.
V.A. use quantitative these XPS data of model of a homogeneous layer of the relative sensitivity factor and supposition.This analysis volume is a product of analyzing area (luminous point size or hole size) and information depth.In X ray penetration depth (typically a lot of micron), produce photoelectron, but only detect the photoelectron in three the photoelectron escaped depths in top.Select the rank of the degree of depth at
Figure BDA0000126277010001953
, this causes the analysis depth of
Figure BDA0000126277010001954
approximately.Typically, 95% signal source is in this degree of depth.
V.A. table 5 provides detected atoms of elements ratio.The analytical parameters that is used for XPS is following:
Instrument PHI Quantum 2000
X-ray source Monochromated Alk α1486.6eV
Accept angle ± 23 °
45 ° of emission angle
Analyzed area 600 μ m
Charged correction C1s 284.8eV
Ion gun condition Ar +, 1keV, 2 * 2mm grating
Injection rate (SiO 2Equivalent)
V.A.XPS does not detect hydrogen or helium.For the experiment number (last column) that uses detected element, the value that provides is standardized to Si=1, calculates and instance for uncoated polyethyleneterephthalate, and the value that provides is standardized to O=1.Limit of detection is about 0.05 to 1.0 atomic percent.The value that provides alternately is normalized to the 100%Si+O+C atom.
V.A. instance of the present invention has 2.4 times of indicated SiO xThe Si/O ratio of compsn has the remaining carbon from the incomplete oxidation of coating.This analytical proof be applied to the SiO of polyethyleneterephthalate pipe according to the present invention xThe formation on blocking layer.
V.A. table 4 shows SiO xSample thickness uses the TEM according to following method to confirm.Through using a K575X Emitech application system to be used for focused ion beam (FIB) section gauge with the sample that the platinum (50-100nm is thick) of a jetted layers applies these specimen preparations.The sample of these coatings is placed FEI FIB200FIB system.Through the platinum of an extra play of injection organic metal gas FIB deposition, use the gallium ion beam raster scanning interesting areas of 30kV simultaneously.Select the interesting areas of each sample, be used for being positioned at length half the of this pipe.Measure thin cross section and be about 15 μ m (" micron ") length, 2 μ m are wide and 15 μ m are dark, use proprietary original position FIB lift technique to take out from die surface.Use the sedimentary platinum of FIB that this interface is attached to 200 sieve mesh copper TEM grids.Measurement one or two window in each interface is that about 8 μ m are wide, uses the gallium ion beam of FEI FIB that window is thinned to electron lucent property.
V.C. utilize transmission electron microscope (TEM) to carry out the cross-sectional image analysis of the sample of these preparations.These view data of digital recording.
The sample grid is transferred to a Hitachi HF2000 transmission electron microscope.Obtain the transmitted electron image with suitable ratio of enlargement.Being given in the pertinent instruments of using during the IMAQ below sets.
Figure BDA0000126277010001971
Instance 5
Plasma uniformity
V.A. process the COC syringe cylinder according to the experimental program that is used to form the COC syringe cylinder, use SiO xApply the inner experimental program of COC syringe cylinder and handle this syringe cylinder, have following variation.Syringe cylinder for applying (for example has SiO xFilm 250), test three kinds of different plasma generation patterns.V.A. in pattern 1, in inlet mouth 310, restricted areas 292 and processing vessel inner chamber 304, produce the hollow cathode plasma igniting, and in the remainder of container intracavity 300, produce plasma body common or non-hollow cathode.
V.A. in pattern 2, in restricted areas 292 and processing vessel inner chamber 304, produce the hollow cathode plasma igniting, and in the remainder of container intracavity 300 and inlet mouth 310, produce plasma body common or non-hollow cathode.
V.A. in mode 3, in entire container inner chamber 300 and inlet mouth 310, produce plasma body common or non-hollow cathode.This lights a fire through any hollow cathode of hoisting power to quencher and accomplishes.Table 6 shows the condition that is used to reach these patterns.
V.A. then syringe cylinder 250 is exposed to ru oxide and is infected with technology.This dyestuff is by sodium hypochlorite bleaching agent and Ru (III)The muriate hydrate is processed.With 0.2g Ru (III)The muriate hydrate is put into medicine bottle.Adding 10ml SYNTHETIC OPTICAL WHITNER and thorough mixing dissolves up to Ru (III) muriate hydrate.
V.A. with each syringe cylinder of plastic luer sealing member sealing, and be infected with mixture with 3 and be added into each syringe cylinder.Seal these syringe cylinders and allow to leave standstill 30-40 minute with the aluminium glue band then.In each group syringe cylinder of test, be infected with a uncoated syringe cylinder at least.Restricted areas 292 is faced up store these syringe cylinders.
V.A. be infected with based on this, draw to draw a conclusion:
V.A.1. in 0.25 hour exposure duration, this is infected with and begins to attack uncoated (or applying very poor) zone.
V.A.2. the igniting in restricted areas 292 causes the SiO of restricted areas 292 xCoating.
V.A.3. through perhaps perhaps in restricted areas 292, not using the test of hollow cathode plasma igniting to produce best syringe cylinder at inlet mouth 310.Have only restriction opening 294 to be infected with, most probable is because the seepage of dyestuff.
V.A.4. being infected with is the good qualitative instrument of guiding homogeneity work.
V.A. based on all above contents, we conclude:
V.A.1. under test condition, perhaps cause the very poor homogeneity of this coating at inlet mouth 310 or the hollow cathode plasma in restricted areas 292.
Thereby V.A.2. or at inlet mouth 310 perhaps in restricted areas 292, do not use hollow cathode plasma to reach best homogeneity.
Instance 6
Jamming pattern-predictive instance from reflection measurement
VI.A. the software that uses a UV visible source (Ocean Optics DH2000-BALDeuterium Tungsten 200-1000nm), a fibre optics reflection probe (with about 3mm probe area bonded projector/scoop Ocean Optics QR400-7SR/BX), small detector (Ocean Optics HR4000CG UV-NIR Spectrometer) and the spectrograph signal is converted into the transparence/wavelength graph picture on the notebook computer; Simultaneously around the internal circumference of this pipe and vertically (use emission and collect radially probe from the light of the medullary ray of this pipe along the inwall scanning of this pipe; Therefore perpendicular to the surface that applies) a uncoated PET pipe (Becton Dickinson (U.S. Franklin Lakes; New Jersey) production number 366703; 13 * 75mm; (not having additive)), use this probe to observe the visible jamming pattern.Then as being used to SiO xDescribed in the experimental program of coated inside, with the SiO of 20 nanometer thickness 2Coating applies SiO xBD 366703 pipes (Becton Dickinson production number 366703,13 * 75mm, (not having additive)) of plasma coated.Mode with similar uncoated pipe scans this pipe.Observe jamming pattern clearly with the pipe of this coating, wherein strengthened some wavelength and in circulation pattern, cancelled other wavelength, be illustrated on this PET pipe and have coating.
Instance 7
Enhanced light transmission from the integrating sphere detection
VI.A. the equipment that uses is an xenon light source (Ocean Optics HL-2000-HP-FHSA-20W output halogen lamp source (185-2000nm)), the integrating sphere detector (Ocean Optics ISP-80-8-I) and the HR2000+ES reinforcement sensitivity UV.VIS spectrograph that are used to accept its inside of PET pipe entering through machining; Have light transmission source and optical receiver fibre optics source (QP600-2-UV-VIS-600um Premium optical fiber; UV/VIS, 2m) and signal transform software (SPECTRASUITE-intersection-platform spectroscopy function software).To be inserted on the TEFZEL tube support (disk) according to the uncoated PET pipe that the experimental program that is used to form the PET pipe is processed, and insert this integrating sphere.Use the Spectrasuite software of absorbancy pattern, will absorb (at 615nm) and be set at zero.That to process according to the experimental program that is used to form PET pipe then and according to being used to SiO xThe SiO that the inner experimental program of (except what in table 16, change) coated applies xThe pipe that applies is installed on this disk, inserts integrating sphere and is recorded in the absorbancy of 615nm wavelength.Data are recorded in the table 16.
Use SiO xThe pipe that applies is observed with respect to uncoated article, the increase on absorbing; The coating number of times that increases causes the absorption that increases.This measures the time that spends less than 1 second.
VI.A. the restriction of these spectrographies collection mode that should not be considered to applied (for example reflection contrast transparence contrast absorbancy), frequency or radiation type or other parameters.
Instance 8
Venting about PET is measured
VI.B. adapt from USP 6,584, Figure 15 of 828, what Figure 30 showed is the synoptic diagram of setting the test that is used for operational instances, this operational instances is used for measuring passes through SiO xThe venting of barrier coat 348 is according to being used to SiO xThe inner experimental program of coated applies coating 348, above-mentioned SiO xBe positioned on the inside of wall 346 of PET pipe 358, process PET pipe 358, with generally at 362 indicated this PET pipes of sealing members 360 sealings on the upstream extremity of microfluidic technology measuring cell according to the experimental program that is used to form the PET pipe.
VI.B. a vacuum pump 364 is connected to measuring cell 362 (intelligent gas seepage system that has seepage testing tool model M E2, has s-generation IMFS transmitter that commerce can get; (10 μ/minute whole process); Absolute pressure transducer scope: 0-10Torr, flow measurement is uncertain: reading+/-5%, at calibration range; Employing is used for the Leak-Tek program of ADA (using PC), and the mark of leakage flow/drawing reduced time.By ATC Inc. this equipment is provided) downstream end, and, dispose this vacuum pump and be used for from the inside sucking-off gas of pet container 358 detecting the mass rate of flow that steam that arrow through measuring cell 362 is used for the confirming venting wall from it gets into container 358.
VI.B. be understood that basically by following content work at this measuring cell 362 of describing and illustrate according to diagram that though from the actual use angle of operation and equipment, this information possibly some depart from.Pond 362 has a conical passage 368, guides this bleed flow through this passage.At two lateral aperture of vertically separating 370 and 372 drain pressures, and be fed to the chamber 374 and 376 that part is formed by barrier film 378 and 380 respectively along passage 368.In the chamber 374 and 376 of correspondence the accumulation pressure deflection these corresponding barrier films 378 and 380.Measure these deflections with suitable manner, as through measuring change near electric capacity between the conductive surface of barrier film 378 and 380 and conductive surface (for example 382 and 384).Thereby randomly can provide a bypass 386 through walking around measuring cell 362 the vacuum level that quickens initially to find time up to reaching the hope that is used to test.
The PET wall 350 of the container that VI.B. in this test, uses is in the thick rank of 1mm, and coating 348 is in the thick rank of 20nm (nanometer).Therefore, wall 350 is 50,000 with the thickness ratio of coating 348: 1 rank.
VI.B. in order to confirm flow velocity through measuring cell 362; This pond comprises container seal 360; And Glass Containers that build up to container 358 essentially identical in size with 15 is placed on the container seal 360 continuously; Be pumped to the internal pressure of 1Torr, collect capacitance data and be converted into " venting " flow velocity with measuring cell 362 then.About each container, this test is carried out twice.After carrying out the first time, before proceeding for the second time, allow time of recovery to reaching balance with nitrogen release vacuum and these containers.Because Glass Containers is considered to have very little venting; And the wall through it is impermeable basically; This measurement is understood that to point out at least the amount of the seepage of this container and the connection in measuring cell 362, and if have any real venting or infiltration, reflection is really seldom so.These results are in table 7.
VI.B. the family of the drawing in Figure 31 390 shows independent pipe " venting " flow velocity, also representes with the microgram PM, and this flow velocity is corresponding to the secondary data in the above table of mentioning 7.Because the flow velocity of these drawing does not increase basically in time, and well below the flow velocity shown in other, so this flow velocity should be owing to seepage.
VI.B. the family of table 8 and the drawing in Figure 31 392 illustrates the class likelihood data of uncoated pipe, processes these pipes according to the experimental program that is used to form the PET pipe.
VI.B. these data of uncoated pipe illustrate bigger flow velocity far away: these increase owing on the interior region of wall of container or within the bleed flow of the gas of catching.Between these containers, have some gaps, the fine difference of seeing for these containers and/or they are how to be placed on the test set, and it is the indication of the sensitivity of test.
VI.B. the family of table 9 and the drawing in Figure 31 394 and 396 shows SiO xThe class likelihood data of barrier coat 348 is used SiO according to being used on the inside of the wall 346 that PET manages xApply the inner experimental program of PET pipe and apply coating 348, process this PET pipe according to the experimental program that is used to form the PET pipe.
VI.B. the SiO of this instance xThe family of the curve 394 of PET pipe that apply, injection moulding illustrates SiO xCoating plays and is used for limiting the effect from the barrier of pet container wall venting, because compare with uncoated PET pipe, the flow velocity in this test is lower all the time.(this SiO xCoating self is considered to exit considerably less.) separation between the curve 394 of corresponding container shows that this test is for the SiO of difference on different pipes xThe slightly difference of coating stop that effect is enough responsive.With the variation in the venting between the pet container wall or settle the variation (it has far away the more curve family 392 of sealing) in the integrity opposite, this gap in family 394 is mainly owing at SiO xBe coated with the variation in the air seal degree of interlayer.Like following proof, sample 2 and two curves 396 of 4 are outliers, and they are considered to illustrate the SiO of these pipes from the difference of other data xCoating is defective.This shows this test and can very clearly tell by the sample of different treatment or damage.
VI.B. with reference to more than the table 8 mentioned and 9 and Figure 32, these data of statistical study with find out average and on the average (MV) with under the value of the first and the 3rd standard deviation.These values are plotted among Figure 32.
VI.B. the sample 2 and 4 of the table 9 of the PET pipe that representative applies at first is shown is outlier clearly in this statistical study, departs from average more than+3 times standard deviation.Yet these outliers that illustrate have some and stop effect, because their flow velocity still clearly differentiates (being lower than) with those values of uncoated PET pipe.
VI.B. this statistical study also illustrate be used for very fast and pipe and the uncoated pipe accurately analyzing the barrier coat of nano thickness and be used for distinguishing coating (at this coat-thickness; If end user's sensation, this cup is thought indistinguishable) the ability measured of venting.With reference to Figure 32; Venting level shown in the pet container that applies shown in the bar of top group, has the venting littler than uncoated pet container than average Senior Three times standard deviation; Venting level shown in this uncoated container is than the low three times of standard deviations of average, shown in the bar of low group.These data illustrate for the determinacy level that surpasses 6 σ (six sigma), and data do not have overlapping.
VI.B. based on the success of this test, consideration can detect SiO on these pet containers far away in than the shorter test of this operational instances xThe existence of coating or do not exist is particularly because produce the statistical value of the sample that is used for bigger quantity.This is significantly, for example from sample, even in time T=12 second for 15 containers, and the family of slick, the sharp separation of drawing, representative about one second test time after about T=11 starting point of second.
VI.B. also consider, based on these data, through optimizing SiO xCoating can obtain near glass or equals the SiO of glass xThe pet container that applies stop effect.
Instance 9
The PET pipe instance of wet tension-plasma coated
VII.A.1.a.ii. the wet tension method is the modification of the method for description in ASTM D 2578.Wet tension is for the hydrophobicity on a surface or hydrophilic a kind of specific measuring.This method uses standard wet tension solution (being called dyne solution) to confirm to approach most the solution that a moistening plastics film surface continues two seconds exactly.Here it is film wet tension.
VII.A.1.a.ii. this step of utilizing changes from ASTM D 2578; Wherein these substrates are not the plastics films of putting down, but the pipe of processing according to the experimental program that is used to form the PET pipe and (except contrast) applies according to the experimental program with hydrophobic coating coated inside.Also tested silicone coated glass syringe (with
Figure BDA0000126277010002031
tip Becton? Dickinson
Figure BDA0000126277010002032
PRTC glass prefilled syringes) (1mL).The result of this test lists in the table 10.
Surprisingly; Through changing plasma process conditions, (40 dyne/cm) can reach or the surface of the identical SWS-F 221 of use (HMDSO) feed gas of higher (more hydrophilic) or lower (more hydrophobic) energy the plasma coating of uncoated PET pipe.According to being used to SiO xThin (about 20-40 nanometer) SiO that the inner experimental program of coated is processed xCoating (not shown data in these tables) provides the similar wettability like hydrophilic bulk glass substrate.Provide like the similar non-wettability of hydrophobic siloxanes liquid (in the not shown data of these tables) with thin (less than about 100 nanometers) hydrophobic coating that the inner experimental program of hydrophobic coating coated is processed according to being used for.
Instance 10
Vacuum via the pipe of accelerated deterioration keeps research
The VII.A.3 accelerated deterioration provides identifying sooner of prolonged shelf life product.At USP 5,792,940, the 1 hurdles, the 11-49 line description be used for the accelerated deterioration of the heparin tube that vacuum keeps.
VII.A.3 has tested the pipe of polyethyleneterephthalate (PET) 13 * 75mm (wall that 0.85mm is thick) moulding of three types:
Becton Dickinson production number 36670313 * 75mm (not having additive) manages (545 days or 18 months quality guaranteed period), with
Figure BDA0000126277010002041
system red stopper and uncoloured protection [commercial contrast] sealing;
PET pipe according to the experimental program that is used to form the PET pipe is processed seals with stopper and uncoloured protection that
Figure BDA0000126277010002042
system of same type is red; And
PET 13 * 75mm pipe of injection moulding is processed according to the experimental program that is used to form the PET pipe, according to being used to SiO xThe inner experimental program of coated applies, with same type
Figure BDA0000126277010002043
Stopper that system is red and uncoloured protection [sample of invention] sealing.
