CN102459693B - Use the PECVD coating of organosilicon precursor - Google Patents

Abstract

There is provided herein for a kind of method by PECVD coated substrate surface, the method comprises from comprising a kind of organosilicon precursor and optionally O ₂a kind of gaseous reactant produce a kind of plasma body.By arranging O in this gaseous reactant ₂with the ratio of this organosilicon precursor, and/or the oilness of this coating, hydrophobicity and/or barrier properties are set by arranging the electric power used for generation of this plasma body.Particularly, a kind of slip coating manufactured by described method is provided.Additionally provide the container and these containers that apply by described method for the protection of a kind of compound being received or being received in described coating container or composition the machinery from the surface of this uncoated container material and/or the purposes of chemical action.

Description

Use the PECVD coating of organosilicon precursor

Invention field

The present invention relates to the technical field of the manufacture of the coating container storing biologically active compound or blood.Especially, the present invention relates to a kind of container processing systems for container coating, for the container processing systems that container applies and checks, relate to a kind of carry-case support for container processing systems, relate to a kind of plasma enhanced chemical vapor deposition unit of the internal surface for coating container, relate to a kind of method of the internal surface for coating container, relate to a kind of method for checking container coating, relate to a kind of method of processing vessel, relate to a kind of purposes of container processing systems, relate to a kind of computer-readable medium and relate to a kind of program element.

The invention provides for a kind of method by PECVD coated substrate surface, the method comprises produce a kind of plasma body from a kind of gaseous reactant comprising a kind of organosilicon precursor and optionally O2.Wherein by arranging the ratio of O2 and this organosilicon precursor in this gaseous reactant, and/or the oilness of this coating, hydrophobicity and/or obstacle character are set by arranging the electric power used for generation of this plasma body.Particularly, the invention provides a kind of lubricating coating manufactured by described method.Present invention also offers the purposes of container and these containers applied by described method, this purposes is a kind of compound or mixture that to be contained in described coating container according to the machinery on this uncoated container material surface and/or chemical effect protection package or to be received by described coating container.

This disclosure also relates to improving one's methods for the treatment of container, and such as, the multiple identical container collected for venipuncture and other medical sample, pharmaceutical preparation store and transport and other object.This container is by a large amount of for these objects, and these containers must be relatively economical in the mill and also be very reliable in storage and transport.

Background of invention

Such as, vacuum test tube is used for extracting from patient the blood being used for medical analysis.These pipes are evacuated and sell.By piercing through the closure member of this vacuum test tube at the other end of this two ends syringe needle in the blood vessel that one end of a two ends hypodermic needle is inserted into patient, the blood of patient is communicated to the inside of a pipe.Vacuum in vacuum test tube is entered blood draw (or precisely, the blood pressure of patient has promoted blood) in this vacuum test tube by syringe needle, increases pressure in this pipe and because this reducing the pressure reduction causing blood flow.Typically blood flow continue until this pipe from syringe needle remove or this pressure reduction too little and can not support flowing.

Vacuum test tube should have a substantial quality guaranteed period with contribute to these pipe before the use effectively and distribute easily and store.Such as, quality guaranteed period of 1 year makes us wishing, and progressive longer quality guaranteed period in some cases, as 18 months, 24 months, or within 36 months, be also desired.This pipe desirably keeps perfect vacuum substantially, at least reach and extract enough necessary degree of blood (common standard is that this pipe will keep 90% of at least original extraction volume) for analyzing, for the whole quality guaranteed period, seldom (not having best) provides defective pipe.

A defective pipe likely causes bleeder that this pipe can not be used to extract enough blood.So bleeder may need to obtain and use one or more other pipe to obtain an enough blood sample.

Again such as, precharging type syringe is normally ready and sells, and therefore this syringe does not need to fill before use.In some instances, can with salts solution, a kind of dyestuff for injecting or a kind of pharmaceutical activity preparation pre-filled syringe.

Normally, precharging type syringe is add cap (as with a cap) at far-end, and is closed at the plunger that pulls proximally by it.Before the use can by prefilled injector package in a kind of sterile packed.In order to use this precharging type syringe, remove packaging and cap, optionally 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 in the blood vessel by hypodermic needle being inserted into patient or the content being with this syringe stand-by carry out in the device rinsed), and this plunger advances the content injecting this in this.

In manufacture precharging type syringe process, important consideration is that the content of this syringe desirably will have a substantial quality guaranteed period, making the material of this syringe of filling be important with isolating containing the barrel of this material during this period, entering in these pre-filled contents to avoid the leaching material from this or vice versa.

Because these many containers are inexpensive and are widely used, will usefully for some application, the necessary quality guaranteed period is reliably obtained when manufacturing cost not being increased to a high untouchable level.And, for some application, make us desirably avoiding Glass Containers (Glass Containers may damaged and be expensive for manufacture) and prefer during normal use seldom damaged plastic containers (and if breakage does not form the sharp-pointed fragment of the residue from container yet, and the fragment as Glass tubing can be formed).Glass Containers by preference be because compared with untreated plastics for the content of pre-filling glass be more bubble-tight and inertia.Further, because its tradition uses, glass is generally accepted, since it is known when glass contacts with medical sample or pharmaceutical preparation etc. be relative harmless.

Further consider it is guarantee that it can move with constant speed and constant power when plunger to be compressed into tin about one of syringe.For this purpose, a slip coating on one of cylinder and plunger or both makes us wishing.

The patent portfolio that may be correlated with of a non-exhaustive nothing left comprises United States Patent (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 is to provide a kind of manufacture of coating container of improvement.

The device multiple method being described below and manufacturing according to these methods, wherein these methods can be undertaken by the container processing systems further described below and these devices can be manufactured by this system.

The invention provides a kind of method carrying out coated surface (interior surface of such as container) by coating (being manufactured by organosilicon precursor by PECVD).In addition, the invention provides the coating of generation, be coated with the purposes (such as, as slip coating, hydrophobic coating or barrier coat) of the container of such coating and this coating.And, provide for carrying out device of the present invention and several equipment.Present invention also offers the inspection method for this coating, particularly the venting of the volatile species (volatilespecies) by coated surface is used for a kind of method of described inspection.

PECVD coating method

The present invention relates to the method that a kind of chemical vapor deposition process by plasma enhancing (PECVD) prepares coating, and the method for such as a kind of interior surface of coating container.

Provide a surface (such as an inner container surface), as being both a kind of reaction mixture, this mixture comprises a kind of organic silicon compound gas, optionally a kind of oxidizing gas, and optionally a kind of appropriate hydrocarbon gas.

This surface contacts with this reaction mixture.Plasma body is formed in the reactive mixture.Preferably, described plasma body is non-hollow cathode plasma, or in the another kind statement of same case, described plasma body is gone up substantially not containing hollow cathode plasma.This coating is deposited at least one part (part of such as this container inner wall) on this surface.

The method is following realization.

Provide a kind of precursor.Preferably, described precursor is a kind of silicoorganic compound (being also appointed as below " organosilicon precursor "), more preferably be selected from a kind of silicoorganic compound of lower group, this group is made up of the following: two or more combination any of the aza analogues of linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, alkyl trimethoxysilane, these precursors any (that is, linear silicon azane, monocycle silazane, many cyclosilazanes, poly-sesquialter silazane) and these precursors.Under the condition effectively forming a kind of coating by PECVD, this precursor is applied in a kind of substrate.So this precursor is polymerized, be cross-linked, partially or even wholly oxidation or any combination among these.

In one aspect of the invention, this coating is a slip coating, and namely it forms a surface with the friction resistance lower than uncoated substrate.

In another aspect of the present invention, this coating is a kind of passivating coating, such as a kind of hydrophobic coating causing less precipitation of the component of the composition such as contacted with this coated surface.The feature of such hydrophobic coating is 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 in, this coating is a kind of barrier coat, such as a kind of SiO _xcoating.Typically, this blocking layer is anti-gas or liquid, preferably water vapor, oxygen and/or air.This blocking layer can also be used set up and/or maintain the vacuum of the internal tank (such as a heparin tube inside) being coated with this barrier coat.

In addition, method of the present invention can comprise the applying of the one or more other coating manufactured from a kind of organosilicon precursor by PECVD.Optional other step be with substantially by oxygen form and a kind of process gas being substantially free of volatile silicon compound to this SiO _xcoating carries out aftertreatment.

Slip coating

In concrete at one, the invention provides a kind of slip coating.

This coating is by PECVD method and use precursor as above and advantageously manufacture.

Such as, the invention provides a kind of method of the lubricating property for arranging a kind of coating on the surface of the substrate, the method comprises the following steps:

A () provides a kind of gaseous reactant near this substrate surface, this gaseous reactant comprises a kind of organosilicon precursor and optionally O ₂; And

B () produces a kind of plasma body from this gaseous reactant, therefore on this substrate surface, form a coating by the chemical vapour deposition (PECVD) of plasma enhancing, wherein the lubricating property of this coating is by arranging O in this gaseous reactant ₂with the ratio of organosilicon precursor and/or by arranging, the electric power used for generation of this plasma body carries out arranging.

A preferred precursor for this slip coating is monocycle siloxanes, such as octamethylcyclotetrasiloxane (OMCTS).

Compared with untreated substrate, the coated surface produced has lower friction resistance.Such as, when this coated surface is the inside of syringe cylinder and/or syringe plunger, this slip coating effectively provide the starting force (breakoutforce) or plunger sliding force that are less than the corresponding power required when this slip coating lacks or both.

The article being coated with slip coating can be (preferably on inwall) a kind of containers with slip coating on wall, such as syringe cylinder or there is a kind of container parts or the container cap of described coating on container contact surface, such as a kind of syringe plunger or a kind of container cap.

In one aspect, this slip coating can have formula Si _wo _xcyH _z, such as wherein w is 1, x be 1, x be from about 0.5 to about 2.4, y is from about 0.6 to about 3, and z is from about 2 to about 9, preferably wherein w to be 1, x be from about 0.5 to 1, y is from about 2 to about 3, and z is from 6 to about 9.

Passivation, such as hydrophobic coating

Passivating coating according to the present invention is such as a kind of hydrophobic coating.

The preferred precursor of one for passivation (such as hydrophobic coating) is a kind of linear siloxane, such as hexamethyldisiloxane (HMDSO).

A kind of passivating coating according to the present invention prevent or reduces uncoated surface to the machinery of the compound comprised in this embodiment or composition and/or chemical action.Such as, prevent or reduce a kind of compound of the composition contacted with this surface or the precipitation of component and/or solidify or platelet activation, such as, preventing blood coagulation or platelet activation or insulin precipitation or uncoated surface to be soaked 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, such as wherein w is 1, x be from about 0.5 to about 2.4, y is from about 0.6 to about 3, and z is from about 2 to about 9, preferably wherein w to be 1, x be from about 0.5 to 1, y is from about 2 to about 3, and z is from 6 to about 9.

The article being coated with passivating coating can be (preferably on inwall) a kind of containers with this coating on wall, such as pipe or there is a kind of container parts or the container cap of described coating on container contact surface, such as a kind of container cap.

The coating of container

When using PECVD to carry out coating container by above-mentioned coating method, this coating method comprises several step.Provide a kind of container, this container has an opening end, a closing end and an interior surface.At least one gaseous reactant is introduced in this container.Within this container, plasma body is formed under the condition of reaction product (i.e. a coating in the interior surface of this container) effectively forming this reactant.

Preferably, the method is by making the opening end of this container be seated on a pan straddle as described herein, sets up a sealing be communicated with and carry out between this pan straddle and inside of this container.In this is preferred, this gaseous reactant is introduced in this container by this pan straddle.Of the present invention one particularly preferred in, by comprise a pan straddle, internal electrode, an outer electrode and a power supply plasma enhanced chemical vapor deposition (PECVD) device be used for according to coating method of the present invention.

This pan straddle has a port, with by container reception a position of taking a seat for the treatment of.This internal electrode is located thus is needed to be received within the container that is seated on a pan straddle.This outer electrode has an internal portion, and this internal portion is located to receive the container be seated on this pan straddle.Alternating-current to be input on these inner and/or outer electrodes thus to form a kind of plasma body being seated in the container on this pan straddle by this power supply.Typically, alternating-current is input on this outer electrode that this internal electrode is ground connection by this power supply.In this embodiment, this plasma-reaction-chamber is the container defined.

Of the present invention one concrete in, PECVD device as in the previous paragraph comprises the eduction pipe that must not comprise vacuum source, for by gas transfer to the inside of the container of taking a seat on that port or transmit from the gas of the inside of this container, to limit a closed-chamber.

Of the present invention one further concrete in, this PECVD device comprises a pan straddle, first clamp, a seat on this pan straddle, reactant feeding mechanism, a plasma generator and a container releasing device.

This pan straddle be arranged to be seated at a container opening end on.This first clamp is arranged to the closing end that optionally keeps and discharge container and clamps the closing end of this container simultaneously, is transported near this pan straddle by this container.This pan straddle has a seat, and this is arranged to sets up being communicated with of sealing between this pan straddle and the internal space of this first container.

This reactant feeding mechanism is operably connected for being incorporated in this first container by least one gaseous reactant by this pan straddle.This plasma generator forms plasma body under being arranged to the condition of the reaction product of effective forming reactions thing in the interior surface of this first container in this first container.

Provide this container releasing device for being removed by this first container from this pan straddle.Clamp (this clamp is the first clamp or another clamp) is arranged to axially transports this first container and leaves this pan straddle and then discharge this first container.

Of the present invention one concrete in, the method is the internal surface of the opening for carried out coating container by PECVD one restriction, the such as container of a generally tubular.The opening that this container comprises an outer surface, define an internal surface of an inner chamber, have one of internal diameter larger opening and a restriction, the opening of this restriction limit by the internal surface and compared with the internal diameter of big uncork, there is less internal diameter compared to this.Provide a kind of processing vessel, this processing vessel has an inner chamber and a processing vessel opening.This processing vessel opening is connected with the opening of the restriction of this container thus opening via this restriction is communicated with having to set up between the inner chamber of pending container with processing vessel inner chamber.At least part of vacuum is pumped into by having within the inner chamber of pending container and processing vessel inner chamber.PECVD reactant is flowed through this first opening, then by there being the inner chamber of pending container, then by the opening of this restriction, then enters the inner chamber of this processing vessel.Near the opening of this restriction, plasma body is produced under condition on the internal surface of the opening coating of a PECVD reaction product being effectively deposited on restriction.

The container of coating and container parts

Invention further provides the coating produced from method as above, the surface being coated with described coating and be such as coated with the container of described coating.

The surface (such as wall of container or its part) being coated with this coating can be glass or a kind of polymkeric substance, preferably a kind of thermoplastic polymer, more preferably be selected from a kind of polymkeric substance of lower group, this group is made up of the following: a kind of polycarbonate, a kind of olefin polymer, a kind of cyclic olefine copolymer and a kind of polyester.Such as, it is a kind of cyclic olefine copolymer, a kind of polyethylene terephthalate or a kind of polypropylene.

Of the present invention one concrete in, this wall of container have by least one external polymer layer around an inner polymeric layer.These polymkeric substance can be identical or different.Such as, one of these polymer layers of cyclic olefine copolymer (COC) resin (such as, defining a water vapor barrier layer), another polymer layer is a layer of vibrin.Such container is that by COC and polyester resin layer, a kind of method introduced in an injection mold manufactures by comprising by concentric injection nozzle.

Coating container of the present invention can be empty, find time or (in advance) be filled with a kind of compound or composition.

A concrete aspect of the present invention is the container with a kind of passivating coating (such as a kind of hydrophobic coating as defined above).

A further concrete aspect of the present invention is the surface with a slip coating as defined above.It can be (preferably on inwall) a kind of container with slip coating on wall, such as syringe cylinder or there is a kind of container parts or the container cap of described coating on container contact surface, such as 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, a syringe cylinder and the slip coating as defined above of (preferably on the inwall of this syringe cylinder) on one of these syringe parts or both.This syringe cylinder comprises a cylinder, and this has the interior surface that receives a plunger slidably.In the interior surface that this slip coating can be disposed in this syringe cylinder or contact on this plunger surface or on described both surfaces.This slip coating effectively reduces for the necessary starting force of mobile plunger in cylinder or plunger sliding force.

A further concrete aspect of the present invention be coated with as in earlier paragraphs the syringe cylinder of slip coating that defines.

Of syringe cylinder of described coating concrete in, this syringe cylinder comprises a cylinder, and this defines an inner chamber and has the interior surface that receives a plunger slidably.This syringe cylinder is advantageously made up of thermoplastic material.By the chemical vapour deposition (PECVD) of plasma enhancing a slip coating is applied to this interior surface, this plunger or both on.A kind of solute restraining mass (soluteretainer) is applied on this slip coating by surface treatment by the amount such as entered in this inner chamber effectively to reduce this slip coating, this thermoplastic material or both leachings.This slip coating and solute restraining mass effectively provide a starting force, plunger sliding force or both relative quantity less than the corresponding power required when lacking this slip coating and solute restraining mass form and exist.

Another aspect again of the present invention is a kind of syringe, and this syringe comprises a plunger, syringe cylinder and inner and exterior coating.This has the interior surface and an outer surface that receive this plunger slidably.A slip coating is positioned in interior surface, and can by SiO _xthe other barrier coat of (wherein x is from about 1.5 to about 2.9) one is provided in this interior surface.Such as 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, a syringe cylinder and a female Luer (Luerfitting).This syringe cylinder has the interior surface receiving this plunger slidably.This female Luer comprises a Luer taper (Luertaper), and this Luer taper has the internal passages limited by an internal surface.This female Luer is formed with the form of the separation member be separated with this syringe cylinder and is connected on this syringe cylinder by a junctor.The internal passages of Luer taper has the barrier coat of SiOx (wherein x is from about 1.5 to larger about 2.9).

Another aspect of the present invention is a kind of plunger for syringe, and this plunger comprises a piston and a push rod.This piston has before one, the side of a substantial cylindrical and a rear section, and this side is configured to be seated within 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 piston is advanced in syringe cylinder.This plunger additionally can comprise a SiO _xcoating.

A further aspect of the present invention is the container only with an opening, namely for collecting or store a kind of container of a kind of compound or composition.In concrete at one, such container is a kind of pipe, such as a kind of sampling tube, such as a kind of heparin tube.Described pipe can close with a closure member (such as a cap or stopper).Such lid or stopper can comprise one according to slip coating of the present invention on its surface contacted with pipe, and/or it can comprise one according to passivating coating of the present invention on the surface of its inner chamber towards this pipe.In concrete at one, such stopper or its part can be made up of a kind of elastomer material.

A kind of stopper like this can manufacture as follows: be placed at by stopper in a room of substantially finding time.There is provided a kind of reaction mixture, this reaction mixture comprises a kind of organic silicon compound gas, optionally a kind of oxidizing gas and optionally a kind of appropriate hydrocarbon gas.Plasma body is formed in the reaction mixture contacted with this stopper.A painting is deposited upon going up at least partially of this stopper.

A further aspect of the present invention is a kind of container had according to barrier coat of the present invention.This container is generally tubular and can be made up of thermoplastic material.This container has an opening and at least partly by an inner chamber that wall limits.This wall has an internal surface of demarcating with this inner chamber.In preferred at one, by SiO as defined above _xone that makes at least substantially continuous print barrier coat be applied on the internal surface of this wall.This barrier coat effectively keeps its initial vacuum level of in this container at least 90%, and optionally its initial vacuum level of 95%, continues the quality guaranteed period of at least 24 hours.Provide a closure member, this closure member cover this container opening and make the inner chamber of this container and ambient air isolated.

The coating using the PECVD of organosilicon precursor as described in this description to manufacture and PECVD coating method are also useful for coating conduit or cuvette to form a barrier coat, a hydrophobic coating, a slip coating or among these more than one.Cuvette be a kind of have circle or square-section, one end sealing, by polymkeric substance, glass or fused quartz (for UV light) manufacture and be designed to hold the miniature valve of sample for spectrum experiment.Best cuvette is transparent as far as possible, does not have possibility to affect the impurity of spectrum reading.As same test tube, cuvette can be to atmosphere opening or have a cap thus by its hermetically closing.The coating of applying PECVD of the present invention can be very thin, transparent and optics is smooth, therefore 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 a kind of coating container as above, and this container is filled with a kind of compound or composition by pre-fill or for filling with a kind of compound or composition in its inner chamber.Described compound or composition can be

A kind of bioactive compounds or composition, preferred a kind of medicament, more preferably Regular Insulin or comprise a kind of composition of Regular Insulin; Or

A kind of biofluid, preferred a kind of body fluid, more preferably blood or a kind of blood ingredient (such as, hemocyte); Or

In this embodiment for a kind of compound of directly combining mutually with another kind of compound or composition or composition, such as in heparin tube for preventing a kind of compound of blood coagulation or platelet activation, as Citrate trianion or the composition containing Citrate trianion.

Usually, coating container of the present invention is for collection or to store the machinery on the surface of uncoated container material and/or a kind of compound of chemical action sensitivity or composition be useful especially, preferably for preventing or reducing a kind of compound of the composition contacted with the interior surface of this container or a kind of precipitation of component and/or solidify or platelet activation.

Such as, have the wall of a kind of hydrophobic coating of the present invention is equipped with and the cell accommodating a kind of aqueous citric acid sodium reagent prepare pipe and be suitable for collecting blood and preventing or reduce blood coagulation.This aqueous citric acid sodium reagent is disposed in the inner chamber of this pipe effectively to suppress to introduce an amount of the blood coagulation in this pipe.

A concrete aspect of the present invention is the container for a kind of container or a kind of containment blood collecting/receive blood.This container has a wall; This wall has the internal surface defining an inner chamber.The internal surface of this wall has an at least part of hydrophobic coating of the present invention.This coating can be thin as monomolecular thickness or thick in about 1000nm.The blood being collected or storing in this embodiment preferably turns back in the vascular system of patient in the mode that can live and is disposed in the inner chamber contacted with coating.Compared with the uncoated wall of identical type, this coating effectively reduces solidifying of the blood being exposed to this internal surface or platelet activation.

Another aspect of the present invention is a kind of container holding Regular Insulin, and this container comprises a wall with the internal surface defining an inner chamber.This internal surface has an at least part of hydrophobic coating of the present invention.This coating can be thick to about 1000nm from monomolecular thickness on an internal surface.Regular Insulin or a kind of composition comprising Regular Insulin are disposed in this inner chamber contacted with this coating.Optionally, compared with lacking the similar face of this coating, this coating effectively reduces and forms precipitation from the Regular Insulin of contact internal surface.

Therefore about the purposes of coating method, coated product and described product, the invention provides following instance:

(1) for arranging a method for the lubricating property of coating on the surface of the substrate, the method comprises the following steps:

A () provides and comprises a kind of organosilicon precursor or optionally O near this substrate surface ₂a kind of gaseous reactant; And

B () produces a kind of plasma body from this gaseous reactant, form a coating thus by the chemical vapour deposition (PECVD) of plasma enhancing on this substrate surface,

Wherein the lubricating property of this coating is by arranging O in gaseous reactant ₂with the ratio of organosilicon precursor, and/or arranged for generation of the electric power that this plasma body uses by setting.

(2) for preparing a method for hydrophobic coating in a kind of substrate, the method comprises the following steps:

A () provides and comprises a kind of organosilicon precursor and optionally O near this substrate surface ₂gaseous reactant; And

B () produces a kind of plasma body from this gaseous reactant, form a kind of coating thus by the chemical vapour deposition (PECVD) of plasma enhancing on this substrate surface,

Wherein the hydrophobic property of this coating is by arranging O in gaseous reactant ₂with the ratio of this organosilicon precursor, and/or arranged for generation of the electric power that this plasma body uses by setting.

(3) method as described in (1) or (2), which results in a kind of coating, this coating is characterized as being a total formula, and wherein compared with total formula of organosilicon precursor, atomic ratio C: O is increase and/or atomic ratio Si: O is reduce.

(4) method Gen Ju (1) to any one in (3), wherein O ₂with existing with lower volume-volumetric ratio relative to gaseous reactant: from 0: 1 to 5: 1, optionally from 0: 1 to 1: 1, optionally from 0: 1 to 0.5: 1, optionally from 0: 1 to 0.1: 1, preferably wherein in this gaseous reactant, at least there is not oxygen in fact.

(5) method Gen Ju (1) to any one in (4), wherein this gaseous reactant comprises the O being less than 1 volume % ₂, be more specifically less than the O of 0.5 volume % ₂, and be most preferably not containing O ₂.

(6) method Gen Ju (1) to any one in (5), wherein this plasma body is non-hollow cathode plasma.

(7) method Gen Ju (1) to any one in (6), wherein this substrate is the inwall of the container with 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) method Gen Ju (1) to any one in (7)

I () wherein this plasma body electrode produces, these electrodes with enough power energy supplies thus on the surface of the substrate form a coating, preferably use the electrode providing 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 from 4W/ml to 0.1W/ml, is most preferably from 2W/ml to 0.2W/ml.

(9) for preparing an a kind of method of coating on the surface of the substrate, the method comprises the following steps

A () provides and comprises a kind of organosilicon precursor and optionally O near this substrate surface ₂a kind of gaseous reactant; And

B () under reduced pressure produces a kind of non-hollow cathode plasma from this gaseous reactant, form a coating thus by the chemical vapour deposition (PECVD) of plasma enhancing on this substrate surface,

Wherein by arranging O in this gaseous reactant ₂with the ratio of this organosilicon precursor, and/or the physics and chemistry characteristic of this coating is set by arranging the electric power used for generation of this plasma body.

(10) for preparing a method for a barrier coat in substrate, the method comprises the following steps:

A () providing package near this substrate surface contains a kind of organosilicon precursor and O ₂a kind of gaseous reactant; And

B () under reduced pressure produces a kind of non-hollow cathode plasma from this gaseous reactant, form a coating thus by the chemical vapour deposition (PECVD) of plasma enhancing on this substrate surface,

Wherein by arranging O in this gaseous reactant ₂with the ratio of this organosilicon precursor, and/or the barrier properties of this coating is set by arranging the electric power used for generation of plasma body.

(11) according to the method for (10)

I () wherein this plasma body electrode produces, these electrodes carry out energy supply with enough power thus form a coating on this substrate surfaces, preferably use the electrode providing 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) 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 from 7W/ml to 100W/ml, is most preferably from 7W/ml to 20W/ml.

(12) according to the method for (10) or (11), wherein O ₂with relative to this gaseous reactant with lower volume: volumetric ratio exists: relative to containing silicon precursor from 1: 1 to 100: 1, preferably with from 5: 1 to 30: 1 ratio, more preferably with from 10: 1 to 20: 1 ratio, even more preferably with 15: 1 ratio.

(13) method as described in (1) to any one in (12), wherein this organosilicon precursor is selected from lower group, this group is made up of the following: two or more combination any of linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, linear silicon azane, monocycle silazane, many cyclosilazanes, poly-sesquialter silazane, alkyl trimethoxy siloxane and these compounds, preferably linear or monocycle siloxanes.

(14) method as described in (1) or (2), wherein this organosilicon precursor is a kind of monocycle siloxanes, preferred OMCTS.

(15) method as described in (2) or (10), wherein this organosilicon precursor is a kind of linear siloxane, preferred HMDSO.

(16) method Gen Ju (1) to any one in (15), wherein this PECVD carries out under the flow rate of following organosilicon precursor: be equal to or less than 6sccm (" standard cubic centimeter/per minute "), be preferably equal to or less than 2.5sccm, be more preferably equal to or less than 1.5sccm, be most preferably equal to or less than 1.25sccm.

(17) method Gen Ju (1) to any one in (16), wherein this substrate is selected from a kind of polymkeric substance of lower group, this group is made up of the following: polycarbonate, olefin polymer, cyclic olefine copolymer and polyester, and is preferably cyclic olefine copolymer, polyethylene terephthalate or polypropylene.

(18) method Gen Ju (1) to any one in (17), wherein this substrate surface is the part or all of of the internal surface of a container with at least one opening and an internal surface, and wherein this gaseous reactant fills the inner lumen of this container, and the inner lumen of this container part or all in produce this plasma body.

(19) method Gen Ju (1) to any one in (18), wherein this plasma body is used in the electrode of energy supply under following radio frequency to produce: preferably from 10kHz under the frequency being less than 300MHz, more preferably from 1 to 50MHz, even more preferably from 10 to 15MHz, most preferably at 13.56MHz.

(20) method Gen Ju (1) to any one in (19), wherein this plasma body be under reduced pressure produce and this decompression is less than 300mTorr, is preferably less than 200mTorr, is even more preferably less than 100mTorr.

(21) according to the method described in any one of (1) to (20), wherein this PECVD depositing time is from 1 to 30 second, preferably from 2 to 10 seconds, more preferably from 3 to 9 seconds.

(22) according to the method described in any one of (1) to (21), wherein produced coating has from the thickness in the scope of 1 to 100nm, preferably from the scope of 20 to 50nm.

(23) coating, this coating can be obtained by the method according to any one of above claim.

(24) coating as described in (23), it is a kind of slip coating and/or hydrophobic coating.

(25) coating as described in (24), compared with organosilicon precursor, wherein the atom ratio of carbon and oxygen increases, and/or compared with organosilicon precursor, wherein the atom ratio of oxygen and silicon reduces.

(26) coating as described in any one of (23) to (25), wherein this precursor is octamethylcyclotetrasiloxane, and wherein this coating has a density, this density higher than under identical PECVD reaction conditions from the density of coating that HMDSO manufactures.

(27) according to the coating described in any one of (24) to (26), its floating coat (i) has the friction resistance lower than uncoated surface, compared with uncoated surface, wherein this friction resistance is preferably reduced by least 25%, more preferably be reduced by least 45%, be even more preferably reduced by least 60%.

(28) according to the coating described in any one of (24) to (27), this coating

I () has the wet tension lower than uncoated surface, preferably from the wet tension of 20 to 72 dyne/cm, more preferably from the wet tension of 30 to 60 dyne/cm, more preferably from the wet tension of 30 to 40 dyne/cm, preferably 34 dyne/cm; And/or

(iv) more hydrophobic than uncoated surface.

(29) it interior surface at least partially on a kind of container carrying out applying according to the coating described in any one of (23) to (28), preferably a kind of container is:

(i) a kind of sample collection tube, specifically a kind of heparin tube; Or

(ii) a kind of bottle; Or

(iii) syringe or an a kind of syringe part, specifically a kind of syringe cylinder or a kind of syringe plunger; Or

(iv) a kind of pipe; Or

(v) a kind of cuvette.

(30) container of the coating Gen Ju (29), 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 the coating container described in any one of (29) to (30), this container contains at least one other layer on its outer surface, a preferably other blocking layer be made up of plastics or SiOx, wherein x is from 1.5 to 2.9.