VII.A.3 uses the commercial contrast of BD as receiving.The find time sample of internal contrast and invention and cover with blind system and to be used for after sealing, the partial pressure (vacuum) of hope being provided in the inside of pipe.All samples is placed in one the three gallons wide mouth pressurized vessels of (3.8L) 304SS (Sterlitech No.740340).With this pressurized vessel be forced into 48psi (3.3atm, 2482mm.Hg).Move 3-5 sample through (a) in the timed interval that increases; (b) allow water to suck the pipe of finding time through 20 gauge blood collecting adapters, (c) and measured before the water inspiration and to carry out volume of water with quality change afterwards and suck to change and measure from one liter Plastic Bottle holder.
VII.A.3 shows the result on table 11.
VII.A.3 changes the average decay rate divided by supercharging fate and initial mass suction [quality change/(fate x initial mass)] normalized through the time in the quality.Also calculated pick-up period (month number) to 10% loss.Both data are all listed in the table 12.
These data of VII.A.3 show that commercial contrast all has identical vacuum leak speed with uncoated internal contrast, and surprisingly, have improved the vacuum hold-time in conjunction with SiOx coating to PET inwall with 2.1 the factor.
Instance 11
Slip coating
VII.B.1.a. in this test, use following material:
Has
Figure BDA0000126277010002051
tip; (ca1mL) commercial; ( PRTC) glass pre-encapsulated injector
The COC syringe cylinder of processing according to the experimental program that is used to form the COC syringe cylinder;
Commercialization plastic injector plunger (as prefilled brinish syringe, obtaining) with elastomer tips of taking from Becton Dickinson production number 306507;
Normal salts solution (taking from the syringe of Becton-Dickinson production number 306507 prefilled);
Dillon test-bed (model AFG-50N) with advanced ergometer
Syringe rack and draining guide plate (manufacturing is used for installing the Dillon test-bed)
VII.B.1.a. in this test, use following steps.
VII.B.1.a. guide plate is installed on the Dillon test-bed.Adjustment platform probe moves to 6 inch per minute clocks (2.5mm/ second) and sets the upper and lower closed position.Use empty syringe and tube to change these closed positions.Marked articlesization be full of the brinish syringe, remove plunger, and, discharge salts solution via the open end of these syringe cylinders in order to reuse.Obtain extra plunger in an identical manner, be used for using with COC and glass infuser.
VII.B.1.a. that syringe plunger is inserted the COC syringe cylinder, like this second horizontal form point of each plunger in addition with syringe cylinder tip (the about 10mm in end at distance tip) together.Use another syringe and needle assemblies, charge into the salts solution of 2-3 milliliter to the test injection device, keep capillary end the highest via kapillary.Kowtow the side of hitting syringe removing, and carefully any bubble is released syringe, keep the vertical orientation of plunger simultaneously at it at plunger/fluid interface and along the bubble of any size of these walls.
VII.B.1.a. each syringe cylinder/plunger assembly that is full of is installed in the syringe anchor clamps.Through moving towards plunger with the metal hammer of ahead running, thereby begin test by the downward switch that is pressed on the test-bed.In the time of in the metal hammer of motion moves to apart from the top 5mm of contact plunger; Repeatedly kowtow the data button of hitting on the Dillon module and be recorded in the power of depressed time of data button each time, thus from before this syringe plunger initially contacts up to stopping this plunger through contacting with the antetheca of syringe cylinder.
VII.B.1.a. the syringe cylinder of all reference points and coating carries out repeating for five times (reusing new plunger and tube each time).
VII.B.1.a. apply the COC syringe cylinder of processing according to the experimental program that is used to form the COC syringe cylinder with the OMCTS slip coating; Apply the OMCTS coating that the inner experimental program of COC syringe cylinder applies the COC syringe cylinder according to being used for the OMCTS slip coating; Install and be full of salt solution, and as abovely be used for testing as described in the instance of slip coating at this.According to being used for applying Vestolen PP 7052 chamber permission OMCTS steam (and the oxygen that the inner experimental program of COC syringe cylinder uses with the OMCTS slip coating; If add-referring to table 13) flow into Vestolen PP 7052 chamber (though in this instance, in the capillary tube segment of this syringe, possibly not need slip coating) through syringe cylinder and through the syringe kapillary.Test some different coated conditions, as shown in the above table of mentioning 13.On from the COC syringe cylinder of identical production batch, accomplish all depositions.
According to the experimental program of this instance, use the plunger sliding force to test the test of the sample that applies then, the result of generation uses made in Great Britain and metric system unit of force in table 13.For the COC syringe of COC and coating, these data are shown clearly in low power and anaerobic provides minimum plunger sliding force.Notice that when at low power (6W) (lower power is favourable) interpolation oxygen more the plunger sliding force is from 1.09Ib, 0.49Kg (increases to 2.27Ib, 1.03Kg with power=11W).This shows in order to reach minimum possible plunger sliding force, possibly not hope to add oxygen.
VII.B.1.a. be also noted that best plunger sliding force (power=11W; Plunger sliding force=1.09lb, 0.49Kg) very near the present industrial standards of the glass of silicone-coated (plunger sliding force=0.58lb, 0.26Kg), avoided the problem (for example friability and more expensive ME) of glass syringe simultaneously.Use extra optimization, with the present glassy phase ratio with silicone resin performance, expectation reaches the value that is parity with or superiority over.
VII.B.1.a. apply the inner experimental program of COC syringe cylinder according to being used for the OMCTS slip coating, apply these samples through applying the COC syringe cylinder.Alternative embodiment in this technology will be at another film coating (SiO for example x) on apply slip coating, for example according to being used to SiO xApplying the inner experimental program of COC syringe cylinder applies.
Instance 12
Improved syringe cylinder slip coating
VII.B.1.a. the syringe that applies for inwall confirms to use plug made of plastics material to discharge the required power of 0.9 percentage brine of useful load from syringe through the kapillary opening.
VII.B.1.a. tested three types the COC syringe cylinder of processing according to the experimental program that is used to form the COC syringe cylinder: a type does not have coated inside [uncoated contrast]; Another type has the inside coating [HMDSO contrast] of the basic plasma coated of SWS-F 221 (HMDSO); This coating applies the inner experimental program of COC syringe cylinder according to being used for the HMDSO coating; And the 3rd inside coating of type with the basic plasma coated of octamethylcyclotetrasiloxane [OMCTS invents instance], apply this coating according to being used for applying the inner experimental program of COC syringe cylinder with the OMCTS slip coating.Fresh plug made of plastics material with elastomer tips of taking from BD product B ecton-Dickinson production number 306507 is used for all instances.Also use salt solution from production number 306507.
VII.B.1.a., plasma coated scheme and the device that is used to apply the syringe cylinder inwall described in other experimental sections of the application.Be used for the inner experimental program of HMDSO coating coating COC syringe cylinder, be used for having listed the specific coated parameter that is used for HMDSO base and OMCTS base coating with OMCTS slip coating coating COC syringe cylinder inner experimental program and table 14.
VII.B.1.a. plunger is inserted about 10 millimeters of this syringe cylinder, the syringe kapillary through opening is vertically filled the experiment syringe with the brinish syringe/needle system that is full of separately subsequently.When this experiment syringe has been filled in the kapillary opening, kowtow and hit this syringe, and allow their to rise through this kapillary opening with any bubble that adheres to inwall of permission release.
VII.B.1.a. this experiment syringe cylinder/plunger assembly that is full of is vertically placed homemade hollow metal anchor clamps, this injector assembly is supported in the finger-type flange on the anchor clamps.These anchor clamps have the water shoot in the bottom, and are set on the Dillon test-bed with advanced ergometer (model AFG-50N).This test-bed has a metal hammer, moves vertically downward with the speed of six inches (152 millimeters) PMs.The plunger that this metal hammer contact is extended is discharged salts solution through this kapillary.In case this plunger has contacted this syringe cylinder/kapillary interface, stop experiment.
VII.B.1.a. during the plunger of metal hammer/extension moves downward, at be delivered to the resistance this hammer on of record as measuring on this ergometer on the electrical form.From the data of this form, differentiate the power of the maximum of each experiment.
VII.B.1.a. table 14 has been listed for each instance; From the MV of the power of the maximum of the COC syringe cylinder of repetitive coatings, and the power of the standardized maximum confirmed divided by the MV of the power of uncoated maximum of the MV of the power of the maximum through the syringe cylinder that applies.
VII.B.1.a. these data show; The COC syringe cylinder of all OMCTS base inwall plasma coated (invention instance C, E, F, G, H) proves well below the plunger sliding force of uncoated COC syringe cylinder (uncoated case of comparative examples A and D); And surprisingly, equally well below the plunger sliding force of the COC syringe cylinder (HMDSO case of comparative examples B) of HMDSO base inwall plasma coated.More surprisingly, at silicon oxide (SiO x) OMCTS base coating on the gas barrier coating keeps fabulous low plunger sliding force (invention instance F).Best plunger sliding force be instance C (power=8, plunger sliding force=1.1lb, 0.5Kg).Very (plunger sliding force=0.581b 0.26Kg), has avoided the problem (for example friability and more expensive ME) of glass syringe simultaneously near the present industrial standards of the glass of silicone-coated for it.Use extra optimization, with the present glassy phase ratio with silicone resin performance, expectation reaches the value that is parity with or superiority over.
Instance 13
Processing has the instance of the COC syringe cylinder-prophesy of exterior coating
VII.B.1.c. with the disposable COC syringe cylinder that closes at sealed at both ends according to the experimental program formation that is used to form the COC syringe cylinder.The COC syringe cylinder of adding a cover is bathed through 8100 saran latex (Owensboro Specialty Plastics).This latex contains surface tension to 32 dyne/cm that 5 percent Virahol is used for reducing said composition.This latex composition is the outside of moistening this COC syringe cylinder fully.Put do 30 seconds after, the COC syringe cylinder of this coating is exposed to table heat-up time, this timetable is included in 275 ° of F (135 ℃) 25 seconds (latex coalescence) and 122 ° of F (50 ℃) four hours (finishing to solidify) in the corresponding high wind stove.The PvDC film that generates is that 1/10mil (2.5 microns) is thick.Use MOCON board Oxtran 2/21 an oxygen permeability instrument and this COC syringe cylinder of Permatran-W3/31 water vapor permeability apparatus measures and PvDC-COC to laminate the OTR and the WVTR of COC syringe cylinder respectively.
VII.B.1.C. the OTR and the WVTR value of prediction are listed in the table 15, and it shows the stacking material barrier improvement factor (BIF) of expectation with being 4.3 (OTR-BIF) and 3.0 (WVTR-BIF) respectively.
Instance 15
Apply the atomic building of the PECVD of OMCTS and HMDSO coating
VII.B.4. provide according to the experimental program that is used to form the COC syringe cylinder and processed COC syringe cylinder sample, applied with HMDSO with OMCTS coating (according to being used for applying the inner experimental program of COC syringe cylinder) or according to being used for applying the inner experimental program of COC syringe cylinder with the HMDSO coating with the OMCTS slip coating.Use the characteristic of x-ray photoelectron spectroscopy (XPS) expression derived from the atomic building of the coating of OMCTS or HMDSO.
VII.B.4. use the quantitative XPS data of model of the relative sensitivity factor and supposition homogeneous layer.This analysis volume is the product of analyzed area (luminous point size or hole size) and information depth.In X ray penetration depth (typically a lot of micron), produce photoelectron, but only detect the photoelectron in three the photoelectron escaped depths in top.Select the rank of the degree of depth at
Figure BDA0000126277010002091
, this causes the analysis depth of
Figure BDA0000126277010002092
approximately.Typically, 95% signal source is in this degree of depth.
VII.B.4. use following analytical parameters:
Instrument PHI Quantum 2000
X-ray source Monochromated Alk α 1486.6eV
Accept angle ± 23 °
45 ° of emission angle
Analyzed area 600 μ m
Charged correction C1s 284.8eV
Ion gun condition Ar +, 1keV, 2 * 2mm grating
Injection rate
Figure BDA0000126277010002093
/ min (SiO 2Equivalent)
VII.B.4. table 17 provides detected atoms of elements concentration.XPS does not detect hydrogen or helium.Use detected element, the value that provides is standardized to 100%.Limit of detection is about 0.05 to 1.0 atomic percent.
VII.B.4.b. constitute the initial monomers precursor elements per-cent of result and calculating from the coating shown in the table 17; With respect to initial HMDSO free carbon atomic percent, the atomic percent carbon of HMDSO base coating reduces (reducing to 44.4% from 54.1%), surprisingly simultaneously; With respect to OMCTS free carbon atomic percent; OMCTS base coating atomic percent carbon increases (rising to 48.4% from 34.8%), has increased by 39 atom %, calculates as follows:
100% [(48.4/34.8)-1]=39 atom %.
And; With respect to initial HMDSO monomer atomic percent silicon; When the atomic percent silicon of HMDSO base coating does not almost change (21.8% to 22.2%), surprisingly, with respect to OMCTS monomer atomic percent silicon; OMCTS base coating atomic percent silicon significantly reduces (42.0% reduces to 23.6%), has reduced by 44 atom %.Carbon and silicon all change, and apply the OMCTS monomer of behavior and observed trend and inequality in common precursor monomer (for example HMDSO).Referring to for example Hans J.Griesser, Ronald C.Chatelier, Chris Martin, Zoran R.Vasic, Thomas R.Gengenbach, George Jessup J.Biomed.Mater.Res. (Appl Biomater) 53:235-243,2000.
Instance 16
From plasma-coated volatile constituent (" venting ")
VII.B.4. provide according to the experimental program that is used to form the COC syringe cylinder and processed COC syringe cylinder sample, applied (according to being used for applying the inner experimental program of COC syringe cylinder) or apply (according to being used for applying the inner experimental program of COC syringe cylinder) with the HMDSO coating with HMDSO with the OMCTS slip coating with OMCTS.Use venting vapor-phase chromatography/mass spectrum (GC/MS) analysis to measure from the volatile matter of OMCTS or HMDSO coating.
VII.B.4. syringe cylinder sample (four COC syringe cylinders that the length aspect cuts in half) is placed 1 of dynamic head space sampling system (CDS 8400 automatic samplers) 1/ 2" (37mm) in the chamber of diameter.Before sample analysis, analytical system is blank.Analytic sample on Agilent7890A gas chromatograph/Agilent 5975 mass spectrographs uses following parameter, in table 18, has showed the data that produce:
GC post: 30m X 0.25mm DB-5MS (J and W Scientific),
0.25 the film thickness of micron
Flow velocity: 1.0ml/ minute, constant current mode
Detector: mass selective detector (MSD)
Injection pattern: shunting injection (10: 1 splitting ratios)
Venting condition: 1 1/ 2 " (37mm) chamber was cleaned flow rate 60ml/ minute three hours at 85 ℃
Furnace temperature: 40 ℃ (5 minutes) are warming up to 300 ℃ with 10 ℃/minute; Kept 5 minutes at 300C.
Clearly be illustrated in the HMDSO base and the difference of the formation between the OMCTS base lubricating coat of test from the venting result of table 18.HMDSO compsn venting trimethyl silanol [(Me) 3SiOH], do not contain repetition-(Me) and do not exit 2The higher oligomers of the measurement of SiO-part, the OMCTS based composition and use thereof in packaging is not exitted trimethyl silanol [(Me) simultaneously 3SiOH], and venting contains repetition-(Me) 2The higher oligomers of SiO-part.Consider that this test maybe be useful for difference HMDSO base coating and OMCTS base coating.
There are not scope or accuracy limit the present invention according to following theory; Consider that this result can explain through the ring structure of considering OMCTS; Have only two methyl groups to be connected to each Siliciumatom, with respect to the non-annularity structure of HMDSO, wherein each Siliciumatom connects three methyl groups.Consideration through ring opening OMCTS react form have repetition-(Me) 2The divalent group of SiO-part, this has been an oligopolymer, and can condensation to form higher oligomers.On the other hand, consider that HMDSO contains just like (Me) through cutting an O-Si key reaction, staying 3A fragment of single O-Si key of the same condensation again of SiOH, and do not contain just like [(Me) 3Si] 2The same other fragments of the O-Si key of condensation again.
The character of the ring of OMCTS is considered to cause ring opening and these to have the open loop condensation partly of the venting of senior MW oligopolymer (26ng/ test).On the contrary, HMDSO base coating is considered to not provide any higher oligomers, based on the fragment from the lower molecular weight of HMDSO.