(32) according to the coating container described in any one of (29) to (31), this container holds a kind of compound or composition in its inner chamber, preferably a kind of bioactive compounds or composition or a kind of biofluid, more preferably (i) Citrate trianion or a kind of composition containing Citrate trianion, (ii) a kind of medicament, Regular Insulin or a kind of composition containing Regular Insulin specifically, or (iii) blood or hemocyte.

(33) according to the coating container described in any one of (29) to (32), this coating container is a kind of syringe cylinder that method according to claim 1 manufactures, wherein this precursor is a kind of siloxanes, more preferably a kind of monocycle siloxanes, even more preferably octamethylcyclotetrasiloxane, and wherein in step (a), there is no O ₂gas is provided in this gaseous reactant, wherein compared with uncoated syringe cylinder, decreases at least 25%, more preferably decreases at least 45%, even more preferably decrease at least 60% for mobile plunger by the power of the cylinder of described coating.

(34) have the coating of total formula SiwOxCyHz, wherein w is 1, x be 0.5 to 2.4, y is 0.6 to 3, and z is from 2 to 9, as the purposes of the following

I () has a kind of slip coating of the friction resistance lower than uncoated surface; And/or

(ii) more hydrophobic than uncoated surface a kind of hydrophobic coating.

(35) purposes as described in (34), wherein this coating be as in (24) any one to (28) a kind of coating of defining.

(36) purposes as described in (34) or (35), wherein with uncoated surface and/or with the use HMDSO Gen Ju (1) as precursor method coated by surface compared with, this coating prevent or reduces the precipitation of a kind of compound in a kind of composition contacted with this coating or component, prevent or reduces insulin precipitation or blood coagulation particularly.

(37) according to the purposes of the coating container described in any one of (29) to (33); for the protection of a kind of compound being received or being received in described coating container or composition from the machinery on the surface of this uncoated container material and/or chemical action, be preferably used for preventing or reducing a kind of compound of the composition contacted with the interior surface of this container or a kind of precipitation of component and/or solidify.

(38) purposes as described in (37), wherein this compound or composition are

(i) a kind of bioactive compounds or composition, preferably a kind of medicament, more preferably Regular Insulin or comprise a kind of composition of Regular Insulin, wherein insulin precipitation is reduced or prevents; Or

(ii) biofluid, 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 according to coating container of the present invention or diagnostic kit, this test kit can additionally comprise: a kind of medicament or diagnostic reagent, and this medicine or diagnostic reagent are accommodated in described coating container; And/or a kind of hypodermic needle, two ends syringe needle or other delivery catheters; And/or an instruction book.

Invention further provides following embodiment:

I. there is the container processing systems of multiple treatment station and multiple pan straddle

According to an aspect of the present invention, provide a kind of container processing systems for container coating, this system comprises first treatment station, second treatment station, a pan straddle and a transfer roller and arranges.This first treatment station is arranged to and carries out one first process, such as, check the interior surface of this container or apply.This second treatment station is based on this first treatment station, and is arranged to and carries out one second process, such as, check the interior surface of this container or apply.This pan straddle comprises a container port, and this port is configured to the opening of a reception container and makes its take a seat for processing via the interior surface of container port to the container that this is taken a seat being positioned at this first treatment station and being positioned at this second treatment station (check and/or coating and/or check).This transfer roller arranges that the container being adapted to this pan straddle and this be taken a seat after this first process is used for carrying out the second process at this second treatment station to the interior surface of the container that this is taken a seat after this first treatment station is transported to this second treatment station.

These containers are broadly defined as the container comprising any type in this manual, include but not limited to for collecting or the sample hose of storing blood, urine or other samples, for storing or send the syringe of a kind of bioactive compounds or composition, for storing the bottle of biomaterial or bioactive compounds or composition, for transporting the conduit of biomaterial or bioactive compounds or composition, and for the cuvette of containment of biological materials or bioactive compounds or composition.

All process with one for the treatment of system described below or device with these containers undefined.In other words, with regard to a kind of device or treatment system, these features described below also can be implemented as method steps and can affect the container of so process.

Cuvette be have circle or square-section, one end sealing, by plastics, glass or fused quartz (for UV light) make and be designed to hold sample for spectrum experiment a kind of tubule.Best cuvette is transparent as far as possible, does not have possibility to affect the impurity of spectrum reading.As same test tube, tubule can be top to atmosphere opening, or with a cap by its hermetically closing.

Term " inside of container " refers to and may be used for storing blood or according to a kind of bioactive compounds of another exemplary or the hollow space at internal tank (hollowspace) of composition.

Term process can comprise a coating step and/or an inspection step or a series of coating and check step, such as an initial inspection step, and then a coating step, then and then one second or even the 3rd or the 4th inspection.This second, third and the 4th check can carry out simultaneously.

According to an exemplary of the present invention, this pan straddle comprises a vacuum pipe of withdrawing gas in the internal space of the container for taking a seat from this, wherein this pan straddle is adapted to the vacuum of the inside of the container keeping this to take a seat, and making like this does not need other vacuum chamber to process this container.In other words, this pan straddle and this container of taking a seat together form a vacuum chamber, and this vacuum chamber is adapted in the internal space of this container, provide a vacuum.This vacuum is important for some treatment step (chemical vapour deposition (PECVD) or other chemical vapor deposition step as plasma enhancing).In addition, the vacuum of this internal tank may be important for a certain inspection carrying out this container, is specifically such as applied by the interior surface of specific conductivity to this wall of container of the outgassing rate or this wall of measuring this wall.

According to another exemplary of the present invention, carry out this first process 30 seconds or less time durations.And this second process is carried out 30 seconds or less time durations.

Therefore, provide a kind of container processing systems for container coating, this container processing systems allows the quick manufacture of these containers.

According to another exemplary of the present invention, this first process and/or the second process comprise carries out an inspection to the interior surface of this container, then applies this interior surface.

According to another exemplary of the present invention, this pan straddle comprise for by gas delivery to the gas entry ports of in the inside of this container.

According to another exemplary of the present invention, this system is adapted to when detecting holiday, automatically carries out reprocessing to this container.Such as, this container processing systems and particularly this pan straddle can comprise different detector (such as fluorescence detector, pressure probe, gas detector, for electrometric electrode etc.) a layout.

In addition, according to another exemplary of the present invention, this container processing systems, such as one or more treatment station, comprise for container being transported to this pan straddle and/or being 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 entry ports for delivering gas in the inside of this container.

According to another exemplary of the present invention, this container processing systems is adapted to automatically carry out reprocessing to container when detecting holiday.

The gas be delivered in the internal space of this container can be used interior surface that PECVD applies this container.

According to another exemplary of the present invention, this first process and/or this second process comprise and applying the interior surface of this container.

According to another exemplary of the present invention, this first treatment station and/or the second treatment station comprise a PECVD device for applying the interior surface of this container.

According to another exemplary of the present invention, this system is included in an outer electrode around at least upper part of this container of taking a seat further.

According to another exemplary of the present invention, this pan straddle comprises a conductive probe for providing a counter electrode in this embodiment.

According to another exemplary of the present invention, this first process and/or second processes to comprise and checks for the interior surface of defect to this container

According to another exemplary of the present invention, this system comprises first detector further, and the container port that this first detector is adapted to be via this first treatment station and/or this second treatment station is inserted in this container for checking for the interior surface of defect to this container

According to another exemplary of the present invention, this container processing systems comprises second detector being positioned at this container exterior further, and this second detector is used for checking for the interior surface of defect to this container.

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 for the formation of this container.

According to another aspect of the present invention, set forth the purposes of container processing systems above and described below, for the manufacture of for storing blood a kind of heparin tube, for store a kind of bioactive compounds or composition a kind of syringe, for store a kind of bioactive compounds or composition a kind of bottle, for transporting a kind of conduit of multiple bioactive compounds or composition or a kind of transfer pipet for pipetting a kind of bioactive compounds or composition.

This container processing systems can also be adapted to check container and can be adapted to one first inspection carrying out this container for defect particularly, first coating is applied to the interior surface of this container, then for defect, the second inspection is carried out to the interior surface of this coating container.In addition, the data that this system can be adapted to obtaining during difference inspection are assessed, and wherein this second to check and data evaluation is consuming time is less than 30 seconds.

According to another aspect of the present invention, provide a kind of container processing systems for applying container and checking, this system comprises a treatment station and arranges, this treatment station is arranged to be arranged to and is carried out carrying out one first inspection for defect to this container, first coating is applied to the interior surface of this container, carry out one second for defect to the interior surface of the container of this coating check and assess the data obtained in checking process, wherein this second to check and data evaluation is consuming time is less than 30 seconds.

The applying of this first coating can also be called as the first or second process and carry out the second inspection to the interior surface of this coating container and can be called as the second process.

According to another exemplary of the present invention, this treatment station is arranged to comprise and first is checked, the interior surface of the container that this is taken a seat applied to this first coating and carry out first treatment station of the second inspection in addition for carrying out this, 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 of this container of reception and makes it take a seat for checking via the interior surface of container port to the container that this is taken a seat being positioned at this first treatment station and apply the first coating.

According to another exemplary of the present invention, this treatment station is arranged and is comprised second treatment station further, this second treatment station and this first treatment station spaced apart and be arranged to and carry out the second inspection, apply second coating and after applying this second coating, carry out the 3rd inspection.In addition, this container processing systems comprises a transfer roller and arranges, this transfer roller arranges that the container for this pan straddle and this being taken a seat after applying this first coating is transported to this second treatment station for the second coating being applied at this second treatment station the interior surface of the container that this is taken a seat from this first treatment station.The container port of this pan straddle is arranged to the opening that receives this container and makes it take a seat thus apply via the interior surface of container port to the container of taking a seat being positioned at this first treatment station and being positioned at this second treatment station and check.

According to another exemplary of the present invention, this pan straddle comprises a vacuum pipe of the inside withdrawing gas of the container for taking a seat from this, wherein this pan straddle is adapted to the vacuum of the inside maintaining the container that this is taken a seat, and making like this does not need other vacuum chamber to apply this container and check.

According to another exemplary of the present invention, each inspection carries out in 30 seconds or less time durations.

According to another exemplary of the present invention, this container processing systems is adapted to automatically carry out reprocessing to this container when detecting holiday.

According to another exemplary of the present invention, this first treatment station and/or this second treatment station comprise a PECVD device for applying coating to the interior surface of this container.

According to another exemplary of the present invention, this first coating is a barrier coat, and wherein this system is adapted to confirmation blocking layer is exist or lack.

According to another exemplary of the present invention, this second coating is a slip coating, and wherein this system is adapted to confirm that this slip coating (i.e. this lubricant film) exists or lacks.

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 adapted to confirm that this blocking layer or this lubricant film exist or lack.

According to another exemplary of the present invention, this system is adapted to confirm that this blocking layer or this lubricant film exist or lack (reaching the determinacy of at least six σ levels).

According to another exemplary of the present invention, this first to check and/or this second checks at least one item comprised in the following: the outgassing rate measuring the gas from this coating container, carry out the optical monitoring of coating applying, measure the optical parametric of the interior surface of this coating container, and measure the electrical characteristic of this coating container.

Then can be analyzed corresponding take off data by treater.

According to another exemplary of the present invention, this treatment system comprises first detector for measuring outgassing rate and/or further for second detector measuring rate of diffusion and/or for the 3rd detector measuring optical parametric and/or the 4th detector for measuring electrical parameter.

According to another exemplary of the present invention, this first coating and/or this second coating are that to be less than 100nm thick.

According to another exemplary of the present invention, this container processing systems comprises a treater for assessing the data obtained during inspection further.

One aspect of the present invention is a kind of container processing systems, and this container processing systems comprises first treatment station, the second treatment station, multiple pan straddle and a transfer roller.This first treatment station is configured to the container for the treatment of the wall with an opening and a restriction interior surface.This second treatment station and this first treatment station separate and are configured to for the treatment of having an opening and limiting the container of wall of an interior surface.

At least some, optionally all pan straddles comprise a container port, and this port is configured to the opening of a reception container and makes it take a seat for the interior surface via the container port process container of taking a seat at this first treatment station place.This transfer roller is configured to for a series of pan straddle and the container of taking a seat are transported to from this first treatment station the interior surface that the second treatment station is used for processing via the container port at this second treatment station the container that is taken a seat.

II pan straddle

II.A. the pan straddle of the non-specificity sealing arrangement quoted as proof

It is coated and carry out checking for defect and this container be transported to second treatment station of this container processing systems from first treatment station simultaneously that the carry-case support of this container processing systems can be adapted to the interior surface of accommodation container this container simultaneously, this pan straddle comprises a container port, and this container port is arranged to and this container opening is taken a seat and for processing to the first treatment station and the interior surface of container port to the container that this is taken a seat that be positioned at this second treatment station via being positioned at.

According to another exemplary of the present invention, this carry-case support comprises second port for receiving an extraneous gas supply or ventage and further for making a kind of gas be landed at one the pipeline passed through between vessel port on this container port and this second port.

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 comprises a vacuum pipe and the external vacuum port of the inside withdrawing gas of container for taking a seat from this via this container port further, wherein this pan straddle is adapted to the vacuum of the inside maintaining the container that this is taken a seat, and making like this does not need other vacuum chamber to process this container.

According to another exemplary of the present invention, this carry-case support comprises a vacuum pipe and the external vacuum port of the inside withdrawing gas of container for taking a seat from this via this container port further, wherein this pan straddle is adapted to the vacuum of the inside maintaining the container that this is taken a seat, and making like this does not need other vacuum chamber to process this container

According to another exemplary of the present invention, this external vacuum port also combines a gas entry ports, and this gas entry ports is accommodated in this vacuum ports for delivering the gas in the inside of the container that this is taken a seat.

According to another exemplary of the present invention, the process of this container is comprised the interior surface of the container that this is taken a seat is applied.

According to another exemplary of the present invention, this pan straddle is made up of thermoplastic material in fact.

According to another exemplary of the present invention, this carry-case support comprise further a cylindrical wall for receiving this container a cylindrical form interior surface, in this cylindrical form interior surface and a coaxial with it first ring connected in star and being disposed in this first ring connected in star enclose for the O shape providing to seal between the container of taking a seat at this and this pan straddle.

According to another exemplary of the present invention, this carry-case support comprises radial extension bearing (radiallyextendingabutment) that is adjacent to this cylindrical form interior surface (opening end of this container of taking a seat can dock thereon) further.

According to another exemplary of the present invention, this carry-case support comprise further be arranged in this cylindrical form interior surface and coaxial with it and with this first ring connected in star axially spaced second annular recesses.In addition, this pan straddle comprises a 2nd O type circle, and the 2nd O type circle is disposed in this second annular recesses and seals between the container that provides this to take a seat and this pan straddle.

According to another exemplary of the present invention, this carry-case support comprise further for via container port to inquire after first detector of the internal space of this container thus to check for the interior surface of defect to the container that this is taken a seat.

According to another exemplary of the present invention, this carry-case support comprises a mould for the formation of this container.

According to another exemplary of the present invention, the container processing systems for container coating comprises pan straddle that is above and the following stated.

According to another aspect of the present invention, this carry-case support comprises a container port, second port, a pipeline and one can carry housing.This container port is configured to a vessel port is seated in a relation be interconnected.This second port is configured to reception extraneous gas supply or ventage.This pipeline is configured to pass through for making one or more gases be landed between vessel port on this container port and this second port at one.This container port, the second port and pipeline are attached to this with the relation of rigidity in fact can carry on housing.Optionally, 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 a container port, a vacuum pipe, a vacuum ports and one can carry housing.This container port is configured to relation that seal with, that be interconnected and receives a vessel port.This vacuum pipe be configured to for from the container be landed on container port via this container port withdrawing gas.This vacuum ports is configured between vacuum pipe with outer vacuum source and is communicated with.This vacuum source can be have a pump of power more at low pressure than this vacuum pipe or reservoir or ballast box.This container port, vacuum pipe and vacuum ports are attached to this with the relation of rigidity in fact can carry on housing.Optionally, the weight of this carry-case support is less than five pounds.

II.B. the pan straddle of sealing arrangement is comprised

Another aspect again of the present invention is a kind of pan straddle of the opening end for receiving a kind of container, and this container has a columniform wall substantially near its open end.This pan straddle can have a substantial cylindrical internal surface (such as a cylindrical form interior surface), an annular recesses and an O type circle.Run through this specification sheets should be understood that, it is only exemplary for 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 (such as commonly when this container is cuvette), " circle " periphery of this pan straddle can be non-circular, and noncircular seals can be used seal, such as a kind of packing ring or be made into definite shape for being sealed to a kind of sealing member on this noncircular cross section (outside requiring especially unless otherwise).In addition, " cylindrical " does not require the cylinder of rounded section, and comprises other cross-sectional shapes, such as, have the square of fillet.

The internal surface of substantial cylindrical is made into a certain size for receiving the columniform wall of this container.

This annular recesses to be disposed in this circular internal surface and coaxial with it.This first ring connected in star has an opening on this substantial cylindrical internal surface and a diapire isolated with this substantial cylindrical inner surface radial direction.

This O type circle is disposed in this first ring connected in star.Relative to this first ring connected in star, this O type circle be made into a certain size for normally extend radial through this opening and the container that receives by the internal surface by this substantial cylindrical radially to external pressure.This being arranged in forms one between this container and this first ring connected in star and seals.

According to another aspect of the present invention, provide a kind of method for applying container and checking, wherein for defect, one first inspection is carried out to the interior surface of this container, afterwards a coating is applied to the interior surface of this container.Then, for defect, one second inspection is carried out to the interior surface of the container of this coating, and then to this first and second check during the data that obtain assess, wherein this second to check and this data evaluation is consuming time is less than 30 seconds.

According to another aspect of the present invention, provide the method for the treatment of container, wherein an opening of this container is seated on the container port of a pan straddle, after this applies the interior surface of this container via this container port.Then, this coating is checked for defect via this container port.After this, this container is transported to second treatment station from this first treatment station, wherein this container of taking a seat is held by this pan straddle during coating, inspection and transport.

III is for the method-process the container be seated on pan straddle of conveying containers

III.A. pan straddle is transported to treatment station

Another aspect of the present invention is a kind of method for the treatment of container.Provide first treatment station and second treatment station isolated with this first treatment station, for the treatment of container.Provide and a kind ofly there is an opening and define the container of a wall of an interior surface.Provide a kind of pan straddle comprising container port.The opening of this container is seated on this container port.Process via the interior surface of container port to the container that this is taken a seat being positioned at 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.Then, process via the interior surface of container port to the container that this is taken a seat being positioned at this second treatment station.

III.B. treatment facility is transported to pan straddle or vice versa

Another aspect of the present invention is a kind of method for processing the container comprising several parts.Provide first treatment facility and second treatment facility, for the treatment of container.Provide and a kind ofly there is an opening and define a kind of container of a wall of an interior surface.Provide a kind of opening comprising this container of pan straddle of container port to be seated on this container port.

In this first treatment facility being moved into engage with the operability of this pan straddle, or vice versa.The interior surface of this first treatment facility to the container that this is taken a seat is used to process via this container port

Then in making this second treatment facility move into engage with the operability of this pan straddle, or vice versa.The interior surface of this second treatment facility to the container that this is taken a seat is used to process via this container port.

III.C. use clamp to be transported by pipe enter and leave treatment station

Another aspect again of the present invention is a kind of method that the chemical vapour deposition (PECVD) carrying out plasma enhancing to first container processes, and comprises following step.Provide at least one first clamp of first container with an opening end, a closing end and an interior surface and be arranged to the closing end optionally keeping and discharge this first container.Clamped by the closing end of this first container with this first clamp, and use this first clamp to be transported near a pan straddle, this pan straddle is configured to the opening end of this first container is taken a seat.Then use this first clamp axially to advance this first container and make its opening end be seated on this pan straddle, between this pan straddle and the inside of this first container, setting up being communicated with of sealing.

At least one gaseous reactant is introduced within this first container by this pan straddle.In the interior surface of this first container, plasma body is formed under the condition of reaction product effectively forming this reactant.

Then make this first container disseat from this pan straddle, and use this first clamp or another clamp, this first container is axially transported and leaves this pan straddle.Then this first container is discharged from used clamp thus axially it is transported and leave this pan straddle.

IV is for the manufacture of the PECVD device of container

IV.A. pan straddle, internal electrode, PECVD device as the container of reaction chamber is comprised

According to another aspect of the present invention, a kind of plasma enhanced chemical vapor deposition (PECVD) device for applying the interior surface of container is provided.This PECVD device can be a part for this container processing systems and comprise a pan straddle, as the support at above and the following stated, this support comprises a container port, this container port is arranged to first opening of this container of reception and makes it take a seat, for processing via the interior surface of this container port to the container that this is taken a seat.In addition, this PECVD device comprise for being disposed in the container that this is taken a seat internal space within an internal electrode and there is an outer electrode of an external portion for receiving the container that this is taken a seat.In addition, provide a power supply for producing plasma body in this container, wherein this container of taking a seat and this pan straddle are adapted to restriction plasma-reaction-chamber.

According to another exemplary of the present invention, the vacuum source found time in the internal space of the container that this PECVD device comprises further for this being taken a seat, wherein this container port and this container of taking a seat are adapted to restriction vacuum chamber.

According to another exemplary of the present invention, this PECVD device comprises a gas feed device for being fed from a reactant gas source by reactant gas the internal space of this container further.

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 by the distal portions locating to extend into one heart in this container of taking a seat.

According to another exemplary of the present invention, this outer electrode has a cylindrical cross-section and extends with one heart around the container that this is taken a seat.

According to another exemplary of the present invention, this PECVD device comprises a clamp further, this clamp is used for selectivity and keeps and discharge a closing end of this container, and clamps the closing end of this container, for being transported near this pan straddle by this container simultaneously.

According to another exemplary of the present invention, this PECVD device is adapted to form a kind of plasma body 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 comprises a detector of the internal space for inquiring after this container via this container port further for checking for the interior surface of defect to this fixed container.

According to another exemplary of the present invention, this PECVD device comprises the processing vessel with a processing vessel opening further, 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 limited of this container.

According to another exemplary of the present invention, a far-end of this internal electrode is to be less than locating to the distance of the opening of this second restriction compared with big uncork from first of this container of taking a seat of half.

According to another exemplary of the present invention, the far-end of this internal electrode is positioned in first of the container that this is taken a seat compared with the outside of big uncork.

In addition, provide a kind of method for applying the interior surface of container, wherein an opening of this container is received and the interior surface be seated at for the container of taking a seat to this on a container port of pan straddle processes.Then, an internal electrode is arranged in the internal space of the container that this is taken a seat, after this 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 an internal portion of outer electrode.The container of taking a seat in this pan straddle is adapted to restriction plasma-reaction-chamber.

Specifically, the container can taken a seat by this container port and this is limited a vacuum chamber and extracts out the internal space of the container of being taken a seat from this by gas, and making like this does not need outer vacuum chamber for coating.

In a further step, in the internal space of this container, form a kind of plasma body and a kind of coating material is deposited in the interior surface of the container that this is taken a seat.

According to another exemplary of the present invention, a processing vessel opening is connected to allow reactant gas to flow into this processing vessel from the internal space of this container with an opening limited of this container.

According to another aspect of the present invention, above and the purposes of PECVD device described below be, for the manufacture of for storing blood a kind of heparin tube, for store a kind of bioactive compounds or composition a kind of syringe, for store a kind of bioactive compounds or composition a kind of bottle, for transporting a kind of conduit of multiple bioactive compounds or composition or a kind of cuvette for holding a kind of bioactive compounds or composition.

Another aspect of the present invention is a kind of PECVD device comprising a pan straddle, internal electrode, an outer electrode and a power supply.

This pan straddle have by a container reception in the position of taking a seat to carry out the port processed.This internal electrode is located to be received in this outer electrode within the container that is seated on a pan straddle and is had an internal portion, and this internal portion is located to receive to be seated at this power supply of container on this pan straddle and to be input to by alternating-current on inside and/or outer electrode thus to form plasma body within the container on this pan straddle and the container define a plasma-reaction-chamber being seated at.

Even another aspect of the present invention is a kind of PECVD device as in the previous paragraph, which provide the eduction pipe that must not comprise vacuum source, for by gas transfer to the inside of the container of taking a seat on that port or transmit from the gas of the inside of this container, to limit a closed-chamber.

IV.B. use and pipe is transported the PECVD device entering and leave the clamp of coating station

Another aspect of the present invention is the device for carrying out PECVD process to first container, 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, reactant feeding mechanism, a plasma generator and a container releasing device.

This pan straddle is arranged to and the opening end of a container is taken a seat.This first clamp is arranged to the closing end that optionally keeps and discharge container and clamps the closing end of this container simultaneously, this container is transported to this pan straddle near this pan straddle and has a seat, this is configured between this pan straddle and the internal space of this first container and sets up being communicated with of sealing.

This reactant feeding mechanism is operably connected for being incorporated within this first container by least one gaseous reactant by this pan straddle.In the interior surface that this plasma generator is configured in this first container the effective reaction product of forming reactions thing condition under in this first container, form plasma body.

This container releasing device is provided for this first container is disseated from this pan straddle.Clamp (this clamp is the first clamp or another clamp) is arranged to axially transports this first container and leaves this pan straddle and then discharge this first container.

V.PECVD method

Provide a kind of method for applying (and/or inspection) to the interior surface of container according to another aspect of the present invention, wherein an opening of this container be received and be seated on a pan straddle for the interior surface of the container that this is taken a seat carry out process it should be noted that term process can refer to a coating step or several coating step or even refer to a series of coating and check step.

In addition, carrying out one first process to the interior surface of the container that this is taken a seat is carry out via a container port of the pan straddle being positioned at first treatment station.Then, after this first treatment station place carries out the first process, then this pan straddle and this container of taking a seat are transported to second treatment station, and at this second treatment station place, the container port via this pan straddle carries out one second process to the interior surface of the container that this is taken a seat.

V.A. plasma body is used 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 by a kind of SiO _xa kind of method that barrier coat is applied on a surface inside of a container (preferably on), wherein in this formula, x is from about 1.5 to about 2.9, alternately from about 1.5 to about 2.6, alternately about 2.The method comprises several step.

Provide a surface (as a wall of container), as being both a kind of reaction mixture, this mixture comprises a kind of organic silicon compound gas, optionally a kind of oxidizing gas, and optionally a kind of appropriate hydrocarbon gas.

Plasma body is formed in the reactive mixture, is substantially free of hollow cathode plasma.This wall of container is contacted with this reaction mixture, and by SiO _xbe coated with and be deposited at least one part of this wall of container.

The vessel port (capillary injector) of V.B.PECVD coating restriction

Another aspect of the present invention is a kind of method for applying the internal surface of the opening having the restriction of the container of the generally tubular of stand-by PECVD process.The method comprises these steps.

Provide the container of a pending generally tubular.The opening that this container comprises an outside surface, define an internal surface of an inner chamber, have one of internal diameter larger opening and a restriction, the opening of this restriction is limited by an internal surface and the internal diameter had is less than the internal diameter of this larger opening.

Provide a kind of processing vessel, this processing vessel has an inner chamber and a processing vessel opening.This processing vessel opening is connected with the opening of the restriction of this container, has being communicated with via the opening of this restriction between the inner chamber of pending container with this processing vessel inner chamber to set up this.

This is had in the inner chamber of pending container and the inner chamber of this processing vessel and be pumped at least part of vacuum.Making a kind of PECVD reagent flow by this first opening, then by there being the inner chamber of pending container, then by the opening of this restriction, then entering the inner chamber of this processing vessel.Near the opening of this restriction, plasma body is produced under condition on the internal surface of opening effectively PECVD reaction product being deposited to this restriction.

V.C. the method for slip coating is applied

Another aspect again of the present invention is that a kind of slip coating is applied to a kind of suprabasil method.The method is following realization.

Provide a kind of precursor.This precursor preferably a kind of silicoorganic compound, two or more the one combination any more preferably among linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane or these precursors.Also contemplate other precursors, such as, contain the Organometallic precursor of the III-th family of periodic system and the metal of IV race.Under the condition effectively forming a kind of coating, this precursor is applied in a kind of substrate.By this coated polymeric or crosslinked (or both), thus form a kind of surface of lubrication, compared to the surface of untreated this lubrication of substrate have lower as in this specification sheets " the plunger sliding force " or " starting force " that define.

VI container inspection

VI.A. the container process of precoating and rear coating inspection is comprised

Even another aspect of the present invention is a kind of container-treatment for the treatment of plastic containers, and these plastic containers have the wall of an opening and a restriction interior surface.The method is undertaken by following steps: for defect to as the interior surface of this container that provides check; To as this container of providing check after a coating is applied to the interior surface of this container; And for defect, this coating is checked.

Another aspect of the present invention is a kind of container-treatment, is applied on this container by a barrier coat after wherein checking such as shaping container, and the interior surface for this container of defect after applying this barrier coat checks.

VI.B. according to the container inspection of test example as the venting of the wall of container by blocking layer

Another aspect of the present invention is by measuring a kind of method (" venting method ") of volatile species for checking coating of being released by coated article.The product of described method to coating processes can be used to check, wherein a kind of coating has been applied to the surface of substrate to form a kind of coated surface.Specifically, the method is used as the on-line plan for a coating processes so that qualification and eliminating do not meet the coated product of a preassigned or the coated product of damage.

Usually, " volatile species " is a kind of gas or steam under test conditions, and be preferably selected from lower group, this group is made up of the following: air, nitrogen, oxygen, water vapour, volatility coating ingredients, volatility substrate components and their one combine, more preferably air, nitrogen, oxygen, water vapour or their one combination.The method can be used for measuring only one or more volatile species, but in step (c), preferably measure multiple different volatile species, and in step (c), preferably substantially measure all volatile species from check object release.

This bleed method comprises the following steps:

There is provided this product as check object;

Measure at least one volatile species from this check object to the release in the gas space contiguous with this coated surface; And

The result of step (c) is compared with for the result of the step (c) of at least one references object measured under same test conditions, thus determines the existence of this coating or the physics of shortage and/or this coating and/or chemical property.

In described bleed method, have the physics of coating to be determined and/or chemical property can be selected from lower group, this group is made up of the following: its barrier effect, its wet tension and its formation and preferably its barrier effect.

Advantageously, step (c) is carried out with the mass flow rate of at least one volatile species in the gas space of this coated surface vicinity or volumetric flow rate by measuring.

Preferably, references object is a kind of (i) uncoated substrate; Or (ii) be a kind of substrate with reference to coating coating.This depends on, such as, whether this bleed method is used to determine the existence of a coating or shortage (so this references object can be a kind of uncoated substrate) or is used to determine the characteristic (such as comparing with a kind of coating with known features) of this coating.In order to determine the consistence of this coating and a kind of specific coating, a kind of also will be typical selection with reference to coating.