Instance 17
Use the plasma-coated density measurement of X ray reflection rate (XRR)
(0.5 * 0.5 * 0.1cm) pastes the inwall of PET pipe separately, processes these pipes according to the experimental program that is used to form the PET pipe with sapphire evidence sample.Apply the PET pipe (all apply the inner experimental program of COC syringe cylinder with the OMCTS slip coating, all depart from) that contains the sapphire evidence with 2x power according to being used for OMCTS or HMDSO.Remove the sapphire samples of coating then and on a PANalytical X ' Pert diffractometer that is equipped with parabolic multilayer incident light monochromator and parallel plate diffracted beam collimator, obtain X ray reflection rate (XRR) data.Use two-layer Si wO xC yH zModel is confirmed the coating density from the critical angle measuring result.Considering provides separation real Si with this model wO xC yH zThe best approach of coating.In these results shown in the table 19.
From the result of the instance shown in the table 17 15, to compare with HMDSO, the lower oxygen (28%) of OMCTS and higher carbon (48.4%) constitute should have lower density, owing to atomic mass reason and valency (oxygen=2; Carbon=4).Surprisingly, XRR density result shows that is exactly that OMCTS density is higher than HMDSO density with observing opposite result.
Not according to scope or accuracy limit the present invention of following theory, consider in forming corresponding HMDSO base and OMCTS base coating, in reaction mechanism, there is basic difference.The HMDSO fragment maybe be more easily nucleation or reaction to form intensive nano particle, then these particle depositions from the teeth outwards and further reaction from the teeth outwards, and OMCTS very more can not form intensive gas phase nano particle.The condensation very more from the teeth outwards of OMCTS active ingredient more to be similar to the monomeric form of initial OMCTS far away, causes overall more not intensive coating.
Instance 18
The thickness evenness of the coating that PECVD applies
To sample the COC syringe cylinder of processing according to the experimental program that is used to form the COC syringe cylinder is provided, and respectively according to being used to SiO xApply the inner experimental program of COC syringe cylinder and use SiO xApply, perhaps apply with the OMCTS base lubricating coat according to being used for applying the inner experimental program of COC syringe cylinder with the OMCTS slip coating.Return sample the PET that processes according to the experimental program that is used to form the PET pipe is provided pipe, respectively according to being used to SiO xThe inner experimental program of coated applies or does not apply, and experience accelerated deterioration experiment.Use transmission electron microscopy (TEM) to measure the thickness of the coating that PECVD applies on these samples.Use the TEM step of the instance 4 of above statement.Through the SiO that in this instance, uses xThe method and apparatus of describing with the slip coating experimental program has proved as at the uniform coating shown in the table 20.
Instance 19
Venting on COC is measured
VI.B. process the COC pipe according to the experimental program that is used to form the COC pipe.Some pipes provide according to being used to SiO xThe SiO of the experimental program that coated is inner xInner barrier coat, and uncoated other COC pipes.Also as more than the heparin tube of the commercialization Becton Dickinson 13x75mm glass with similar size is provided.In the room of the ambient air that contains 45% relative humidity and 70 ° of F (21 ℃), store about 15 minutes of this pipe, and carry out following test with equivalent environment relative humidity.According to ATC miniflow measuring process and with equipment (intelligent gas seepage system that has seepage testing tool model M E2, has s-generation IMFS transmitter of instance 8; (10 μ/minute gamut); Certificate is to pressure transmitter scope: 0-10Torr; Flow-rate measurement is uncertain: reading+/-5%, at calibration range, be used for the Leak-Tek program (using PC) of automaticdata data gathering and the mark/drawing of leakage flow relative time) test the venting of this pipe.Under this situation, 22 second the body moisture steps of exhausting of each pipe experience under the pressure of 1mm Hg, with nitrogen pressure 2 seconds (to 760 mm Hg), emptying nitrogen then, and under 1 mm Hg pressure, carried out the miniflow measuring process about 1 minute.
VI.B., the result has been shown in Figure 57, and this is similar to the Figure 31 that in instance 8, produces.In Figure 57, the drawing of uncoated COC pipe is 630, SiO xThe drawing of the COC pipe that applies is 632, and with the drawing of the Glass tubing that compares 634.Once more, in the time of about 4 seconds, begin venting and measure, and after several second, the drawing 630 and the SiO of uncoated COC pipe xDrawing 632 bifurcated clearly that stops the pipe of coating, proof stops the pipe of coating and the rapid difference between the uncoated pipe once more.Recognize uncoated COC (60 seconds time＞2 micrograms) and SiO xThe separation of the unanimity that the COC that applies (in the time of 60 seconds less than 1.6 micrograms) compares.
Instance 20
Slip coating
VII.B.1.a. use slip coating (according to being used for applying the inner experimental program of COC syringe cylinder) to apply COC syringe cylinder (experimental program according to being used to form the COC syringe cylinder is processed) with the OMCTS slip coating.These results in table 21, have been offered.These results show under oxygen-free situation, increase the trend of power level, increase to 14 watts to improve the oilness of coating from 8 watts.Further experiment with power and flow velocity can provide the further enhancing of oilness.
Instance 21
The instance of slip coating-supposition
Process cyclic olefine copolymer (COC) the plastic injector tube of injection moulding according to the experimental program that is used to form the COC syringe cylinder.Some uncoated (" contrasts ") and other carry out the lubricated coating of PECVD (" lubricated syringe ") according to being used for applying the inner experimental program of COC syringe cylinder with the OMCTS slip coating.Use the automatic injection device power tstr of a Genesis packing, the lubricated syringe of model AST test is measured the power (starting force) that causes the motion of plunger in this with contrast, and the power (plunger sliding force) that keeps plunger in this, to move.
This test is the revision of ISO 7886-1:1993 test.Following steps are used for each test.Shift out fresh plug made of plastics material (as prefilled brinish syringe, obtaining) with elastomer tips of taking from Becton Dickinson production number 306507 from injector assembly.This elastomer tips of compressed air drying with clean dry.Then elastomer tips is inserted the COC syringe cylinder, will test with the plunger of placing, even test with the bottom of syringe cylinder.As needing, regulate the syringe that is full of then to reaching with state to be tested.For example, if test target is find to store this syringe after three months,, so just store these syringes three months to reach the state of hope about the effect of the slip coating of the starting force of syringe.
Syringe is installed into the specification sheets of the automatic injection device power tstr of Genesis packing according to manufacturers, when beginning this test, calibrates this tstr.This tstr input variable is speed=100mm/ minute, scope=10,000.On this tstr, press start button.Accomplishing should test the time, to measure starting force (in this tube, move) and plunger sliding force (being used for keeping moving), and be found in the data that contrast syringe and compare to cause plunger, the data of the syringe that lubricates are lower basically.
Figure 59 shows the container processing systems 20 according to an exemplary embodiment of the present invention.Container processing systems 20 especially comprises, one first treatment station 5501 and one second treatment station 5502.Instance for this type of treatment station is the reference number 24,26,28,30,32 and 34 that for example is described among Fig. 1.
Described heparin tube 80 though first container processing systems 5501 contains pan straddle 38. Figure 59 of the container 80 that grips, this container can be a syringe body, medicine bottle or transfer pipet for example.For example this container can be processed by glass or plastics.Under the situation of plastic containers, this first treatment station can also comprise that a mould is used for these plastic containers of moulding.
First treatment station is first handle after (current processing can comprise that container molding, initial examination container are damaged, the internal surface of coating container and check container damaged (particularly coated inside) for the second time), pan straddle 38 is transported to the second container treatment station 5502 with container 82.Arrange that through transfer roller 70,72,74 transport.For example, thus can provide a clamp or some clamps to be used to clamp this pan straddle 38 and/or container 80 moves to next treatment station 5502 with this container/holder combination.Alternately, can only move this container and not move this support.Yet, maybe be advantageously this support be moved with this container, in this case, thereby this support is made it to be arranged by this transfer roller to transport by adaptive.
Figure 60 shows the container processing systems 20 according to another exemplary embodiment of the present invention.Once more, two container treatment station 5501,5502 are provided.In addition, extra container treatment station 5503,5504 is provided, they have been arranged in order, and can processing vessel in them, promptly check and/or apply.
Can container be moved to left treatment station 5504 from a kind of raw material.Alternately, can container molding at first treatment station 5504.Under any circumstance, one first container is handled and in treatment station 5504, is carried out, and like moulding, inspection and/or coating, after it, can carry out one second inspection.Then, container is arranged that via transfer roller 70,72,74 move to next treatment station 5501.Typically, this container moves with this pan straddle.One second processing is carried out in second treatment station 5501, and thereafter, this container and support are moved in the next treatment station 5502, carry out one the 3rd processing here.Then this container is moved (once more with this support) and be used for one the reason everywhere in the 4th treatment station 5503, it is transported in the storer thereafter.
Before the step of each coating step or forming step or any other operation vessel,, can once check, check whole container, part container and particularly inner surface of container with afterwards.Via DB 5507, can the result who check each time be passed to central processing unit 5505.Each treatment station is connected to DB 5507.Treater 5505, the form that it can be adapted to be central authorities' control and regulate unit is handled the inspection data, analyzes these data and is confirmed whether last treatment step is successful.
If confirm that the treatment step after the group is not successful; Because for example coating comprises that hole is rule or level and smooth inadequately because confirm the surface of coating perhaps; Container can not get into next treatment station so; But or from this production technique, shift out (referring to transfer roller station 7001,7002,7003,7004), perhaps carry and go back to handle again.
Treater 5505 is connected to user interface 5505, is used for input control or adjusting parameter.
Figure 61 shows the container treatment station 5501 according to exemplary embodiment of the present invention.This station comprises that a PECVD device 5701 is used to apply an internal surface of this container.In addition, provide plurality of detection device 5702-5707 to be used for container inspection.This type of detector can for example be to be used to carry out electrometric electrode, photodetector, like CCD photographic camera, gas detector or pressure detector.
Figure 62 shows the pan straddle 38 according to an exemplary embodiment of the present invention, illustrates with plurality of detection device 5702,5703,5704 and electrode with gas input port 108,110.
Be placed in 38 last times of support at container, electrode and detector 5702 can be adapted for the internal space that moves into container 80.
During coating step, can carry out optical check especially, for example under the help of the fluorescence detector outside the container that is arranged in arrangement 80 5703,5704, perhaps even under the help of the fluorescence detector in the internal space that is arranged in container 80 5705.
These detectors can comprise color filter, during coating procedure, can detect different wavelengths like this.This processing unit 5505 is analyzed optical datas and is confirmed that whether this apply successfully the determinacy of a predeterminated level.If confirm to apply most possible unsuccessful, then the container of correspondence is separated from this treatment system or handle again.
Though the present invention's quilt diagram and description in detail in accompanying drawing and above-mentioned explanation, these diagrams will be considered to illustrative or exemplary with explanation, rather than restrictive; The present invention is not limited to the embodiment that disclosed.Through studying these accompanying drawings, disclosure and appending claims, those of ordinary skill in the art and the personnel that putting into practice the claim that the present invention proposes are appreciated that and carry out other changes for the embodiment that is disclosed.In these claims, word " comprises " does not get rid of other key elements or step, and indefinite article " " or " a kind of " do not get rid of a plurality of.Only fact is, some measure of in the dependent claims that differs from one another, quoting as proof does not show that the combination of these measures can not be used for producing advantage.Should not to be interpreted as be to limit its scope to any reference symbol in claim.
Table 1: the OTR and the WVTR of the COC pipe of coating measure
Figure BDA0000126277010002171
Table 2: the OTR and the WVTR of the PET pipe of coating measure
Figure BDA0000126277010002172
Table 2 is continuous
Figure BDA0000126277010002181
Table 2A. has the OTR of PET pipe of the coating of mechanical scratch defect
Figure BDA0000126277010002182
* two pipes is average
Table 4: through the SiO of TEM detection xCoat-thickness (nanometer)
Figure BDA0000126277010002201
Table 5: detected atoms of elements ratio (in bracket, use the per-cent indicated concentration, be normalized to 100% detected element)
Figure BDA0000126277010002202
Table 6: the scope of hollow cathode plasma igniting
Table 7: the flow velocity that uses Glass tubing
Figure BDA0000126277010002211
Table 8: the flow velocity that uses the PET pipe
Figure BDA0000126277010002221
Table 9:SiO xThe flow velocity of the PET pipe that applies
Figure BDA0000126277010002231
Table 10: the wet tension with uncoated pipe coating is measured
Figure BDA0000126277010002241
Table 11: suction quality (gram)
Table 12: the standardized average-volume decay rate of calculating and to time of 10% VOLUME LOSS
Figure BDA0000126277010002243
Table 13: have the syringe cylinder of slip coating, English unit
Figure BDA0000126277010002251
Table 13: have the syringe cylinder of slip coating, metric unit
Figure BDA0000126277010002261
Figure BDA0000126277010002271
Table 15:OTR and WVTR measure (prophesy)
Figure BDA0000126277010002281
Table 16.SiO xThe optical absorption of the PET pipe that applies (being normalized to uncoated PET pipe)
Figure BDA0000126277010002282
Table 17: atomic percent (in bracket: precentagewise is normalized to 100% detected element)
Figure BDA0000126277010002283
Table 18: from the volatile matter of syringe cylinder
Figure BDA0000126277010002291
Table 19: from the plasma coating density of XRR mensuration
Figure BDA0000126277010002292
Table 20: through the PECVD coat-thickness of TEM
Figure BDA0000126277010002301
Table 21:OMCTS slip coating performance (English unit)
Figure BDA0000126277010002302
* 4 multiple are average
Table 21:OMCTS slip coating performance (metric unit)
Above power measurement is the MV of 4 samples.
In below listing,, exemplary embodiment of the present invention has been described for example with reference to Figure 59 to 62.Though, should be noted that following being meant exemplary embodiment and not being meant claims of listing at following middle term " claim " or " omnibus claims of listing " of having used.
I has the container processing systems of a plurality of treatment station and a plurality of pan straddles
1. container processing systems 20 comprises:
One first treatment station 5501,24,26,28,30, this first treatment station are arranged to be handled the container that has an opening and define a wall of an inner surface;
One second treatment station 5502,24,26,28,30, this second treatment station and this first treatment station are spaced apart and be arranged to the container that has an opening and define a wall of an inner surface is handled;
A plurality of pan straddles 38; Each pan straddle comprises a container port 92, and the opening that this container port is arranged to a reception and a fixing container is used for through the container port that is positioned at this first treatment station the inner surface of a fixed container being handled; And
A handling machinery 70,72,74, this transfer roller are used for that a series of pan straddles and fixed container are transported to this second treatment station from this first treatment station and are used for through the container port that is positioned at this second treatment station the inner surface of a fixed container being handled.
2. invention as claimed in claim 1; Further comprise one the 3rd treatment station 5503; The 3rd treatment station and this first and second treatment station are spaced apart, and are configured to be used for the container that has an opening and define a wall of an inner surface is handled (referring to for example Figure 60).
3. invention as claimed in claim 2, wherein this transfer roller is configured to be used for that a series of pan straddles and the container of taking a seat are transported to the 3rd treatment station from this second treatment station and is used for via the container port that is positioned at the 3rd treatment station the inner surface of a container of taking a seat being handled.
4. like each described invention of claim 1 to 3, wherein one or more pan straddles further comprise a vacuum pipe, and this vacuum pipe is used for from being seated at the container withdrawing gas on one or more container ports.
5. like each described invention of claim 1 to 4, wherein one or more pan straddles further are included in the vacuum ports of a connection between an external vacuum source of this vacuum pipe and vacuum.
6. like each described invention of claim 1 to 5, wherein one or more vacuum ports have an O type circle to receive and to be formed on a sealing on the external vacuum source.
7. like each described invention of claim 1 to 6; Wherein one or more pan straddles further comprise a gas input port, and this gas input port is used for a kind of gas delivery entering is seated at a container on one or more container ports.
8. like each described invention of claim 1 to 7; Wherein one or more pan straddles further comprise a composite gas input port and the vacuum ports that is connected with one or more container ports, and these ports are used for a kind of gas delivery is got into the container that is seated on one or more container ports and from wherein extracting a kind of gas out accordingly.
9. make by thermoplastic material like each wherein one or more pan straddles of described invention of claim 1 to 8.
10. like each described invention of claim 1 to 9, wherein one or more container ports have a sealing element that is used to receive and form a sealing in this vessel port.
10a invention as claimed in claim 10, wherein the sealing element is an O type circle.
11. like claim 1 each described invention to 10a, one of them treatment station is configured to defective the inner surface of a container is checked.
12. like each described invention of claim 1 to 11, one of them treatment station is configured to a coating is applied on the inner surface of a container.
13. like each described invention of claim 1 to 12, one of them treatment station is configured to defective a coating is checked.
14. like each described invention of claim 1 to 13, one of them treatment station is configured to the atmospheric pressure lost of measuring through a wall of container.
15. like each described invention of claim 1 to 14, one of them treatment station comprises an area supported, this area supported is used for supporting one or more pan straddles in the predetermined position, handles the inner surface at the container of taking a seat of this treatment station simultaneously.
16. each described invention like claim 1 to 15; Wherein another treatment station comprises one second area supported; This second area supported is used for supporting one or more pan straddles in the predetermined position, handles the inner surface at the container of taking a seat of other treatment station simultaneously.
17. each described invention like claim 1 to 16; Wherein another treatment station comprises one the 3rd area supported; The 3rd area supported is used for supporting one or more pan straddles in the predetermined position, simultaneously via the inner surface of handling this container of taking a seat at one or more container ports of other treatment station.
18. each the described invention like claim 1 to 17 further comprises one the 3rd treatment station, the 3rd treatment station and this first and second treatment station be spaced apart to be used to handle a plurality of containers.
19. invention as claimed in claim 18 further comprises one the 4th treatment station, the 4th treatment station and this first, second and the 3rd treatment station is spaced apart is used to handle a plurality of containers.
20. invention as claimed in claim 19 further comprises one the 5th treatment station, the 5th treatment station and this first, second, third and the 4th treatment station be spaced apart to be used to handle a plurality of containers.
21. invention as claimed in claim 20 further comprises one the 6th treatment station, the 6th treatment station and this first, second, third, fourth and the 5th treatment station be spaced apart to be used to handle a plurality of containers.
22. each the described invention like claim 1 to 21 further comprises a transfer roller, this transfer roller is used for the one or more pan straddles and the container of taking a seat are transported to the 3rd treatment station from this second treatment station.
23. invention as claimed in claim 22 further comprises a transfer roller, this transfer roller is used for the one or more pan straddles and the container of taking a seat are transported to the 4th treatment station from the 3rd treatment station.
24. each the described invention like claim 1 to 23 further comprises a transfer roller, this transfer roller is used for the one or more pan straddles and the container of taking a seat are transported to the 5th treatment station from the 4th treatment station.
25. each the described invention like claim 1 to 24 further comprises a transfer roller, this transfer roller is used for the one or more pan straddles and the container of taking a seat are transported to the 6th treatment station from this May 4th treatment station.
26. each the described invention like claim 1 to 25 further comprises a spreader, this spreader is used on the inside of a container, forming a coating via the one or more container ports at a treatment station.
27. like each described invention of claim 1 to 26, one of them treatment station comprises the PECVD device.
28. invention as claimed in claim 27, wherein this PECVD device comprises:
An interior electrode, electrode is positioned to wait that the inside that is received as and is seated at a container on the pan straddle is in fluid connection in this;
An outer electrode, this outer electrode have an internal portion, and this internal portion is positioned and is seated at a container on this pan straddle with reception;
A power supply, this power supply is input in these on the electrode and outer electrode alternating-current within the container that is seated on this pan straddle, to form plasma body;
A vacuum source, this vacuum source is used for the inner pumping with container, and this container defines a Vakuumkammer;
A reactant gas source; And
A gas feed device, this gas feed device is fed into a kind of reactant gas the container that is seated on this pan straddle from this reactant gas source.
29. invention as claimed in claim 28 wherein should extend in this container by interior electrode.
30. invention as claimed in claim 28, electrode is positioned in the outside of this container in wherein being somebody's turn to do.
31., wherein should be positioned within this pan straddle by interior electrode like claim 28 or 30 described inventions.
32. invention as claimed in claim 28 should interior electrode be a probe with a distal portions wherein, this distal portions is positioned roughly to extend into concentrically in the container that is seated on this pan straddle.
33. like claim 28 or 32 described inventions, this gas feed device distal portions that is electrode in this wherein.
34. like claim 28,32 or 33 described inventions, further comprise a reactant gas source and in this passage within electrode, this passage is used for this reactant gas is delivered to from this reactant gas source the distal portions of electrode in this.
35. invention as claimed in claim 34, the distal portions of electrode comprises a long and narrow porous sidewall in wherein being somebody's turn to do, and this sidewall is centered around the passage within electrode in this, and this passage is used for laterally discharging from this passage at least a portion of this reactant gas.
36. invention as claimed in claim 35, wherein should in the external diameter of electrode be equivalent to this container the contiguous internal diameter of side direction at least 50%.
37. invention as claimed in claim 35, wherein should in the external diameter of electrode be equivalent to this container the contiguous internal diameter of side direction at least 60%.
38. invention as claimed in claim 35, wherein should in the external diameter of electrode be equivalent to this container the contiguous internal diameter of side direction at least 70%.
39. invention as claimed in claim 35, wherein should in the external diameter of electrode be equivalent to this container the contiguous internal diameter of side direction at least 80%.
40. invention as claimed in claim 35, wherein should in the external diameter of electrode be equivalent to this container the contiguous internal diameter of side direction at least 90%.
41. invention as claimed in claim 35, wherein should in the external diameter of electrode be equivalent to this container the contiguous internal diameter of side direction at least 95%.
42. like each described invention of claim 28 to 34, further comprise a carrier gas source and in this passage within electrode, this passage is used for this carrier gas is delivered to from this carrier gas source the distal portions of electrode in this.
43. like each described invention of claim 28 to 42, further comprise an interior electrode stretcher and retractor, be used for removing with electrode this pan straddle of insertion in this and from it.
44. like each described invention of claim 28 to 43, further comprise an array of at least two interior electrodes, wherein should in electrode stretcher and retractor be configured to be used for remove with interior electrode this pan straddle of insertion of this array and from it.
45. invention as claimed in claim 44, electrode moved between with respect to the position of propelling fully, mid-way and the retracted position of pan straddle in electrode stretcher and retractor were configured to be used to make in wherein being somebody's turn to do.
46. like claim 44 or 45 described inventions; Further comprise an interior electrode driver that can be operatively connected with this interior electrode stretcher and retractor; This driving mechanism is used for electrode in first moved to from its extended position its retracted position; Replace this first interior electrode with a second inner electrode, and advance the extended position of this second inner electrode to it.
47. like claim 28,32,33,34 or 42 described inventions, wherein this outer electrode be substantial cylindrical and be positioned roughly to extend concentrically around being seated at container on this pan straddle.
48. like each described invention of claim 28 to 47, wherein this outer electrode comprises an end cap.
49. invention as claimed in claim 48 is wherein at this end cap and to be seated at the gap that is limited between the far-end of a container on this pan straddle be basically identical.
50. like each described invention of claim 28 to 49, wherein at this outer electrode and to be seated at the gap that is limited between the container on this pan straddle be basically identical.
51. each the described invention like claim 1 to 50 further comprises a detector, this detector is configured to via the one or more container ports at a treatment station and is inserted into the situation that is used to detect this internal tank surface in this container.
52. each the described invention like claim 1 to 51 further comprises a kind of detector, this detector is positioned on the treatment station of this external container.
53. each the described invention like claim 1 to 52 further comprises a kind of energy that is positioned at a treatment station, this treatment station be used for guiding energy inwardly through this wall of container and internal tank surface to detect through detector.
54. each described invention like claim 1 to 53; Further comprise a kind of energy that is positioned at a treatment station, this treatment station is used for energy is directed on the wall of container and reflects the energy one of at least of a coating and this wall surface on this wall surface.
55. each the described invention like claim 1 to 54 further comprises a kind of energy that is positioned at a treatment station, this treatment station be used for guiding energy outwards through this wall of container and internal tank surface to detect through detector.
56. each the described invention like claim 1 to 55 comprises a kind of energy, this energy is arranged to via a vessel port and inserts in the container.
57. like each described invention of claim 51 to 56, wherein this detector is configured to be used to detect the situation on the internal tank surface of the lip-deep position at a plurality of tight spacings of this internal tank.
58. like each described invention of claim 51 to 57, wherein this detector is positioned to receive the energy from this energy.
59. like each described invention of claim 1 to 58, further be included in a collector of a treatment station, be used for after the inner surface of the container of taking a seat of this second treatment station, this container being removed from one or more pan straddles in processing.
II.VESSEL?HOLDERS
II.A. pan straddle
60. a carry-case support is used for when container is handled, keeping and carrying the container with an opening, this pan straddle comprises:
A container port, this container port are configured to be used for the relation that interconnects a vessel port is taken a seat;
One second port, this second port are configured to and receive extraneous gas supply or ventage;
A pipeline, this pipeline are used to make one or more gases between the vessel port and this second port that are seated on this container port, to pass through; And
Can carry housing for one, this container port, second port and pipeline are attached on it with the relation of inflexible in fact.
The weight of this carry-case support is less than five pounds.
II.B
61. a carry-case support is used for when container is handled, keeping and carrying the container with an opening, this pan straddle comprises:
A container port, this container port are configured to be used for receive a vessel port with relation sealing, that interconnect;
A vacuum pipe is used for via this container port from being seated at a container withdrawing gas on this container port;
A vacuum ports, this vacuum ports are configured between this vacuum pipe and the external vacuum source and are communicated with; And
Can carry housing for one, this container port, vacuum pipe and vacuum ports are attached on it with the relation of inflexible in fact;
The weight of this carry-case support is less than five pounds.
62. invention as claimed in claim 61, wherein this container port has a sealing element that receives a vessel port and form a sealing above that.
62a invention as claimed in claim 61, wherein the sealing element is an O type circle.
63. like claim 61 each described invention to 62a, wherein this vacuum ports has an O type circle that receives an external vacuum source and form a sealing above that.
64. like each described invention of claim 61 to 63, wherein this gas input port has an O type circle that receives an inlet mouth and form a sealing above that.
65. each described invention like claim 61 to 64; Wherein thereby this vacuum ports is further disposed and is worked as a gas input port that is communicated with this container port, is used for a kind of gas delivery to a container that is seated on this container port.
66. like each described invention of claim 61 to 65, wherein this housing is processed by thermoplastic material.
67. each described invention like claim 61 to 66; Further comprise a gas input port, this gas input port is attached to this in fact rigidly and can carries on the housing and be configured to be used for a kind of gas delivery to a container that is seated on this container port.
II.C. comprise the pan straddle that sealing is arranged.
68. a pan straddle is used to be received in a near opening end of the container of the wall that has a substantial cylindrical its opening end, comprising:
The internal surface of a substantial cylindrical, this internal surface are made into a certain size cylindrical wall that is used to receive this container;
Be arranged in the internal surface of this substantial cylindrical and co-axial with it one first annular recesses, this first annular recesses has an opening and separates with the inner surface radial direction of this substantial cylindrical on the internal surface of this substantial cylindrical a diapire; And
One first sealing element; This first sealing element be disposed in this first annular recesses and with respect to this O type circle of this first annular recesses be made into a certain size be used for normally extending radially through this opening and by by the container that internal surface received of this substantial cylindrical radially to external pressure, thereby between the diapire of this container and this first annular recesses, form a sealing.
68a. like the described container of claim 68, wherein the sealing element is an O type circle.
69. like the described pan straddle of claim 68, further comprising can be with near an opening end butt joint bearing that radially extends the internal surface of this substantial cylindrical above that of this container.
70. like claim 68 or 69 described pan straddles; Further comprise first upper side wall and lower wall; These sidewalls are disposed between the opening and diapire of this first annular recesses; When an O type circle is radially outward pressed by a container, thereby these the first side walls are positioned and are docked on the O shape circle.
71. like each described pan straddle of claim 68 to 70, wherein an O type circle has when unstressed greater than this first diameter of section of the radial depth of annular groove roughly.
72. each the described pan straddle like claim 68 to 71 further comprises
In the internal surface of this substantial cylindrical and one second annular recesses co-axial with it and that open with this first annular recesses axially spaced-apart, this second annular recesses on the internal surface of this substantial cylindrical, have an opening and with the isolated diapire of the inner surface radial direction of this substantial cylindrical; And
One the 2nd O type circle; The 2nd O type circle is disposed in this second annular recesses and processes a certain size with respect to this second annular recesses and is used for normally radially extending through this opening and remains radially outward being pressed by the container that internal surface received of this substantial cylindrical, thereby between the diapire of this container and this annular recesses, forms a sealing.
73. like the described pan straddle of claim 72; Further comprise first upper side wall and lower wall; These sidewalls are disposed between the opening and diapire of this second annular recesses; When the 2nd O type circle is radially outward pressed by a container, thereby these second sidewalls are positioned and are docked on the 2nd O shape circle.
74. like each described pan straddle of claim 72 to 73, wherein the 2nd O type circle has when unstressed greater than this first diameter of section of the radial depth of annular groove roughly.
75. like each described pan straddle of claim 69 to 74, further be included in a vacuum source in this bearing, this vacuum source is positioned for a container that is seated in the pan straddle is vacuumized, wherein the opening of this container is towards this bearing.
76. each described pan straddle like claim 69 to 75; Further be included in a process gas source in this bearing; This process gas source is positioned for and is seated at the internal communication of a container in this pan straddle, and wherein the opening of this container is towards this bearing.
III is used to transport the method that container-processing is landed in the container on the pan straddle
III..A. transport pan straddle to treatment station.
77. be used for a kind of method of processing vessel, this method comprises:
First treatment station that is used for processing vessel is provided;
One and isolated second treatment station of this first treatment station are provided, are used to handle these containers;
A kind of container is provided, the wall that this container has an opening and defines an inner surface;
A pan straddle is provided, and this pan straddle comprises a container port;
The opening of this container is seated on this container port;
Through via the inner surface of handling this container of taking a seat at the container port of this first treatment station;
This pan straddle and the container of taking a seat are transported to this second treatment station from this first treatment station; And
Via the inner surface of handling this container of taking a seat at the container port of this second treatment station.
78. like the described invention of claim 77, wherein this container is a generally tubular.
79. like each described invention of claim 77 or 78, wherein this opening is positioned at an end of this container.
80. like each described invention of claim 77 to 79, wherein this container is processed by thermoplastic material.
81. like each described invention of claim 77 to 80, wherein this container is processed by polyethyleneterephthalate.
82. like each described invention of claim 77 to 80, wherein this container is processed by polyolefine.
83. like each described invention of claim 77 to 80, wherein this container is processed by Vestolen PP 7052.
84. like each described invention of claim 77 to 83, wherein this container is processed by glass.
85. like each described invention of claim 77 to 84, wherein this container is processed by borosilicate glass.
86. like each described invention of claim 77 to 85, wherein this container is made by soda-lime glass.
87. like each described invention of claim 77 to 86, wherein this container is processed by silica glass.
88. like each described invention of claim 77 to 87, wherein when being exposed to the external pressure of one 760 holder, this container can be the sufficiently solid not distortion in fact to stand a kind of inner vacuum in fact completely.
89. like each described invention of claim 77 to 88, wherein it provides this container through injection moulding.
90. like each described invention of claim 77 to 88, wherein it provides this container through blow molding.
91. like each described invention of claim 77 to 90, wherein this container is that end through a closed pipe provides.
92. like each described invention of claim 77 to 91, wherein this pan straddle further comprises a vacuum pipe, this vacuum pipe is used for from being seated at a container withdrawing gas on this container port.
93. like the described invention of claim 92, wherein this pan straddle further comprises a vacuum ports, this vacuum ports is communicated with between this vacuum pipe and an external vacuum source.
94. like the described invention of claim 93, wherein this vacuum ports has an O type circle that receives and be formed on a sealing on the external vacuum source.
95. like each described invention of claim 77 to 94, wherein this pan straddle further comprises a gas input port, this gas input port is used for delivering the gas to a container that is seated on this container port.
96. each described invention like claim 77 to 95; Wherein this pan straddle comprises a composite gas input port and the vacuum ports that is communicated with this container port, and these ports are used for the gas delivery entering is seated at a container on this container port and therefrom extracts a kind of gas out accordingly.
97. like each described invention of claim 77 to 96, wherein this pan straddle is processed by thermoplastic material.
98. like each described invention of claim 77 to 97, wherein this pan straddle is included in a top and base that a joint links together.
99., further be included in the joint and be captured in the O type circle that being used between this top and this base seals this joint like the described invention of claim 98.
100. like each described invention of claim 77 to 99, the O type circle that wherein is trapped between this top and this base also receives this container and around this vessel port, forms a sealing.
101. each described invention like claim 77 to 100; Wherein this container port has the O type circle that first and second axially spaced-aparts are opened; Each O type circle has an internal diameter with the external diameter of receiving vessel of processing a certain size, is used between this container port and a container, sealing.
102. like each described invention of claim 77 to 101, wherein this container port has a near abutment surface of radially extending that is positioned at these O type circles and centers on this vacuum pipe.
103. like each described invention of claim 77 to 102, one of them treatment station is configured to defective the inner surface of a container is checked.
104. like each described invention of claim 77 to 103, one of them treatment station is configured to a coating is applied on the inner surface of a container.
105. like each described invention of claim 77 to 104, the coating that one of them treatment station is configured to a barrier coat or other types is applied on the inner surface of a container.
106. like each described invention of claim 77 to 105, one of them treatment station is configured to defective a coating is checked.
107. like each described invention of claim 77 to 106, one of them treatment station is configured to defective a barrier coat is checked.
108. like each described invention of claim 77 to 107, one of them treatment station is configured to the atmospheric pressure lost of measuring through a wall of container.
109. like each described invention of claim 77 to 108, one of them treatment station comprises an area supported, this area supported is used for supporting this pan straddle to handle the inner surface at the container of taking a seat of this treatment station simultaneously in a predetermined position.
110. like the described invention of claim 109, wherein, after the opening with this container was seated on this container port, this pan straddle was transported and gets into and the engaging of this area supported.
111. each described invention like claim 77 to 110; Wherein another treatment station comprises one second area supported, and this second area supported is used for supporting this pan straddle to handle the inner surface at the container of taking a seat of other treatment station simultaneously in a predetermined position.