This bleed method can also comprise step (b) as the other step of between step (a) and (c), this step (b) changes the air pressure in the gas space contiguous with coated surface, which provide one through the pressure reduction of coated surface and can realize this volatile species compared to the higher mass flow rate when not having pressure reduction or volumetric flow rate.In this case, this volatile species moves on the direction compared with low voltage difference side.If this coating to as if a container, then determine that pressure reduction between this container intracavity and its outside is to measure the venting of this volatile species from this coating container wall.This pressure reduction can such as by finding time the gas space in a reservoir and providing at least partly.In this case, the volatile species being released and entering this container intracavity can be measured.

If application of vacuum produces a pressure reduction, this measurement can be carried out by using a measuring cell be inserted between the coated surface of substrate and a vacuum source.

On the one hand, preferably in order to allow described volatile species to absorb this check object material on or absorb the material entering this check object, this check object can be made in step (a) to contact with a kind of volatile species, preferably this volatile species is selected from lower group, and this group is made up of the following: air, nitrogen, oxygen, water vapour and their combination a kind of.Then, in step (c), measure the follow-up release of volatile species from this check object.Because different materials (as, such as, this coating and this substrate) there is different absorption and characterization of adsorption, this can simplify the existence of a coating and the determination of characteristic.

This substrate can be a kind of polymerizable compound, is optionally the one 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 characterized by this bleed method is a kind of a kind of coating prepared by PECVD from such as a kind of organosilicon precursor as described herein typically.Of the present invention concrete in, (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 changes the oilness of this coated substrate and/or capillary a kind of coating, the preferably layer of a kind of SiwOxCyHz, wherein w is 1, x is from about 0.5 to 2.4, y is from about 0.6 to about 3, and z is from 2 to about 9.

When being checked that by this bleed method the coating processes of its product is a kind of PECVD coating carried out under vacuum, its venting is subsequently measured even can when not have carry out when destroying the vacuum for PECVD.

The volatile species measured can be a kind of discharge from this coating volatile species, a kind of volatile species of discharging from this substrate or both combination a kind of.On the one hand, this volatile species is a kind of volatile species, preferably a kind of volatility coating ingredients of discharging from this coating, and carries out this inspection to determine the existence of this coating, characteristic and/or formation.On the other hand, this volatile species is a kind of volatile species of discharging from this substrate and carries out this inspection with the barrier effect of the existence and/or this coating of determining this coating.

Bleed method of the present invention is particularly suitable for existence and the characteristic of the coating determined on the wall.Therefore, this coated substrate can be a kind of container, this container have one during coating processes within it surface or outside surface on wall coated at least partly.Such as, this coating is placed on the internal surface of this wall of container.

The existence of effective this coating of differentiation or shortage and/or determine that the physics of this coating and/or the condition of chemical property comprise the test time (testduration) being less than a hour or being less than a minute or be less than 50 seconds or be less than 40 seconds or be less than 30 seconds or be less than 20 seconds or be less than 15 seconds or be less than 10 seconds or be less than 8 seconds or be less than 6 seconds or be less than 4 seconds or be less than 3 seconds or be less than 2 seconds or be less than 1 second.

In order to be increased in the difference of the kind about rate of release and/or measured volatile species between a references object and this check object, the rate of release of this volatile species can be changed by changing environmental stress and/or temperature and/or humidity.

In concrete at one, a kind of microcantilever beam measuring technology is used to measure venting.Such as, this measurement can be undertaken by following steps:

I () (a) provides at least one microcantilever beam, when a kind of material of releasing exists, this microcantilever beam has mobile or changes to a difform characteristic;

B this microcantilever beam is exposed to the material of this releasing by () under effectively causing this microcantilever beam to move or change to a difform condition; And (c) detect this to move or different shapes, preferably by reflection a kind of come comfortable this micro-cantilever is exposed to venting before and after change high energy incident beam such as a kind of laser beam of a part for this microcantilever beam of shape, and measure and the deflection of reflected beam that produces of the some place at this socle girder interval; Or pass through

(ii) (a) provides at least one micro-cantilever, and when a kind of material of releasing exists, this micro-cantilever is with a different frequency resonance;

B this micro-cantilever is exposed in the material of this releasing by () under the condition effectively causing this micro-cantilever frequency resonance different with; And (c) detect the resonant frequency that these are different, such as, use a resonant transducer.

Also contemplate a kind of device for carrying out this bleed method, such as a kind of device comprising micro-cantilever described above.

Use bleed method of the present invention, such as can check a blocking layer on a kind of material of letting off steam, wherein this inspection method has several step.Provide release a kind of gas and there is the sample of the material at least part of blocking layer.Of the present invention one concrete in, provide the pressure reduction that one is crossed over this blocking layer, the material of such at least some venting is the high-tension side on this blocking layer.Measure the gas of the releasing through this blocking layer.If there is a pressure reduction, then this measurement is optionally carry out in the low-tension side on this blocking layer.

The container of VIIPECVD process

VII.A.1.a.i. from the hydrophobic coating of organosilicon precursor deposition

Another aspect of the present invention is a kind of hydrophobic coating deposited from a kind of organosilicon precursor, such as, have in the container of hydrophobic coating on inner side-wall.This coating is the type manufactured by following steps.

Provide a kind of precursor, this precursor is a kind of organometallic compound, preferably a kind of silicoorganic compound, more preferably be selected from a kind of compound of lower group, this group is made up of the following: two or more the one combination any among linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, alkyl trimethoxysilane, linear silicon azane, monocycle silazane, many cyclosilazanes, poly-sesquialter silazane or these precursors.Alternately, the organometallic compound containing III-th family or IV race metal can be thought of as precursor.

Under the condition effectively forming a kind of coating, this precursor is applied in a kind of substrate.This coating is polymerized or crosslinked (or both), thus forms a hydrophobic surface with the contact angle higher than untreated substrate.

The coating generated can have total formula: Si _wo _xc _yh _z, wherein w is 1, x be from about 0.5 to about 2.4, y is from about 0.6 to about 3, and z is from about 2 to about 9, preferably wherein w to be 1, x be from about 0.5 to 1, y is from about 2 to about 3, and z is from about 6 to about 9.

These values running through w, x, y and z that this specification sheets uses should be understood to the ratio (such as, for a coating) in an empirical formula, instead of the restriction of number to the atom in a molecule.Such as, there is molecular formula Si ₄o ₄c ₈h ₂₄octamethylcyclotetrasiloxane can be described, by w, x, y and the z in this molecular formula is obtained Si divided by 4 (greatest common factors) separately by following empirical formula (term is changed by us) ₁o ₁c ₂h ₆.And the value of w, x, y and z is also not limited to integer.Such as, (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 of the wall of the hydrophobic coating be coated with from organosilicon precursor deposition

Another aspect of the present invention is a kind of cell preparation pipe, and this pipe has and is equipped with a hydrophobic coating wall and accommodates a kind of aqueous citric acid sodium reagent.

This wall is made up of thermoplastic material, has the internal surface defining an inner chamber.

This hydrophobic coating is provided on the internal surface of this pipe.This hydrophobic coating is by providing a kind of organometallic compound to manufacture, this organometallic compound is a kind of silicoorganic compound preferably, more preferably be selected from a kind of compound of lower group, this group is made up of the following: two or more the one combination any among linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, alkyl trimethoxysilane, linear silicon azane, monocycle silazane, many cyclosilazanes, poly-sesquialter silazane or these precursors.Use PECVD to form a coating on an internal surface.The coating generated can have following structure: Si _wo _xc _yh _z, wherein w is 1, x be from about 0.5 to about 2.4, y is from about 0.6 to about 3, and z is from about 2 to about 9, preferably wherein w to be 1, x be from about 0.5 to 1, y is from about 2 to about 3, and z is from 6 to about 9.

By aqueous citric acid sodium reagent with the inner chamber effectively suppressing solidify the amount being introduced in the blood in this pipe to be placed in this pipe.

VII.A.1.c.SiO _xdouble-walled plastic container-the COC of blocking layer coating, PET, SiO _xlayer

Another aspect of the present invention has at least partly around a kind of container of the wall of an inner chamber.This wall have by an external polymer layer around an inner polymeric layer.One of these polymer layers are the layers defining thick cyclic olefine copolymer (COC) resin of at least 0.1mm of a water vapor barrier layer.Another kind in these polymer layers is a layer of the vibrin that at least 0.1mm is thick.

This wall comprises a SiO _xoxygen barrier, wherein in this formula, x is from about 1.5 to about 2.9, alternately from about 1.5 to about 2.6, alternately about 2, this blocking layer has from about 10 to the thickness of about 500 dusts.

VII.A.Ld. method-COC, PET, SiO of double-walled plastic container is manufactured _xlayer

Another aspect of the present invention be manufacture have make an interior polymeric thing side by an external polymer layer around a wall, the layer manufactured by COC and a kind of method of the container of other parts manufactured by polyester.This container manufactures by comprising every a kind of technique below: COC and polyester resin layer are incorporated in an injection mold by concentric injection nozzle.

An optional other step is, by PECVD, a kind of amorphous carbon coating is put on this container, as a coated inside, an exterior coating or as the interlayer of between these layers or interlayer coating.

An optional other step is by a SiO _xblocking layer puts on the inside of this wall of container, wherein SiO _xas previously defined.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.

Optionally, this SiO can be formed by silazane feed gas at least in part _xcoating.

VII.A.1.e. the barrier coat be made up of glass

Another aspect of the present invention is the container comprising a wall of container, a barrier coat and a closure member.This container is roughly tubulose and is made up of thermoplastic material.This container has an opening and at least partly by the inner chamber that a wall limits, this wall has an internal surface of demarcating with this inner chamber.The internal surface of this wall exists be made up of glass one continuous print barrier coat at least substantially.A closure member covers this opening and is isolated from ambient air by the inner chamber of this container.

Related fields of the present invention are a kind of containers as in the previous paragraph, and wherein this barrier coat is made up of the glass of soda-lime glass, borosilicate glass or another kind of type.

VII.A.2 stopper

VII.A.2.a. in a vacuum chamber slip coating is applied to the method on stopper

Another aspect of the present invention be by a kind of coating such as a kind of slip coating defined above is applied to a kind of a kind of method in elastomeric stopper such as, a stopper is positioned in a room of substantially finding time.Provide a kind of reaction mixture, this reactant comprises plasma body and forms gas, i.e. a kind of organic silicon compound gas, optionally a kind of oxidizing gas, and optionally a kind of appropriate hydrocarbon gas.Plasma body is formed in this reaction mixture, and this reaction mixture contacts with this stopper.By a kind of slip coating (such as Si _wo _xc _yh _za coating, preferably wherein w is 1, in this formula, x is from about 0.5 to 2.4, 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) be deposited at least partially of this stopper.

VII.A.2.b. by PECVD, a coating of III-th family or IV race element and carbon is applied on a stopper

Another aspect of the present invention is that a kind of coating of the composition of one or more elements by comprising carbon and III-th family or IV race is applied to a kind of method in an elastomeric stopper to realize this method, is positioned in a sediment chamber by a stopper.

A kind of reaction mixture is provided in sediment chamber, this reaction mixture comprises a kind of plasma body and forms gas and a kind of iii group element (such as Al), the gas source of a kind of IV race element (such as, Si, Sn) or the one of two or more combination among these.This reaction mixture optionally comprises a kind of oxidizing gas and optionally comprises a kind of gaseous compound with one or more c h bond.Plasma body is formed in this reaction mixture, and this stopper contacts with this reaction mixture.A painting of iii group element or compound, a kind of IV element or compound or a kind of combination of two or more among these is deposited upon going up at least partially of this stopper.

VII.A.3. the plastic containers with barrier coat that stopper clogs, this barrier coat effectively provides the vacuum of 95% to keep continuing 24 months

Another aspect of the present invention is the container comprising a wall of container, a barrier coat and a closure member.This container is generally tubular and is made up of thermoplastic material.This container has an opening and at least partly by an inner chamber that wall limits.This wall has an internal surface of demarcating with this inner chamber.By one at least substantially continuous print barrier coat be applied on the internal surface of this wall.This barrier coat effectively keeps its initial vacuum level of in this container at least 90%, and optionally its initial vacuum level of 95%, continues the quality guaranteed period of at least 24 months.Provide a closure member, this closure member covers this opening and is isolated from ambient air by the inner chamber of this container.

VII.B.1.a. there is the syringe of the cylinder of the slip coating be coated with from Organometallic precursor deposition

Another aspect again of the present invention is a kind of container, and this container has the slip coating be made up of a kind of organosilicon precursor.It is also conceivable to a kind of different Organometallic precursor as defined herein.

This coating can be the type manufactured by the following method.

Provide a kind of precursor, this precursor is a kind of Organometallic precursor, a preferably organosilicon precursor, two or more the one combination any more preferably among linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, linear silicon azane, monocycle silazane, many cyclosilazanes, poly-sesquialter silazane or these precursors.

Under the condition effectively forming a kind of coating, this precursor is applied in a kind of substrate.By this coated polymeric or crosslinked (or both), thus form a kind of surface of lubrication, compared to the surface of untreated this lubrication of substrate, there is lower plunger sliding force or starting force.

Another aspect of the present invention is a kind of syringe comprising a plunger, a syringe cylinder and a lubricant film.This syringe cylinder has the interior surface receiving this plunger slidably.In the interior surface that this lubricant film is disposed in this syringe cylinder and comprise from as this specification sheets the Si that manufactures of the organosilicon precursor that defines _wo _xc _yh _za coating of lubricant film.This lubricant film has the thickness that is less than 1000nm and effectively reduces the necessary starting force of mobile plunger in cylinder or plunger sliding force.

Another aspect of the present invention is a slip coating on the inwall of syringe cylinder.This coating uses following material and condition to produce according to PECVD process.Have employed a kind of cyclic precursor, this cyclic precursor is selected from the combination of monocycle siloxanes, many cyclosiloxane or the one of two or more among these.At least there is no that oxygen joins in this process.Provide enough plasma generation power inputs to induce coating formation.Relative to uncoated syringe cylinder, the mobile syringe plunger sliding force by this syringe cylinder or starting force are effectively reduced at least 25% by the material adopted and condition.

The coating generated can have following formula: Si _wo _xc _yh _z, wherein w is 1, x be from about 0.5 to about 2.4, y is from about 0.6 to about 3, and z is from about 2 to about 9, preferably wherein w to be 1, x be from about 0.5 to 1, 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 comprising a cylinder, and this defines an inner chamber and has the interior surface that receives a plunger slidably.This syringe cylinder is made up of thermoplastic base material.By PECVD a slip coating is applied to such as this interior surface, this plunger or both on.This slip coating be make from a kind of organosilicon precursor and be that to be less than 1000nm thick.Effectively to reduce this lubricant film, the amount of leaching of this thermoplastic base material (or both) carries out surface treatment on this slip coating.This slip coating is configured to solute restraining mass (soluteretainer) and effectively to provide starting force, the relative quantity of plunger sliding force or both (this power is less than and is lacking the corresponding power required for slip coating and solute restraining mass) and existing.

VII.B.1.b has and uses SiO _xthe syringe of the cylinder of the outside of the inside of coating and blocking layer coating

Another aspect again of the present invention is a kind of syringe cylinder comprising a plunger, a cylinder and inside and outside barrier coat.This blocking layer is manufactured by the thermoplastic base material defining an inner chamber.This has the interior surface and an outer surface that receive this plunger slidably.A SiO _xbarrier coat is provided in this interior surface, and wherein in this formula, x is from about 1.5 to about 2.9, and alternately from about 1.5 to about 2.6, optionally about 2.A kind of resin barrier coat is provided on this outer surface.

VII.B.1.c manufactures to have and uses SiO _xthe method of the syringe of the cylinder of the outside of the inside of coating and blocking layer coating

Even another aspect of the present invention is a kind of method manufacturing syringe, and this syringe comprises a plunger, a cylinder and inner and outer barrier coating.Provide to have and receive an interior surface of this plunger and a kind of cylinder of an outer surface slidably.By a SiO _xbarrier coat is provided in this interior surface by PECVD, and wherein in this formula, x is from about 1.5 to about 2.9, 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 cylinder are carried out assembling thus provides a kind of syringe.

VII.B.2 plunger

VII.B.2.a. have blocking layer coating piston before

Another aspect of the present invention is a kind of plunger for syringe, and this plunger comprises a piston and a push rod.This piston has before one, the side of a substantial cylindrical and a rear section, and this side is configured to be seated within syringe cylinder movably.Before being somebody's turn to do, there is a barrier coat.This push rod engages this rear section and is configured to this piston is advanced in syringe cylinder.

VII.B.2.b. there is the slip coating had a common boundary with side

Another aspect again of the present invention is a kind of plunger for syringe, and this plunger comprises a piston, a slip coating and a push rod.This piston has before one, the side of a substantial cylindrical and a rear section.This side is configured to be seated within syringe cylinder movably.This lubricant film and this side meet boundary.This push rod engages the rear section of this piston and is configured to this piston is advanced in syringe cylinder.

VII.B.3 two-piece type syringe and female Luer

Another aspect of the present invention is the syringe comprising a plunger, a syringe cylinder and a female Luer.This syringe cylinder comprises the interior surface receiving this plunger slidably.This female Luer comprises a Luer taper, and this Luer taper has the internal passages limited by an internal surface.This female Luer is formed with the form of the separation member be separated with this syringe cylinder and is connected on this syringe cylinder by a junctor.The internal passages of this Luer taper has a kind of SiO _xbarrier coat, wherein in this formula, x is from about 1.5 to about 2.9, alternately from about 1.5 to about 2.6, alternately about 2.

The slip coating that VII.B.4 is manufactured by in-situ polymerization organosilicon precursor

VII.B.4.a. by the product processed and lubricate

Another aspect again of the present invention is a kind of slip coating made from organosilicon precursor.This coating is the type be made up of following methods.

Provide a kind of precursor, this precursor is selected from a kind of Organometallic precursor, a preferably organosilicon precursor, two or more the one combination any among preferred linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, linear silicon azane, monocycle silazane, many cyclosilazanes, poly-sesquialter silazane or these precursors.Under the condition effectively forming a kind of coating, this precursor is applied in a kind of substrate.By this coated polymeric or crosslinked (or both), thus form a kind of surface of lubrication, compared to the surface of untreated this lubrication of substrate, there is lower plunger sliding force or starting force.

The coating generated can have following structure: Si _wo _xc _yh _z, wherein w is 1, x be from about 0.5 to about 2.4, y is from about 0.6 to about 3, and z is from about 2 to about 9, preferably wherein w to be 1, x be from about 0.5 to 1, y is from about 2 to about 3, and z is from 6 to about 9.

VII.B.4.b. the product of technique and analytical characteristics

Even another aspect of the present invention is the slip coating deposited by 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, many cyclosilazanes, poly-sesquialter silazane or the combination of the one of two or more among these.As being had by X ray reflection rate (XRR) this coating determined 1.25 and 1.65g/cm ³between density.

It is also conceivable to use containing III-th family (namely, boron, aluminium, gallium, indium, thallium, scandium, yttrium or lanthanum), or a kind of metal of IV race (that is, silicon, germanium, tin, lead, titanium, zirconium, hafnium, thorium) or two or more a kind of Organometallic precursor of combination any among these.It is also conceivable to other volatile organic compoundss.But, preferably have organic silicon compound to carry out the present invention.

Another aspect again of the present invention is a slip coating by depositing from the PECVD of feed gas, this feed gas comprises a kind of Organometallic precursor, preferably a kind of organosilicon precursor, more preferably linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, linear silicon azane, monocycle silazane, many cyclosilazanes, poly-sesquialter silazane or the combination of the one of two or more among these.It is also conceivable to the precursor using a kind of metal containing III-th family or IV race.

As by vapor-phase chromatography/mass spectroscopy determined, this coating have as a kind of component of exitting containing repeat-(Me) ₂one or more oligopolymer of SiO-part.Optionally, this coating meets the restriction of any embodiment VII.B.4.a. or VII.B.4.

Another aspect again of the present invention is a slip coating by depositing from the PECVD of feed gas, this feed gas comprises a kind of Organometallic precursor, preferably a kind of organosilicon precursor, more preferably linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, linear silicon azane, monocycle silazane, many cyclosilazanes, poly-sesquialter silazane or the combination of the one of two or more among these.As determined by x-ray photoelectron spectroscopy (XPS), this coating can have and is normalized to the carbon of 100%, the atomic percent of oxygen and silicon, has the carbon being less than 50% and the silicon being greater than 25%.Optionally, this coating meets the restriction of any embodiment VII.B.4.a or VII.B.4.b..

It is also conceivable to a kind of Organometallic precursor using the metal containing III-th family or IV race.

Another aspect of the present invention is a kind of slip coating deposited from a kind of feed gas by PECVD, this feed gas contains a kind of organosilicon precursor, preferably monocycle siloxanes, monocycle silazane, many cyclosiloxane, many cyclosilazanes or any combination of two or more among these.This coating has as determined by x-ray photoelectron spectroscopy (XPS), and be normalized to the atomic percent of a carbon of the carbon of 100%, oxygen and silicon, this concentration is greater than the atomic percent of carbon in the atomic formula of feed gas.Optionally, this coating meets the restriction in embodiment VII.B.4.a or VII.B.4.b.

Another aspect of the present invention is a kind of slip coating deposited from a kind of feed gas by PECVD, this feed gas comprises a kind of organosilicon precursor, preferred monocycle siloxanes, monocycle silazane, many cyclosiloxane, many cyclosilazanes or any combination of two or more among these.This coating has as determined by x-ray photoelectron spectroscopy (XPS), and be normalized to the atomic percent of a silicon of the carbon of 100%, oxygen and silicon, this concentration is less than the atomic percent of silicon in the atomic formula of feed gas.Optionally, this coating meets the restriction in embodiment VII.B.4.a or VII.B.4.b.

VII.C.1. the container with the coating deposited by organosilicon precursor of the blood that can live is accommodated

Even another aspect of the present invention is a kind of container of containment blood.This container has a wall; This wall has the internal surface defining an inner chamber.The internal surface of this wall has an at least part of hydrophobic coating as defined above, a preferably Si _wo _xc _yh _zhydrophobic coating, preferably wherein w is 1, and in this formula, x is from about 0.5 to 2.4, 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 2 to about 3 from about 0.5 to 1, y, and z is from 6 to about 9.This coating can be thin as monomolecular thickness, or thick 1000nm according to appointment.This container holds the blood that can live of the vascular system for returning patient, and this blood is disposed in this inner chamber and this Si _wo _xc _yh _zcoating layer touch.

VII.C.2. solidifying or platelet activation is on the wall decreased from the coating of organosilicon precursor deposition

Another aspect of the present invention is the container with a wall.This wall has the internal surface and the such as hydrophobic coating with at least part of passivation manufactured from a kind of organosilicon precursor by PECVD that define an inner chamber, preferably a kind of Si _wo _xc _yh _zcoating, preferably wherein w is 1, and in this formula, x is from about 0.6 to about 3 from about 0.5 to 2.4, y, and z is from 2 to about 9, more preferably wherein w to be 1, x be from about 0.5 to 1, y is from about 2 to about 3, and z is from 6 to about 9.In this interior surface, the thickness of this coating is thick to about 1000nm from monoatomic thickness.Compared with the uncoated wall of same type, this coating effectively minimizing Trisodium Citrate additive treating cross and be exposed to the platelet activation of the blood plasma of this internal surface.Compared with the uncoated wall of same type, this coating effectively reduces solidifying of the blood being exposed to this internal surface.

VII.C.3. the container of the blood that can live, the coating with III-th family or IV race metallic element is held

Another aspect of the present invention is a kind of container of containment blood, and this container has a wall, and this wall has the internal surface defining an inner chamber.This internal surface has an a kind of at least part of coating of formation, and this formation comprises the combination of carbon, one or more metals of III-th family, one or more metals of IV race or the one of two or more among these.The thickness of this coating is in this interior surface at monomolecular thickness and approximately between 1000nm thickness, comprises end value.This container holds the blood that can live of vascular system for returning patient, and this blood is disposed in this inner chamber of contacting with this coating.

VII.C.4. the coating of III-th family or IV race element decreases solidifying or platelet activation of blood in this container

Optionally, in the container described in above paragraph, the coating of this III-th family or IV race element effectively reduces solidifying of the blood of the internal surface being exposed to this wall of container or platelet activation.

VII.D.1. the container with the coating deposited by organosilicon precursor of Regular Insulin is held

Another aspect of the present invention is a kind of container holding Regular Insulin, and this container has a wall, and this wall has the internal surface defining an inner chamber.This inwall has the coating of an at least part of passivation of being made from a kind of organosilicon precursor by PECVD, preferably a kind of Si _wo _xc _yh _zcoating, preferably wherein w is 1, and in this formula, x is from about 0.6 to about 3 from about 0.5 to 2.4, y, and z is from 2 to about 9, more preferably wherein w to be 1, x be 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 to about 1000nm from monomolecular thickness in this interior surface.Regular Insulin is disposed in and Si _wo _xc _yh _zin the inner chamber of coating layer touch.

VII.D.2. the coating deposited by organosilicon precursor decreases the precipitation of Regular Insulin in container

Optionally, in the container of above paragraph, with shortage Si _wo _xc _yh _zthe similar face of coating compare, this Si _wo _xc _yh _zthe precipitation that effectively reduces due to this internal surface of insulin exposure of coating formed.

VII.D.3. the container with the coating of III-th family or IV race element of Regular Insulin is held

Another aspect of the present invention is a kind of container holding Regular Insulin, and this container comprises a wall, and this wall has the internal surface defining an inner chamber.This internal surface has an a kind of at least part of coating of formation, and this formation comprises the combination of carbon, one or more metals of III-th family, one or more metals of IV race or the one of two or more among these.This coating can be from monomolecular thickness to about 1000nm thickness in this interior surface.Regular Insulin is disposed in this inner chamber of contacting with this coating.

VII.D.4. the coating of III-th family or IV race element decreases the precipitation of Regular Insulin in container

Optionally, in the container described in above paragraph, compared with lacking the similar face of coating, comprise carbon, one or more metals of III-th family, precipitation that the coating of formation of one or more metals of IV race or a kind of combination of two or more among these effectively reduces due to insulin exposure internal surface formed.

VILE. cuvette

PECVD coating method described in this manual etc. is also useful for coating cuvette to form a barrier coat, a hydrophobic coating, a slip coating or more than one among these.Cuvette be have circle or square-section, one end sealing, by plastics, glass or fused quartz (for UV light) make and be designed to hold a kind of tubule of sample for spectrum experiment.Best cuvette is transparent as far as possible, does not have possibility to affect the impurity of spectrum reading.As test tube or sampling tube, cuvette can be to atmosphere opening or use a cap by its hermetically closing.The coating that PECVD of the present invention applies can be very thin, transparent and optics is smooth, therefore do not disturb the optic test of this cuvette or its content.

VII.F. bottle

PECVD coating method described in this specification sheets etc. is also useful for applying bottle to form a combination of a coating, such as a barrier coat or a hydrophobic coating or these coatings.Bottle is a kind of small vessels or bottle, in particular for the medicine of the powder type of storage of liquids, powder or freeze-drying.They can also be sampling receptacles, such as, in the automatic sampler equipment in analytical chromatography.Bottle can have tubular form or have the bottle sample shape of a neck.Different from test tube or sampling tube (they have rounded bottom usually) is normally flat bottom this.These tubules can be such as made up of plastics (such as polypropylene, COC, COP).

Computer-readable medium and program element

In addition, provide a kind of computer-readable medium, store the computer program for applying and/or check container wherein, when this computer program is performed by the treater of a container processing systems, cause this treater to carry out method steps that is above or that mention below.

In addition, provide a kind of program element for applying container and/or checking, when this program element is performed by the treater of a container processing systems, cause this treater to carry out method steps that is above or that mention below.

According to this disclosure and accompanying drawing, other aspects of the present invention will be clearly.

Brief Description Of Drawings

Fig. 1 is a schematic diagram, the figure illustrates a kind of container processing systems of an embodiment according to this disclosure.

Fig. 2 is a diagrammatic cross-sectional view according to a pan straddle in a coating station of an embodiment of this disclosure.

Fig. 3 is the view being similar to Fig. 2 of the alternative embodiment of of this disclosure.

Fig. 4 is a diagrammatic orthographic plan of the alternative embodiment of of this pan straddle.

Fig. 5 is a diagrammatic plan view of another alternative embodiment of this pan straddle.

Fig. 6 is the view being similar to Fig. 2 of container inspection arrangement.

Fig. 7 is the view being similar to Fig. 2 of alternative container inspection arrangement.

Fig. 8 is the cross section intercepted along the section line A-A of Fig. 2.

Fig. 9 is the alternative embodiment of of structure shown in Fig. 8.

Figure 10 is the view (have employed a CCD detector) being similar to Fig. 2 of a pan straddle in a coating station of another embodiment according to this disclosure.

Figure 11 is the detailed view (they are contrary compared with the corresponding section of Fig. 6) being similar to Figure 10 of light source and detector.

Figure 12 is the view (adopting microwave energy to produce plasma body) being similar to Fig. 2 according to a pan straddle in a coating station of another embodiment again of this disclosure.

Figure 13 is the view being similar to Fig. 2 according to a pan straddle in a coating station of another embodiment of this disclosure, wherein this container can be seated at and be positioned on the pan straddle of this treatment station.

Figure 14 is the view being similar to Fig. 2 according to a pan straddle in a coating station of even another embodiment of this disclosure, and wherein this electrode can be configured to a kind of coil.

Figure 15 is the view (adopting pipe transporter to be moved into by container and to leave this coating station) being similar to Fig. 2 according to a pan straddle in a coating station of another embodiment of this disclosure.

Figure 16 is that a kind of container transportation system of middle operation (system as shown in Figure 15) is to place at treatment station and to keep a diagrammatical view of container.

Figure 17 is the mould of an aspect for the formation of container according to this disclosure and a diagrammatical view of mould cavity.

Figure 18 is the diagrammatical view being equipped with the mould cavity of Figure 17 of a kind of container coating equipment according to an aspect of this disclosure.

Figure 19 is the view being similar to Figure 17 being equipped with an alternative container coating equipment according to an aspect of this disclosure.

Figure 20 be an adaptation be used as a precharging type syringe syringe and one of cap decompose longitudinal cross-section view.

Figure 21 is that display adds the syringe cylinder of cap and the view being roughly similar to Fig. 2 of pan straddle according in a coating station of an embodiment of this disclosure.

Figure 22 is that figure shows and do not add the syringe cylinder of cap and the view being roughly similar to Figure 21 of pan straddle according in a coating station of another embodiment of this disclosure.

Figure 23 is the skeleton view with the heparin tube assembly of a closure member according to 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 a sectional view be separated of an elastomeric insert of the closure member of Figure 23 and 24.

Figure 26 be another embodiment of the invention for the treatment of syringe cylinder and other containers be similar to 22 a view.

Figure 27 is a partial view amplified of the processing vessel of Figure 26.

Figure 28 is a schematic diagram of an alternative processing vessel.

Figure 29 be display through coating a schematic diagram of material outgassing.

Figure 30 is for causing the test set that a wall of container is deflated to the inside of this container and the diagrammatic cross-sectional view using the venting of a measuring cell be inserted between this container and a vacuum source to measure.