112. like the described invention of claim 110, wherein, after the opening with this container was seated on this container port, this pan straddle was transported and gets into and the engaging of this second area supported.
113. each described invention like claim 77 to 112; Wherein another treatment station comprises one the 3rd area supported, and the 3rd area supported is used for supporting this pan straddle simultaneously through handle the inner surface of the container of taking a seat at the container port of other treatment station in a predetermined position.
114. like the described invention of claim 113, wherein, after the opening with this container was seated on this container port, this pan straddle was transported and gets into and the engaging of the 3rd area supported.
115. each the described invention like claim 77 to 114 further comprises:
One the 3rd treatment station is provided, and the 3rd treatment station and this first and second treatment station are spaced apart, are used for processing vessel;
This pan straddle and the container of taking a seat are transported to the 3rd treatment station from this second treatment station; And
Via the inner surface of handling this container of taking a seat at the container port of the 3rd treatment station.
116., further be included in a treatment station opening of this container be seated on this container port like each described invention of claim 77 to 115.
117., further be included in a treatment station and on the inner surface of a container, form a coating via this container port like each described invention of claim 77 to 116.
118. like each described invention of claim 77 to 117, wherein the processing at a treatment station place comprises that being directed against defective checks the inner surface of a container.
119. like the described invention of claim 118, wherein this inspection is to carry out through the situation of inserting in this container via this container port a detection probe and use this probe to detect this internal tank surface.
120., further comprise the inside radiation of energy through this wall of container and internal tank surface and with this detected energy of popping one's head in like the described invention of claim 119.
121., further be included in the situation of the position detection receptacle inner surface of the lip-deep a plurality of tight spacings of this internal tank like claim 119 or 120 described inventions.
122. like each described invention of claim 118 to 121, wherein inspection is through a source of radiation is inserted in this container and through using a detector to detect the radiation of this source of radiation from the beginning to carry out with the condition of detection receptacle inner surface via this container port.
123., further comprise making the outside radiation of energy detect this energy through this internal tank surface and with a detector that is positioned at this external container like each described invention of claim 118 to 122.
124., further comprise reflecting and detect this energy from the radiation on internal tank surface and with a detector that is positioned at this internal tank like each described invention of claim 120 to 123.
125., further be included in the situation of the position detection receptacle inner surface of the lip-deep a plurality of tight spacings of this internal tank like each described invention of claim 118 to 124.
126. like each described invention of claim 77 to 125, wherein the processing at a treatment station place comprises a coating is applied on the inner surface of a container.
127. like each described invention of claim 77 to 126, wherein the processing at a treatment station place comprises a barrier coat is applied on the inner surface of a container.
128. like each described invention of claim 77 to 127, wherein the processing at a treatment station place comprises a liquid obscures coating is applied on the inner surface of a container.
129. like each described invention of claim 77 to 128, wherein the processing at a treatment station place comprises that being directed against defective checks the coating on the inner surface of a container.
130. like each described invention of claim 77 to 129, wherein the processing at a treatment station place comprises that being directed against defective checks the barrier coat on the inner surface of a container.
131. like each described invention of claim 77 to 130, wherein the processing at a treatment station place comprises that being directed against defective checks a coating that on the inner surface of a container, applies as a kind of liquid.
132., comprise a detection probe inserted in this container via this container port and used the situation of this this coating of probe detection like each described invention of claim 126 to 131.
133., further comprise the inside radiation of energy detected this energy through this wall of container and with this probe like each described invention of claim 127 to 132.
134. like each described invention of claim 127 to 133, the situation of this coating is detected in the position that further is included in the lip-deep a plurality of tight spacings of this internal tank.
135. each described invention like claim 129 to 134; Further be included in the step that this inspection is carried out in the position of the enough numbers that spread all over internal tank surface, to confirm that this coating will effectively prevent to be increased to greater than 20% of ambient atmosphere pressure during the quality guaranteed period in 1 year at the pressure of (when it initially is evacuated and its wall is exposed to ambient atmosphere following time) within this container.
136. like each described invention of claim 129 to 135, wherein this inspection step is within each container 30 seconds or shorter elapsed time, to carry out.
137. like each described invention of claim 129 to 135, wherein this inspection step is within each container 25 seconds or shorter elapsed time, to carry out.
138. like each described invention of claim 129 to 135, wherein this inspection step is within each container 20 seconds or shorter elapsed time, to carry out.
139. like each described invention of claim 129 to 135, wherein this inspection step is within each container 15 seconds or shorter elapsed time, to carry out.
140. like each described invention of claim 129 to 135, wherein this inspection step is within each container 10 seconds or shorter elapsed time, to carry out.
141. like each described invention of claim 129 to 135, wherein this coating and inspection step are within each container 5 seconds or shorter elapsed time, to carry out.
142. like each described invention of claim 129 to 135, wherein this coating and inspection step are within each container 3 seconds or shorter elapsed time, to carry out.
143 each described inventions like claim 129 to 135, wherein this coating and inspection step are within each container 2 seconds or shorter elapsed time, to carry out.
144. like each described invention of claim 129 to 135, wherein this coating and inspection step are within each container 1 second or shorter elapsed time, to carry out.
145. like each described invention of claim 129 to 135, wherein this coating and inspection step are within each container 30 seconds or shorter elapsed time, to carry out.
146. like each described invention of claim 129 to 135, wherein this coating and inspection step are within each container 25 seconds or shorter elapsed time, to carry out.
147. like each described invention of claim 129 to 135, wherein this coating and inspection step are within each container 20 seconds or shorter elapsed time, to carry out.
148. like each described invention of claim 129 to 135, wherein this coating and inspection step are within each container 15 seconds or shorter elapsed time, to carry out.
149. like each described invention of claim 129 to 135, wherein this coating and inspection step are within each container 10 seconds or shorter elapsed time, to carry out.
150. like each described invention of claim 129 to 135, wherein this coating and inspection step are within each container 8 seconds or shorter elapsed time, to carry out.
151. like each described invention of claim 129 to 135, wherein this coating and inspection step are within each container 7 seconds or shorter elapsed time, to carry out.
152. like each described invention of claim 129 to 135, wherein this coating and inspection step are within each container 6 seconds or shorter elapsed time, to carry out.
153. like each described invention of claim 129 to 135, wherein this coating and inspection step are within each container 5 seconds or shorter elapsed time, to carry out.
154. like each described invention of claim 129 to 135, wherein this coating and inspection step are within each container 4 seconds or shorter elapsed time, to carry out.
155. like each described invention of claim 129 to 135, wherein this coating and inspection step are within each container 3 seconds or shorter elapsed time, to carry out.
156. each described invention like claim 129 to 135; Further be included in the step that this detection is carried out in the position of the enough numbers that spread all over internal tank surface, to confirm that this container will effectively prevent during the quality guaranteed period of pressure at least 18 months of (when it initially is evacuated and its wall is exposed to ambient atmosphere following time) within this container, to be increased to greater than 20% of ambient atmosphere pressure.
157. each described invention like claim 129 to 135; Further be included in the step that this detection is carried out in the position of the enough numbers that spread all over internal tank surface, to confirm that this container will effectively prevent during the quality guaranteed period of pressure at least two years of (when it initially is evacuated and its wall is exposed to ambient atmosphere following time) within this container, to be increased to greater than 20% of ambient atmosphere pressure.
158. each described invention like claim 129 to 135; Further be included in the step that this detection is carried out in the position of the enough numbers that spread all over internal tank surface, to confirm that this container will effectively prevent to be increased to greater than 15% of ambient atmosphere pressure during the quality guaranteed period in 1 year at the pressure of (when it initially is evacuated and its wall is exposed to ambient atmosphere following time) within this container.
159. each described invention like claim 129 to 135; Further be included in the step that this detection is carried out in the position of the enough numbers that spread all over internal tank surface, to confirm that this container will effectively prevent to be increased to greater than 10% of ambient atmosphere pressure during the quality guaranteed period in 1 year at the pressure of (when it initially is evacuated and its wall is exposed to ambient atmosphere following time) within this container.
160. like each described invention of claim 129 to 159, wherein this inspection is through inserting in this container via this container port a source of radiation and using a detector to carry out through the radiation from this source of radiation is detected with the situation that detects this coating.
161., further comprise making the outside radiation of energy detect this energy through this coating and wall of container and with a detector that is positioned at this external container like each described invention of claim 129 to 160.
162., further comprise reflecting and detect this energy from the radiation of this coating and wall of container and with a detector that is positioned at this internal tank like each described invention of claim 129 to 161.
163. like each described invention of claim 129 to 162, the situation of this coating is detected in the position that further is included in the lip-deep a plurality of tight spacings of this internal tank.
164., be to stop to render a service through the air pressure of measuring the wall of container that the blocking layer applies to carry out to the coating inspection on the inner surface of container wherein to defective like each described invention of claim 129 to 163.
165. like each described invention of claim 117 to 164, wherein this coating has reduced in atmospheric gas this container of inner surface transmission entering through it.
166. like each described invention of claim 117 to 165, wherein this coating has reduced the content of container and contacting of inner surface.
167. like each described invention of claim 117 to 166, wherein this coating comprises SiO x, elemental carbon or these a kind of combination, wherein x is from about 1.5 to about 2.9 in this formula, alternately from about 1.5 to about 2.6, alternately about 2.
168., further be included in this second treatment station and this container removed from this pan straddle after handling the inner surface of the container of taking a seat like each described invention of claim 77 to 167.
169., further comprise like the described invention of claim 168:
After removing step, one second container is provided, the wall that this second container has an opening and defines an inner surface; And
The opening of this second container is seated on this container port.
170., further be included in this first treatment station is handled second container of taking a seat via this container port inner surface like each described invention of claim 168 to 169.
171., further comprise pan straddle and second container of taking a seat are transported to this second treatment station from this first treatment station like each described invention of claim 168 to 170.
172., further be included in this second treatment station and handle this second container of taking a seat via this container port like each described invention of claim 168 to 171.
173. like each described invention of claim 77 to 172, further be included in and form this container in the mould, container is removed from mould, and after container is removed from mould, within 60 seconds, vessel port is seated on this container port.
174. like each described invention of claim 77 to 173, further be included in and form this container in the mould, container is removed from mould, and after container is removed from mould, within 30 seconds, vessel port is seated on this container port.
175. like each described invention of claim 77 to 174, further be included in and form this container in the mould, container is removed from mould, and after container is removed from mould, within 25 seconds, vessel port is seated on this container port.
176. like each described invention of claim 77 to 175, further be included in and form this container in the mould, container is removed from mould, and after container is removed from mould, within 20 seconds, vessel port is seated on this container port.
177. like each described invention of claim 77 to 176, further be included in and form this container in the mould, container is removed from mould, and after container is removed from mould, within 15 seconds, vessel port is seated on this container port.
178. like each described invention of claim 77 to 177, further be included in and form this container in the mould, container is removed from mould, and after container is removed from mould, within 10 seconds, vessel port is seated on this container port.
179. like each described invention of claim 77 to 178, further be included in and form this container in the mould, container is removed from mould, and after container is removed from mould, within 5 seconds, vessel port is seated on this container port.
180., further be included in the mould and form this container like each described invention of claim 77 to 179, container is removed from mould, and after container is removed from mould within 3 seconds, vessel port is seated on this container port.
181. each the described invention like claim 77 to 180 further is included in and forms container in the mould, container is removed from mould, and after container is removed from mould, within 1 second, vessel port is seated on this container port.
III.B. be transported to treatment facility on the pan straddle or vice versa.
182. a method that is used for processing vessel, this method comprises:
First treatment facility that is used for processing vessel is provided;
Second treatment facility that is used to handle these containers is provided;
A kind of container is provided, the wall that this container has an opening and defines an inner surface;
A pan straddle is provided, and this pan straddle comprises a container port;
The opening of this container is seated on this container port;
This first treatment facility is moved into during the operability of this pan straddle engages, or vice versa;
Use this first treatment facility to handle the inner surface of this container of taking a seat via this container port;
This second treatment facility is moved into during the operability of this pan straddle engages, or vice versa; And
Use this second treatment facility to handle the inner surface of this container of taking a seat via this container port.
183., further comprise like the described invention of claim 182:
The 3rd treatment facility that is used for processing vessel is provided;
The 3rd treatment facility is moved into during the operability of this pan straddle engages, or vice versa;
Use the 3rd treatment facility to handle the inner surface of this container of taking a seat via this container port;
184. like claim 182 or 183 described inventions, wherein this container is a generally tubular.
185. like each described invention of claim 182 to 184, wherein this opening is positioned at an end of this container.
186. like each described invention of claim 182 to 185, wherein this container is processed by thermoplastic material.
187. like each described invention of claim 182 to 186, wherein this container is processed by polyethyleneterephthalate.
188. like each described invention of claim 182 to 187, wherein this container is processed by polyolefine.
189. like each described invention of claim 182 to 186, wherein this container is processed by Vestolen PP 7052.
190. like each described invention of claim 182 to 189, wherein when being exposed to the external pressure of one 760 holder, this container can be the sufficiently solid not distortion in fact to stand a kind of inner vacuum in fact completely.
191. like each described invention of claim 182 to 190, wherein this container provides through it is carried out injection moulding.
192. like each described invention of claim 182 to 191, wherein this container provides through it is carried out blow molding.
193. like each described invention of claim 182 to 192, wherein this pan straddle further comprises a vacuum pipe, this vacuum pipe is used for from being seated at a container withdrawing gas on this container port.
194. like the described invention of claim 193, wherein this pan straddle further comprises a vacuum ports, this vacuum ports is communicated with between this vacuum pipe and an external vacuum source.
195. like the described invention of claim 194, wherein this vacuum ports has an O type circle that receives an external vacuum source and form a sealing above that.
196. like each described invention of claim 182 to 195, wherein this pan straddle further comprises a gas input port, this gas input port is used for delivering gas to a container that is seated on this container port.
197. each described invention like claim 182 to 196; Wherein this pan straddle comprises a composite gas input port and the vacuum ports that is communicated with this container port, and these ports are used for a kind of gas delivery entering is seated at a container on this container port and therefrom extracts a kind of gas out accordingly.
198. like each described invention of claim 182 to 197, wherein this pan straddle is processed by thermoplastic material.
199. like each described invention of claim 182 to 198, wherein this container port has an O type circle that receives a vessel port and form a sealing above that.
200. like each described invention of claim 182 to 199, one of them treatment facility is configured to defective the inner surface of a container is checked
201. like each described invention of claim 182 to 200, one of them treatment facility is configured to a coating is applied on the inner surface of a container.
202. like each described invention of claim 182 to 201, one of them treatment facility is configured to defective a coating is checked.
203. like each described invention of claim 182 to 202, one of them treatment facility is configured to the atmospheric pressure lost of measuring through a wall of container.
204. each described invention like claim 182 to 203; One of them treatment facility comprises an area supported, and this area supported is used for supporting this pan straddle to handle the inner surface of this container of taking a seat simultaneously with this treatment facility in a predetermined position.
205. like the described invention of claim 204, wherein, after the opening with this container is seated on this container port, this pan straddle be transported get into the engaging of this area supported in.
206. each described invention like claim 182 to 205; Wherein another treatment facility comprises one second area supported, and this second area supported is used for supporting this pan straddle to handle the inner surface of this container of taking a seat simultaneously with other treatment facilities in a predetermined position.
207. like the described invention of claim 206, wherein, after the opening with this container is seated on this container port, this pan straddle be transported get into the engaging of this second area supported in.
208. each described invention like claim 182 to 207; Wherein another treatment facility comprises one the 3rd area supported, and the 3rd area supported is used for supporting this pan straddle to handle the inner surface of the container of taking a seat simultaneously via this container port with other treatment facilities in a predetermined position.
209. like the described invention of claim 208, wherein, after the opening with this container is seated on this container port, this pan straddle be transported get into the engaging of the 3rd area supported in.
210. each the described invention like claim 182 to 209 further comprises:
One the 3rd treatment facility is provided, and the 3rd treatment facility and this first and second treatment facility are spaced apart, are used for processing vessel;
This pan straddle and the container of taking a seat are transported to the 3rd treatment facility from this second treatment facility; And
Use the 3rd treatment facility to handle the inner surface of this container of taking a seat via this container port.
211., further be included in a treatment facility place opening of this container be seated on this container port like each described invention of claim 182 to 210.
212., further be included in a treatment facility place and on the inside of a container, form a coating via this container port like each described invention of claim 182 to 211.
213. like each described invention of claim 182 to 212, wherein the processing at a treatment facility place comprises that being directed against defective checks the inner surface of a container.
214. like the described invention of claim 213, wherein this inspection is to carry out through the situation of inserting in this container via this container port a detection probe and use this probe to detect this internal tank surface.
215., further comprise the inside radiation of energy through this wall of container and internal tank surface and with this detected energy of popping one's head in like the described invention of claim 214.
216., further be included in the situation of the position detection receptacle inner surface of the lip-deep a plurality of tight spacings of this internal tank like claim 214 or 215 described inventions.
217. like each described invention of claim 213 to 216, wherein inspection is through a source of radiation is inserted in this container and through using a detector to detect the radiation of this source of radiation from the beginning to carry out with the condition of detection receptacle inner surface via this container port.
218., further comprise making the outside radiation of energy detect this energy through this internal tank surface and with a detector that is positioned at this external container like each described invention of claim 213 to 217.
219., further comprise reflecting and detect this energy from the radiation on internal tank surface and with a detector that is positioned at this internal tank like each described invention of claim 215 to 216.
220., further be included in the situation of the position detection receptacle inner surface that the lip-deep a plurality of tight spacings of this internal tank open like each described invention of claim 213 to 219.
221. like each described invention of claim 182 to 220, the processing at one of them treatment facility place comprises a coating is applied on the inner surface of a container.
222. like each described invention of claim 182 to 221, the processing at one of them treatment facility place comprises a coating is applied on the inner surface of a container with liquid form.
223. like each described invention of claim 182 to 222, wherein the processing at a treatment facility place comprises that being directed against defective checks the coating on the inner surface of a container.
224., comprise a detection probe inserted in this container via this container port and used the situation of this this coating of probe detection like each described invention of claim 221 to 223.
225., further comprise the inside radiation of energy detected this energy through this wall of container and with this probe like each described invention of claim 221 to 224.
226. like each described invention of claim 221 to 225, the situation of this coating is detected in the position that further is included in the lip-deep a plurality of tight spacings of this internal tank.
227. each described invention like claim 223 to 131; Further be included in the step that this inspection is carried out in the position of the enough numbers that spread all over internal tank surface, to confirm that this container will effectively prevent to be increased to greater than 20% of ambient atmosphere pressure during the quality guaranteed period in 1 year at the pressure of (when it initially is evacuated and its wall is exposed to ambient atmosphere following time) within this container.
228. like each described invention of claim 223 to 227, wherein this inspection step is within each container 30 seconds or shorter elapsed time, to carry out.
229. like each described invention of claim 223 to 227, wherein this inspection step is within each container 25 seconds or shorter elapsed time, to carry out.
230. like each described invention of claim 223 to 227, wherein this inspection step is within each container 20 seconds or shorter elapsed time, to carry out.
231. like each described invention of claim 223 to 227, wherein this inspection step is within each container 15 seconds or shorter elapsed time, to carry out.
232. like each described invention of claim 223 to 227, wherein this inspection step is within each container 10 seconds or shorter elapsed time, to carry out.
233. like each described invention of claim 223 to 227, wherein this coating and inspection step are within each container 30 seconds or shorter elapsed time, to carry out.
234. like each described invention of claim 223 to 227, wherein this coating and inspection step are within each container 25 seconds or shorter elapsed time, to carry out.
235. like each described invention of claim 223 to 227, wherein this coating and inspection step are within each container 20 seconds or shorter elapsed time, to carry out.
236. like each described invention of claim 223 to 227, wherein this coating and inspection step are within each container 15 seconds or shorter elapsed time, to carry out.
237. like each described invention of claim 223 to 227, wherein this coating and inspection step are within each container 10 seconds or shorter elapsed time, to carry out.
238. each described invention like claim 223 to 227; Further be included in the step that this detection is carried out in the position of the enough numbers that spread all over internal tank surface, to confirm that this coating will effectively prevent during the quality guaranteed period of pressure at 18 months of (when it initially is evacuated and its wall is exposed to ambient atmosphere following time) within this container, to be increased to greater than 20% of ambient atmosphere pressure.
239. each described invention like claim 224 to 227; Further be included in the step that this detection is carried out in the position of the enough numbers that spread all over internal tank surface, to confirm that this coating will effectively prevent during the quality guaranteed period of pressure at least two years of (when it initially is evacuated and its wall is exposed to ambient atmosphere following time) within this container, to be increased to greater than 20% of ambient atmosphere pressure.
240. each described invention like claim 223 to 227; Further be included in the step that this detection is carried out in the position of the enough numbers that spread all over internal tank surface, to confirm that this coating will effectively prevent to be increased to greater than 15% of ambient atmosphere pressure during the quality guaranteed period in 1 year at the pressure of (when it initially is evacuated and its wall is exposed to ambient atmosphere following time) within this container.
241. each described invention like claim 223 to 227; Further be included in the step that this detection is carried out in the position of the enough numbers that spread all over internal tank surface, to confirm that this coating will effectively prevent to be increased to greater than 10% of ambient atmosphere pressure during the quality guaranteed period in 1 year at the pressure of (when it initially is evacuated and its wall is exposed to ambient atmosphere following time) within this container.
242. like each described invention of claim 223 to 241, wherein this inspection is through inserting in this container via this container port a source of radiation and using a detector to carry out through the radiation from this source of radiation is detected with the situation that detects this coating.
243., further comprise making the outside radiation of energy detect this energy through this coating and wall of container and with a detector that is positioned at this external container like each described invention of claim 223 to 242.
244., further comprise reflecting and detect this energy from the radiation of this coating and wall of container and with a detector that is positioned at this internal tank like each described invention of claim 223 to 243.
245. like each described invention of claim 223 to 244, the situation of this coating is detected in the position that further is included in the lip-deep a plurality of tight spacings of this internal tank.
246., be to stop to render a service through the air pressure of measuring the wall of container that applies to carry out to the coating inspection on the inner surface of container wherein to defective like each described invention of claim 223 to 245.
247. like each described invention of claim 212 to 246, wherein this coating has reduced in atmospheric gas this container of inner surface transmission entering through it.
248. like each described invention of claim 212 to 247, wherein this coating has reduced the content of container and contacting of inner surface.
249. like each described invention of claim 212 to 248, wherein this coating comprises SiO x, wherein x is from about 1.5 to about 2.9 in this formula, alternately from about 1.5 to about 2.6, and alternately about 2, elemental carbon, a kind of material, Si based on fluorine wO xC yH z, wherein w is 1, and x is from about 0.5 to 2.4, and y is from about 0.6 to about 3, and z is from 2 to about 9, or these a kind of combination.
250. like each described invention of claim 182 to 249, the inner surface that further is included in the container of taking a seat with the processing of second treatment facility is removed container afterwards from pan straddle.
251., further comprise like the described invention of claim 250:
After this removes step, one second container is provided, the wall that this second container has an opening and defines an inner surface; And
The opening of this second container is seated on this container port.
252., further comprise the inner surface of handling second container of taking a seat with first treatment facility via this container port like each described invention of claim 250 to 251.
253., further comprise this pan straddle and second container of taking a seat are transported to this second treatment facility from this first treatment facility like each described invention of claim 250 to 252.
254., further comprise with second treatment facility and handle second container of taking a seat via this container port like each described invention of claim 250 to 253.
255. like each described invention of claim 182 to 254, further be included in and form this container in the mould, container is removed from mould, and after container is removed from mould, within 60 seconds, vessel port is seated on this container port.
256. like each described invention of claim 182 to 255, further be included in and form this container in the mould, container is removed from mould, and after container is removed from mould, within 30 seconds, vessel port is seated on this container port.
257. like each described invention of claim 182 to 256, further be included in and form this container in the mould, container is removed from mould, and after container is removed from mould, within 25 seconds, vessel port is seated on this container port.
258. like each described invention of claim 182 to 257, further be included in and form this container in the mould, container is removed from mould, and after container is removed from mould, within 20 seconds, vessel port is seated on this container port.
259. like each described invention of claim 182 to 258, further be included in and form this container in the mould, container is removed from mould, and after container is removed from mould, within 15 seconds, vessel port is seated on this container port.
260. like each described invention of claim 182 to 259, further be included in and form this container in the mould, container is removed from mould, and after container is removed from mould, within 10 seconds, vessel port is seated on this container port.
261. like each described invention of claim 182 to 260, further be included in and form this container in the mould, container is removed from mould, and after container is removed from mould, within 5 seconds, vessel port is seated on this container port.
262. like each described invention of claim 182 to 261, further be included in and form this container in the mould, container is removed from mould, and after container is removed from mould, within 3 seconds, vessel port is seated on this container port.
263. like each described invention of claim 182 to 260, further be included in and form this container in the mould, container is removed from mould, and after container is removed from mould, within 1 second, vessel port is seated on this container port.
III.C. use clamp to be used for pipe is transported entering or leaves the coating station
264. the method that one first container is carried out the PECVD processing, this method comprises:
One first container is provided, and this first container has an opening end, a closing end and an inner surface;
At least one first clamp is provided, and this first clamp is configured to be used for the closing end that optionally keeps and discharge this first container;
Clamp the closing end of this first container with this first clamp;
Use this first clamp, with this first container be transported to a pan straddle near, this pan straddle is configured so that the opening end of this first container is taken a seat;
Use this first clamp, axially advance and make its opening end to be seated on this pan straddle in this first container, be based upon being communicated with of sealing between the inside of this pan straddle and this first container;
Through this pan straddle at least a gaseous reactant is introduced in this first container;
Under the condition of a kind of reaction product that effectively forms reactant, in this first container, forming plasma body on the inner surface of this first container.
This first container is disseated from this pan straddle; And
Use this first clamp or another clamp, this first container is axially transported leave this pan straddle; And
This first container is discharged from being used for axially it being transported the clamp that leaves from this pan straddle.
265., further comprise like the described invention of claim 264:
A reaction vessel different with this first container is provided, and this reaction vessel has an opening end and an internal space;
The opening end of this reaction vessel is seated on this pan straddle, is based upon being communicated with of sealing between the internal space of this pan straddle and this reaction vessel;
A PECVD reactant conduit is provided in this internal space;
Form plasma body in the internal space at reaction vessel under the condition of sedimental at least a portion of effectively from reactant conduit, removing the PECVD reaction product;
This reaction vessel is disseated from this pan straddle; And
Transport this reaction vessel and leave this pan straddle.
266., further comprise like claim 264 or 265 described inventions:
At least one second clamp is provided;
Operationally at least the first and second clamps are connected on the placed in-line transfer roller;
One second container is provided, and this second container has an opening end, a closing end and an inner surface.
A clamp is provided, and this clamp is configured to be used for the closing end that optionally keeps and discharge this second container;
Clamp the closing end of this second container with this clamp;
Use this clamp, with this second container be transported to a pan straddle near, this pan straddle is configured to make this opening end to this second container to take a seat;
Use this clamp, axially advance and make its opening end to be seated on this pan straddle in this second container, be based upon being communicated with of sealing between the inside of this pan straddle and this second container;
Through this pan straddle at least a gaseous reactant is introduced in this second container;
Under the condition of a kind of reaction product that effectively forms reactant, in this second container, forming plasma body on the inner surface of this second container;
This second container is disseated from this pan straddle; And
Use this second clamp or another clamp, axially transport this second container and leave this pan straddle; And
This second container is discharged from being used for axially it being transported the clamp that leaves from this pan straddle.
IV. be used to make the PECVD device of container
IV.A. comprise pan straddle, interior electrode, as the PECVD device of the container of reaction chamber
267. a PECVD device comprises:
A pan straddle, this pan straddle have a port, and this port is received in the position of taking a seat to handle with a container;
An interior electrode, thus electrode is positioned to be received in and is seated in the container on the pan straddle in this;
An outer electrode, this outer electrode have an internal portion, and this internal portion is positioned and is seated at a container on this pan straddle with reception; And
A power supply, thus this power supply with alternating-current be input to this inside and outer electrode one of at least in form plasma body in the container on being seated at pan straddle, this container defines a plasma-reaction-chamber;
268. like the described invention of claim 267, wherein should in electrode be a probe with distal portions, thereby this distal portions is positioned and roughly extends into concentrically in the container that is seated on this pan straddle.
268a. like claim 267 or 268 described inventions; Further comprise a reactant gas source and a kind of gas feed device, this gas feed device is seated at a kind of reactant gas the container on this pan straddle from this reactant gas source feeding.
269. like the described invention of claim 268a, wherein this gas feed device is the distal portions that is positioned at this electrode.
270. like claim 268a or 269 described inventions, further be included in a passage within the electrode in this, this passage is used for this reactant gas is delivered to from this reactant gas source the distal portions of electrode in this.
271. like each described invention of claim 267 to 270, further comprise a carrier gas source and in this passage within electrode, this passage is used for a kind of carrier gas is delivered to from this carrier gas source the distal portions of electrode in this.
272. like each described invention of claim 267 to 271, wherein this outer electrode be substantial cylindrical and be positioned roughly to extend concentrically around being seated at container on this pan straddle.
273. like each described invention of claim 267 to 272, wherein this outer electrode comprises an end cap.
274. like the described invention of claim 273, wherein at this end cap and to be seated at the gap that is limited between the far-end of a container on this pan straddle be basically identical.
275. like each described invention of claim 267 to 274, wherein at this outer electrode and to be seated at the gap that is limited between the container on this pan straddle be basically identical.
276. like each described invention of claim 117 to 167 or 212 to 168, wherein this coating comprises a SiO xLayer and a Si wO xC yH zLayer, wherein w is 1, and x is from about 0.5 to about 2.4 in this formula, and y is from about 0.6 to about 3, and z is from 2 to about 9.
278. like claim 276 or 277 described inventions, wherein this Si wO xC yH zLayer is deposited on the SiOx layer this SiO xLayer is deposited on the inner surface of this container.
279. like claim 276 or 277 described inventions, wherein this SiO xLayer is deposited over this Si wO xC yH zBetween the inner surface of layer and container.
280. like each described invention of claim 276 to 279, wherein this SiO xLayer is deposited over Si wO xC yH zNear the layer.
281. like each described invention of claim 276 to 280, wherein this SiO xLayer is deposited near the inner surface of container.
282. like each described invention of claim 276 to 280, wherein this Si wO xC yH zLayer is deposited near the inner surface of this container.
283. each described invention, wherein SiO like claim 280 to 282 xWith Si wO xC yH zLayer is a kind of Si wO xC yH zTo SiO xThe gradient mixture.
284. like each described invention of claim 267 to 283, wherein this container further comprises a closure member.
285. like the described invention of claim 284, wherein this closure member comprises a surface towards inside that is exposed to the inner chamber of container.
286. like claim 284 or 285 described inventions, wherein this closure member comprises the surface of a contact wall, this surface contacts with the inner surface of this wall of container.
287. like each described invention of claim 284 to 286, wherein this closure member comprises a stopper.
288. like the described invention of claim 287, wherein this closure member comprises a shield [support, this stopper is clamped among this shield [support.
289. like claim 287 or 288 described inventions, wherein this stopper comprises the surface of a contact wall, this surface contacts with the internal surface of this wall of container
290. like each described invention of claim 284 to 289, wherein this stopper comprises a surface towards inside, this surface is exposed to the inner chamber of container.
290a., comprise further being used for removing a vacuum source of gas that this container of taking a seat defines a Vakuumkammer from being seated at container on the pan straddle like each described invention of claim 267 to 290.
291., wherein be coated with a Si with the part of the surperficial contacted wall of container that contacts wall of this closure member like claim 284 each described invention to 290a wO xC yH zSlip coating
301. like each described invention of claim 284 to 300, wherein this Si wO xC yH zCoating applies through PECVD.
302. like each described invention of claim 291 to 301, wherein this Si wO xC yH zCoating has the thickness between 0.5nm and 5000nm.
303. like each described invention of claim 291 to 301, wherein this Si wO xC yH zCoating has the thickness between 100nm and 5000nm.
304. like each described invention of claim 291 to 301, wherein this Si wO xC yH zCoating has the thickness between 200nm and 5000nm.
305. like each described invention of claim 291 to 301, wherein this Si wO xC yH zCoating has the thickness between 500nm and 5000nm.
306. like each described invention of claim 291 to 301, wherein this Si wO xC yH zCoating has the thickness between 1000nm and 5000nm.
307. like each described invention of claim 291 to 301, wherein this Si wO xC yH zCoating has the thickness between 2000nm and 5000nm.
308. like each described invention of claim 291 to 301, wherein this Si wO xC yH zCoating has the thickness between 3000nm and 5000nm.
309. like each described invention of claim 291 to 301, wherein this Si wO xC yH zCoating have in 4000nm and 10 thickness between the 000nm.
310.PECVD device comprises:
A pan straddle, this pan straddle have a port so that a container is received in the position of taking a seat to handle;
An interior electrode, thus electrode is positioned to be received in and is seated in the container on the pan straddle in this;
An outer electrode, this outer electrode have an internal portion, and this internal portion is positioned and is seated at a container on this pan straddle with reception,
A power supply, thus this power supply is input to alternating-current on inner and the outer electrode and forms plasma body in the container on being seated at this pan straddle;
An eduction pipe, thus this eduction pipe is used for gas is transferred to the inside that is seated at the container on the port or leaves from its transfer limiting a closed-chamber;
A reactant gas source; And
A gas feed device, this gas feed device is seated at a kind of reactant gas the container on this pan straddle from this reactant gas source feeding.