Figure 31 is a graphic representation for measure on the test set of Figure 30 venting mass flow rate of multiple container.

Figure 32 is a bar graph being presented at the statistical study of the end-point data shown in Figure 31.

Figure 33 is the vertical section receiving volume according to the syringe cylinder of a kind of combination of another embodiment of the invention and gas.

Figure 34 is the view (comprising an electrode extension) being similar to Figure 34 of another embodiment of the invention.

Figure 35 is the view intercepted from the section line 35-35 of Figure 34, shows the extension electrode of remote 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 the view being similar to Figure 22 of another embodiment of display.

Figure 38 shows and the view being similar to Figure 22 of another embodiment.

Figure 39 shows and the view being similar to Figure 22 of another embodiment.

Figure 40 is the view being similar to Figure 22 showing even another embodiment.

Figure 41 is an orthographic plan of the embodiment of Figure 40.

Figure 42 be can with Fig. 1,2,3,6-10,12-16,18,19,33 and 37-41 embodiment together with the partial longitudinal section of the fracture for container being seated at the alternative sealing arrangement of on pan straddle one that uses.Figure 42 also show can with such as Fig. 2,3, a kind of alternative syringe cylinder that uses together with the embodiment of 6-10,12-22,26-28,33-34 and 37-41 constructs.

Figure 43 is the partial view of the other amplification of of the sealing arrangement shown in Figure 42.

Figure 44 be can with such as Fig. 1,2,3,8,9,12-16,18-19,21-22,33, the view being similar to Fig. 2 of use together with the embodiment of 37-43,46-49 and 52-54 one alternative gas delivery/interior electrode.

Figure 45 be can with such as Fig. 1,2,3,6-10,12-16,18,19,21,22,26,28, a kind of alternative structure of pan straddle that uses together with the embodiment of 33-35 and 37-44.

Figure 46 be gas delivery an array and for gas delivery to be inserted in a pan straddle and from a diagrammatic cross-sectional view of the mechanism that it is removed, shows the gas delivery being in the position that it advances completely.

Figure 47 is the view being similar to Figure 46 showing the gas delivery mediated.

Figure 48 is the view being similar to Figure 46 that display is in a gas delivery of complete retracted position.The array of the gas delivery of Figure 46-48 can with such as Fig. 1,2,3,8,9,12-16,18-19,21-22,26-28,33-35,37-45,49 and 52-54 embodiment together with use.The mechanism of Figure 46-48 can with such as Fig. 2,3,8,9,12-16,18-19,21-22,26-28,33-35,37-45,49 and 52-54 gas delivery embodiment and with Fig. 6 with 7 container inspection arrangement probe together with use.

Figure 49 is the view being similar to Figure 16 of display for will pending container and cleaning reactor be had to be delivered to a mechanism of a PECVD coating unit.The mechanism of Figure 49 can with such as Fig. 1,9, use together with the container inspection arrangement of 15 and 16.

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 process of 53-54 use together with inspection units.

Figure 51 is the two-piece type syringe cylinder of Figure 50 and an assembled view of luer lock joint.

Figure 52 is the view being similar to Figure 42 without a syringe cylinder of flange or finger stop that display is processed.This syringe cylinder can with Fig. 1-19,27,33,35, the container process of 44-51 and 53-54 uses together with inspection units.

Figure 53 is a schematic diagram of the assembly for the treatment of container.This assembly can use together 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 the diagrammatical view being 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 for mechanism gas delivery inserted in pan straddle and remove from it.

Figure 57 is a graphic representation of venting mass flow rate measured in example 19.

Figure 58 shows a linear gear rack, and other are similar to Fig. 4.

Figure 59 shows an indicative icon of a container processing systems according to an exemplary of the present invention.

Figure 60 shows an indicative icon of a container processing systems according to another exemplary of the present invention.

Figure 61 shows a treatment station of a container processing systems according to an exemplary of the present invention.

Figure 62 shows a carry-case support according to an exemplary of the present invention.

Be used in these figures below with reference to symbol:

Detailed description of preferred embodiments

To describe the present invention more completely now with reference to accompanying drawing, illustrated therein is some embodiments.But the present invention can be embodied in many different forms, and should not be interpreted as being limited to these embodiments proposed at this.More exactly, these embodiments are examples of the present invention, and the present invention has by the bright four corner of the denotation of claims.Run through same numeral in full and refer to key element that is same or correspondence.

In the context of the present invention, employ to give a definition and abridge:

RF is radio frequency; Sccm is standard cubic centimeter/per minute.

In the context of the present invention, term " at least " refers to the entirety of " being equal to or greater than " follow-up described term.Word " comprises " does not get rid of other key elements or step, and except as otherwise noted, indefinite article " " or " one " are not got rid of multiple.

" first " and " second " or the similar treatment station or the equipment that refer to the minimum quantity of existence see, for example treatment station or treatment facility, but must not represent order or the sum for the treatment of station and equipment.The quantity of concrete process that these terms do not limit treatment station or carry out at the station of correspondence.

For the purposes of the present invention, a kind of " organosilicon precursor " has at least one following a kind of compound connected: it is the tetravalence Siliciumatom connected with a Sauerstoffatom and an organic carbon atoms (organic carbon atoms is the carbon atom be connected with at least one hydrogen atom).A kind of volatile organosilicon precursor, be defined as so a kind of precursor, it can be supplied to as the steam in a PECVD device, and it is a kind of preferred organosilicon precursor.Preferably, this organosilicon precursor is selected from lower group, and this group is made up of the following: two or more the combination any among linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, alkyl trimethoxysilane, linear silicon azane, monocycle silazane, many cyclosilazanes, poly-sesquialter silazane and these precursors.

In the context of the present invention, in some embodiments, " there is no oxygen " or (synonymously) " does not have oxygen in fact " and be added in this gaseous reactant.This represents that some residual aerial oxygens may reside in reaction compartment, and feed in preceding step and the residual oxygen be not fully drained may reside in reaction compartment, they are defined as there is no that oxygen exists at this.Specifically, if gaseous reactant comprises be less than 1 volume %O ₂, be more specifically less than 0.5vol%O ₂, and even more specifically if it is not containing O ₂if if do not have oxygen to be added in this gaseous reactant or in PECVD process there is no oxygen at all, then there is no that oxygen is present in this gaseous reactant, this is also within the scope of " there is no oxygen ".

In the context of the present invention, a kind of " container " can be the container of any type of the wall with at least one opening and a restriction internal surface.In the context of the present invention, term " at least " refers to the entirety of " being equal to or greater than " the following stated term.Therefore, therefore, container in the context of the present invention has one or more opening.One or two opening, 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 size.If there is more than one opening, opening may be used for the inlet mouth according to PECVD coating method of the present invention, simultaneously other opening or added cap or opening.According to container of the present invention can be sampling tube (such as collect or store biofluid (as blood or urine)), for storing or syringe (or it parts of delivery of bioactive compounds or composition (such as medicament or pharmaceutical composition), such as syringe cylinder), for storing the bottle of biomaterial or bioactive compounds or composition, pipe (such as transporting the conduit of biomaterial or bioactive compounds or composition), or for the cuvette (such as containment of biological materials or bioactive compounds or composition) of containing fluid.

Container can have any shape, and the container with the cylindrical wall substantially of at least one its opening end contiguous is preferred.Usually, the inwall of this container is columniform, just as such as in stopple coupon or syringe cylinder.Stopple coupon and syringe or their parts (such as syringe cylinder) are particularly preferred.

In the context of the present invention, " hydrophobic layer " represents compared with corresponding uncoated surface >, and this coating reduces the wet tension on the surface being coated with described coating.Therefore, hydrophobicity is the function of uncoated base and coating.Be suitable for the appropriate change for wherein using term " hydrophobic " other backgrounds equally.Term " hydrophilic " represents the contrary meaning, and namely compared with reference sample, wet tension adds.Hydrophobic coating concrete in context of the present invention can be have empirical formula or total formula Si _wo _xc _yh _za kind of coating, wherein w is 1, x be 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 a surperficial hydrophobicity or hydrophilic one is specific measures.A kind of preferred wet tension measuring method is in the context of the present invention the one amendment of ASTMD2578 or the method that describes in ASTMD2578.The method uses standard wet tension solution (being called dyne solution) to determine the solution continuing for two seconds closest to a moistening Plastic film surface.Here it is film wet tension.Step used herein is different from ASTMD2578 part and is, wherein substrate is not smooth plastics film, but according to the scheme for the formation of PET pipe make and according to for use hydrophobic layer apply pipe inside scheme (see example 9) and coating (except contrast except) pipe.

" slip coating " according to the present invention is a coating with the friction resistance lower than uncoated surface.In other words, compared with uncoated reference surface, which reduce the friction resistance of coated surface." friction resistance " can be static frictional drag (staticfrictionalresistance) and/or friction of motion resistance (kineticfrictionalresistance).An optional embodiment of the present invention is the syringe part with a lubricant film coating, such as a syringe cylinder or plunger.In this preferred embodiment, static frictional drag relevant is in the context of the present invention starting force as defined in this, and friction of motion resistance relevant is in the context of the present invention plunger sliding force as defined in this.Such as, in the context of the present invention as defined herein and the plunger sliding force determined is suitable for determining the existence of a slip coating or shortage and lubricating property, whenever this coating is applied on any syringe or syringe part, such as, be applied on the inwall of a syringe cylinder.This starting force is suitable especially for assessment of the coating effect on a precharging type syringe, this precharging type syringe be filled after coating and again can move (must by " startings ") at plunger and store for some time before, such as some months or even several years.

" plunger sliding force " in context of the present invention is the power that maintenance plunger moves required for (such as between suction or allotment period) in syringe cylinder.This can be used advantageously in ISO7886-1:1993 described in this and as known in the art test and determine.The synonym of " the plunger sliding force " that often use in this area is " plunger force " or " thrust ".

" starting force " in context of the present invention is used to the starting force in syringe (such as in precharging type syringe) required for mobile plunger.

Illustrate in greater detail in the further part of this specification sheets " plunger sliding force " and " starting force " both and for their measure method.

" slidably " refer to that this plunger is allowed to slide in syringe cylinder.

In the context of the present invention, " in fact rigidity " represents these parts assembled (port, pipeline and housings, further illustrate following) can be moved by this housing of operation as a unit, and the parts of any assembling about other can not be moved significantly.Exactly, these parts are not all connected by the flexible pipe of the substantive relative movement during normal use allowed between part or analogue.The regulation of the rigid relation in fact of these parts allows the position of the container be seated on this pan straddle to be that to be fixed to as these parts the position on housing be close to know and accurate.

Below, first will illustrate and be used for carrying out device of the present invention, be thereafter the container according to coating method of the present invention, coating and coating and purposes.

I. there is the container processing systems of multiple treatment station and multiple pan straddle

I. consider a kind of container processing systems, it comprises first treatment station, the second treatment station, multiple pan straddle and a transfer roller.This first treatment station is configured to the container for the treatment of the wall with an opening and a restriction internal surface.This second treatment station and this first treatment station separate and are configured to for the treatment of having an opening and limiting the container of wall of an internal surface.

I. at least some, optionally all pan straddles comprise a container port, and this port is configured to the opening of a reception container and makes it take a seat for the interior surface via the container port process container of taking a seat at this first treatment station place.This transfer roller is configured to for a series of pan straddle and the container of taking a seat are transported to from this first treatment station the interior surface that the second treatment station is used for processing via the container port at this second treatment station the container that is taken a seat.

I. first see Fig. 1, the container processing systems being typically expressed as 20 is shown.This container processing systems can comprise multiple treatment station, more broadly considers that these treatment station are multiple treatment facilities.This container processing systems 20 of the embodiment shown 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 one exports 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, such as treatment station 28, and second treatment station, and such as 30,32 or 34.

I. any one treatment station 22-36 in shown embodiment can be first treatment station, and any other treatment station can be second treatment station, etc.

I. shown in FIG embodiment can comprise eight treatment station or equipment: 22,24,26,28,30,32,34 and 36.Exemplary container processing systems 20 comprises 26, one, precoating inspection station, an injection moulding machine 24, one, 22, aftershaping inspection station coating station 28, and applies light sources transmit station 34 and the output station 36 that 32, one, the light sources transmit station inspection holiday of the thickness of coating is determined in 30, one, inspection station afterwards.

I. this system 20 can comprise a transmission mechanism 72 for container is moved to pan straddle 38 from injection moulding machine 22.This transmission mechanism 72 can be configured to a such as robotic arm, container 80 is located by this robotic arm, move to, grasp, transmit, directed, take a seat and discharge they removed from container forming machine 22 and attach it to pan straddle such as 38.

I. system 20 can also comprise a transmission mechanism at treatment station 74 place for being removed from one or more pan straddle such as 66 by container, then processes the interior surface (Fig. 1) of the container such as 80 of taking a seat.Therefore these containers 80 can move to packaging, storage or another suitable region or processing step (being typically expressed as 36) from pan straddle 66.This transmission mechanism 74 can be configured to a such as robotic arm, container 80 is located by this robotic arm, move to, grasp, transmit, directed, place and release they are removed from pan straddle such as 38 and are placed on other equipments at station 36.

I. at independent container 80 from after pan straddle such as 64 is removed, treatment station shown in Figure 1 or equipment 32,34 and 36 optionally carry out one or more suitably in the step of coating with check system 20 downstream.Some limiting examples of the function of these stations or equipment 32,34 and 36 comprise:

Process and checked container 80 are placed on a transfer roller to other treatment unit;

Chemical is joined in container;

These containers are added cap;

These containers are placed in suitable processing rack;

By these container packages; And

By the container sterilization of packaging.

I. the container processing systems 20 shown in FIG can also comprise multiple accordingly 38 to 68 pan straddle (or " rubber disc " (puck), as they can also a similar hockey rubber disc in some embodiments), and a transfer roller, this transfer roller is typically expressed as endless belt 70, for by one or more pan straddle 38-68 and therefore container such as 80 be transported to treatment station 22,24,26,28,30,32,34 and 36 or from their transport leave.

I. this treatment station or equipment 22 can be the equipment for shaped container 80.The equipment 22 considered can be an injection moulding machine.Another equipment 22 considered can be a blow molding machine.Also contemplate vacuum forming machine, stretch forming press (drawmoldingmachine), cutting or shredder, can the glass drawing machine of stretch forming material or the container forming machine of other types for glass or other.Optionally, container forming position 22 can be omitted, because can obtain the container be shaped.

II pan straddle

II.A. carry-case support 38-68 is provided for holding and carry a container with opening to process container simultaneously.This pan straddle comprises a container port, second port, a pipeline and one can carry housing.

II.A. this container port is configured to a vessel port is seated in a relation be interconnected.This second port is configured to reception extraneous gas supply or ventage.This pipeline is configured to pass through for making one or more gases be landed between vessel port on this container port and this second port at one.This container port, the second port and pipeline are attached to this with the relation of rigidity in fact can carry on housing.Optionally, the weight of this carry-case support is less than five pounds.A kind of advantage of lightweight container support it more easily can be transported to another station from a treatment station.

II.A. in the embodiment of some pan straddle, this pipeline more specifically vacuum pipe and this second port more specifically vacuum ports.This vacuum pipe be configured to for from the container be landed on container port via this container port withdrawing gas.This vacuum ports is configured between vacuum pipe with outer vacuum source and is communicated with.This container port, vacuum pipe and vacuum ports can be attached to this by the relation of rigidity in fact and can carry on housing.

II.A. such as figure 2 illustrates the pan straddle of embodiment II.A. and II.A.1..The pan straddle 50 with container port 82 is configured to the opening of receiving vessel 80 and makes it take a seat.The interior surface of the container 80 of taking a seat can process via container port 82.Pan straddle 50 can comprise a pipeline, such as vacuum pipe 94, for from container 80 withdrawing gas be landed on container port 92.Pan straddle can comprise second port, such as, be communicated with the vacuum ports 96 between vacuum pipe 94 and outer vacuum source (as vacuum pump 98).Container port 92 and vacuum ports 96 can have sealing element, such as O shape circle Butt sealing part, be respectively 100 and 102, or the side seal between the inside or outer cylinder wall of the inside of container port 82 or outer cylinder wall and container 80, also form a sealing with it for receiving vessel 80 or outer vacuum source 98, allow to be communicated with by this port simultaneously.(or also using) packing ring or other sealing arrangements can be used.

II.A. pan straddle (as 50) can be made with any material, such as thermoplastic material and/or non-conducting material.Such as, or pan straddle (as 50) can part or to be even mainly made up of electro-conductive material and towards non-conducting material, in the passage limited by container port 92, vacuum pipe 94 and vacuum ports 96.The example of the material for pan straddle 50 be applicable to is: polyacetal, such as, by E.I.duPontDeNemours and WilmingtonDelaware Company acetal material; Tetrafluoroethylene (PTFE), such as, by E.I.duPontDeNemours and WilmingtonDelaware Company pTFE; Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE); High density polyethylene(HDPE) (HDPE); Known in the art or newfound other materials.

II.A. Fig. 2 also illustrates this pan straddle (such as 50), when it is close or when being landed on port 92, can have an axle collar 116 for making container 80 placed in the middle.

The array of pan straddle

But another kind of process, check and or can be the array using a kind of pan straddle by the method for production system moving-member II.A..This array can comprise independent rubber disc or load the entity array of these devices wherein.Tested the while that array can allowing to need, to carry or process/apply more than one device (optionally many devices).This array can be (being similar to a bucket or tower tray) of one dimension (such as being gathered to be formed a linear gear rack) or two dimension.

II.A. Fig. 4,5 and 58 shows three array approach.Fig. 4 shows wherein (or thereon) is loaded with the entity array 120 of these devices or container 80.In this case, these devices or container 80 can move through production process as a solid array, although they can be removed and be passed on independent pan straddle in this production process.A single pan straddle 120 has multiple for carrying the container port (as 122) of an array of the container (as 80) of taking a seat, and this array moves as a unit.In this embodiment, multiple independent vacuum ports (as 96) can be provided to receive the array of a vacuum source 98.Or, the vacuum ports that of being connected to all container ports (as 96) is single can be provided.Multiple inlet mouth can also be provided in an array to pop one's head in (as 108).The array of gas port probe or vacuum source can be installed into move as a unit, thus process many containers (as 80) simultaneously.Or, in a treatment station, can once or one by one by a row for multiple container port (as 122) addressing (addressed) or arrange more.The quantity of device in an array can be relevant with the quantity of device shaping in a single step, or with can consider efficiency during operation other test or step relevant.When processing/a coating array, electrode can or combine (to form a large electrode) or can be independent electrode (each have its power supply).All above methods can be applicable (viewpoints from geometric electrode, frequency etc.).

II.A. in Figure 5, independent rubber disc or pan straddle (as discussed above) are gathered together become an array (as by an external frame 130 around them).When this is desired, this is arranged and provides the advantage of the solid array of Fig. 4, and in other treatment steps allowing this array to be disbanded for the different array of the addressed one-tenth of container 80 or single array wherein.

II.A. Figure 58 shows a linear gear rack, and other are similar to Fig. 4.If use a linear gear rack, except described above except those, another option transports this tooth bar by a treatment station with single column fashion, thus process these containers continuously.

II.B. the pan straddle that O shape circle is arranged is comprised

II.B. Figure 42 and 43 is equipped with an alternative sealing arrangement, can with such as Fig. 2,3,6,7,19,12,13,16,18,19, the longitudinal cross-section view of a local of rupturing for container being seated at a pan straddle 450 on pan straddle that uses together with the pan straddle embodiment of 30 and 43 and a partial view.With reference to Figure 42, this container (being such as seated at a syringe cylinder 438 on 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 identical type usually, but does not have flange 440, and therefore alternatively can be seated on pan straddle 450.

In II.B embodiment as demonstrated, pan straddle 450 comprises the internal surface 456 of a substantial cylindrical, and in illustrated embodiment, this cylindrical form interior surface is used 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 on pan straddle 450, this annular lip 452 is resisted against on the bearing of this general toroidal.Provide the dimple of a general toroidal or groove 460 that are formed in internal surface 456 for keeping sealing element, a such as O shape circle 462.The radial depth of this dimple 460 is less than the radial section of sealing element (such as O shape circle 462 (as shown in Figure 42)), and preferably the internal diameter of this O shape circle 462 is preferably slightly less than the external diameter of this annular lip 452.

II.B is when container (such as 438) is taken a seat (as shown in Figure 42), and the radial section that these relative dimensions cause O shape to enclose 462 flatly compresses (as shown generally at 42) between the outer wall 464 and the substantial cylindrical sidewall 454 of syringe cylinder 438 of at least dimple 460.The area supported that this compression makes O shape enclose 462 flattens, and defines one and seal between the outer wall 464 and the substantial cylindrical sidewall 454 of syringe cylinder 438 of at least this dimple 460.

II.B. optionally, dimple 460 can be constructed relative to the size of O shape circle 462 thus diapire 466 and formed between roof 468 and sidewall 454 plural sealing (by approximately at a distance of enclose as far as corresponding O shape 462 radial section diameter and by roof 468 and diapire 466 spaced apart).When O shape circle 462 is compressed between the outer wall 464 of this dimple 460 and the sidewall 454 of substantial cylindrical, its elasticity will cause it to expand up and down (as shown in Figure 43), so also engage roof 468 and diapire 466 and to make them flatten smooth.Therefore O shape circle 462 optionally will vertically and flatly be out of shape in the two directions, tends to its common rounded section be become square.Additionally, annular lip 452 on this bearing 458 is seated at by restricted passage or the contiguous PECVD process reaction thing of this aft opening 442 and the flow rate of other gases be introduced into and material.

II.B is as the result of this structure optionally, and only the gap (as shown in Figure 43) at lower right corner place of O shape circle 462 is the outside of O shape circle and is therefore exposed to the process gas, plasma body etc. that to be introduced in the inside of container 438 or to produce.This establishing protective O shape circle 462 and neighbouring surface (neighbouring surface as the outer surface of sidewall 438) are from the sedimental accumulation of unwanted PECVD and attacked by the chemical species activated in plasma body.Additionally, as contrary with elastic surface (this elastic surface is represented being taken a seat by the direct docking of annular lip 452 against this O shape circle (and as other figure some in show)), container 438 is more positively located by the hard surface of bearing 458.In addition, when container 438 is limited to prevent any substantial shake, the power on the main circumference corresponding part of this O shape circle 462 is more uniformly distributed.

II.B. or, dimple 460 can be formed together with its diapire 466 on the bearing 458 shown in Figure 43.In another embodiment, when container 438 is seated on this bearing 458, can provide more than one axially spaced dimple 460 with a dual seal or higher levels of sealing are provided and thus further restriction container 438 avoid shake.

II.B. Figure 45 is for one of pan straddle 482 alternative structure, this structure can with such as Fig. 1,2,3,6-10,12-16,18,19,21,22,26,28, use together with the embodiment of 33-35 and 37-44.Pan straddle 482 is included in a upper part 484 and a base 486 of the connection of connecting joint 488 place.Between a upper part 484 and a base 486 at connecting joint 488 place, a sealing element (such as an O shape circle 490 (cut to allow this dimple to keep it with to be described, on the right side of it)) is captured.In the embodiment of this displaying, when upper part 484 is connected on base 486, this O shape circle 490 is received in an annular concave seat 492 so that this O shape is drawn a circle to approve position.

II.B. in this embodiment, when upper part 484 is connected (being connected by screw 498 and 500 in this case) with base 486, O shape circle 490 is captured and leans the wall 496 of the abutment surface 494 of radial direction extension and the radial direction extension of part restriction dimple 492.So O shape circle 490 is seated between upper part 484 and base 486.The O shape of catching between upper part 484 and base 486 is enclosed 490 and also be have received container 80 (being removed to clearly demonstrate other feature in this drawing) and define a first seal with O ring part of the container port 502 about the opening of container 80, and the seal with O ring around container aft opening 442 be similar in Figure 42 is arranged.

II.B. in this embodiment (although not requiring), container port 502 has the O shape that an O shape encloses 490 sealing members and the second axially spaced-apart and encloses both 504 sealing members, there is an internal diameter (as being sized to 506) separately with the external diameter of receiving vessel (as 80) (being similar to the sidewall 454 in Figure 43), for sealing between container port 502 and container (as 80).Spacing between O shape circle 490 and 504 is that container (as 80) provides and supports at (the some places at two axially spaced-aparts), prevents this container (as 80) to enclose 490 and 504 or container port 502 and tilting relative to O shape.In this embodiment (although not requiring), the radial abutment surface 494 extended be positioned at O shape circle 490 and 506 sealing members nearside and around vacuum pipe 508.

III. the method for the container on pan straddle is landed in for conveying containers-process

III.A. pan straddle is transported to treatment station

III.A. Fig. 1,2 and 10 shows a kind of method for the treatment of container 80.The method can be carried out as follows.

III.A., the container 80 of the wall 86 having opening 82 and limit internal surface 88 can be provided.As an embodiment, can in the mould (as 22) shaped container 80 and then therefrom it being removed.Optionally, removing from this mould in 60 seconds 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 can be moved once container 80 in 1 second or during processing and will its (assuming that it is made at an increased temperature, it is gradually cooled as it passes through the cooler hereafter) of distortion vessel port 82 just can be made to be landed on container port 92.Container 80 decreases the adhesion of the dust or other impurity and prevention that may arrive surface 88 or the coating 90 preventing barrier coat or other types from the rapid movement of mould 22 to container port 92.And the vacuum of being pumped on container 80 after it is made into is faster, then the chance that adheres on internal surface 88 of any granulometric impurity is less.

III.A., the pan straddle comprising container port 92 (as 50) can be provided.The opening 82 of container 80 can be landed on container port 92.Before the opening 82 of container 80 is seated in container port 92, period or afterwards, pan straddle enter with the joint of one or more area supported 220 to 240 as 40 (such as in figure 6) can be transported thus relative to treatment facility or treatment station (as 24) positioning vessel support 40.

III.A. when process is positioned at the interior surface 88 of the container 80 of taking a seat for the treatment of station or equipment (as 24), one in these treatment station (as 24-34), more than one or all treatment station (as station 24 as shown in by Fig. 6 show) area supported for supporting one or more pan straddle (as 40) in predetermined position can be comprised, one or more as in area supported 220,222,224,226,228,230,232,234,236,238 or 240.These area supporteds can be the structures of partial silence or piecemeal activity, such as, be guide simultaneously at this container of process and locate track or the guiding piece of this pan straddle (as 40).Such as, when probe 108 is inserted in pan straddle 40, these area supporteds 222 and 224 to be downwards positioned on pan straddle 40 and to serve as the reaction surface stoping pan straddle 40 to move up.Reaction surface 236 to be positioned on pan straddle and to stop pan straddle 40 to be moved to the left, and vacuum source 98 (according to Fig. 2) is seated in vacuum ports 96 simultaneously.These area supporteds 220,226,228,232,238 and 240 to be positioned at similarly on pan straddle 40 and to stop during processing and move horizontally.Area supported 230 and 234 is positioned at pan straddle (as 40) similarly and goes up and stop its vertical mobile displacement.Therefore, first area supported, second area supported, the 3rd area supported or a more area supported can be provided at each treatment station.

III.A. then can process the interior surface 88 of the container 80 of taking a seat via container port 92 at the first treatment station, this first treatment station can be, as an example, blocking layer applies the coating station 28 of coating station or other types shown in figure 2.Pan straddle 50 and the container 80 of taking a seat are transported to the second treatment station (such as treatment station 32) from the first treatment station 28.The interior surface 88 of the container 80 of taking a seat can be processed via container port 92 at the second treatment station (as 32).

III.A. any above method can comprise the step further removing container 80 from pan straddle (as 66), the interior surface 88 of the container 80 of taking a seat at the second treatment station or device processes afterwards.

III.A. any above method can comprise the step of the second container 80 further providing the wall 86 having opening 82 and limit interior surface 88 after removing step.The opening 82 of second container (as 80) can be landed on the container port 92 of another pan straddle (as 38).The interior surface of the second container 80 of taking a seat can be processed via container port 92 at the first treatment station or equipment (as 24).Pan straddle (as 38) and the second container 80 of taking a seat can be transported to the second treatment station or equipment (as 26) from the first treatment station or equipment 24.The second container 80 of taking a seat can be processed via container port 92 by the second treatment station or equipment 26.

III.B. treatment facility is transported to pan straddle or vice versa

III.B. or, these treatment station can be more broadly treatment facilities, and or these pan straddles can be transferred relative to these treatment facilities, these treatment facilities can be transferred relative to pan straddle, or some of each layout can be provided in a given system.Still, in another is arranged, these pan straddles can be delivered to one or more station, and more than one treatment facility can be adopted at least one or the station close at least one.Therefore, corresponding one to one between treatment facility with treatment station is not required.

III.B. the method comprising some parts is considered for processing a kind of container.There is provided first treatment facility (as 108 (Fig. 2) that pop one's head in) and second treatment facility (as light source 170, Figure 10) for the treatment of container (as 80).The container 80 provided has an opening 82 and limits the wall 86 of interior surface 88.Provide the pan straddle 50 comprising a container port 92.The opening 82 of container 80 is landed on container port 92.

III.B. in making the first treatment facility (as popped one's head in 108) move into engage with the operability of pan straddle 50, or vice versa.The first treatment facility or probe 108 is used to process the interior surface 88 of the container 80 of taking a seat via container port 92.

III.B. in then making the second treatment facility (as 170, Figure 10) move into engage with the operability of pan straddle 50, or vice versa.The second treatment facility (as light source 170) is used to process the interior surface 88 of the container 80 of taking a seat via container port 92.

III.B. optionally, any amount of other treatment step can be provided.Such as, the 3rd treatment facility 34 can be provided for the treatment of container 80.In the 3rd treatment facility 34 can being made to move into engage with the operability of pan straddle 50, or vice versa.The 3rd treatment facility 34 can be used via container port 92 to process the interior surface of the container 80 of taking a seat.

III.B. for the treatment of in the another kind of method of container, the container 80 of the wall 86 that there is opening 82 and limit interior surface 88 can be provided.A pan straddle (as 50) comprising container port 92 can be provided.The opening 82 of container 80 can be made to be landed on container port 92.Can process the interior surface 88 of the container 80 of taking a seat via container port 92 at the first treatment facility, this first treatment facility can be, as an example, 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 the second treatment facility (treatment facility 34 such as shown in Fig. 1 and 10) from the first treatment facility 28.Then can be processed the interior surface 88 of the container 80 of taking a seat via container port 92 by the second treatment facility (as 34).

III.C. clamp is used to be used for pipe to transport enter and leave coating station

III.C. another embodiment is a kind of method of the PECVD process of first container again, and the method comprises several step.Provide first container, this container has an opening end, a closing end and an interior surface.At least one first clamp is arranged to the closing end optionally keeping and discharge this first container.Clamp the closing end of the first container with this first clamp, and use this first clamp to be transported near pan straddle, this pan straddle is configured to the opening end of this first container is taken a seat.Then use this first clamp axially to advance this first container and make its opening end be seated on this pan straddle, between this pan straddle and the inside of this first container, setting up being communicated with of sealing.

III.C. at least one gaseous reactant is introduced within this first container by this pan straddle.In the interior surface of this first container, plasma body is formed under the condition of reaction product effectively forming this reactant.

III.C. then make this first container disseat from this pan straddle, and use this first clamp or another clamp, this first container is axially transported and leaves this pan straddle.Then this first container is discharged from used clamp thus axially it is transported and leave this pan straddle.

III.C. refer again to Figure 16 and 49, a transfer roller of connecting 538 can be used to support and transport multiple clamp (as 204) and process by this device and as said.The transfer roller 538 clamp 204 being operably connected to this series connection is arranged to and at least two containers 80 a series is in turn transported near this pan straddle 48, and carries out other steps of purging method as described herein.

IV is for the manufacture of the PECVD device of container

IV.A. pan straddle, interior electrode, PECVD device as the container of reaction chamber is comprised

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 be landed on pan straddle defines a plasma-reaction-chamber, and it can be optionally vacuum chamber.Optionally, can be used for vacuum source, reacting gas source, gas feed or the combination of two or more among these.Optionally, provide the eduction pipe that must not comprise vacuum source, for by gas transfer to the inside of the container of taking a seat on that port or transmit from the internal gas of this container, to limit a closed-chamber.

IV.A. this PECVD device may be used for normal atmosphere PECVD, and plasma-reaction-chamber does not need to work as vacuum chamber in this case.

In the embodiment of IV.A. showing in fig. 2, pan straddle 50 comprises gas entry ports 104, for delivering gas in the container be landed on container port.Gas entry ports 104 has one and encloses by the O shapes that O shape is enclosed or three are connected in series of at least one O shape circle 106 or two serial connections the sliding seal provided, when probe 108 is inserted into by gas entry ports 104, cylindrical probe 108 can be leaned on and take a seat.Probe 108 can be an air inlet conduit, and this air inlet conduit extends to the gas delivery port at far-end 110 place at it.The far-end 110 of the embodiment of showing can be inserted in container 80 deeply for providing one or more PECVD reactants and other process gass.

In the embodiment of IV.A. optionally showing in fig. 2, or more generally in the embodiment of any disclosure, such as Fig. 1-5,8,9,12-16,18,19,21,22, the embodiment of 26-28,33-35,37-49 or 52-55, and as disclosed especially in Figure 55, the volume of a plasma body net 610 for the plasma body be usually formed in container 80 being limited in plasma body net more than 610 can be provided.Plasma body net 610 is a kind of conductive porous material, and its some examples are Steel Wool, porous sintered metal or be coated with the stupalith of conductive material or the porous plate be made up of metal (such as brass) or other conductive materials or dish.An example is the salver having centre hole (its size is confirmed as by inlet mouth 108) for a pair and have the hole (spaced apart with 0.04 inch (1mm)) of 0.02 inch (0.5mm), and these centers provide the open area of 22% in the ratio of the surface-area of this dish to the hole of center (center-to-center).

IV.A. in particular for wherein popping one's head in 108 also as the embodiment that counter electrode works, at opening 82 place of (or close) processed pipe, syringe cylinder or other containers 80, plasma body net 610 can with inlet mouth 108 intimate electrical contact.Alternately, plasma body net 610 can ground connection, optionally has common potential with inlet mouth 108.Plasma body net 610 reduce or eliminates the plasma body in pan straddle 50 and its internal passages and connection (other devices of the vicinity of such as vacuum pipe 94, gas entry ports 104, O shape circle 106, vacuum ports 96,0 shape circle 102 and contiguous inlet mouth 108).Meanwhile, the porosity of plasma body net allows process gas, air and analogue to flow out from container 80 and enters vacuum ports 96 and downstream unit.

IV.A. in shown in figure 3 coating station 28, pan straddle 112 comprises gas entry ports and the vacuum ports 96 of the compound be communicated with vacuum ports 92, and these two ports are accordingly for delivering into (via probe 108) and withdrawing gas from the container be seated at container port 92 (via vacuum source 98) in the container 80 that is seated on container port 92 by gas.In this embodiment, gas inlet probe 108 and vacuum source 98 can provide with the form of combined probe.As desired, these two can be popped one's head in the form of a unit or advance dividually.This arrangement eliminates the needs for the 3rd sealing member 106 and allow to use Butt sealing part throughout.Butt sealing part allows such as by extracting vacuum in container 80 being applied an axial force thus by making O shape annular strain positively take a seat container 80 and vacuum source 98, and this tends to the existence of any irregularity in the sealing face on one of closed two sides by enclosing O shape and any gap of staying.In the embodiment of Fig. 3, be contrary by container 80 and vacuum source 98 axial force be applied on pan straddle 112, this tends to container 80 and pan straddle 112 to keep together and maintains corresponding Butt sealing part.

IV.A. Figure 13 is the view being similar to Fig. 2 according to a pan straddle 48 in a coating station of another embodiment again of this disclosure, and wherein this container 80 can be landed in and be positioned on the pan straddle 48 of this treatment station.This can be used for processing vessel 80, this container does not such as move together with 48 with pan straddle, or it may be used in the coating station 28 of blocking layer coating station or other types, before by system 20 container 80 of taking a seat being delivered to other devices, first the coating station of this blocking layer coating station or other types makes container 80 be seated in a pan straddle (as 48).

IV.A. as a replacement scheme of the U-shaped electrode of Fig. 2 and 9, Figure 13 shows the cylindrical electrode 160 being suitable for the frequency from 50Hz to 1GHz.Or by before electrode being moved down or pan straddle being moved up, can be mobile in place by this pan straddle (or this electrode).Or, the movement in vertical surface of this pan straddle and electrode can be avoided by setting up an electrode 160, this electrode is configured to similar clam shell (two semicylinders, when pan straddle go up in position and prepare for the treatment of/coating time, these semicylinders can combine from opposite side).IV.A. optionally, if this process is a continuous print process (wherein pipe is moved through this coating station (such as 28) simultaneously by probe 108 extracting vacuum and by gas introducing), at coating station 28 place, vacuum source 98 forms one and seals (can be maintained during this pan straddle mobile) together with rubber disc or pan straddle 50.Or, a static process can be adopted, wherein this rubber disc or pan straddle 50 are moved and enter a static position, now upwards to be pushed by probe 108 in this equipment and then pump or vacuum source 98 are connected at vacuum ports 96 place and activate thus produce vacuum.Once probe 108 in position and create vacuum, can set up plasma body with an external stability electrode 160 in the inside of pipe or container 80, this external stability electrode is independent of this rubber disc or pan straddle 50 and manage or other containers 80.

IV.A. Figure 53 show can with such as Fig. 1,2,3,6-10,12-16,18,19,21,22,26-28,30,33-35,37-44 and 52 embodiment together with the other optional details of coating station 28 that use.Leading in the vacuum pipeline 576 of pressure transmitter 152 at it, coating station 28 can also have a main vacuum valve 574.A manual bypass valve 578 is provided in by-pass line 580.Vent valve 582 controls the flow rate at ventage 404 place.

The outflow of IV.A.PECVD gas source 144 is controlled by the main reaction gas trap 584 of the flow rate of main reaction thing feeding line 586 by adjustment.An assembly of gas source 144 is silicone fluid reservoirs 588.Extracted the content of reservoir 588 by organosilicon capillary line 590, provide pipeline 590 to provide desired flow rate with suitable length.The flow rate of organosilicon steam is controlled by organosilicon stopping valve 592.Pressure is applied to liquid reservoir 588 headspace 614, such as one scope from pressure source 616 (as being connected to the forced air of headspace 614 by pressure line 618), at the pressure of 0-15psi (0 to 78cm.Hg), is sent to set up the repeatably silicone fluid not relying on normal atmosphere (and fluctuation wherein).Reservoir 588 is sealing and kapillary connection 620 is in the bottom of reservoir 588, to guarantee only having pure silicone fluid (not being the gas under pressure from headspace 614) to flow through kapillary 590.If necessary or wish, optionally can heat this silicone fluid to higher than envrionment temperature to make this organosilicon liquid evacuator body, form a kind of organosilicon steam.There is provided oxygen from oxygen canister 594 via oxygen feeding pipeline, this oxygen feeding pipeline is controlled by mass flow rate controller 598 and is equipped with an oxygen stop valve 600.

IV.A., in the embodiment of Fig. 7, this station or equipment 26 can comprise and is adapted to be seated at a vacuum source 98 in vacuum ports 96, is connected to a wing passage 134 on probe 108 or both (as shown).In the embodiment of this displaying, this wing passage 134 comprises a stopping valve 136, and this stopping valve regulates the flow rate between probe port 138 and vacuum ports 140.In the embodiment of this displaying, this selector valve 136 has at least two states: a vacuum state, port one 38 is connected with 140 wherein, this provide two parallel paths (because this increasing pumping rate and reducing pumping force) for gas flow, and an off-state, port one 38 is separated with 140 wherein.Optionally, selector valve 136 can have the 3rd port, as a PECVD gas entry ports 142 for introducing PECVD reactant gas and process gas from gas source 144.This stopgap measure allows same vacuum supply and probe 108 to be used to leak or penetration testing and both the coatings for applying this barrier coat or other types.

IV.A., in the embodiment of this displaying, the vacuum pipeline (as 146) towards vacuum source 98 can also comprise a stopping valve 148.Stopping valve 136 and 148 can be closed when probe 108 and vacuum source 98 are not connected in pan straddle example (as 44), make when container 80 moves to another from a pan straddle 44 like this, do not need the wing passage 134 leaving container 80 be positioned on valve 136 and 148 side and vacuum pipeline 146 to find time.In order to promote axially to be removed from gas entry ports 104 by probe 108, a flexible pipe line 150 can be provided to move axially relative to the position of port 96 independent of vacuum pipeline 146 to allow probe 108.

IV.A. Fig. 7 also show the ventage 404 leading to ambient air of another optional feature that can use together with any embodiment-controlled by valve 406.After processing vessel 80, no matter whether from pan straddle 44, discharge container 80, be released in from vacuum source 98 pan straddle 44 of vacuum ports 96 or optionally both, can by open for valve 406 with breaking vacuum rapidly.

IV.A. in the embodiment of this displaying (still with reference to figure 7), probe 108 can also to be connected on a pressure warning unit 152 and can be communicated with the inside 154 of container 80, to allow the pressure in container 80 to be measured.

IV.A. in the device of Fig. 1, container coating station 28 can be a PECVD device such as further described hereinafter, and it is operated with by SiO under suitable conditions _xthe coating 90 of blocking layer or other types deposits in the interior surface 88 of container 80, as shown in FIG. 2.

IV.A. particularly with reference to Fig. 1 and 2, treatment station 28 can comprise an electrode 160 of being powered by radio-frequency power supply 162, for providing an electric field to produce plasma body in container 80 during processing.In this embodiment, probe 108 is also conduction and ground connection, therefore in container 80, provides a counter electrode.Alternately, in another embodiment, outer electrode 160 ground connection can be made and probe 108 is directly connected on power supply 162.

IV.A. in the embodiment of fig. 2, this outer electrode 160 can be or substantial cylindrical as is depicted in figures 2 and 8 or the gallery being a roughly U-shaped as shown in Fig. 2 and 9 (Fig. 8 and 9 is the alternative embodiments along the cross section that the section line A-A of Fig. 2 intercepts).Each embodiment of showing has one or more sidewall, as 164 and 166 and optional top 168, configures very closely around container 80.

IV.A., IV.B. Figure 12 to 19 shows other variants (as previously described) of container coating station or equipment 28.Any one or more in these variants can the container coating station shown in alternate figures 1-5 or equipment 28.

IV.A. Figure 12 shows an alternative electrode system, this electrode system can use under the frequency of more than 1GHz (with same way discussed above, use identical pan straddle and inlet mouth).At these frequencies, the electric energy from power supply can be passed to the inside of pipe by one or more guide wave device, these guide wave devices are connected on a cavity, this cavity or absorb energy or make this energy resonance.This energy resonance is made to allow it to be attached on gas.Different cavity can be provided for using together with different frequency, and because container 80 will interact with this cavity, container (as 80) changes its resonance point, creates the plasma body for applying and/or processing.

IV.A. Figure 12 shows coating station 28 and can comprise a microwave power supply 190, this microwave power supply by guide wave device 192 by micro waveguide to microwave cavity 194, this microwave cavity is at least in part around producing the container 80 of plasma body within it.This microwave cavity 194 can regulate with selecting relative to the dividing potential drop of micro-wave frequency and gas, to absorb microwave and to be attached on the gas of generation plasma body.Figure 13 and the embodiment of showing any one in, a small―gap suture 196 can be left thus avoid damaging the scuffing of container 80 or other between container 80 and cavity 194 (or electrode, detector or other surrounding structures).Also in fig. 13, microwave cavity 194 has a flush end wall 198, makes the circular edge place of gap 196 in particular relative to end wall 198 on width be uneven like this.Optionally, end 198 can be made bending to provide a uniform gap 196 substantially.Figure 44 is the view being similar to Fig. 2 of an alternative gas delivery/interior electrode 470, this alternative gas delivery/interior electrode can such as with Fig. 1,2,3,8,9,12-16,18-19,21-22,33, use together with the embodiment of 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 this interior electrode.Internal passages 476 is connected on gas feed device 144 by extending to the proximal part 478 of electrode 470 in outside container 80.The far-end 480 of interior electrode 470 can also be optionally porous.Porous sidewall 474 and, if present, the porosity of porous distal 480 allows laterally selecting from passage 476 at least partially thus being provided to by reactant gas the neighbouring part of interior surface 88 of container 80 of the reactant gas fed from gas feed device 144.In this embodiment, the porous part of this porous sidewall 474 extends the whole length of the interior electrode 470 in container 80, although this porous part may be more not widely, only extends a part for the length of interior electrode 470.Pointed by other places in this manual, interior electrode 470 can also be length relative to container 80 and longer or shorter than shown in Figure 44, and this porous part can be continuous or discontinuous.

IV.A. the external diameter of 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 internal diameter of the side direction vicinity of container.Adopt relative to electrode 470 in the larger diameter of the internal diameter of container 80, if particularly electrode 470 is concentric with container 80, then decrease the distance between the outside and the contiguous interior surface 88 of container 80 of interior electrode 470, plasma body is limited to a less region, in this region it can be evenly.When live gas is incorporated in plasma body at the multiple somes places closely separated of the length along interior surface 88 (very near the position of initial reaction), adopt the interior electrode 470 of larger diameter additionally provide reactant gas and/or carrier gas along interior surface 80 evenly distribution, with from relative to for the formation of the flowing opposite of a single point of interior surface 88.

IV.A. in a layout considered, represent with solid line, power supply that power supply 162 has towards electrode 200 connects, and 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, a capacitive load can be used within container 80 to produce plasma body.In the layout that another is considered, represent (and eliminating with the connection of solid line display) with imaginary line, the wire of the correspondence of power supply 162 is connected on the corresponding end of coil 200, and this coil can be called as " electrode " again in this manual for convenience's sake.In this configuration, an inductive load can be used within container 80 to produce plasma body.In an alternative embodiment, a combination of inductance and capacitive load can also be used.

IV.A. Figure 46-48 shows an array of two or more gas delivery (as 108 (also shown in Figure 2), 510 and 512), and they are also 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, removes from it for gas delivery/interior electrode 108,510 and 512 being inserted into one or more pan straddle such as 50 or 48 neutralization.These features are the optional stopgap measures for using gas delivery.

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 (by omitting slack by these flexible pipes by far and near scale smaller in Figure 46-48) on a common gas supply device 144 via stopping valve 522,524 and 526 accordingly by flexible pipe 516,518 and 520.Briefly with reference to topic Figure 56, flexible pipe 516,518 and 520 can be alternately connected to independently in gas source 144.Provide a mechanism 514 to extend and an interior electrode (as 108) of retracting.This interior electrode extender and retractor are configured to for making interior electrode move relative between the position of propelling completely of pan straddle, mid-way and retracted position.

IV.A., in Figure 46 and 56, interior electrode 108 is extended on its work point that extends within this pan straddle 50 and container 80, and its stopping valve 522 is open.And electrode 510 and 512 is contracted and their stopping valve 524 and 526 is closed in figures 4-6 can, idle.In the embodiment of this displaying, one or more in idle in electrode 510 and 512 are disposed within an electrode clean equipment or station 528.Optionally, one or more electrode within station 528 can be cleaned and other be replaced.These cleaning operations can relate to chemical reaction or container process to remove settling, grind physically to remove settling, or Cement Composite Treated by Plasma is using the settling (as limiting examples) of accumulation of burnouting in fact.

IV.A. in Figure 47, in idle, electrode 510 and 512 is as before, and has made electrode 108 in work leave container 80 to retract, and wherein its far-end is retained within pan straddle 50, and its valve 522 is closed.In this case, container 80 can be removed and a new container is seated on pan straddle 50, and without any the danger making electrode 108 contact with the container 80 being removed or replacing.After container 80 is replaced, interior electrode 108 can be advanced on the position of Figure 46 and 56, and stopping valve 522 can be reopened, with use with identical above in electrode 108 start to apply new container 80.Therefore, a series of container 80 to be seated on pan straddle 50 and to arrange from one that wherein removes wherein, the station place of electrode 108 in being in use, when container 80 is mounted or when removing from pan straddle 50, interior electrode 108 can be extended with repeatedly partially retracted.

IV.A., in Figure 48, pan straddle 50 and its container 80 are replaced with a new pan straddle 48 and another container 80.With reference to figure 1, in the embodiment of this type, when its pan straddle reaches coating station, each container 80 remains on the upper and interior electrode (as 108) of its pan straddle (as 50 or 48) and is inserted in each container.

IV.A. additionally, in Figure 48, interior electrode 108,510 and 512 is all fully retracted, and compared with position respective in Figure 47, the array of interior electrode 108,510 and 512 has been moved to the right side relative to pan straddle 48 and electrode clean station 528, make like this relative to electrode 108 in pan straddle 48 be moved displacement and interior electrode 510 has been moved to suitable position.

IV.A. should be understood that the movement of the array of interior electrode can independent of the movement of pan straddle.They can be movement together or independent movements, thus side by side or are independently transformed into a new pan straddle and/or a new interior electrode.

IV.A. Figure 46-48 shows an array of two or more gas delivery (as 108 (also shown in Figure 2), 510 and 512), and they are also interior electrodes.This array can be linear or a carousel.Carousel array allows these electrodes periodically to be reused.

IV.A. Figure 46-48 also show an interior electrode extender and retractor 514, removes from it for gas delivery/interior electrode 108,510 and 512 being inserted into one or more pan straddle (as 50 or 48) neutralization.These features are the optional stopgap measures for using gas delivery.

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 (by omitting slack by flexible pipe by far and near scale smaller in Figure 46-48) on a common gas supply device 144 via stopping valve 522,524 and 526 accordingly by flexible pipe 516,518 and 520.Provide a mechanism 514 for extending and an interior electrode (as 108) of retracting.This interior electrode extender and retractor are configured to for being moved advancing completely relative to one of this pan straddle between position, a mid-way and a retracted position by an interior electrode.

IV.A. in Figure 46 and 56, interior electrode 108 is lengthened on its work point within this pan straddle 50 and 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, in idle, electrode 510 and 512 is disposed within an electrode clean or station 528.Optionally, some electrodes within station 528 can be cleaned and other be replaced.These cleaning operations can relate to chemical reaction or solvent treatment removing settling, grind physically to remove settling or Cement Composite Treated by Plasma using the settling (as limiting examples) of accumulation of burnouting in fact.

IV.A. in Figure 47, in idle, electrode 510 and 512 is as before, and has made electrode 108 in work leave container 80 to retract, and wherein its far-end is retained within pan straddle 50, and its valve 522 is closed.In this case, container 80 can be removed and a new container is seated on pan straddle 50, and without any the danger making electrode 108 contact with the container 80 being removed or replacing.After container 80 is replaced, interior electrode 108 can be advanced on the position of Figure 46 and 56, and stopping valve 522 can again be opened to use with identical above in electrode 108 start to apply new container 80.Therefore, a series of container 80 to be seated on pan straddle 50 and to arrange from one that wherein removes wherein, the station place of electrode 108 in being in use, when container 80 is mounted or when removing from pan straddle 50, interior electrode 108 can be extended with repeatedly partially retracted.

IV.A., in Figure 48, pan straddle 50 and its container 80 are replaced with a new pan straddle 48 and another container 80.With reference to figure 1, in the embodiment of this type, when its pan straddle reaches coating station, each container 80 remains on the upper and interior electrode (as 108) of its pan straddle (as 50 or 48) and is inserted in each container.

IV.A. additionally, in Figure 48, interior electrode 108,510 and 512 is all fully retracted, and compared with position respective in Figure 47, the array of interior electrode 108,510 and 512 has been moved to the right side relative to pan straddle 48 and electrode clean station 528, make like this relative to electrode 108 in pan straddle 48 be moved displacement and interior electrode 510 has been moved to suitable position.

IV.A. should be understood that the movement of the array of interior electrode can independent of the movement of pan straddle.They can be movement together or independent movements, thus side by side or are independently transformed into a new pan straddle and/or a new interior electrode.

IV.A. in two or more, an array of electrode 108,510 and 512 is useful, because bound gas delivery tube/interior electrode 108,510 and 512 independent when they are for applying a series of container (such as 80) in some cases will tend to accumulate the reactant gas of polymerization or the settling of some other types.These settlings can be accumulated to this point of the homogeneity of their impairment coating speed or generation, and this may be undesirable.In order to maintain a uniform process, in these, electrode can be stopped periodically operation, replace or cleaning, and new or cleaned electrode can be put into operation.Such as, from Figure 46 to Figure 48, interior electrode 108 with up-to-date or in repairing electrode 510 replace, this interior electrode that is up-to-date or that repaired to be ready to be extended in pan straddle 48 and container 80 thus to be applied on new container by a coated inside.

IV.A. therefore, an interior electrode driver 530 is operationally connected with retractor 514 with interior electrode stretcher, for electrode 108 in first to be removed the retracted position arriving it from its extended position, this electrode 108 in first is replaced 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 such as with Fig. 1,2,3,8,9,12-16,18-19,21-22,26-28,33-35,37-45,49 and 52-54 embodiment together with use.Extension and the retraction mechanism 514 of Figure 46-48 be can such as with Fig. 2,3,8,9,12-16,18-19,21-22,26-28,33-35,37-45,49 and 52-54 gas delivery embodiment with together with and with Fig. 6 with 7 container inspection arrangement probe together with use.

Electrode 160 shown in IV.A Fig. 2 can be shaped as similar " U " shape passage, and its length enters the page, and this rubber disc or pan straddle 50 can be moved by (energy supply) electrode activated during process/coating processes.It is noted that because employ outside and internal electrode, this device can adopt between 50Hz and 1GHz, be applied to the frequency this U electrode 160 from power supply 162.Probe 108 can ground connection to improve circuit, allow electric current to be flow to the inside of container 80 by one or more low-pressure gases.This electric current produces plasma body to allow selectivity process and/or the coating of the interior surface 88 of this device.

IV.A electrode in fig. 2 can also by pulse power energy supply.Pulse allows the consumption of reactant gases, and then removes by product before activation and consumption (again) reactant gases.Typically the feature of pulse power system is their work period, and this work period determines the time quantum of the electric field (and being therefore plasma body) of existence.Conduction time is relative with power-off time.The work period of such as 10% can corresponding to the conduction time in 10% cycle, and wherein the time power supply of 90% is closed.As a concrete example, can be energized 0.1 second and power-off 1 second.The active power that pulse power system decreases for given power supply 162 inputs, because power-off time result in the treatment time of increase.When this system is pulse system, the coating of generation can be very pure (not having by product or pollutent).Another result of pulse system possible realize ald (ALD).In this case, can the work period be adjusted, cause the deposition of the desired material of individual layer such conduction time.By this way, consider and deposit a monoatomic layer in each cycle.This method can cause high purity and the coating of highly structural (although deposit the temperature of needs on polymer surfaces under, optionally keep low temperature (< 100 DEG C) and low temperature coating can be amorphous phase).

IV.A. an alternative coating station is disclosed in Figure 12, and its adopts microwave cavity to replace outer electrode.The energy applied can be a kind of microwave frequency, such as 2.45GHz.

IV.B. use and pipe is transported the PECVD device entering and leave the clamp of coating station

IV.B. another embodiment is a device for carrying out PECVD process to container, and this device adopts foregoing clamp.Figure 15 and 16 shows usually with the device for carrying out PECVD process to the first container 80 of 202 instructions, the internal space that this first container has an opening end 82, closing end 84 and limited by surface 88.This embodiment comprises a pan straddle 48, at least one first clamp 204 (in this embodiment, such as, a suction cup), the seat limited by container port 92 on this pan straddle 48, reactant feeding mechanism 144, by electrode 108 and the plasma generator of representated by 160, a container releasing device (it can be that a vent valve is as 534) and or identical clamp 204 or second clamp (in fact, optionally second clamp 204).

IV.B. this first clamp 204, and any one as demonstrated in clamp 204, be configured to for optionally keeping and discharging the closing end 84 of container 80.When clamping the closing end 84 of container, this container can be transported near pan straddle 48 by this first clamp 204.In the embodiment of this displaying, this delivery functions is promoted by a serial transfer roller 538, and wherein clamp 204 is attached on it in a series of mode.

IV.B. pan straddle 48 has combined with other embodiments above and has been illustrated, and is configured to the opening end 82 for being seated in container 80.The seat limited by container port 92 has combined with other embodiments above and has been illustrated, and sets up to seal between the internal space 88 being configured in pan straddle 48 and this first container (and be in this case container 80 any one) and be communicated with.Reactant feeding mechanism 144 has combined with other embodiments above and has been illustrated, and is operably connected for being introduced within this first container 80 by pan straddle 48 by least one gas reactant.The plasma generator limited by electrode 108 and 160 has combined with other embodiments above and has been illustrated, and the interior surface being configured in this first container forms plasma body under the condition of the reaction product of effective forming reactions thing within this first container.

IV.B. container releasing device 534 or other stopgap measures can be used, within the container 80 of taking a seat as a kind of reactant gas, a kind of carrier gas or a kind of cheap gas (as compressed nitrogen or air) are introduced, disseat from this pan straddle 48 to make this first container 80.

IV.B. clamp 204 is configured to leave pan straddle 48 for axially being transported by this first container 80, and then discharges this first container 80, as the suction by discharging between comfortable clamp 48 and container ends 84.

IV.B. Figure 15 and 16 also show a kind of method of first container being carried out to PECVD process, and the method comprises following step.There is provided first container 80, this container has an opening end 82, closing end 84 and an interior surface 88.There is provided at least one first clamp 204, this first clamp is configured to for optionally keeping and discharging the closing end 84 of this first container 80.Clamp the closing end 84 of the first container 80 with this first clamp 204, and be transported near pan straddle 48 thus, this pan straddle is configured to the opening end of this first container is taken a seat.In the embodiment of Figure 16, provide two pan straddles 48, this allows once to complete and to be advanced by container 80 and to be seated on pan straddle 48, therefore makes useful efficiency double.Then, use this first clamp 204 for axially being advanced by this first container 80 and making its opening end 82 be seated at this pan straddle 48, between this pan straddle 48 and inside of this first container, set up being communicated with of sealing.Then, introduce within this first container, optionally illustrated by earlier embodiments by this pan straddle to a kind of gas reactant of major general.

IV.B. following, the interior surface of this first container defines plasma body, optionally illustrated by earlier embodiments under a kind of condition of reaction product effectively forming this reactant in this first container.This first container is disseated from this pan straddle, optionally illustrated by earlier embodiments.Optionally illustrated by earlier embodiments, use this first clamp or another clamp axially to be transported by this first container and leave this pan straddle.Then this first container can being discharged from clamp, leaving this pan straddle, optionally illustrated by earlier embodiments for axially it being transported.

IV.B. another the optional step can carried out according to this method comprises the reaction vessel providing different from this first container, this reaction vessel has an opening end and an internal space, and make the opening end of this reaction vessel be seated on this pan straddle, between this pan straddle and internal space of this reaction vessel, set up being communicated with of sealing.A PECVD reactant conduit can be provided within this internal space.Within the internal space of reaction vessel, plasma body is formed under effective sedimental condition at least partially removing PECVD reaction product from reactant conduit.These reaction conditionss have combined with embodiment noted earlier and have been illustrated.Then reaction vessel can be made to disseat from pan straddle and be transported and to leave this 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 transfer roller of a series connection;

There is provided a second container, this second container has an opening end, a closing end and an interior surface;

There is provided a clamp, this clamp is configured to for optionally keeping and discharging the closing end of this second container;

The closing end of this second container is clamped with this clamp;

Use this clamp to be transported to by this second container near a pan straddle, this pan straddle is configured to make the opening end of this second container to take a seat;

Use this clamp axially to be advanced by this second container and make its opening end be seated on this pan straddle, between this pan straddle and inside of this second container, setting up being communicated with of sealing;

By this pan straddle, at least one gas reactant is introduced within this second container;

The interior surface of this second container forms plasma body under the condition of a kind of reaction product of effective forming reactions thing in this second container;

This second container is disseated from this pan straddle; And

Use this second clamp or another clamp axially to be transported by this second container and leave this pan straddle; And

Discharging this second container from this clamp, leaving this pan straddle for axially transporting it.

IV.B. Figure 16 be use suction cup type equipment to keep an example of the end of sampling tube (in this example), this sampling tube can move by a production line/system.Specific examples of this display be one of coating/process may step (summarize as above and following multiple may one of steps).This pipe can move in this coating step/region, and the reduction of this pipe can be entered in this pan straddle and (at this example) cylindrical electrode.Then this pan straddle, sampling tube and suction cup can move to next step together, and this electrode is undertaken processing/apply by energy supply there.Any one in above type electrode can be used in this example.

IV.B. therefore, Figure 15 and 16 shows the pan straddle 48 be similar in the coating station 28 of Figure 13, and this pan straddle adopts the conveyor system of container being usually designated as 202 that container 80 is moved into and leave coating station 28.Conveyor system of container 202 can be equipped with a fixture 204, and in illustrated transporter 202, this fixture can be a suction cup.An adhesive pad, active vacuum source (use pump extracting air from this fixture, produce vacuum actively) or other stopgap measures can also be used as fixture.Such as, conveyor system of container 202 can be used to enter in a seated position of container port 92 to reduce container 80 thus to be located to apply by container 80.After the process being positioned at station 28 place can be done, conveyor system of container 202 can also be used to carry out increase container 80 and 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.This conveyor system of container can also be used to drive container 80 to be resisted against on its seat on container port 92.Further, although Figure 15 can be directed to show from vertically being raised by container 80, can consider a kind of invert orientation above, conveyor system of container 202 is under container 80 and supports it from below wherein.