IV.B. use clamp to be used for pipe is transported to or leaves the PECVD device that applies the station
311. be used for one first container is carried out the device that PECVD handles, this first container has an opening end, a closing end and an internal space, and this device comprises:
A pan straddle, this pan straddle are configured to be used to make the opening end of container to take a seat;
One first clamp, this first clamp is configured to be used for optionally keeping and discharging the closing end of container, and clamps the closing end of container simultaneously, with this container be transported to this pan straddle near;
A seat on this pan straddle, this is configured to be used to be based upon being communicated with of sealing between the internal space of this pan straddle and this first container;
A reactant feeding mechanism, this reactant feeding mechanism are operably connected to be used for through this pan straddle at least a gaseous reactant being incorporated in this first container;
A plasma generator, this plasma body producer are configured under the condition of a kind of reaction product that effectively forms reactant on the inner surface of this first container and in this first container, form plasma body;
A kind of container releasing device, this container releasing device are used to make this first container to disseat from this pan straddle; And
A clamp, this clamp are this first clamp or another clamp, and this clamp is configured to be used for axially transport this first container and leaves this pan straddle, and then discharge this first container.
312., further comprise like the described invention of claim 311:
A reaction vessel different with this first container, this reaction vessel have an opening end and an internal space and are configured to its opening end is seated on this pan straddle and is based upon being communicated with of sealing between the internal space of this pan straddle and this reaction vessel; And
A PECVD reactant conduit, thus this conduit is positioned and is located within the internal space of reaction vessel when this reaction vessel is seated on this pan straddle;
Wherein this plasma body producer is can be configured to be used for forming plasma body in the internal space at reaction vessel under the condition of sedimental at least a portion of effectively removing the PECVD reaction product from reactant conduit.
313., further comprise like claim 311 or 312 described inventions:
A placed in-line transfer roller, this placed in-line transfer roller is configured to be used to transport clamp; And
One second clamp, this second clamp is configured to be used for optionally keeping and discharging the closing end of container, clamps the closing end of container simultaneously, with this container be transported to this pan straddle near.
This first and second clamp be operably connected on this placed in-line transfer roller and be configured to be used in turn a series with at least two containers be transported to this pan straddle near; The opening end of these containers is seated on this pan straddle; Be based upon being communicated with of sealing between the inside of this pan straddle and this second container; These containers are axially transported leave this pan straddle, and from these clamps, discharge these containers.
V.B. the opening (capillary injection device) of the PECVD coating of container restriction
316. one kind be used for through PECVD apply a generally tubular the restriction that pending container is arranged opening inner surface method, this method comprises:
Provide having of a generally tubular pending container; This container comprises an outside surface, defines an internal surface of an inner chamber, has big opening of an internal diameter and the opening of a restriction, and the opening of this restriction is limited an internal surface and has than the less internal diameter of internal diameter of this big opening.
A processing vessel is provided, and this container has an inner chamber and a processing vessel opening;
Thereby this processing vessel opening is connected being communicated with between inner chamber that opening via this restriction is based upon pending container and the processing vessel inner chamber with the opening of the restriction that pending container is arranged;
To have in inner chamber and the processing vessel inner chamber of pending container and be pumped into partial vacuum at least;
Make the PECVD reagent flow through this first opening,, through the opening of this restriction, get into the processing vessel inner chamber then then then through the inner chamber of pending container is arranged; And
Effectively be deposited under the condition on the internal surface of opening of restriction near the generation plasma body opening of this restriction in coating with a PECVD reaction product.
317. like the described method of claim 316, it is a syringe cylinder that pending container is wherein arranged.
318. like claim 316 or 317 described methods; Wherein the opening of this restriction has one first joint; And this processing vessel opening has one second joint, thereby this second joint is based upon being communicated with between this processing vessel inner chamber and the inner chamber that pending container is arranged by adaptive to be seated on this first joint.
319. like the described method of claim 318, wherein this first and second joint is the luer lock joint.
320. like the described method of claim 319, wherein this first and second joint is processed by electro-conductive material one of at least.
321. like claim 299,319 or 320 described methods, wherein this first and second joint is processed by electro-conductive material one of at least.
322. like claim 299,319,320 or the described method of 299a2, wherein this first and second joint is processed by stainless steel one of at least.
323. like the described method of claim 319, the first and second wherein corresponding luer lock joints are outer luer lock joint and interior luer lock joint.
324., further comprise a sealing member that is positioned between this first and second joint like claim 299,319 or 323 described methods.
325. like the said method of claim 324, wherein the sealing part comprises an O type circle.
326. like claim 319,323,324 or 325 described methods; Wherein when these joints are engaged; One of these joints comprise a lock collar; This lock collar have a kind of screw thread and define an axial plane to, first bearing of general toroidal, and other joints comprise one towards the axial plane of this first bearing to, second bearing of general toroidal.
327., further comprise a lip ring that is bonded between this first and second bearing like the described method of claim 326.
328., be leakproof at least basically being communicated with between the inner chamber that wherein is based upon pending container via the opening of this restriction and the processing vessel inner chamber like each described method of claim 316 to 318.
329., a kind of PECVD reagent flow is carried out through following steps through the big opening that pending container is arranged like each described method of claim 316 to 328:
The interior electrode of a generally tubular is provided, the distal openings that this electrode has an internal passages, a near-end, a far-end and contiguous this far-end and is communicated with this internal passages;
This electrode distal end is inserted with near big opening of pending container or wherein; And
The feeding reactant gas has in the inner chamber of pending container through the distal openings entering of electrode.
330. like the described method of claim 329, wherein when the far-end of feeding electrode during reactant gas to locate less than the half the of the distance of the opening of big opening to this restriction that pending container is arranged from this.
331. like the described method of claim 329, wherein when the far-end of feeding electrode during reactant gas with less than from the distance of the opening of big opening to this restriction that pending container is arranged 40% and locate.
332. like the described method of claim 329, wherein when the far-end of feeding electrode during reactant gas with less than from the distance of the opening of big opening to this restriction that pending container is arranged 30% and locate.
333. like the described method of claim 329, wherein when the far-end of feeding electrode during reactant gas with less than from the distance of the opening of big opening to this restriction that pending container is arranged 20% and locate.
334. like the described method of claim 329, wherein when the far-end of feeding electrode during reactant gas with less than from the distance of the opening of big opening to this restriction that pending container is arranged 15% and locate.
335. like the described method of claim 329, wherein when the far-end of feeding electrode during reactant gas with less than from the distance of the opening of big opening to this restriction that pending container is arranged 10% and locate.
336. like the described method of claim 329, wherein when the far-end of feeding electrode during reactant gas with less than from the distance of the opening of big opening to this restriction that pending container is arranged 8% and locate.
337. like the described method of claim 329, wherein when the far-end of feeding electrode during reactant gas with less than from the distance of the opening of big opening to this restriction that pending container is arranged 6% and locate.
338. like the described method of claim 329, wherein when the far-end of feeding electrode during reactant gas with less than from the distance of the opening of big opening to this restriction that pending container is arranged 4% and locate.
339. like the described method of claim 329, wherein when the far-end of feeding electrode during reactant gas with less than from the distance of the opening of big opening to this restriction that pending container is arranged 2% and locate.
340. like the described method of claim 329, wherein when the far-end of feeding electrode during reactant gas with less than from the distance of the opening of big opening to this restriction that pending container is arranged 1% and locate.
341. like the described method of claim 329, wherein the far-end of electrode is positioned in this big opening that pending container is arranged when the feeding reactant gas.
342. like the described method of claim 329, wherein the far-end of electrode is positioned in the outside that this has the big opening of pending container when the feeding reactant gas.
343. like each described method of claim 329 to 342, the far-end of this electrode is positioned in the far-end of the opening of this restriction.
344. like each described method of claim 329 to 343, wherein this electrode is axially moved during deposition PECVD reaction product.
345. like each described method of claim 316 to 344, wherein this plasma body fills the air the opening that spreads all over syringe inner chamber and this restriction basically.
346. like each described method of claim 316 to 345, wherein this plasma body fills the air opening and this processing vessel inner chamber that spreads all over this syringe inner chamber, this restriction basically.
347. like each described method of claim 316 to 346, wherein this plasma body opening of spreading all over syringe inner chamber and this restriction has the color of basically identical.
348. like each described method of claim 316 to 347, wherein this plasma body opening and this processing vessel inner chamber of spreading all over this syringe inner chamber, this restriction basically has the color of basically identical.
349. like each described method of claim 316 to 348, wherein to spread all over the opening of this syringe inner chamber and this restriction be stable basically to this plasma body.
350. like each described method of claim 316 to 349, wherein to spread all over opening and this processing vessel inner chamber of this syringe inner chamber, this restriction be stable basically to this plasma body.
351. like each described method of claim 316 to 350, wherein the vessel port of this processing vessel is unique opening.
352. like each described method of claim 316 to 351, wherein the volume of this processing vessel inner chamber has 3 times of volume of the inner chamber 300 of pending container 250 less than this.
353. like each described method of claim 316 to 352, wherein the volume of this processing vessel inner chamber has 2 times of cavity volume of pending container less than this.
354. like each described method of claim 316 to 353, wherein the volume of this processing vessel inner chamber has the volume of the inner chamber of pending container less than this.
355. like each described method of claim 316 to 354, wherein the volume of this processing vessel inner chamber less than this have pending container 250 inner chamber 300 volume 50%.
356. like each described method of claim 316 to 355, wherein the volume of this processing vessel inner chamber be less than this have pending container 250 inner chamber 300 volume 25%.
357., further be included in before being pumped into partial vacuum at least in the inner chamber that pending container 250 is arranged 300 and make this have the big opening of pending generally tubular container to be seated on the pan straddle like each described method of claim 316 to 356.
358., further comprise the big opening of pending container is seated on the port of this pan straddle like the described method of claim 357.
359., further comprise with an interior positioning of electrode having in the pending container on being seated at this pan straddle like claim 357 or 358 described methods.
360. like claim 357,358 or 359 described methods; Further comprise there being pending container to locate with respect to an outer electrode; This outer electrode has an internal portion, and this internal portion is positioned to have with reception and is seated at the container on the pan straddle pending the time.
361., thereby further comprise with this outer electrode of power feed alternating current driver and form plasma body being seated at having within the pending container on this pan straddle like claim 357,358,359 or 330 described methods.
362., further comprise making electrode grounding in this like the described method of claim 361.
363. like claim 357,358,359,360 or 361 described methods, comprise further the inside of a vacuum source with the pending container of finding time is provided that this has pending container to define a Vakuumkammer.
364., further comprise one second Vakuumkammer that pending container is arranged around this is provided like the described method of claim 363.
365. like the described method of claim 364, wherein the inside of this container is maintained at than under the lower vacuum level of this second Vakuumkammer.
366. like the described method of claim 363, wherein this processing vessel be with pan straddle in a conduit being communicated with of a vacuum ports.
367. each described method like claim 357 to 366; Further comprise a reactant gas source and a gas feed device, this gas feed device is seated at having the pending container on this pan straddle with a kind of reactant gas from this reactant gas source feeding.
VI. container inspection
V1.A. comprise that precoating and back apply the container processing of inspection
399. one kind is used for container-treatment that the plastic containers of moulding are handled, the wall that this container comprises an opening and defines an inner surface, and this method comprises:
To defective the inner surface of institute's container for moulding is checked;
After institute's container for moulding is checked, a coating is applied on the inner surface of this container; And
To defective this coating is checked.
400. one kind is used for container-treatment that the plastic containers of moulding are handled, the wall that this container comprises an opening and defines an inner surface, and this method comprises:
To defective the inner surface of institute's container for moulding is checked;
After institute's container for moulding is checked, a barrier coat is applied on this container; And
After applying this barrier coat, the inner surface of container is checked to defective.
401. like the described invention of claim 400, wherein the position of a plurality of tight spacings on the inner surface of this container is checked the inner surface of institute's container for moulding.
402., wherein after applying this barrier coat, the inner surface of this container is checked in the position of the lip-deep a plurality of tight spacings of this internal tank like claim 400 or 401 described inventions.
403. like claim 400,401 or 402 described inventions; Wherein the position of the lip-deep a plurality of tight spacings of this internal tank is positioned and on institute's container for moulding, checks; Apply with barrier coat, and after applying this barrier coat, reexamine.
VI.B. carry out container inspection through detection through the venting of the wall of container on blocking layer
404. a method that is used to check the blocking layer on the material of letting off steam, this method comprises:
The material sample on the blocking layer that emits gas and have at least a portion is provided; And
Measure the gas that this is emitted.
405. like the described method of claim 404, wherein this material of emitting gas comprises a kind of polymer compound.
406. like claim 404 or 405 described methods, wherein this material of emitting gas comprises a kind of thermoplastic compound.
407. like each described method of claim 404 to 406, wherein this material of emitting gas comprises a kind of polyester.
408. like each described method of claim 404 to 407, wherein this material of emitting gas comprises polyethyleneterephthalate.
409. like each described method of claim 404 to 408, wherein this material of emitting gas comprises a kind of polyolefine.
410. like each described method of claim 404 to 409, wherein this material of emitting gas comprises Vestolen PP 7052.
411. like each described method of claim 404 to 410, wherein this material of emitting gas comprises a kind of cyclic olefine copolymer.
411a., further be included in and this blocking layer contacted before measuring the gas emit with water like each described method of claim 404 to 411.
411b., further be included in and the blocking layer contacted before measuring the gas emit with steam like each described method of claim 404-411.
411c., further be included in to measure this blocking layer contacted with air under 35% to 100% the relative humidity like each described method of claim 404 to 411.
411d., further be included in to measure this blocking layer contacted with air under 40% to 100% the relative humidity like each described method of claim 404 to 411.
411e., further be included in to measure this blocking layer contacted with air under 40% to 50% the relative humidity like each described method of claim 404 to 411.
411f., further be included in and the blocking layer contacted before measuring the gas emit with oxygen like each described method of claim 404 to 411.
411g., further be included in and the blocking layer contacted before measuring the gas emit with nitrogen like each described method of claim 404 to 411.
411h. like each described method of claim 411a to 411g, wherein be from 10 seconds to one hour this duration of contact.
411i. like each described method of claim 411a to 411g, wherein be from one minute to 30 minutes this duration of contact
The described method of each of 411j such as claim 411a to 411g, wherein be from 5 minutes to 25 minutes this duration of contact
411k. like each described method of claim 411a to 411g, wherein be from 10 minutes to 20 minutes this duration of contact.
411l. like claim 404 each described method to 411k, wherein this gas of emitting is under 0.1 holder to the pressure of 100 holders, to measure.
411m. like claim 404 each described method to 411k, wherein this gas of emitting is under 0.2 holder to the pressure of 50 holders, to measure.
411n. like claim 404 each described method to 411k, wherein this gas of emitting is under 0.5 holder to the pressure of 40 holders, to measure.
411o. like claim 404 each described method to 411k, wherein this gas of emitting is under 1 holder to the pressure of 30 holders, to measure.
411p. like claim 404 each described method to 411k, wherein this gas of emitting is under 5 holders to the pressure of 100 holders, to measure.
411q. like claim 404 each described method to 411k, wherein this gas of emitting is under 10 holders to the pressure of 80 holders, to measure.
411r. like claim 404 each described method to 411k, wherein this gas of emitting is under 15 holders to the pressure of 50 holders, to measure.
411s. like claim 404 each described method to 411r, wherein this gas of emitting is under 0 ℃ to 50 ℃ temperature, to measure.
411t. like claim 404 each described method to 411r, wherein this gas of emitting is under 0 ℃ to 21 ℃ temperature, to measure.
411u. like claim 404 each described method to 411r, wherein this gas of emitting is under 5 ℃ to 20 ℃ temperature, to measure.
412. like claim 404 each described method to 411u, wherein the form with container with a wall provides the material of emitting gas, this wall has an outside surface and an internal surface, and this internal surface is around an inner chamber.
413. like the described method of claim 412, wherein this blocking layer is disposed on the internal surface of this wall of container.
414., wherein a pressure difference of crossing this blocking layer is provided through the inner chamber of finding time at least in part like claim 412 or 413 described methods.
415. like each described method of claim 412 to 414, further comprise with inner chamber via on pipe connection to a vacuum source with this inner chamber of finding time at least in part.
416., further comprise the venting measuring cell of a connection between this inner chamber and this vacuum source is provided like the described method of claim 415.
417. like each described method of claim 404 to 416, wherein measuring is to carry out through the volume of definite each timed interval through the material of emitting of this blocking layer venting.
418. like each described method of claim 404 to 417, wherein measurement is to use microfluidic technology to carry out.
419. like each described method of claim 404 to 418, the mass flow rate of the material that wherein measure to be to emit through measurement is carried out.
420., wherein measure with the mobile operation scheme of molecule and carry out like each described method of claim 404 to 419.
420a., wherein measure and carry out through following steps like each described method of claim 404 to 420:
At least one micro-cantilever is provided, and this micro-cantilever has and when a kind of material of emitting exists, moves or change over difform characteristic;
Causing that effectively this micro-cantilever moves or changes under the difform condition, this micro-cantilever is exposed in this material of emitting; And
Detect then and should move or different shapes.
420b such as the described method of claim 420a, wherein the different shapes before or after micro-cantilever is exposed to venting can detect through high energy incident beam of a part that reflects the micro-cantilever that changes shape certainly and the deflection of measuring the reflected beam that produces at a some place with this micro-cantilever interval.
420c. like the described method of claim 420b, wherein this energy incident beam is to be selected from a kind of photon beam, a kind of electron beam or these two kinds or more kinds of combinations.
420d. like the described method of claim 420b, wherein this high energy incident beam is a kind of photon beam.
420e. like the described method of claim 420b, wherein this high energy incident beam is a kind of laser beam.