IV.B. Figure 16 shows the embodiment of a method, wherein conveyor system of container 202 (as suction cup 204) flatly transport box 80, such as from a station to next one station, and (or alternatively) vertically enter and leave a station (such as 28).Container 80 can be raised and transport in any direction.Therefore Figure 16 represents a kind of method of first container 80 being carried out to PECVD process, and the method comprises several step.

IV.B. in the embodiment of Figure 13, outer electrode 160 can be substantial cylindrical, and it has multiple opening end, and can be static.Container 80 can be raised by outer electrode 160 until opening 82 is seated on container port 96.In this embodiment, probe 108 can be optionally permanent shaped or is additionally fixed in gas entry ports 104, and to seal (wipingseal) contrary with the wiping of the relative movement allowed between port one 04 and probe 108.

IV.B. Figure 14 shows for electric energy being attached under 50Hz to 1GHz the other replacement scheme of in plasma body one.This can be made up of a coil, this coil or can be lowered in place or this pan straddle (having device) and can be pushed upwardly in place.Round electrode is called as inductive coupled device, and a magnet assembly can be given to the inside of the equipment that can produce plasma body wherein.

IV.B. can also use as in Fig. 2 and Figure 13 the probe 108 discussed.Other aspects of this pan straddle or pan straddle discussed above 48 can keep identical.

IV.B. such as shown in figure 49, a reaction vessel 532 different from this first container 80 can be provided, the internal space that this container also has an opening end 540 and limited by this interior surface 542.Be similar to container 80, this reaction vessel 532 can make its opening end 540 on pan straddle 48, and sets up being communicated with of sealing between pan straddle 48 and the internal space 542 of this reaction vessel.

IV.B. Figure 49 is the view being similar to Figure 16, shows a mechanism for will pending container 80 and cleaning reactor 532 be had to be delivered to a PECVD coating unit.In this embodiment, interior electrode 108 optionally can by cleaning without the need to removing it from pan straddle 48.

IV.B. Figure 49 shows when reaction vessel is seated at alternate container 80 (this container is provided for coating as previously described) on pan straddle 48, and PECVD reactant conduit 108 is placed thus is positioned within the internal space 542 of reaction vessel 532 as elucidated before.Figure 49 display reactant conduit 108 in this configuration, although 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 meets this object and these claims.

IV.B. such as, the mechanism of Figure 49 as demonstrated can use together with the embodiment of at least Fig. 1 with 15-16.In an alternative embodiment, cleaning reactor 532 can also be provided as and be seated at the upper and a kind of simple receptacle of transporting of pan straddle (as 48) thereon.In this configuration, cleaning reactor 532 can with such as at least Fig. 1-3,8,9,12-15,18,19,21,22, use together with the device of 26-28,33-35,37-48 and 52-54.

IV.B. the plasma generator limited by electrode 108 and 160 can be configured to for forming plasma body under the sedimental condition at least partially effectively removing PECVD reaction product from reactant conduit 108 in the internal space of reaction vessel 532.Above it is considered that, interior electrode and gas source 108 can be a kind of contact tubes, such as a kind of metal tube, and reaction vessel 532 can be made up of any applicable preferably heat-stable material (e.g., ceramic, quartz, glass maybe can stand the other materials of more high calorie than thermoplastic container).The material of reaction vessel 532 can also be desirably chemical or plasma body, and this chemical or plasma body are resistance for what use in this reaction vessel by the sedimental condition removing reaction product.Optionally, reaction vessel 532 can be made up of electro-conductive material, and it self serves as the special purpose outer electrode in order to be removed from reactant conduit 108 by settling.As another replacement scheme again, reaction vessel 532 can be configured to a cap, and this cap is seated on outer electrode 160, and in this case, outer electrode 160 to be preferably seated on pan straddle 48 thus to define a closed cleaning reaction room.

IV.B. institute it is considered that, the sedimental reaction conditions at least partially effectively removing PECVD reaction product from reactant conduit 108 comprises: the oxidation reactant introducing major portion is as oxygen or ozone (or produce respectively or produced by plasma device), than being used for the higher power level of deposited coatings, than being used for deposited coatings longer cycling time or known other stopgap measures sedimental for removing the undesired type run in reactant conduit 108.For another example, mechanical mill can also be used to remove undesired settling.Or, solvent or other reagent can be forced by reactant conduit 108 with rid.These conditions can be strict more than what have container 80 to be coated to withstand, because reaction vessel 532 does not need the normal use being suitable for container 80.But optionally, container 80 can be used as reaction vessel, and in an alternative embodiment, if settling to remove condition too strict, the container 80 being used as reaction vessel can be discarded.

V. for the manufacture of the PECVD method of container

V.1PECVD coating precursor

Precursor for PECVD coating of the present invention is broadly defined as a kind of Organometallic precursor.The metallic element compound from the III-th family in the periodic table of elements and/or IV race understood of organic residue (such as hydrocarbon, aminocarbonyl or oxygen carbon (oxycarbon) residue) is defined as in this manual for a kind of Organometallic precursor of all objects.The organometallic compound defined as current comprises and has any precursor of Direct Bonding (or carrying out bonding optionally by oxygen or nitrogen-atoms) to the organic moiety on silicon or other III/IV race atoms metals.The Its Related Elements 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 Its Related Elements of periodic table of elements IV race is silicon, germanium, tin, lead, titanium, zirconium, hafnium and thorium, and wherein silicon and tin are preferred.It is also conceivable to other volatile organic compoundss.But silicoorganic compound are preferred for carrying out the present invention.

Preferred a kind of organosilicon precursor, wherein a kind of " organosilicon precursor " runs through this specification sheets and is the most broadly defined as and has at least one following compound connected:

Or

Just be connected to the tetravalence Siliciumatom on a Sauerstoffatom and an organic carbon atoms (organic carbon atoms is bonded to the carbon atom at least one hydrogen atom) in the first above structure.Just be connected to NH-to connect and tetravalence Siliciumatom on an organic carbon atoms (organic carbon atoms is bonded to the carbon atom at least one hydrogen atom) in the second above structure.Preferably, this organosilicon precursor is selected from lower group, and this group is made up of the following: two or more the combination any among linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, linear silicon azane, monocycle silazane, many cyclosilazanes, poly-sesquialter silazane and these precursors.What be also considered as precursor is a kind of alkyl trimethoxysilane (although not in above two formulas).

If use a kind of oxygen containing precursor (such as a kind of siloxanes), then the empirical formula of the representational prediction generated from PECVD under the condition forming a kind of hydrophobic or slip coating will be Si _wo _xc _yh _z, wherein w is 1, be from about 0.5 to about 1, y is from about 2 to about 3 for this formula x, and z is from 6 to about 9, and the empirical combination thing of the representational prediction generated from PECVD under the condition of a formation barrier coat is SiO _x, wherein in this formula, x is from about 1.5 to about 2.9.If use a kind of containing nitrogen precursor (such as a kind of silazane), then the composition predicted will be Si _w*n _x*c _y*h _z*, namely at Si according to the present invention _wo _xc _yh _zmiddle O is replaced by N and these subscripts are adapted to the N (3 instead of 2) of higher valence compared with O.For subscript corresponding in its azepine counterpart (azacounterpart), the ratio of w, x, y and z that the adaptation of the latter will be followed in siloxanes usually.In 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 identical with for w, x, y and the z in siloxanes counterpart, except except the deviation of the quantitative aspects of optional hydrogen atom.

The precursor parent material with a type of above empirical formula is a kind of linear siloxane, such as, have a kind of material of following formula:

Wherein, R is selected from alkyl independently of one another, such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, vinyl, alkynes or other, and n is 1,2,3,4 or larger, is optionally two or more.Several examples of the linear siloxane considered are

Hexamethyldisiloxane (HMDSO),

Octamethyltrisiloxane,

Decamethyl tetrasiloxane,

Ten dimethyl five siloxanes,

Or the combination of two or more among these.For manufacturing similar coating, similar silazane is also useful, and wherein-NH-instead of the Sauerstoffatom in above structure.Several examples of the linear silicon azane considered are prestox three silazane, decamethyl four silazane or the combination of two or more among these.

V.C. the precursor parent material of another kind of type is a kind of monocycle siloxanes, such as, have a kind of material of following structural formula:

Wherein R be as this linear structure define and " a " is from 3 to about 10, or similar monocycle silazane.The assorted replacement considered and several examples of unsubstituted monocycle siloxanes and silazane comprise:

1,3,5-trimethylammonium-1,3,5-tri-(3,3,3-trifluoro propyl) methyl] cyclotrisiloxane

2,4,6,8-tetramethyl--2,4,6,8-tetravinyl cyclotetrasiloxane,

Pentamethyl-cyclopentasiloxane,

Five vinyl pentamethyl-cyclopentasiloxanes,

Hexamethyl cyclotrisiloxane,

Hexaphenyl cyclotrisiloxane,

Octamethylcyclotetrasiloxane (OMCTS),

Octaphenylcyclotetrasiloxane,

Decamethylcyclopentasiloxane

Ten diformazan basic ring six siloxanes,

Methyl (3,3,3-trifluoro propyl) cyclosiloxane,

Also contemplate epoxy/organosilicon azane, as

Octamethylcyclotetrasilazane,

1,3,5,7-tetravinyl-1,3,5,7-tetramethyl cyclotetrasiloxane silazane pregnancy basic ring three silazane,

Octamethylcyclotetrasilazane,

Decamethyl ring penta silazane,

Ten dimethyleyelohexane silazane, or

Two or more combination any among these.

V.C. the precursor parent material of another kind of type is a kind of many cyclosiloxane, such as, have a kind of material of one of following structural formula:

Wherein Y can be oxygen or nitrogen, and E is silicon, and Z is a hydrogen atom or organic substituent, such as an alkyl, as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, vinyl, alkynes or other.When each oxygen naturally of Y, from left to right the structure of these correspondences is hetero nitrogen silicon tricyclic (silatrane), accurate hetero nitrogen silicon tricyclic (silquasilatrane) and front hetero nitrogen silicon tricyclic (silproatrane).When Y is nitrogen, then the structure of these correspondences is hetero nitrogen silicon tricyclics (azasilproatrane) before azepine hetero nitrogen silicon tricyclic (azasilatrane), the accurate hetero nitrogen silicon tricyclic of azepine (azasilquasiatrane) and azepine.

V.C. many cyclosiloxane precursor parent material of another kind of type is a kind of polysilsesquioxane, has empirical formula RSiO _1.5and following structural formula:

Wherein R is a hydrogen atom or organic substituent, such as an alkyl, as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, vinyl, alkynes or other.The material of such two kinds of business is SST-eM01 poly-(methyl silsesquioxanes), wherein each methyl naturally of R; And SST-3MH1.1 poly-(methyl-hydrogen silsesquioxanes), wherein the R group of 90% is methyl, and 10% is hydrogen atom.In the tetrahydrofuran solution of such as a kind of 10%, this material is operational.Also contemplate the combination of two or more among these.Other examples of precursor considered are methyl hetero nitrogen silicon tricyclics (CAS 2288-13-3) (wherein each Sauerstoffatom naturally of Y and Z is methyl), poly-(methyl silsesquioxane) (wherein R can be optionally methyl separately) of methyl azepine hetero nitrogen silicon tricyclic (methylazasilatrane), SST-eM01, SST-3MH1.1 poly-(methyl-hydrogen silsesquioxanes) (wherein the R group of 90% is methyl and 10% is hydrogen atom), or two or more the combination any among these.

V.C. for manufacturing similar coating, similar poly-sesquialter silazane is also useful, and wherein-NH-instead of the Sauerstoffatom in above structure.The example of the poly-sesquialter silazane considered is poly-(methyl sesquialter silazane) (wherein each methyl naturally of R) and poly-(methyl-hydrogenation sesquialter silazane) (wherein the R group of 90% is methyl, and 10% is hydrogen atom).Also contemplate the combination of two or more among these.

V.C. the precursor for a kind of special consideration of lubricant film according to the present invention is a kind of monocycle siloxanes, such as, be octamethylcyclotetrasiloxane.

Precursor for a kind of special consideration of hydrophobic layer according to the present invention is a kind of monocycle siloxanes, such as, be octamethylcyclotetrasiloxane.

Precursor for a kind of special consideration of barrier coat according to the present invention is a kind of linear siloxane, such as, be HMDSO.

V.C., in any one coating method according to the present invention, this applying step optionally can by being provided near this substrate being carried out this front evacuator body.Such as, OMCTS was heated about 50 DEG C and evaporate usually before being applied to this PECVD device.

V.2 common PECVD method

In the context of the present invention, the following PECVD method of application usually, the method comprises the following steps:

A () provides a kind of gas reactant near this substrate surface, this gas reactant comprises a precursor as defined herein, preferably a kind of organosilicon precursor and optionally O ₂; And

B () produces a kind of plasma body from this gas reactant, form a coating thus by the chemical vapour deposition (PECVD) of plasma enhancing on this substrate surface.

In the process, these coating feature set advantageously by one or more following condition: O in the power that plasma characteristics, the pressure applying plasma body, generation plasma body apply, gas reactant ₂existence and relative quantity, volume of plasma and organosilicon precursor.Preferably, these coating feature are by O in gas reactant ₂existence and relative quantity and/or produce that the power that applies of plasma body sets.

In all embodiments of the present invention, be a kind of non-hollow cathode plasma (non-hollow-cathodeplasma) in this plasma body is preferred at one.

In another is preferred, this plasma body produces under decompression (compared with environment or normal atmosphere).Preferably, this decompression is less than 300 millitorrs, is more preferably less than 200 millitorrs, is even more preferably less than 100 millitorrs.

PECVD carries out preferably by the gas reactant that should contain this precursor with electrode excitation, and these electrodes carry out energy supply with microwave frequency or radio frequency (and preferably with radio frequency).The radio frequency being preferred for carrying out embodiment of the present invention can also be called as " RF frequency ".From 10kHz to being less than 300MHz for carrying out typical radio-frequency region of the present invention, more preferably from 1 to 50MHz, even more preferably from the frequency of 10 to 15MHz.The frequency of 13.56MHz is most preferred, and this is the frequency for carrying out PECVD work of government permission.

Relative to a kind of microwave source of use, RF power supply is used to there is several advantage: because RF runs under a lower power, to there is the heating of less substrate/container.Because focus of the present invention is placed in plastic-substrates by plasma coating, lower treatment temp is desired, to prevent the fusing/distortion of this substrate.In order to prevent the substrate when using microwave PECVD overheated, lead to overpowering pulses generation to apply microwave PECVD with short pulse.The pulses generation of power extends the cycling time for applying, and this is undesirable in the present invention.The microwave of upper frequency also causes volatile matter in this plastic-substrates, as the exhaust (offgassing) of residuary water, oligopolymer and other materials.This exhaust can disturb PECVD to apply.The worry using microwave to be used for of PECVD main is the leafing of coating from substrate.Because before this coat of deposition, microwave changes the surface of substrate, so understand, delamination occurs.In order to reducing layer from possibility, have developed multiple interfaces coat for microwave PECVD to realize good combination between this coating and substrate.RFPECVD is used not need such interface coat, because there is not the risk of leafing.Finally, advantageously use lower power to apply according to slip coating of the present invention and hydrophobic coating.Compared to microwave power, RF power runs and provides more for the control of PECVD process under lower power.However, although microwave power is less preferred, be available under suitable processing condition.

In addition, for all PECVD methods described herein, between the volume being used for producing the inner chamber that the power (with wattmeter) of plasma body and plasma body produce wherein, there is a kind of special dependency.Typically, described inner chamber is the inner chamber of a kind of container according to the present invention's coating.If adopt identical electrode system, then RF power should be proportional with this volume of a container.Once set composition (such as this precursor and the O of gas reactant ₂between ratio) and the parameter (except power) of every other PECVD coating method, when the geometrical shape of a container remain unchanged and only its stereomutation time, typically they can not change.In this case, this power will be directly proportional to this volume.Therefore, the power provided from this specification sheets and the ratio of volume, can find easily and complete same or similar coating in the container in order to but there is same geometry different size at and the power that must apply.Illustrate that the geometrical shape of container is on the impact having power to be applied by the result of example compared with the example for pipe for syringe cylinder.

For any coating of the present invention, plasma body produces with having the electrode being enough to the power energy supply forming a coating on this substrate surface.For a slip coating or hydrophobic coating, according in the method for one embodiment of the invention, plasma body produces preferably by the following: (i) uses the electrode providing 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 such as 8W; 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 from 4W/ml to 0.1W/ml, be most preferably from 2W/ml to 0.2W/ml.For a barrier coat or SiO _xcoating, (i) that this plasma body produces preferably by the following uses the electrode providing 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 the ratio of (ii) electrode power and volume of plasma is equal to or greater than 5W/ml, preferably from 6W/ml to 150W/ml, more preferably from 7W/ml to 100W/ml, be most preferably from 7W/ml to 20W/m.

The geometrical shape of container can also affect the selection of the inlet mouth for PECVD coating.In specific at one, can apply a syringe with the tube inlet of an opening, and the inlet mouth that can have multiple aperture with applies a pipe, it is inner that this inlet mouth extends to this pipe.

Power (with wattmeter) for PECVD can also affect coating characteristic.Typically, the increase of power will increase the barrier properties of coating, and the reduction of power will increase oilness and the hydrophobicity of this coating.Such as, for have about 3ml volume a syringe cylinder inwall on coating, the power being less than 30W will cause a kind of coating of mainly barrier coat, and the power being greater than 30W will cause a kind of coating (see example) of mainly slip coating.

Another parameter of decision coating characteristic is for generation of the O in the gas reactant of plasma body ₂the ratio of (or another kind of oxygenant) and this precursor (such as, organosilicon precursor).Typically, O in gas reactant ₂the increase of content will increase the barrier properties of coating, and O ₂the reduction of content will increase oilness and the hydrophobicity of coating.Therefore, the PECVD coating method of the present invention barrier properties of coating that may be used for arranging the lubricating property of coating, the hydrophobic characteristics of coating and prepared by described method.

If a slip coating is desired, then preferably O 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 exist 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 being less than 1 volume % ₂, be more specifically less than the O of 0.5 volume % ₂, and be most preferably not containing O ₂.This is equally for hydrophobic layer.

If on the other hand a, barrier coat or SiO _xcoating is desired, then contain silicon precursor relative 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, the even more preferably ratio of 15: 1.

V.A. plasma body is used to apply SiO _xthe PECVD of barrier coat, this plasma body is substantially free of hollow cathode plasma

V.A. a specific embodiment is a kind of applying SiO _xthe method of barrier coat, this coating is defined as a coating containing silicon, oxygen and other optional elements in this specification sheets (unless illustrating in addition in the embodied case), wherein x, 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 definition substituted of x are applicable to the term SiO of any in this manual use _x.Barrier coat is applied to the inside of a container (such as the container of sampling tube, a syringe cylinder or an another kind of type).The method comprises several step.

V.A. provide a wall of container, as being both a kind of reaction mixture, this mixture comprises and forms the gas of plasma body, that is, a kind of organic silicon compound gas, optionally a kind of oxidizing gas, and optionally a kind of appropriate hydrocarbon gas.

V.A. plasma body is formed in the reactive mixture, is substantially free of hollow cathode plasma.This wall of container is contacted with this reaction mixture, and by SiO _xbe coated with and be deposited at least one part of this wall of container.

V.A. in certain embodiments, be preferred producing a kind of uniform plasma body in the part that this has container to be coated, because have been found that the SiO creating and provide and better stop oxygen in some cases _xcoating.Uniform plasma body represent do not comprise real mass hollow cathode plasma (this plasma body there is the emissive porwer higher than the plasma body of rule and be shown as interrupted regular plasma body evenly the regional area of more high strength of intensity) the plasma body of rule.

V.A. hollow cathode effect is produced by pair of conductive surface, and this effects on surface relative to a common anode with identical negative potential toward each other.Make space charge layer (spacechargesheath) overlapping like this if leave interval (depending on pressure and gas type), then electronics starts to vibrate between the reflectivity electromotive force (reflectingpotential) of contrary parietal layer, cause multiple collision, because these electronics are accelerated by the potential gradient striding across layer region.These electronics are limited in space charge ply, which results in very high ionizing event and the plasma body of high ion density.This phenomenon is described to hollow cathode effect.Those of ordinary skill in the art can change treatment condition, the pressure of such as power level and input speed or gas, thus forms the plasma body that uniform plasma body or formation comprises hollow cathode plasma in various degree throughout.

V.A., in an alternative method, the device of example Figure 12 as elucidated before, can use micro-wave energy thus produce plasma body in the pecvd process.But treatment condition can be different, because the micro-wave energy be applied on a thermoplastic container will excite (vibration) water molecules.Because there is a small amount of water on all plastic materials, so microwave is by these plastics of heating.When plastics are heated, the large motivating force produced by the vacuum in device relative to the normal atmosphere outside device will attractive material free out or easily by its desorption on internal surface 88, these materials will become volatile or will faintly be attached to this on the surface there.These materials faintly combined are then by generation interface, and the coating (from plasma-deposited) stoped subsequently adheres to the plastic interior surfaces 88 of this device by this interface.

V.A. as eliminating a kind of method of this coating inhibition, can with low-down power deposition coating (being higher than 5 to 20 watts in the above example with 2.45GHz), thus create the cap that a coating subsequently can be adhered thereto.Which results in the coating processes (and two coats) of two steps.In above example, initial air-flow (adding cap layers for this) can be changed into the oxygen of 2sccm (" standard cubic centimeter/per minute ") HMDSO and 20sccm, wherein processing power is 5 to 20 watts and continues about 2-10 second.Then by these gas regulation to the flow rate in above example and be increased to the power level of 20-50 watt, deposition SiO can be made it possible to _xcoating, wherein x is from about 1.5 to about 2.9 in this formula, is alternately from about 1.5 to about 2.6, is alternately about 2.It should be noted, in certain embodiments, add (even not having) functionality that cap layers can provide little, unless at the SiO of higher-wattage _xstop material transition on inner surface of container 88 in coating deposition process.Should also be noted that the migration being easy to the material of desorption in device wall is not typically problem, because lower frequency can not excite (vibration) molecular species under lower frequency (such as most RF scopes).

V.A. as the another kind of method eliminating coating inhibition described above, can by container 80 drying to remove the water included before applying micro-wave energy.Container 80 dewater or drying can such as by thermic heating container 80, as used electric heater or forcing air heating and complete.Container 80 dewater or drying can also by the inside of container 80 is exposed in a kind of siccative or the inside of gas contacting container 80 and complete.Other methods easily can also be used, as vacuum-drying carrys out this container dry.These easily method can be undertaken in shown one or more station or equipment or by an independent station or equipment.

V.A. in addition, coating inhibition described above can by select or the water content of this resin to minimize from its shaping resin and solves by processing vessel 80.

The vessel port (capillary injector) of V.B.PECVD coating restriction

V.B. Figure 26 and 27 shows the method and the device that are roughly expressed as 290, for being applied the internal surface 292 of the opening 294 (opened front 294 of the such as restriction of a syringe cylinder 250) of the restriction of the container 250 of a pending generally tubular by PECVD.A processing vessel 296 revises method described above by the opening 294 of this restriction is connected to and optionally carries out some other amendment.

The container 250 of V.B. pending generally tubular comprises an outside surface 298, the internal surface defining an inner chamber 300 or interior surface 254, have the opening 294 of the larger opening 302 of an internal diameter and a restriction, and the opening of this restriction is limited by internal surface 292 and the internal diameter had is less than the internal diameter of this larger opening 302.

V.B. this processing vessel 296 has an inner chamber 304 and a processing vessel opening 306, and this opening is optionally unique opening, although can provide optionally pent second opening in treating processes in other embodiments.This processing vessel opening 306 has the opening 294 of the restriction of pending container 250 to be connected with this, has being communicated with via the opening 294 of this restriction between the inner chamber 300 of pending container 250 with this processing vessel inner chamber to set up this.

V.B. this is had in the inner chamber 300 of pending container 250 and the inner chamber 304 of this processing vessel 296 and be pumped at least part of vacuum.Making a kind of PECVD reactant flow through this first opening 302 from gas source 144 (see Fig. 7), then by there being the inner chamber 300 of pending container 250, then by the opening 294 of restriction, then entering the inner chamber 304 of this processing vessel 296.

V.B. this PECVD reactant can be introduced into by the larger opening 302 of container 250 by providing electrode 308 in a generally tubular, this interior electrode has an interior passageway 310, near-end 312, far-end 314 and a distal openings 316, in alternative embodiment, multiple distal openings to may be provided near this far-end 314 and is communicated with internal passages 310.Near the larger opening 302 that the far-end of electrode 308 can be placed in pending container 250 or within.A kind of reactant gas can be fed in the inner chamber 300 of pending container 250 by the distal openings 316 of electrode 308.This reactant will flow over the opening 294 of this restriction, then enter inner chamber 304, and to be this PECVD reactant be provided its degree under the pressure higher than the vacuum of being initially pumped into before introducing this PECVD reactant.

V.B. near the opening 294 of this restriction, plasma body 318 is produced under the condition on the internal surface 292 of opening 294 effectively PECVD reaction product being deposited to this restriction.In embodiment in fig. 26, by RF to be input on generally u-shaped outer electrode 160 and interior electrode 308 ground connection is produced plasma body.Can also be contrary for the charging of these electrodes and grounding connection, although if container 250 has pending, and movement be by this U-shaped outer electrode therefore to also have the interior electrode 308 when plasma body is generated, and this reversion may introduce complicacy.

V.B. the plasma body 318 produced in container 250 in treating processes at least partially can be included in the hollow cathode plasma of generation in the opening 294 of restriction and/or processing vessel inner chamber 304.The generation of hollow cathode plasma 318 can facilitate the ability successfully applying a barrier coat at opening 294 place of this restriction, although the present invention does not limit according to the accuracy of this theory of operation or suitability.Therefore, in an operator scheme considered, this process can partly be carried out under producing the condition of uniform plasma body throughout container 250 and this inlet mouth, and such as partly near the opening 294 of this restriction produce a kind of hollow cathode plasma condition under carry out.

V.B. desirably the method is carried out in such a situa-tion, and as illustrated in the accompanying drawings illustrated by this, plasma body 318 fills the air the opening 294 throughout this syringe inner chamber 300 and this restriction substantially.It is also desirable that plasma body 318 fills the air the inner chamber 304 of opening 294 throughout this syringe inner chamber 300, this restriction and this processing vessel 296.This assumes that the uniform coating of the inside 254 of container 250 is desired.In other embodiments, inhomogeneous plasma can be desired.

V.B. usually desirably, plasma body 318 has one of the opening 294 basic uniform color throughout this syringe inner chamber 300 and restriction in treating processes, and preferably substantially throughout the basic uniform color of the opening 294 of this syringe inner chamber 300, this restriction and the inner chamber 304 of this processing vessel 296.Desirably this plasma body throughout this syringe inner chamber 300 and restriction opening 294 and also have preferably throughout the inner chamber 304 of this processing vessel 296 be stable.

V.B. do not consider that the order of step is in this approach crucial.

V.B. in the embodiment of Figure 26 and 27, the opening 294 of restriction has first joint 332, and processing vessel opening 306 has second joint 334, this second joint be adapted to be seated on this first joint 332 with the inner chamber 304 being based upon this processing vessel 296 with have being communicated with between the inner chamber 300 of pending container 250.

V.B. in the embodiment of Figure 26 and 27, this first and second joint is outer Rule and interior luer lock joint 332 and 334 respectively, and they are one accordingly with the structure of the opening 294 and processing vessel opening 306 that define restriction.Outside luer lock joint 332 when, one of these joints comprise a lock collar 336, this lock collar there is a threaded internal surface and define an axial plane to the first bearing 338 of general toroidal, and another joint 334 comprise one towards this first bearing 338 axial plane to the second bearing 340 (when joint 332 and 334 engages) of general toroidal.

V.B., in the embodiment of this displaying, an a sealing member such as O type circle 342 can be positioned between this first and this second joint 332 and 334.Such as, a lip ring can be bonded between this first and this second bearing 338 and 340.This interior female Luer 334 can also comprise a claw 344, and this claw engages to capture O type circle 342 between this first and this second joint 332 and 334 with the threaded internal surface of this lock collar 336.Optionally, the opening 294 via this restriction has being communicated with of setting up between the inner chamber 300 of pending container 250 and the inner chamber 304 of processing vessel 296 to be leakproof at least substantially at this.

V.B. alternatively, any one or both in luer lock joint 332 and 334 can be made up of conducting fibre material (such as stainless steel).The opening 294 of this formation restriction or building material adjacent thereto can facilitate the formation of plasma body in the opening 294 of this restriction.

The volume of the inner chamber 304 of V.B. desired processing vessel 296 is considered to be compromise between a little volume and a large volume, this little volume can not make to leave the desired reactant flow of its surface to be coated that has in a large number and turn to, and this large volume supported that before fully filling this inner chamber 304 the reactant gas flow rate of a large amount of openings 294 by this restriction is to be reduced to a more undesirable value (by reducing the pressure reduction striding across the opening 294 of restriction) by this flow rate.The volume of inner chamber 304 considered in one embodiment is three times of the volume being less than the inner chamber 300 having pending container 250, or this is less than the twice that this has the volume of the inner chamber 300 of pending container 250, or be less than the volume that this has the inner chamber 300 of pending container 250, or be less than that this has the volume of the inner chamber 300 of pending container 250 50%, or be less than that this has the volume of the inner chamber 300 of pending container 250 25%.Also contemplate the relation of the volume of other effective corresponding inner chambers.

V.B. ladies and gentlemen contriver also finds that the homogeneity of coating in certain embodiments can by reorientating the far-end of electrode 308 relative to container 250 and improving, and its inside of not penetrating the inner chamber 300 of container 250 is as far as the such as position of electrode in shown in above accompanying drawing like this.Such as, although in certain embodiments, distal openings 316 can be close to the opening 294 of this restriction and locate, this distal openings 316 can be less than in other embodiments has the larger opening 302 of pending container (to be optionally less than this distance 3/4 to 7/8 of the distance of the opening 294 of restriction from this, optionally be less than the half of this distance) and locate, feed reactant gas simultaneously.Or, this distal openings 316 can by being less than 40%, be less than 30%, be less than 20%, be less than 15%, be less than 10%, be less than 8%, be less than 6%, be less than 4%, be less than 2% or be less than 1% have the larger opening of pending container to locate to the distance of the opening 294 of restriction to feed reactant gas from this simultaneously.

V.B. or, the far-end of this electrode 308 can this have the larger opening 302 of pending container 250 slightly in or slightly outer or concordant with it and location is communicated with the inside of this container 250 simultaneously, and feed the inside of reactant gas to this container 250.Have pending container 250 relative to this, the location of distal openings 316 can because concrete size and other treatment condition be by testing and optimizing it in different positions.The particular location of electrode 308 considered for process syringe cylinder 250 is that far-end 314 penetrates into about 1/4th inch (about the 6mm) of container intracavity 300 higher than larger opening 302.

V.B. ladies and gentlemen contriver considers advantageously to be placed in container 250 to the far-end 314 of major general's electrode 308 that it suitably will work as an electrode so at present, although this not necessarily prerequisite.Unexpectedly, the plasma body 318 that produces in container 250 can be made evenly, thus the opening 294 filled the air through restriction enters processing vessel inner chamber 304, and wherein electrode 308 less penetrates in the inner chamber 300 that previously used.Arranged by other, as processed the container of a closing end, the far-end 314 of electrode 308 is placed in usually than the closing end of its entrance closer to this container.

V.B. or, the far-end 314 of electrode 308 can be positioned in opening 294 place of restriction or exceed the opening 294 of restriction, such as, in processing vessel inner chamber 304, as in fig. 33 show.Can optionally provide different stopgap measures, as the air-flow of opening 294 being shaped to improve by this restriction by this processing vessel 296.

V.B. as another replacement scheme, as in Figure 34-35 show, in this compound, electrode and feed tube 398 can have multiple remote gas supply opening such as 400 (being optionally positioned near this larger opening 302) and an extension electrode 402, this extension electrode extends to the far-end of these remote gas supply opening 400, the far-end that the opening 294 optionally extended to and limit is contiguous, and optionally extend to further in this processing vessel 324.This structure is considered to promote to form plasma body in the internal surface 292 that the opening 294 with restriction is contiguous.

V.B., in another embodiment considered again, as electrode 308 in fig. 26 can move in treating processes, such as, first extend in this processing vessel inner chamber 304, then along with the carrying out of process is progressively withdrawn from near-end.If container 250 is longer under selected treatment condition, and the movement of interior electrode is conducive to more uniformly processing internal surface 254, and this stopgap measure is special consideration.Use this stopgap measure, treatment condition (as gas feed speed, vacuum take-off rate, the electric energy be applied on outer electrode 160, the speed withdrawing from interior electrode 308 or other factors) can change along with the carrying out of process, thus for there being the different parts of pending container to customize different processes.

V.B. easily, as in other processes described in this manual, can the larger opening of the container 250 having pending generally tubular be placed on a container support 320, as by making the larger opening 302 of pending container 250 be landed on a port 322 of this pan straddle 320.Then, at least from before having in the inner chamber 300 of pending container 250 and being pumped into a part of vacuum, interior electrode 308 can be positioned in the container 250 that is seated on pan straddle.

V.B. in an alternative embodiment (as in Figure 28 show), can provide processing vessel 324 with the form of conduit, this conduit has first opening 306 (as shown in Figure 26) be fixed on pending container 250 and second opening 328 be communicated with the vacuum ports 330 in pan straddle 320.In this embodiment, pecvd process gas can flow into container 250, and the opening 294 then via restriction enters in processing vessel 324, is then returned by vacuum ports 330.Optionally, by both openings 294 and 302, container 250 can be found time before applying PECVD reactant.

V.B. or, by introducing reactant from source 144 by being positioned at the opening of the rear end 256 of cylinder 250 and using vacuum source 98 by being positioned at the opening extracting vacuum at front end 260 place of cylinder, a syringe cylinder 250 (as shown in Figure 22) adding 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).Such as, vacuum source 98 can be connected by second joint 266 be seated on the front end 260 of syringe cylinder 250.Use this stopgap measure, these reactants can an one direction (upwards, as shown in Figure 22, although this direction is not critical) flow through cylinder 250, and do not need reactant feed gas and the probe that discharge gas separates to be carried within syringe cylinder 250 by one.In an alternative layout, the front end 260 of syringe cylinder 250 and rear end 256 can also be reversed relative to this coating unit.Probe 108 can work as one of the electrodes simply, and can be a tubular rod or solid spar in this embodiment.As front, at least most of length of syringe cylinder 250, being separated between interior surface 254 with probe 108 can be uniform.

V.B. Figure 37 is the view being similar to Figure 22 of another embodiment of display, and joint 266 is independently and is not attached on plate electrode 414 and 416 in this embodiment.Joint 266 can have one and be adapted with to be affixed to the luer lock joint on the corresponding joint of syringe cylinder 250.This embodiment allows vacuum piping 418 to pass through above electrode 416, and simultaneously during coating step, the container 250 of pan straddle 420 and attachment moves between electrode 414 and 416.

V.B. Figure 38 is showing and the view being similar to Figure 22 of another embodiment, in this embodiment the front end 260 of syringe cylinder 250 be open and syringe cylinder 250 be seated at vacuum chamber 422 on pan straddle 424 around.In this embodiment, the pressure P 1 in syringe cylinder 250 and in vacuum chamber 422 is roughly the same, and carrys out the vacuum in extracting vacuum room 422 optionally by the front end 260 of syringe cylinder 250.When these flow of process gases enter syringe cylinder 250, they flow through the front end 260 of syringe cylinder 250 until provide a stable formation in syringe cylinder 250, at this moment electrode 160 by energy supply to form coating.It is considered that, due to the location of the counter electrode 426 within the larger volume relative to syringe 250 of vacuum chamber 422 and syringe cylinder 250, significant settling will do not formed on the wall of vacuum chamber 422 by the process gas of this front end 260.

V.B. Figure 39 be show and another embodiment be similar to 22 a view, the rear flange of this syringe cylinder 250 is clamped between pan straddle 428 and electrode assemblie 430 in this embodiment, and the cylindrical electrode or pair of plates electrode and the vacuum source 98 that are wherein designated as 160 are fixed on this electrode assemblie.Be relatively little around the volume being usually designated as 432 of syringe cylinder 250 outside in this embodiment thus the pumping of the inside of need to be used for find time volume 432 and syringe cylinder 250 is down to minimumly runs PECVD process.

V.B. Figure 40 be similar to Figure 22 a view and Figure 41 is a plan view, this plan view shows even another embodiment of the replacement scheme as Figure 38, wherein by providing a pressure proportioning valve 434, pressure ratio P1/P2 to be maintained at level desired by one.Institute is it is considered that during PECVD process compared with P2, and P1 can be a lower vacuum, namely higher pressure, makes useless process gas and by product will be excluded by the front end 260 of syringe cylinder 250 like this.Further, for the closed volume 432 providing the vacuum pump allowing use to separate to find time larger quickly of the vacuum chamber conduit 436 separated of vacuum chamber 422.

V.B. Figure 41 is a plan view of the embodiment of Figure 40, also show the electrode 160 removed from Figure 40.

V.C. the method for slip coating is applied

V.C. another embodiment is the method applying 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 of the friction resistance reducing coated surface relative to uncoated surface.If this coated article is a kind of syringe (or syringe part, such as syringe cylinder) or any other movable part generally including a plunger or be in this coated surface in sliding contact, then this friction resistance has two main aspect-starting forces and plunger sliding force.

The test of plunger sliding force is the test of the coefficient of sliding friction testing the plunger in a syringe specially, explains a fact: the normal force relevant to the usual coefficient of sliding friction measured on a flat surface is solved by the matching standard between other containers of making plunger or other sliding members and pipe or it and sliding wherein.The parallel force relevant to the coefficient of sliding friction usually measured with as plunger sliding force measured by describing in this manual be comparable.Plunger sliding force can such as in ISO7886-1:1993 test provide and measure.

The test of plunger sliding force can also be adapted to be the friction resistance being measured other types by suitably modifier and step, such as, a stopper is remained on the frictional force in a pipe.In one embodiment, this plunger can replace with closure member and the power of withdrawing from shifting out or insert this closure member can be measured as the counterpart of plunger sliding force.

And this starting force (or replacing this plunger sliding force) can be measured.This starting force is that the static plunger of starting one moves required power in a syringe cylinder, or the static closure member making to take a seat disseats (unseat) and makes the power required for its setting in motion.Measure this starting force by a power being applied on this plunger, this power is from zero or low value and till increasing when this plunger setting in motion.The lubricant of intervention is pushed open or after adhering on cylinder (lubricant breakdown due between this plunger and this), this starting force is tended to increase along with the storage of syringe at this precharging type syringe plunger.Starting force overcomes the power required for " adhesion " (" sticktion "), is for needing the adhesion between plunger and cylinder overcome to start this plunger and to allow it to start an industry slang of movement.

V.C. some practical applications being coated with lubricant film in all or part of (as optionally in the surface contacted with sliding relation with miscellaneous part) of container make to insert or shift out stopper or are easy by a sliding members (as the piston in syringe or the stopper in a sample hose).This container can be made up of glass or a kind of polymer materials such as polyester (such as polyethylene terephthalate (PET)), cyclic olefine copolymer (COC), alkene (as polypropylene) or other materials.The needs that a slip coating could avoid or be reduced by spraying, immersion coating wall of container or closure member or additionally apply organosilicon or other lubricants (normally to use than depositing much bigger amount by PECVD process) are applied by PECVD.

V.C. in officely how go up in embodiment V.C., a kind of plasma body, optionally a kind of non-hollow cathode plasma, optionally can be formed near substrate.

V.C., in any embodiment V.C., this precursor can optionally provide substantially not depositing under oxygen.V.C., in any embodiment V.C., this precursor can optionally provide substantially not existing under carrier gas.V.C., in any embodiment V.C., wherein this precursor can optionally provide substantially not depositing under a nitrogen.V.C., in any embodiment V.C., wherein this precursor optionally can provide by the absolute pressure being less than 1 holder.

V.C., in any embodiment V.C., this precursor optionally can be provided near a plasma emission thing.

V.C., in any embodiment V.C., optionally by the thickness of 1 to 5000nm or 10 to 1000nm or 10-200nm or 20 to 100nm, this coating can be applied in substrate.Such as can pass through transmission electron microscopy (TEM) and measure thickness that is this and other coatings.

V.C. such as TEM can carry out as follows.Can by the next sample for the preparation of focused ion beam (FIB) slice analysis of two kinds of methods.Or a K575XEmitech application system can be used first to use a carbon thin layer (50-100nm is thick) to apply and then apply these samples with sputtering platinum layer (50-100nm is thick), or can sputter Pt layer by protectiveness directly applies these samples.These samples applied can be placed in a FEIFIB200FIB system.Can by a kind of organic metal gas of injection simultaneously on interested region the gallium ion beam of raster scanning 30kV carry out FIB-and deposit an other platinum layer.Can be by interested for each sample regional choice one along the position of this syringe cylinder down to half length.A kind of special original position FIB extrusion technique (in-situFIBlift-outtechnique) can be used to take out from die surface and to be measured as that about 15 μm (" micron ") is long, 2 μm wide and 15 μm of dark thin sections.These sections are attached to 200 object copper TEM and carry on the net by the platinum that FIB-can be used to deposit.The gallium ion beam of FEIFIB can be used to make one or two window (window) being measured as about 8 μm wide in each section be thinned to electron lucent degree.

V.C. transmission electron microscope (TEM) or scanning transmission electron microscope (STEM) or both can be used to carry out cross-sectional image analysis to these samples prepared.All view data can use digital recording.For STEM image, the net that carries with thinning paillon foil can be transferred on a special STEM of HitachiHD2300.The scanning transmission electronic image at suitable enlargement ratio being in ordination number contrastive pattern (ZC) and transmitted electron pattern (TE) can be obtained.Following instrument designing can be used.

V.C. for tem analysis, sample grid can be transferred to a HitachiHF2000 transmission electron microscope and can obtain the transmitted electron image under suitable enlargement ratio.The relevant instrument designing used in image acquisition process can be following provide those.

V.C. in any embodiment V.C., this substrate can comprise glass or a kind of polymkeric substance, such as carbonate polymer, olefin polymer, cyclic olefine copolymer, polyacrylic polymer, polyester polymers, polyethylene terephthalate polymer or two or more the combination any among these.

V.C. in any embodiment V.C., optionally can contain the gas reactant of this precursor as the electrode excitation of RF frequency power defined above energy supply by using and carry out this PECVD, this frequency be such as one from 10kHz to be less than 300MHz frequency, more preferably from 1 to 50MHz, even more preferably from the frequency of 10 to 15MHz, most preferably 13.56MHz.

V.C., in any embodiment V.C., can the gas reactant of this precursor be contained by using the electrode excitation providing the electric power being enough to a formation slip coating and produce this plasma body.Optionally, can the gas reactant of this precursor be contained by the electrode excitation providing following electric power and produce this plasma body, 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 from 4W/ml to 0.1W/ml, be most preferably from 2W/ml to 0.2W/ml.These power levels are suitable for for applying slip coating to the syringe of the void volume had in 1 to 3mL (wherein creating PECVD plasma body) and stopple coupon and the container with similar geometric.For larger or less object institute it is considered that, this process should be determined in proportion according to the size of this substrate, correspondingly increase or reduce the power that applies.

V.C. the product considered can be optionally have the syringe being carried out the cylinder processed by the method for any one or more of embodiment V.C..

V.D. the coating of liquid applying

V.D. another example of the coating of a suitable barrier coat or other types can be a kind of liquid obscures coating, lubricant coating, surface energy customization coating or be applied to the coating 90 of the other types on the internal surface of a container, it can directly use or the coating that can apply with PECVD or other PECVD process disclosed here or the Si applied with the PECVD of one or more intervention _wo _xc _yh _z(SiO _x) coating, slip coating or both be combined.

V.D. can optionally such as by the internal surface that a kind of liquid monomer or other polymerizable or curable materials is applied to container 80 solidifies, to be polymerized or this liquid monomer crosslinked to apply the coating 90 of liquid obscures coating or the other types be applicable to form a kind of solid polymer.Can also by a kind of polymkeric substance of solvent dispersion to be applied on surface 88 and removing changes solvent and provides applicable liquid obscures coating or the coating 90 of other types.

V.D. the inside 88 that any one in above method can be included in a container 80 is formed a step of coating 90 via the container port 92 at a treatment station or equipment 28 place.Example be such as the liquid coating of a kind of curable monomer, prepolymer or polymeric dispersions is applied to container 80 internal surface 88 on and solidified to form a film, the content of container 80 is isolated from its internal surface 88 by this film for physically.Prior art describes the polymer-coated technology being suitable for coating plastic heparin tube.Such as, can be optionally utilized in United States Patent (USP) 6,165, acrylic acid and polyvinylidene dichloride (PVdC) coating material described in 566 and coating method, combine by reference by this patent hereby.

V.D. any one in above method can also comprise or comprise a step as forming coating on the outside outer wall of a container 80.This coating can be optionally a barrier coat, optionally an oxygen barrier coat, or an optionally water resistance barrier coating.The example of an applicable coating is polyvinylidene dichloride, and it works as a barrier and an oxygen barrier layers.Optionally, this barrier coat can apply as a coating based on water.This coating optionally by by this tank immersion wherein, can be ejected on this container, or other stopgap measure and applying.Also contemplate a kind of container with outer barrier coating described above.

VI. container inspection

Shown in V1 Fig. 1 one station or equipment are treatment station or equipment 30, it can be configured to the defect of the interior surface of an inspection container 80, as passed through to measure by the atmospheric pressure lost of a wall of container or the venting of mass flow rate or volumetric flow rate or a wall of container.Equipment 30 can work similarly with equipment 26, except requiring that the better properties of this container (leakage less under given processing condition or infiltration) is with except the inspection provided by equipment 30, because in shown embodiment, before station or equipment 30 arrive, be applied with the coating of a barrier coat or other types by station or equipment 28.In one embodiment, this inspection of coating container 80 can compare with the inspection of the identical container 80 at equipment or 26 places of standing.Indicating this barrier coating in station or the less leakage at equipment 30 place and infiltration is at least play a part to a certain extent.

VI. two different station places measure or the device measuring different by two container 80 personal characteristics can by individual recognition feature (as a barcode, other marks or a kind of RF identification (RFID) equipment or mark) to be placed on each pan straddle 38-68 on and coupling in FIG shown in pool conveyer near the personal characteristics of container of two or more differences measurement determine.Because these pan straddles can be reused, when they arrive the position of the pan straddle 40 in Fig. 1 (only after a new container 80 is landed on pan straddle 40), they can be registered in a Computer Database or other data store organisations, and remove from data register near the destination county of this process or its, such as, when they arrive the position of the pan straddle 66 of Fig. 1 and the container 80 of process is passed when mechanism 74 removes or afterwards.

VI. this treatment station or equipment 32 can be configured to inspection container, such as one defect putting on a barrier coat of this container or the coating of other types.In the embodiment of this displaying, to stand or equipment 32 determines the light sources transmit of coating, as the measuring of thickness of coating.If suitably applied, the coating of this barrier coat or other types can make container 80 more transparent (although being applied with other material) because it provide one evenly surface.

VI. other also contemplating coat-thickness are measured, such as by using interferometry to determine, the difference of the miles of relative movement between the energy wave of rebounding from the inner side (and the air internal tank 154 meets boundary) of coating 90 with the energy wave of rebounding from the interior surface 88 (and outer side joint circle of coating 90) of container 80 is as is well known, relative to test condition can directly (time of arrival as by measuring corresponding ripple with pinpoint accuracy) or indirect (as by determine the wavelength of projectile energy that strengthens or eliminate) determine the difference of miles of relative movement.

VI. can carry out for check coating integrity another kind of measuring technology be the ellipsometry (ellipsometricmeasurement) of related devices.In this case, can or from the inside of container 80 or from outside projection polarized laser beam.When from internal transmission laser beam, this laser beam can by orthogonal sensing from the teeth outwards and then can to or transmitted beam or reflected beam measure.The change in light beam polarity can be measured.Because the coating on device surface or process will affect the polarization of (change) laser beam, the change of polarity can be desired result.The change of polarity be exist from the teeth outwards coating or process direct result and change amount relevant with the amount of process or coating.

If VI. this polarized beam projects from the outside of device, a detector can be positioned on inside to measure the component (and the polarity as above determined) of the transmission of bundle.Or a detector can be placed on a position of the outside of device, this position is corresponding to the reflection spot (on the inside of this device) of the bundle at the interface come between comfortable process/coating.Then one or more reversing can be determined as described above in detail.

VI. except measuring the optical characteristics that as above illustrates and/or leakage rate, the inside of measuring apparatus that other probes and/or device can be inserted into this equipment and be made up of detector means.This device is not subject to 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 Cement Composite Treated by Plasma is set up, a Systems for optical inspection optionally can be used to record plasma emission spectroscopy (wavelength and intensity curve), and this spectrum is corresponding to the distinct chemical feature of plasma environment.This characteristic emission spectrum provides this coating and has been applied in and the confirmation processed.For each part of process, this system additionally provides a kind of real―time precision measurment and data filing instrument.

VI. any above method can comprise a step as checking for the interior surface 88 of defect to container 80 as 24,26,30,32 or 34 places at treatment station.As at station 24,32 and 34 place, can by detection probe 172 to be inserted in container 80 via container port 92 and uses the situation of the coating 90 of probe 172 detection receptacle interior surface 88 or barrier coat or other types to check.As shown in Figure 11, this energy can be detected check with probe 172 by wall of container 86 and internal tank surface 88 by inwardly energy.Or, can by reflection from internal tank surface 88 radiation and carry out detected energy to check with the detector being positioned at container 80 inside.Or, can be checked by the situation of the multiple tight spacing positions detection receptacle interior surface 88 on internal tank surface.

VI. any above method can be carried out in the position of the enough numbers throughout internal tank surface 88, to determine that the coating 90 of a barrier coat or other types is greater than 20% of ambient atmosphere pressure by effectively preventing the pressure of within this container (when it is initially evacuated and its wall is exposed under ambient atmosphere) to be increased to during the quality guaranteed period of 1 year.

VI. this inspection step is carried out within the elapsed time that any above method can be included in 30 seconds or 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.Such as by measuring the effect (as shown in Figure 7) of the wall of container of the coating coating of this barrier coat or other types, this may relate to a measurement for whole container 80, or by checking multiple or even all points having examine abreast, as by using charge coupled device as detector 172 (as shown in Fig. 6,10 and 11 or alternatively), can make it to become possibility.The latter's step may be used for the situation of the position detection barrier coat of the multiple tight spacings within very short total time on internal tank surface 88 or the coating of other types.

VI. in any embodiment of the method, multiple spot container can be accelerated further by following steps and detect (if desired): use charge coupled device 172 to collect data, just checked container 80 is removed in transport, and shortly after that process the data of collecting, container 80 moves in downstream simultaneously.If because data processing determines the defect in container 80 subsequently, defective container 80 can be made to leave circuit at a some place in the downstream of measuring station such as 34 (Figure 10).

VI. in officely how to go up in embodiment, this inspection step can be carried out in the position of enough numbers of the interior surface 88 throughout container 80, to determine that the coating 90 of a barrier coat or other types will effectively prevent the initial vacuum level of within container 80 (when it is initially evacuated and its wall 86 is exposed under ambient atmosphere) (reducing relative to the original pressure of environment) at least 12 months, or at least 18 months, or reduce more than 20% during the quality guaranteed period of at least two years, optionally more than 15%, optionally more than 10%, optionally more than 5%, optionally more than 2%.

VI. initial vacuum level can be a high vacuum, namely surplus pressure is less than 10 holders, or the vacuum that less, as being less than the malleation (namely exceeding the excess pressure of vacuum) of 20 holders or being less than 50 holders or being less than 100 holders or being less than 150 holders or being less than 200 holders or being less than 250 holders or being less than 300 holders or being less than 350 holders or being less than the malleation of 380 holders.In many cases, the initial vacuum level of vacuum test tube is such as decided by the type and suitable amount that have the type of test tube to be used and the reagent be added into during fabrication therefore.This initial vacuum level be usually set with the blood of inspiration appropriate amount thus be filled with the reagent in this pipe and be combined.

VI. in officely how to go up in embodiment, the inspection step of the coating 90 of this barrier coat or other types can be carried out in the position of the enough numbers throughout internal tank surface 88, with determine the coating 90 of this barrier coat or other types by be increased to during the quality guaranteed period effectively preventing the pressure of within this container 80 (when it is initially evacuated and its wall is exposed under ambient atmosphere) at least one year more than ambient atmosphere pressure 15% or more than ambient atmosphere pressure 10%.

VI.A. the container process of precoating and rear coating inspection is comprised

VI.A. even another embodiment is a kind of container-treatment for the treatment of shaping plastic containers, and these shaping plastic containers have the wall that an opening and limit interior surface.The method is undertaken by following steps: by shaping or just in time check the defect of interior surface of container before coating; In inspection by the interior surface of the after-applied coating of shaping container to this container; And check the defect of coating.

VI.A. another embodiment is a kind of container-treatment, is wherein applied on this container by a barrier coat after inspection is by shaping container, and the interior surface for this container of defect after applying this barrier coat checks.

VI.A. in one embodiment, station or equipment 26 (it can also work for applying a coating as station or equipment 28) can be used as follows for barochamber inspection.Under one of valve 136 and 148 or both open, container 80 can be evacuated to the degree desired by, preferably to an one low-down pressure (as 10 holders, being optionally less than 1 holder).In valve 136 and 148, whichever is open at first, can then be closed, and is separated in the inside 154 of the container 80 of finding time and pressure warning unit 152 with envrionment conditions and with vacuum source 98.The change of pressure in Measuring Time process, no matter whether to be entered by wall of container due to gas or exit in coating from the material of this wall and/or on this wall of container, then can be sensed and be used for computing environment air and enter the speed (when being arranged on pan straddle 44) of container 80.In order to this object, venting be defined as optionally under at least part of vacuum from the release of the absorption of wall of container or occluded gas or water vapour.

VI.A. another optional amendment can be providing environmental gas higher than under barometric point.This can increase the speed that gas is displaced through the layer of blocking layer or other types again, if providing a measurable difference than providing in time shorter under compared with low environment pressure.Or can be introduced by gas in container 80 under higher than ambient, this adds the transfer rate by wall 86 again.

VI.A. optionally, at this station place or can check that gas detects it as helium and in downstream side and modifies by providing a kind of at the upstream side (within container 80 or outside) relative to substrate by the container inspection of equipment 26.A kind of low-molecular-weight gas (as hydrogen) or a kind of more not expensive or more available gas (as oxygen or nitrogen) also can be used as a kind ofly to check gas.

VI.A. consider helium and check gas as one, it can increase leakage or the speed of Liquid penetrant testing, this be due to it than common surrounding gas as the nitrogen in normal air and oxygen more faster through the coating of a defective barrier coat or other types or through a Leak seals parts.Helium has by many solid substrates or closely spaced high pass speed, this is due to it: (1) is inertia, thus it is not adsorbed with any large degree by substrate, (2) be not easy to be ionized, thus its molecule is very closely, this is due to the high-caliber attraction between its electronics and nucleus, and the molecular weight that (3) have is 4, relative with oxygen (molecular weight 32) with nitrogen (molecular weight 28), again make molecule more closely and easily by a kind of perforated substrate or gap.Due to these factors, helium will be more faster than other gases many through having a given infiltrative blocking layer.Equally, the helium of air natively containing unusual small proportion, thus the existence of extra helium can relatively easily detect, if particularly helium to be introduced within container 80 and carry out detecting to measure outside container 80 leak and infiltration time.Therefore, helium is detected by the pressure drop upstream (pressuredropupstream) of this substrate or by additive method (spectroscopic analysis as the gas downstream by this substrate).

VI.A. by from O ₂the example that the oxygen concentration of fluoroscopic examination carries out the barochamber inspection determined is followed as follows.

VI.A. the through adapter of a kind of vacuum (as VFT-1000-VIS-275) employing a driving source (OceanOpticsUSB-LS-450 blue pulse LED), optical fiber component (OceanOpticsQBIF6000-VIS-NIR), spectrometer (USB4000-FL spectrofluorometer), oxygen sensor probe (OceanOpticsFOXY-R) and be connected on a vacuum source.A vacuum can be applied and remove ambient air, and when this container is under defined pressure, this detection system can be used determine from ambient air leak or penetrate into thus be full of again this container any oxygen content one coating pipe substitute uncoated pipe and can O be carried out ₂measurement of concetration.Due to (a SiO on the pipe of coating _xsurface, relative to uncoated PET or glass surface) otherness O ₂surface absorption and/or the O from surface ₂the change of rate of diffusion, compared with uncoated sample, proof is reappeared different atmospheric oxygen content by the pipe of coating.Detection time can be less than a second.

VI.A. these gas pressure means should not be considered and be limited to the specific gas of sensed one (can consider that helium detects or gas gas) or a kind of specifically device or layout.

VI.A. this treatment station or equipment 34 can also be configured to check for the coating of defect to barrier coat or other types.In the embodiment of Fig. 1 and 10, treatment station or equipment 34 can be another kind of optical checks, to the coating 90 of barrier coat or other types at least partially, or the characteristic of the coating 90 of whole barrier coat or other types carries out scanning or separate measurement substantially in the position of being at this moment intended to the multiple tight spacings in the coating 90 of barrier coat or other types.In each case or average going up at least partially on this surface, the position of the plurality of tight spacing can be such as 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 measures the some or all of small portions of the coating 90 of barrier coat or other types dividually.In one embodiment, separately scanning is carried out for the independent pin hole of discovery or other defect to each zonule of coating, and may be useful for the local influence (as there is the large regions of coating of too thin or porous) distinguishing needle pore defect from more common defect.

VI.A. can be carried out according to the following steps by station or the inspection of equipment 34: such as by a source of radiation or light source 170 or any other radio frequency, microwave, infrared rays, visible ray, ultraviolet, X-ray or electron beam source be applicable to be inserted in container 80 via container port 92 and uses detector to detect the situation carrying out detection receptacle interior surface such as barrier coat 90 from the radiation of source of radiation transmission.

VI.A. above pan straddle system can also be used for testing this device.Such as, the probe 108 with Fig. 2 of a gas delivery port one 10 can be replaced by a light source 170 (Figure 10).Light source 170 can irradiate the inside of this pipe and the test that then can complete in the outside of this pipe subsequently, measures transmission or other characteristics.Light source 170 can be made in an identical manner to extend into the inside of this pipe, and namely probe 108 is pushed in rubber disc or pan straddle 62, although vacuum and sealing are not required.Light source 170 can be a kind of optical fiber source, a kind of laser, a kind of pointolite (such as a LED) or any other source of radiation.This source can to carry out radiation from dark UV (100nm) to one or more frequencies of far infrared (100 microns) and all frequencies between them.Operable light source is not limited.

VI.A. as a specific examples, see Figure 10.In Fig. 10, pipe or container 80 are positioned in rubber disc or pan straddle 62, and the light source 170 being arranged in the end of probe 108 has been inserted into this pipe.Light source 170 can be need a blue led light source of the sufficient intensity received by the detector 172 of the outside around container 80 in this case.Light source 170 can be a such as three-dimensional charge coupled device (CCD), and this charge coupled device is included in an array (such as 174) of the multiple pixels in interior surface thereof 176.These pixels receive and detect radiation by barrier coat or the coating 90 of other types and the illumination of wall of container 86 as 174.In this embodiment, relative to container 80 detector 172 have than Fig. 2 electrode 164 and container 80 be separated larger internal diameter, and the Cylindrical top portion had near closing end 84 instead of dome end portion.This external detector 172 can have the less radius clearance leaving container 80, and one of its top office near closing end 84 evenly the gap of size.When container 80 is taken a seat, this can such as by providing a common centre of curvature at the top for closing end 84 and detector 172 to realize.This change may provide the more consistent inspection of the bending closing end 84 of container 80, although two kinds of any one change are all considered to be applicable.

VI.A., before light source is opened, CCD is measured, and the value obtained is stored as background (it can be deducted from observed value subsequently).Then light source 170 opened and obtain observed value with CCD.Then the observed value that obtains can be used to calculate total light transmission rate (and compare with uncoated pipe thus determine average coating thicknesses) and defect concentration (if to be compared in they and threshold value by the independent photon counting that obtains on each element of CCD-photon counting is lower, then this is through corresponding to not having enough light).Low light transmission rate may be do not have or the too result-on pipe of shallow layer coating in defect.By measuring the contiguous quantity with the element of low photon counting, can estimate the size of defect.By gathering the size of defect and quantity, can evaluate the quality of pipe, or determine other characteristics, these characteristics may be specific for the frequency of the radiation from light source 170.

VI.A., in the embodiment of Figure 10, energy can, to external irradiation by internal tank surface, as passed through coating 90 and wall of container 86, and use the detector 172 being positioned at this external container to detect.Dissimilar detector 172 can be used.

VI.A. because what launch from source 170 can be larger (comparing with at the reference line of any given angle perpendicular to wall of container 80) by this barrier coat or the coating 90 of other types and the incident radiation of wall of container 80 for less incident angle, be positioned at more more than neighbouring pixel for reception radiation by the pixel (as 174) on the normal of wall of container 86, although more than one pixel can receive by one of the coating of this barrier coat or other types to some light of certain portions, and will be received by a specific pixel (as 174) by the light of certain portions of giving of this barrier coat or the coating 90 of other types and the more than one of wall of container 80.