420f., wherein measure and carry out through following steps like each described method of claim 404 to 420:
At least one micro-cantilever is provided, and this micro-cantilever is with a different frequency resonance when a kind of material of emitting exists;
Effectively causing under the condition of this micro-cantilever with a different frequency resonance, can this micro-cantilever be exposed in this material of emitting; And
Detect this different resonant frequency.
420g. like the described method of claim 420f, wherein this different resonant frequency is through detecting energy input in micro-cantilever before or after this micro-cantilever is exposed to venting to induce it to resonate.
420h. like the described method of claim 420g, wherein this different resonant frequency is to use a resonant transducer to detect.
421. like the described method of claim 404, wherein this material of emitting gas is that form with film provides.
422. like each described method of claim 404 to 421, wherein this blocking layer is the lip-deep coating wholly or in part at the material of venting.
425. like each described method of claim 404 to 424, wherein this blocking layer comprises SiO x, wherein x is from about 1.5 to about 2.9.
426. like each described method of claim 404 to 425, wherein this blocking layer mainly comprises SiO x, wherein x is from about 1.5 to about 2.9.
427. like each described method of claim 404 to 426, wherein this blocking layer is thick less than 500nm.
428. like each described method of claim 404 to 427, wherein this blocking layer is thick less than 300nm.
429. like each described method of claim 404 to 428, wherein this blocking layer is thick less than 100nm.
430. like each described method of claim 404 to 429, wherein this blocking layer is thick less than 80nm.
431. like each described method of claim 404 to 430, wherein this blocking layer is thick less than 60nm.
432. like each described method of claim 404 to 431, wherein this blocking layer is thick less than 50nm.
433. like each described method of claim 404 to 432, wherein this blocking layer is thick less than 40nm.
434. like each described method of claim 404 to 433, wherein this blocking layer is thick less than 30nm.
435. like each described method of claim 404 to 434, wherein this blocking layer is thick less than 20nm.
436. like each described method of claim 404 to 435, wherein this blocking layer is thick less than 10nm.
437. like each described method of claim 404 to 436, wherein this blocking layer is thick less than 5nm.
438. like each described method of claim 404 to 437, wherein the measurement to the gas of emitting is under the condition of the existence of effectively distinguishing this blocking layer or shortage, to carry out.
439., wherein effectively distinguish the existence on this blocking layer or the condition of shortage and comprise test time less than one minute like each described method of claim 438.
440., wherein effectively distinguish the existence on this blocking layer or the condition of shortage and comprise test time less than 50 seconds like the described method of claim 438.
441., wherein effectively distinguish the existence on this blocking layer or the condition of shortage and comprise test time less than 40 seconds like the described method of claim 438.
442., wherein effectively distinguish the existence on this blocking layer or the condition of shortage and comprise test time less than 30 seconds like the described method of claim 438.
443., wherein effectively distinguish the existence on this blocking layer or the condition of shortage and comprise test time less than 20 seconds like the described method of claim 438.
444., wherein effectively distinguish the existence on this blocking layer or the condition of shortage and comprise test time less than 15 seconds like the described method of claim 438.
445., wherein effectively distinguish the existence on this blocking layer or the condition of shortage and comprise test time less than 10 seconds like the described method of claim 438.
446., wherein effectively distinguish the existence on this blocking layer or the condition of shortage and comprise test time less than 8 seconds like the described method of claim 438.
447., wherein effectively distinguish the existence on this blocking layer or the condition of shortage and comprise test time less than 6 seconds like the described method of claim 438.
448., wherein effectively distinguish the existence on this blocking layer or the condition of shortage and comprise test time less than 4 seconds like the described method of claim 438.
449., wherein effectively distinguish the existence on this blocking layer or the condition of shortage and comprise test time less than 3 seconds like the described method of claim 438.
450., wherein effectively distinguish the existence on this blocking layer or the condition of shortage and comprise test time less than 2 seconds like the described method of claim 438.
451., wherein effectively distinguish the existence on this blocking layer or the condition of shortage and comprise test time less than 1 second like the described method of claim 438.
452. like each described method of claim 438-451, wherein the observed value that whether exists of blocking layer is proved the determinacy that reaches at least six σ levels.
453. like each described method of claim 438 to 452, wherein this observed value has the determinacy of at least six σ levels.
454., be effectively to confirm under the condition of the barrier improvement factor on this blocking layer of the same material that does not have the blocking layer, to carry out wherein in the measurement of the gas of emitting of the low-tension side on this blocking layer like each described method of claim 404 to 453.
455. like each described method of claim 404 to 454, the venting of wherein having measured multiple gas with various.
456. like each described method of claim 404 to 455, the venting of wherein having measured all in fact gas of emitting.
457. like each described method of claim 404 to 456, the venting of wherein having measured all in fact gas of emitting simultaneously.
458. like each described method of claim 404 to 457, the venting of wherein having measured all in fact gas of emitting simultaneously.

Claims (28)

1. method that is used to be set in the lubricity of the coating on the substrate surface, this method may further comprise the steps
(a) near this substrate surface, provide and comprise organosilicon precursor and O randomly 2Gaseous reactant; And
(b) from this vapor reaction deposits yields plasma body, on this substrate surface, form coating through plasma body enhanced chemical vapour deposition (PECVD) thus,
Wherein the lubricating property of this coating is through setting O in this gaseous reactant 2Be used to produce that the electric power of this plasma body sets with the ratio of organosilicon precursor and/or through setting.
2. method that is used in substrate, preparing hydrophobic coating, this method may further comprise the steps
(a) near this substrate surface, provide and comprise organosilicon precursor and O randomly 2Gaseous reactant; And
(b) from this vapor reaction deposits yields plasma body, on this substrate surface, form coating through plasma body enhanced chemical vapour deposition (PECVD) thus,
Wherein the hydrophobic property of this coating is through setting O in the gaseous reactant 2Be used to produce that the electric power of this plasma body sets with the ratio of organosilicon precursor and/or through setting.
3. claim 1 or 2 described methods, this method cause being characterised in that compares with total formula of said organosilicon precursor wherein that atomic ratio C: O increases and/or the coating of total formula that atomic ratio Si: O reduces.
4. each described method, wherein O in the claim 1 to 3 2With the volume-volume ratio with gaseous reactant is 0: 1 to 5: 1, randomly is 0: 1 to 1: 1, randomly is 0: 1 to 0.5: 1, randomly is that 0: 1 to 0.1: 1 amount exists, and preferably wherein in said gaseous reactant, does not have oxygen at least in fact.
5. each described method in the above claim, wherein said gaseous reactant comprises the O less than 1 volume % 2, more specifically less than the O of 0.5 volume % 2, and most preferably do not contain O 2
6. each described method in the above claim, wherein said plasma body is non-hollow cathode plasma.
7. each described method in the above claim,
(i) wherein said plasma body produces with the electrode that on substrate surface, forms coating with being provided enough power; Preferably produce with the electrode that is provided following electric power: from 0.1 to 25W; Preferably from 1 to 22W, more preferably from 3 to 17W, even more preferably from 5 to 14W; Most preferably from 7 to 11W, 8W especially; And/or
(ii) wherein the ratio of electrode power and volume of plasma preferably from 5W/ml to 0.1W/ml, more preferably is from 4W/ml to 0.1W/ml less than 10W/ml, most preferably is from 2W/ml to 0.2W/ml.
8. method that is used on substrate surface, preparing coating, this method may further comprise the steps
(a) near this substrate surface, provide and comprise organosilicon precursor and O randomly 2Gaseous reactant; And
(b) under reduced pressure from this vapor reaction deposits yields non-NULL the heart-yin utmost point plasma body, on this substrate surface, form coating through plasma body enhanced chemical vapour deposition (PECVD) thus,
Wherein through setting O in this gaseous reactant 2Set the physics and the chemical property of this coating with the ratio of organosilicon precursor and/or through the electric power that setting is used to produce this plasma body.
9. method that is used in substrate, preparing barrier coat, this method may further comprise the steps
(a) near this substrate surface, provide and comprise organosilicon precursor and O 2Gaseous reactant; And
(b) under reduced pressure from this vapor reaction deposits yields non-NULL the heart-yin utmost point plasma body, on this substrate surface, form coating through plasma body enhanced chemical vapour deposition (PECVD) thus,
Wherein through setting O in this gaseous reactant 2Set the barrier properties of this coating with the ratio of organosilicon precursor and/or through the electric power that setting is used to produce said plasma body.
10. the described method of claim 9,
(i) wherein said plasma body produces with the electrode that on this substrate surface, forms coating with being provided enough power; Preferably use the electrode be provided following electric power to produce: from 8 to 500W; Preferably from 20 to 400W; More preferably from 35 to 350W, even more preferably from 44 to 300W, most preferably from 44 to 70W; And/or
(ii) the ratio of electrode power and volume of plasma is equal to or greater than 5W/ml, preferably from 6W/ml to 150W/ml, more preferably is from 7W/ml to 100W/ml, most preferably is from 7W/ml to 20W/ml.
11. claim 9 or 10 described method, wherein O 2With with said gaseous reactant with lower volume: volumetric ratio exists: with respect to the said silicon precursor that contains from 1: 1 to 100: 1; Preferably with ratio from 5: 1 to 30: 1; More preferably with from 10: 1 to 20: 1 ratio, even 15: 1 ratio more preferably.
12. each described method in the above claim; Wherein said organosilicon precursor is selected from the group of being made up of and the following: linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, linear silicon azane, monocycle silazane, any two kinds or the more kinds of combinations that encircle silazane more, gather sesquialter silazane, alkyl trimethoxy siloxane and these compounds, preferably linearity or monocycle siloxanes.
13. claim 1 or 2 described methods, wherein said organosilicon precursor is the monocycle siloxanes, preferred OMCTS.
14. claim 2 or 9 described methods, wherein said organosilicon precursor is a linear siloxane, preferred HMDSO.
15. each described method in the above claim, wherein said substrate are the polymkeric substance that is selected from down group: polycarbonate, olefin polymer, cyclic olefine copolymer and polyester, and preferably cyclic olefine copolymer, polyethyleneterephthalate or Vestolen PP 7052.
16. each described method in the above claim; The electrode that wherein said plasma body is used in energy supply under the radio frequency produces; Preferably be used in from 10kHz extremely less than 300MHz; More preferably from 1 to 50MHz, even more preferably from 10 to 15MHz, most preferably the electrode of energy supply produces under the frequency of 13.56MHz.
17. a coating, this coating can obtain through each described method in the above claim.
18. the described coating of claim 17, this coating are slip coating and/or hydrophobic coating.
19. the described coating of claim 18, wherein carbon is compared increase with the atom ratio of oxygen with organosilicon precursor, and/or wherein oxygen is compared reduction with the atom ratio of silicon with organosilicon precursor.
20. each described coating, wherein this coating in the claim 18 to 19
(i) have than uncoated surperficial low friction resistance, wherein compare with uncoated surface, this friction resistance preferably is reduced by at least 25%, more preferably is reduced by at least 45%, even more preferably is reduced by at least 60%.
21. each described coating in the claim 18 to 20, this coating
(i) have than uncoated surperficial low wetting tension; Preferably have 20 wetting tensions to 72 dyne/cm; More preferably have 30 wetting tensions, more preferably have 30 wetting tensions, preferably have the wetting tension of 34 dyne/cm to 40 dyne/cm to 60 dyne/cm; And/or
(iv) be more hydrophobic than uncoated surface.
22. the container that has each described coating in the claim 17 to 21 at least a portion on portion surface within it, preferred following container:
(i) sample collection tube, heparin tube particularly; Or
(ii) bottle; Or
(iii) syringe or syringe part, syringe cylinder or syringe plunger particularly; Or
(iv) pipe; Or
(v) cuvette.
23. the container of the described coating of claim 22, it comprises at least one SiO in addition xLayer, wherein x is 1.5 to 2.9, wherein
(i) said coating is positioned at said SiO xBetween layer and the said substrate surface, or vice versa, or wherein
(ii) said coating is positioned at two SiO xBetween the layer or vice versa, or wherein
(iii) a plurality of SiO xLayer and said coating are Si wO xC yH zTo SiO xGradient composites, or vice versa.
24. the container of each described coating in the claim 22 to 23; This container holds compound or compsn in the chamber within it; Preferably bioactive compounds or compsn or biological fluid, more preferably (i) Citrate trianion or contain the compsn of Citrate trianion, (ii) medicament; Regular Insulin or contain the compsn of Regular Insulin particularly, or (iii) blood or hemocyte.
25. the container of each described coating in the claim 22 to 24; The container of this coating is the syringe cylinder that method according to claim 1 is made; Wherein said precursor is a siloxanes; More preferably be the monocycle siloxanes, even more preferably be octamethylcyclotetrasiloxane, and wherein in step (a), do not have O basically 2Gas is provided in the said gaseous reactant, wherein compares with uncoated syringe cylinder, is used for the power of mobile plunger through the socket of said coating and is reduced by at least 25%, more preferably is reduced by at least 45%, even more preferably is reduced by at least 60%.
26. have total formula Si wO xC yH zThe coating conduct
(i) has slip coating than uncoated surperficial low friction resistance; And/or
The purposes of (ii) more hydrophobic hydrophobic coating than uncoated surface, wherein
W is 1,
X is 0.5 to 2.4,
Y is 0.6 to 3, and
Z is 2 to 9.
27. the purposes of the container of each described coating in the claim 22 to 25; Be used for protecting compound or the compsn of the container that is received or is received in said coating to avoid the machinery and/or the chemical action on the surface of uncoated container material, be preferred for preventing or reduce the compound or the component deposition of the compsn that contacts with the inner surface of this container and/or solidify.
28. the described purposes of claim 27, wherein said compound or compsn are
(i) bioactive compounds or compsn, medicament preferably is more preferably Regular Insulin or comprises the compsn of Regular Insulin, and wherein insulin precipitation is reduced or prevents; Or
(ii) biological fluid, preferably body fluid is more preferably blood or blood ingredient, and wherein blood coagulation is reduced or prevents.
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Application Number Priority Date Filing Date Title
US17798409P 2009-05-13 2009-05-13
US61/177,984 2009-05-13
US22272709P 2009-07-02 2009-07-02
US61/222,727 2009-07-02
US21390409P 2009-07-24 2009-07-24
US61/213,904 2009-07-24
US23450509P 2009-08-17 2009-08-17
US61/234,505 2009-08-17
US26132109P 2009-11-14 2009-11-14
US61/261,321 2009-11-14
US26328909P 2009-11-20 2009-11-20
US61/263,289 2009-11-20
US28581309P 2009-12-11 2009-12-11
US61/285,813 2009-12-11
US29815910P 2010-01-25 2010-01-25
US61/298,159 2010-01-25
US29988810P 2010-01-29 2010-01-29
US61/299,888 2010-01-29
US31819710P 2010-03-26 2010-03-26
US61/318,197 2010-03-26
US33362510P 2010-05-11 2010-05-11
US61/333,625 2010-05-11
EP10162757.8 2010-05-12
EP10162761.0A EP2251455B1 (en) 2009-05-13 2010-05-12 PECVD coating using an organosilicon precursor
EP10162761.0 2010-05-12
EP10162758.6A EP2251671B1 (en) 2009-05-13 2010-05-12 Outgassing method for inspecting a coated surface
EP10162755.2A EP2253735B1 (en) 2009-05-13 2010-05-12 Vessel processing
EP10162760.2A EP2251454B1 (en) 2009-05-13 2010-05-12 Vessel coating and inspection
EP10162757.8A EP2251453B1 (en) 2009-05-13 2010-05-12 Vessel holder
EP10162756.0A EP2251452B1 (en) 2009-05-13 2010-05-12 Pecvd apparatus for vessel coating
EP10162760.2 2010-05-12
EP10162755.2 2010-05-12
EP10162756.0 2010-05-12
EP10162758.6 2010-05-12
PCT/US2010/034586 WO2010132591A2 (en) 2009-05-13 2010-05-12 Pecvd coating using an organosilicon precursor

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CN104684592A (en) * 2012-08-29 2015-06-03 心脏起搏器股份公司 Enhanced low friction coating for medical leads and methods of making
CN106337170A (en) * 2015-07-06 2017-01-18 友技科株式会社 Plasma chemical vapor deposition device and film forming method
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CN108463493A (en) * 2015-11-16 2018-08-28 Sio2医药产品公司 The polymer substrate on the surface with the biomolecule adherency for possessing reduction and the thermoplastic article of this substrate
CN108463493B (en) * 2015-11-16 2021-10-15 Sio2医药产品公司 Polymeric substrate having a surface with reduced biomolecule adhesion and thermoplastic articles of such substrate
CN107460448A (en) * 2017-08-04 2017-12-12 中国科学院宁波材料技术与工程研究所 A kind of modified coatings of matrix surface and preparation method thereof
CN109913856A (en) * 2019-04-24 2019-06-21 佛山市思博睿科技有限公司 A kind of method of plasma reinforced chemical vapour deposition hydrophobic membrane in microchannel
CN110158057A (en) * 2019-06-05 2019-08-23 承德石油高等专科学校 A kind of pecvd process chamber bye-pass device and its air-channel system at place
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