VI.A. can by settle CCD increase for the coating 90 by this barrier coat or other types and pixel (as 174) that the radiation of specific part of wall of container 86 detects resolution make its pel array (as 174) and the profile of wall of container 86 be closely and be closely consistent.Can also by selecting less or substantial pointolite (as diagrammatically represented in Fig. 6) increase resolution to illuminate the inside of container 80.Use less pixel also by the resolution of the pel array in raising CCD.

VI.A. pointolite 132 (laser or LED) is positioned in the end of bar or probe in figure 6.(" pointolite " refer to or from be similar to mathematics point small-volume light source launch light (as can by little LED or on an optical fiber radiation light diffusion tip produce in all directions) or refer to the form of small cross-section bundle launch light (coherent light such as transmitted by laser apparatus)).Pointolite 132 can be or static or moveable, such as, can axially move, and measures barrier coat or the coating 90 of other types and the feature of wall of container 80 simultaneously.If removable, pointolite 132 can be moved up and down in device (pipe) 80 inside.Can scan the interior surface 88 of container 80 in above-mentioned similar mode and the measurement undertaken by an external detection apparatus 134 subsequently to determine coating integrity.An advantage of this method to use the linearly polarized or similar coherent source with specificity directivity.

VI.A. the position of pointolite 132 can be pointed to the illumination that (indexed) pixel (such as 174) makes can determine when detector is positioned at a normal angle relative to a Special Areas of coating 90 detector like this.In the embodiment of Figure 10, a cylindrical detector 172 (optionally having the bent ends matched with the curve (if any) of the closing end 84 of container 80) can be used to detect the feature of cylindrical vessel 80.

VI.A. should be understood that by reference to Figure 10, inspection station or equipment 24 or 34 can be changed by reversion light source or the position of other source of radiation 170 and detector 172 thus make light from the inside of external radiation by wall of container 86 to container 80.If select this stopgap measure, in one embodiment, a uniform incident light or other source of radiation can be provided by being inserted in an opening 182 by the wall 184 of an integrating sphere light source 186 by container 80.Integrating sphere light source is outside and this integrating sphere is inner from source 170 to container 80 by dispersed light or radiation, makes the light of the point of the correspondence of the wall 86 by container 80 to be relatively uniform like this.This reduces the distortion that causes of the illusion relevant to by multiple parts with difform wall 86 by tending to.

VI.A., in the embodiment of Figure 11, detector 172 and barrier coat or the coating 90 of other types or the interior surface 88 of container 80 can be shown closely consistent.Because detector 172 can be positioned on the side of the wall of container 86 identical with the coating 80 of barrier coat or other types, this close to tending to the resolution increasing pixel (as 174), although in this embodiment, coating 90 relative to barrier coat or other types is preferably accurately located, to avoid the scraping each other that may damage one of coating or ccd array by detector 172.Immediately detector 172 is placed in the refraction effect that can also reduce near coating 90 and be caused by wall of container 86, in the embodiment of Figure 10, this refraction effect occurs after light or other radiation pass through the coating 90 of this barrier coat or other types, makes signal to be detected differently be reflected (depending on the local shape of container 80 and the incident angle of light or other radiation) like this.

VI.A. and, or, coating Examined effect and the equipment of other barrier coats or other types can be used.Such as, fluorescence measurement can be used characterize the process/coating about 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, this may be used for the characteristic characterizing certain limit, comprises defect, thickness and other performance factors.

VI.A. another example again checked uses X-ray to characterize this process/coating and/or this polymkeric substance self.In Figure 10 or 6, light source can be replaced with X-radiation source, and external detector can be the type for measuring X-ray intensity.This technology can be used to carry out the ultimate analysis of the coating of barrier coat or other types.

V1.A. as in station 22 after a shaping device 80, may occur some potential problems, these problems will make any subsequent disposal or coating be imperfect, and may be invalid.If checked these problems for these devices before coating, these devices can with a kind of height optimization, optionally coated up to the process of 6-δ control, and it can guarantee desired result (or multiple result).

VI.A. some potential problems of process and coating may be disturbed to comprise (depending on the character having coated article to be produced):

VI.A.1. the particle contamination defect (being such as greater than 10 microns separately at its longest dimension place) of large density, or the large particle contamination of less density (being such as greater than 10 microns separately at its longest dimension place).

VI.A.2. chemistry or other surface contaminations (such as silicone molds release or oil).

VI.A.3. high surfaceness, is characterized in that cliffy summit and/or the paddy of height/large quantity.This can also characterize by mean roughness (Ra) by quantifying, and this mean roughness should be less than 100nm.

VI.A.4. any defect (as a hole) in this device vacuum is not allowed.

VI.A.5. any defect (such as the opening end of a sampling tube) on this device surface of generation one sealing is used to.

VI.A.6. large wall thickness heterogeneity, this may hinder or change the coupling power by the thickness in process or coating procedure.

VI.A.7. the other defect that the coating of this barrier coat or other types is invalid will be made.

VI.A. in order to this process/coating operation ensureing the parameter used in process/coating operation is successful, can the one or more above potential problems of this device of preliminary examination or other problems.Disclosed for holding a device (rubber disc or pan straddle are as 38-68) and a kind of device it moved by a production process in the past, this production process comprises different tests and a kind of process/coating operation.Some possible tests can be carried out to guarantee that a device has the suitable surface for the treatment of/coating.These comprise:

VI.A.1. optical check, such as, transmitted by the radiation of this device, the inside from this device or the radiation reflective from outside, the radiation absorption for this device or the radiation interference for this device.

VI.A.2. digit check-such as, use can measure length-specific and geometrical shape digital camera (such as, relative 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. acoustics (ultrasonic) test of device.

VI.A.5.X X-ray analysis X.

VI.A.6. the specific conductivity of device (has plastics tubing material and the SiO of different resistance _x-such as the quartz (as bulk material) of the grade at 1020Ohm-cm and the polyethylene terephthalate for the grade at 1014Ohm-cm).

VI.A.7. the thermal conductivity (such as, the thermal conductivity of quartz (as bulk material) is about 1.3W-° K/m, and the thermal conductivity of polyethylene terephthalate is 0.24W-K/m) of device.

VI.A.8. the venting of wall of container, this carries out under optionally can checking in following rear coating measuring to determine a venting baseline.

VI.A. above test can be carried out in a station 24 as shown in Figure 6.In this drawing, this device (such as a sampling tube 80) can be received in position and a suitable light source (or other source) 132 to be inserted in this device and the outside suitable detector 134 being positioned at this device to measure desired result.

VI.A. when vacuum leak detects, this pan straddle and device can be incorporated into a vacuum pump and one be inserted on the metering facility in this pipe.This test can also be carried out as the detailed description in the other places of this specification sheets.

VI.A. treatment station or equipment 24 can be visual inspection stations, and can be configured to for checking one or more between its surface 88 and 118 of the interior surface 88 of container, its outer surface 118 or the inside of its wall of container 86 for defect.If particularly this container is transparent or translucent for the type of the radiation for checking and wavelength, can carry out from the outside of container 80 inspection of outer surface 118, interior surface 88 or wall of container 86.To the inspection of interior surface 88, if desired, can promote by providing via container port 92 fibre-optical probe be inserted in container 80, the view of the inside of container 80 can be obtained like this from the outside of container 80.Such as, an endoscope or borescope can be used in this environment.

VI.A. another shown in figure 6 stopgap measure can be inserted within a container 80 by a light source 132.The light transmitted by wall of container 86 and can being detected from the outside of container 80 (as by using detectors measure device 134) by the illusion that light becomes clearly container 80.This station or equipment 24 such as can be used to detect and correct or remove correctly be not seated at the unjustified container 80 on container port 96 or there is the container 80 of visible distortion, impurity or other defect in wall 86.Substitute or except machinery survey, also observe container 80 and visual inspection container 80 by workman.

VI.A. treatment station or equipment 26 (being illustrated in greater detail in Fig. 7) can be optionally configured to for checking for the interior surface 88 of defect to container 80, and be such as used for measuring the pressure loss by wall of container 86, this can complete before the coating providing a barrier coat or other types.This test can by producing a pressure difference between two sides of barrier coat 90, such as by pressurizeing to the inside of container 80 or finding time, the inside 154 of container 80 is isolated thus make this pressure around the seal will keep constant No leakage or without gas-permeable by this wall of container, and measure the pressure change that time per unit accumulates from these problems and carry out.This measurement not only can disclose any gas through wall of container 86, but also detection receptacle outlet 82 and O shape is enclosed or leakage sealed between other sealing members 100, this is leakage sealed may indicate or about the aligning of container 80 or the problem of the function about sealing member 100.Under one of two things, maybe this pipe can be taken out from process line by the error recovery pipe of taking a seat, attempt to realize or maintaining suitable process vacuum level and prevent process gas from being saved time by the Dilution air extracted out by inefficacy sealing member.

VI.A. said system can be incorporated in a manufacture and inspection method, the method comprises multiple step.

VI.A. foregoing Fig. 1 shows a kind of schematic diagram (although the invention is not restricted to a kind of single concept or method) of step of possible method.First carry out visual inspection at this station place or by equipment 24 to this container 80, this can comprise the dimensional measurement of container 80.If found any defect, then this device or container 80 be rejected and check this rubber disc or pan straddle as 38 defect, recirculation or remove this disk or pan straddle.

VI.A. next step is as tested a pan straddle 38 and the leakage rate of the assembly of container 80 of taking a seat or other features at station 26 place, and is stored and be used for comparing after coating.Then this rubber disc or pan straddle 38 are moved on in such as coating step 28.With the line frequency of such as 13.56MHz, use a kind of SiO _xor the coating of other barrier coats or other types applies this device or container 80.Once coated, again test the leakage rate of this pan straddle or other features (this can as carried out in testing station 26 or dual or similar second test of station as 30 places, and the use at a dual station can increase throughput of system).

VI.A. the measurement of coating and uncoated measurement can be compared.If the ratio of these values has exceeded the required level preset, indicate a kind of acceptable overall coating performance, this pan straddle and device continue mobile.Such as, a blue-light source and an outside integrating sphere detector are followed to measure total light transmitted by this pipe in optic test station 32.This value can be required to be above a preestablished limit, is rejected or is recycled at this this device of limit place and for other coating.Then (for there is no unaccepted device), a second optic test station 34 can be used.In this case, a pointolite can be inserted into pipe or container 80 inner and slowly pull out, obtain measuring result by the tubulose CCD detector array of this tube outside simultaneously.Then data are carried out computational analysis to determine that defect concentration distributes.Based on these measuring results, this device or be approved for and finally pack or be rejected.

VI.A. above data can optionally record or map (such as electronically) thus guarantee 6 σ quality by Using statistics process control technology.

VI.B is according to the container inspection detected by the venting of the wall of container on blocking layer

VI.B. another embodiment is a kind of method of the layer for checking blocking layer on the material of letting off steam or other types, has some steps.Provide a specimen material, this material is released a kind of gas and is had at least part of blocking layer.Optionally, the pressure reduction striding across this blocking layer can be provided, make the material of venting at least partially be high-tension side on this blocking layer like this.In another option, the gas of releasing can be allowed to spread not providing under a pressure reduction.Measure the gas of releasing.If provide the pressure reduction striding across this blocking layer, venting can be measured at the high pressure on this blocking layer or low-tension side.

VI.B. in addition, measure coated inside (above applied) effect can by measure particular types or adsorb the rate of diffusion of material in the wall (before coating) of device carry out.When comparing with uncoated (untreated) pipe, such measurement can provide the existence of the stop of this coating or process or the characteristic of other types or coating or process or the direct measurement of shortage.The coating detected or process (except being a blocking layer or replace a blocking layer) can be lubricant films, the layer (by increasing or reducing it) changing the venting of this substrate of hydrophobic layer, a decorative coveringn or other types.

VI.B. as a concrete example, use the pan straddle from Fig. 2 and refer again to Fig. 7, a device or container 80 can be inserted in rubber disc or pan straddle 44 (can also from another operation (as coating/process) mobile come loading rubber disc or pan straddle (as 44) in the container 80 of taking a seat carry out this test).Once this pan straddle moves in the test zone of blocking layer, measuring tube or probe 108 can be inserted inner (in the mode similar with the gas-filled valve for applying, although this measuring tube need not extend in this pipe).Both valves 136 and 148 can be open and the inside of this pipe can be evacuated (producing a vacuum).

VI.B. once reach desired measuring stress, can by valve 136 and 148 close and pressure warning unit 152 can start to measure this pressure.By measuring time of reaching specified pressure (higher than initial pressure) or by measuring the pressure that reaches after the time of specified rate, can measuring tube, pan straddle, pump channel and to be connected on this internal volume but the rate of rise (or leakage rate) of the every other part of being isolated by valve 1 and 2.If then this value compares with uncoated pipe, the ratio (applying the value of value divided by uncoated pipe of pipe) of two observed values can produce an observed value of the leakage rate of the coated surface by this pipe.This measuring technology may need this pan straddle, pump channel and to be connected on this internal volume but the internal volume of the every other part of being isolated by valve 1 and 2 (except this pipe/device) is reduced to minimum, thus by gas-permeable or be down to minimum from the exhaust impact on these surfaces.

VI.B. in this disclosure, between " infiltration ", " leakage " and " surface diffusion " or " venting ", differentiation has been made.

" infiltration " of a reference as used in this container the crossing by a wall 346 or other obstacles that be a kind of material, as along the path 350 in Figure 29 or this path the reverse external-to-internal from container or vice versa.

That venting refers to a kind of absorption or absorption material such as gas molecule 354 or 357 or 359 such as enters container 358 (arriving the right side in Figure 29) by coating 348 (if present) from outwards mobile within the wall 346 Figure 29 or coating 348.Venting can also refer to that a kind of material shifts out from wall 346 (left side as shown in Figure 29) as 354 or 357, thus arrives the outside of container 357 as demonstrated.Venting can also refer to the material adsorbed from the surface removal of article, such as, from the gas molecule 355 on the surface of the exposure of barrier coat 90.

Leak and refer to that a kind of material moves instead of moves by or leave the surface of this obstacle around the obstacle represented by wall 346 and coating 348, as passed through to pass through between a closure member and a wall of a container closed with closure member.

VI.B. infiltration indicates gas and moves speed by a kind of material, and very close to each other/defect and not relating to is leaked or venting.With reference to Figure 29, show a wall of container or have other substrates 346 of a barrier coat 348, infiltration is a kind of gas crossing along path 350 completely by this substrate 346 and coating 348, and this path is by these two layers.Infiltration is considered to a kind of thermodynamic (al), therefore process relatively slowly.

VI.B. infiltration is measured is slowly, and this is because infiltration gas must pass completely through the complete wall of of this plastic article.When vacuum test tube, gas is used as this container routinely along with the time by the measurement of the infiltration of its wall and loses the direct instruction of the tendency of vacuum in the past, but normally a pole is measured slowly, the usual needs test time of 6 days, is not therefore enough fast thus can not supports to apply inspection online.Such test is generally used for off-line test container sample.

VI.B. for the stop effect at a kind of thick suprabasil a kind of shallow layer, penetration testing is not a kind of very sensitive measurement equally.Because all gas flow are by this coating and this substrate, not change because the stop effect of coating itself causes flowing through the change in this thick substrate by introducing.

VI.B. ladies and gentlemen contriver to find faster and the method for the barrier properties of a potential sensitiveer measurement coating-measure the gas of the sharp separation in this wall of container or other gaseous states or volatile constituent by the venting of this coating.These gaseous states or volatile constituent can be any material of in fact exitting, can be maybe be selected from one or more concrete materials to be detected.These components can be including, but not limited to: by product prepared by oxygen, nitrogen, air, carbonic acid gas, water vapour, helium, volatile organic material (as alcohol, ketone, hydrocarbon), coating precursor, substrate components, coating prepare as volatile organosilicon, coated substrate by product, occur by chance other components of being introduced by admixture substrate or any these mixture or combination.

Surface diffusion and venting are synonyms.Each term refers to and is adsorbed on fluid that is on a wall 346 (as a wall of a container) or that be absorbed in this wall at first, and cause this fluid to penetrate contiguous space by certain power, as vacuumized (creating the air movement as shown in the arrow 352 of Figure 29) thus force fluid to flow out inside that this wall enters into this container in the container with a wall.Venting or diffusion are considered to dynamic (dynamical), a relative process fast.Institute it is considered that, for a wall 346 of the substantive resistance had the infiltration along path 350, the molecule that will shift out rapidly as 354 of exitting, these molecules are closest to the interface 356 between wall 346 and blocking layer 348.The molecule (as near interface 356 354 of venting display) of logical excessive amount, and other molecules of logical excessive amount (as with interface 356 far away and not as exitting show 358), indicate difference and exit.

VI.B. therefore, considering the another kind of again method for checking the blocking layer on the material of letting off steam, comprising some steps.Provide a specimen material, this material is released a kind of gas and is had at least part of blocking layer.Provide the pressure reduction that one strides across this blocking layer, make the material of initial venting at least partially be high-tension side on this blocking layer like this.Measure in a test process, be transported to the gas of the releasing of the low-tension side on this blocking layer, to determine such information, whether to exist as this blocking layer or how effective it is as blocking layer.

VI.B. in this approach, the material of releasing a kind of gas can comprise a kind of polymer compound, a kind of thermoplastic compounds or have one or more compounds of both characteristics.The material of releasing a kind of gas can comprise polyester, such as polyethylene terephthalate.The material of releasing a kind of gas can comprise a kind of polyolefine, as polypropylene, these two examples of a kind of cyclic olefine copolymer, or these combination.The material of releasing a kind of gas can be the matrix material of two kinds of differing materials, and at least one of this bi-material releases a kind of steam.An example is the bilayer structure of polypropylene and polyethylene terephthalate.Another example is the bilayer structure of cyclic olefine copolymer and polyethylene terephthalate.These materials and matrix material are exemplary; The combination of any applicable material or material can be used.

VI.B. optionally, the material of releasing a kind of gas is that the form of the container with a 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 is optionally placed in and is placed on the internal surface of this wall of container on this wall of container, optionally.This blocking layer can or also be placed on the outside surface of this wall of container.Optionally, the material of releasing 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 blocking layer described at present.This blocking layer can be that to be less than 500nm thick or be less than that 300nm is thick or to be less than 100nm thick or be less than that 80nm is thick or to be less than 60nm thick or be less than that 50nm is thick or to be less than 40nm thick or be less than that 30nm is thick or to be less than 20nm thick or be less than that 10nm is thick or to be less than 5nm thick.

VI.B., when applying wall, ladies and gentlemen contriver finds that diffusion/venting may be used for determining coating integrity.Optionally, by inner chamber or the internal space of this container of finding time at least in part, the pressure reduction striding across this blocking layer can be provided.This can such as by be connected to this inner chamber on a vacuum source via a pipeline thus this inner chamber of finding time at least in part has come.Such as, after evacuation, the interior surface from it is released a certain amount of oxygen with other gas molecules as 354 lasting regular hours by the uncoated PET wall 346 being exposed to a container of ambient air.If identical PET wall is had a kind of barrier coat 348 in internal coat, then this barrier coat by stopping, slowing down or reduce this venting.A such as SiO _xreally so, the venting of this coating is less than a frosting to barrier coat 348.By measuring this venting difference between coating PET wall and uncoated PET wall, the barrier effect of coating 348 with regard to the material of releasing can be determined rapidly.

If VI.B. due to the hole of known or theory, crack, gap or not enough thickness or density or composition region and cause barrier coat 348 to be defective, then this PET wall will preferentially be exitted by defect part, thereby increases the total amount of venting.The primary source of collected gas be in the surface from the plastic article close to this coating (under) dissolved gases or transpirable component, instead of from the outside of these article.Can measure in a different manner the venting more than a basic horizontal amount (such as by one, not there is defect or have minimum accessible degree defect have an average and standard coated of the defect of acceptable degree by or the amount of release) to determine the integrity of this coating.

VI.B. this measurement can such as by providing a venting measuring cell be communicated with between this inner chamber and this vacuum source to carry out.

VI.B. this measuring cell can realize any multiple different measuring technology.An a kind of example of applicable measuring technology is micrometeor technology.Such as, the mass flow rate of the material of releasing can be measured.Operation scheme can be flowed to carry out this measurement by molecule.A kind of exemplary measurement is the mensuration of the amount of the gas of being released by this blocking layer at interval of the time period.

VI.B. the gas that the low-tension side on this blocking layer is released can be measured under effective differentiation existence on blocking layer or the condition of shortage.Optionally, effectively the differentiation existence on this blocking layer or the condition of shortage comprise the test time being less than a minute or being less than 50 seconds or be less than 40 seconds or be less than 30 seconds or be less than 20 seconds or be less than 15 seconds or be less than 10 seconds or be less than 8 seconds or be less than 6 seconds or be less than 4 seconds or be less than 3 seconds or be less than 2 seconds or be less than 1 second.

VI.B., optionally, in above identified any time interval, the determinacy of at least 6-δ level can be proved for the existence on this blocking layer or the measurement of shortage.

VI.B. optionally, the gas of the releasing of the low-tension side on blocking layer is (compared with not the having the same material on blocking layer) of measuring under the condition of the barrier improvement factor (barrierimprovementfactor, BIF) effectively determining this blocking layer.Such as can measure BIF by following steps: by providing two groups of identical containers, blocking layer is joined in one group of container, test has barrier properties (as in per minute micrograms or the another kind of outgassing rate measured be applicable to) on the container on blocking layer, on the container lacking blocking layer, carry out identical test and obtain the material with blocking layer and the ratio of properties of materials without blocking layer.Such as, if be do not have 1/3rd of the outgassing rate under blocking layer by the outgassing rate on blocking layer, then the BIF that this blocking layer has is 3.

VI.B. optionally, when there is the gas more than a type wherein (as at the gas of releasing be nitrogen and oxygen) venting of multiple gas with various can be measured.Optionally, the venting of the gas of all in fact or all releasings can be measured.Optionally, as by using physical measurements (mass flow rate as the merging of all gas), the venting of the gas of releasings all in fact can be measured simultaneously.

VI.B. can complete quickly for the quantity of the independent gaseous species of discharging from sample (such as oxygen or helium) or the measurement of dividing potential drop compared with testing with air pressure, but the part that test rate is reduced to only this exhaust is the degree of measured kind.Such as, compared to the test of the same sensitivity of all kinds measured from wall of container releasing, if nitrogen and oxygen discharge from PET wall with the atmosphere ratio of about 4: 1, but only measure oxygen venting, then this test will need the time of operation five double-length (in order to obtain the result of enough statistical quality, with regard to detected molecule number).

VI.B. for the sensitivity of a given level, institute is it is considered that a kind of so method, and the test of the venting than a measurement particular types (as Sauerstoffatom) is provided desired confidence level by volume quickly that the method illustrate all kinds of releasing from surface.Therefore, the gassing data with actual utility for on-line measurement can be produced.This type of on-line measurement can optionally be carried out on the container of each manufacture, thus reduce speciality or the number of defect that is separated and potentially eliminate they while measuring (at least).

VI.B. in an actual measurement, the factor changing the apparent amount of venting be when exit test in vacuumize time cross the leakage of a defective sealing member (as being landed in the sealing member of the container on a vacuum received block).Leak and represent that a kind of fluid detours a solid walls of these article, such as fluid through a heparin tube and its closure member, one between syringe plunger and syringe cylinder, between a container and its cap or a vessel port and one fix this vessel port thereon sealing member between (due to defect or sealing member that mistake is fixed).Word " leakage " typically refers to the motion/gas of gas by the opening of in plastic article.

VI.B. the factor being thought of as venting basic horizontal with (when one given if necessary) infiltration will can be leaked, acceptable like this test result ensure that this container is suitably landed in (therefore its surface of taking a seat is complete and is suitably shaped and locates) on vacuum received block, this wall of container does not support the infiltration of unacceptable level (therefore this wall of container is complete and is suitably shaped), and this coating has enough stop integrities.

VI.B. venting can be measured in a different manner, as by barometric surveying (after being pumped into initial vacuum, measuring the pressure change in this container in a given time quantum) or by the flow rate of measuring the gas of releasing from sample or dividing potential drop.Available with the equipment of molecule flowing operation scheme measurement quality flow rate.The example adopting the such commercially available equipment of micrometeor technology is available from ATC, Inc., Indianapolis, IN.See U.S. Patent number 5861546,6308556,6584828 and EP1356260, they are combined in this by reference, for further describing this known equipment.Also see the example 8 in this specification sheets, show for quickly and an example measuring with the venting of uncoated pipe of polyethylene terephthalate (PET) pipe reliably carrying out distinguishing blocking layer coating.

VI.B. for the container be made up of polyethylene terephthalate (PET), SiO _xthe surface of coating is very different relative to the miniflow rate on uncoated surface.Such as, in the operational instances 8 in this specification sheets, after test run 30 seconds, the miniflow rate for PET is 8 micrograms or more, as shown in Figure 31.Compared to for SiO _xthe speed (being less than 6 micrograms after test has run 30 seconds) measured by PET of coating, this speed for uncoated PET is much higher, still as shown in Figure 31.

VI.B. be that uncoated PET comprises the equilibrium moisture of roughly 0.7% for the explanation that of this species diversity of flow rate is possible; This high moisture content is considered to cause observed high miniflow rate.For a kind of SiO _xthe PET of coating, this SiO _xcoating has higher levels of surface moisture than uncoated pet sheet mask.But under test conditions, this barrier coat is considered to prevent from body PET additionally desorb moisture, result in lower miniflow rate.From uncoated PET relative to SiO _xthe oxygen of PET or the miniflow rate of nitrogen of coating are diacritic by being expected equally.

VI.B., when using other materials, the above test for PET pipe of amendment may be suitable.Such as, polyolefin plastics tends to have very little moisture content.The polyolefinic example of one with low moisture content is cyclic olefine copolymer (COC), has the equilibrium moisture content (0.01%) more much lower than PET and moisture vapor transmission rate.When COC, uncoated COC plastics can have and SiO _xlike the COC Plastic of coating or even less miniflow rate.This is most likely due to SiO _xthe higher surperficial moisture content of coating and the lower balance body moisture content of uncoated COC frosting and lower infiltration rate.This makes uncoated more difficult with the difference of the COC article of coating.

The present invention shows, and has the surface of COC article to be tested (uncoated with coating) to be exposed to moisture and result at uncoated and SiO _ximprovement between the COC plastics of coating and consistent miniflow be separated.In this example 19 being shown in this specification sheets and Figure 57.This humidity exposure just can be exposed to the relative humidity of scope from 35%-100%, or it is indoor a controlled relative humidity, or be directly exposed to (humidifier) or cold (vaporizer) moisture source of heating, wherein the latter is preferred.

Although VI.B. validity of the present invention and scope are not be restricted according to the accuracy of this theory, relative to saturated SiO _xthe COC surface of coating, the admixture of moisture doping or uncoated COC plastics seems the humidity or other deflatable contents that add it.This can also by comprising oxygen, other gases of nitrogen or their mixture (such as air) come being exposed to uncoated pipe of coating.

VI.B. therefore, before measuring the gas of releasing, blocking layer and water such as water vapour can be made to contact.Can carry out contacting providing water vapour under the relative humidity of 35% to 100%, alternately 40% to 100%, alternately 40% to 50% by such as making blocking layer and air.Replace water or in addition to water, blocking layer can be made to contact with the mixture (such as ambient air) of nitrogen with oxygen, nitrogen or oxygen.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 from the opposite side on a blocking layer 348 by admixture or supplementary, such as by the left side of the wall 346 shown in Figure 11 is exposed to by air inlet (ingas) to a kind of material in wall 346, the left side then shown in Figure 29 or right side venting.By air inlet from left side admixture wall or other materials as 346, then the material measuring admixture is different from infiltration from the venting of right side (or vice versa) and measures, because when measuring venting, this material by admixture within wall 346, with mobile by the material of the All Paths 350 of this wall contrary (when measuring the gas occurred by coating).Air inlet can occur in long time period, as the embodiment applied before coating 348, and as after applying coating 348 and to another embodiment before its test venting.

VI.B. uncoated plastics and SiO is increased in _xthe method that the another kind of the separation of the miniflow response between coating plastic is possible changes measuring stress and/or temperature.Increasing pressure when measuring venting or reducing temperature to cause water molecules at SiO _xthan the larger relative combination in uncoated COC in the COC of coating.Therefore, the gas of releasing can measured to the pressure of 50 holders from 15 holders from 10 holders to 80 holders, alternately from 5 holders to 100 holders, alternately from 1 holder to 30 holders, alternately from 0.5 holder to 40 holders, alternately from 0.2 holder to 50 holders, alternately from 0.1 holder to 100 holders, alternately.The gas of releasing can measured from 0 DEG C to 50 DEG C, alternately from 0 DEG C to 21 DEG C, alternately from the temperature of 5 DEG C to 20 DEG C.

VI.B., in any embodiment of this disclosure, be 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 less of poor quality for what allow to measure in venting, likely 10 ^-12g (pik) is to 10 ^-15on the order of magnitude of g (fly gram).This less quality examination allows being less than in 1 second, being optionally less than in 0.1 second, optionally and carrying out coated surface relative to the differentiation of uncoated surface together with different coating at microseconds.

VLB in some cases, by causing due to molecular absorption bending or additionally moving or change shape, micro-cantilever (MCL) sensor can in response to a kind of releasing or the existence of material that provides in addition.In some cases, micro-cantilever (MCL) sensor can be responded by the change in resonant frequency.In other cases, these MCL sensors can change in both ways or otherwise.They can operate under various circumstances, as atmosphere surrounding, liquid or vacuum.In gas, micro-cantilever beam sensor can operate as an artificial nose, and the beam mode of a micro-manufacturing array of the silicon cantilever of eight kinds of polymer-coated is characterized by the different steam from solvent, seasonings and beverage thus.It is also conceivable to the Electronic Nose by any technological operation using any other type.

Applied and consider some MCL Electronic Design (comprise voltage dependent resistor, piezoelectricity and the method for electric capacity) measure the movement of MCL after being exposed to chemical, change in shape or change of frequency.

VI.B. the specific examples measuring venting can carry out as follows.There is provided at least one micro-cantilever, this micro-cantilever has and to move when a kind of material of releasing exists or to change over difform characteristic.Under effectively causing this micro-cantilever to move or change over difform condition, this micro-cantilever is exposed to the material of this releasing.Then detect this to move or different shapes.

VI.B. as an example, this movement or different shapes can by reflection from mobile or change shape micro-cantilever part high energy incident beam (before or after this micro-cantilever is exposed to venting) and measure and the deflection of reflected beam that produces of the some place at this micro-cantilever interval detect.This shape preferably measures at a some place at and this socle girder interval, this is because the amount of deflection restrainted under given conditions is and distance between this measurement point and reflection spot of bundle is proportional.

VI.B. the several applicable example of a high energy incident beam is a kind of photon beam, a kind of electron beam or these the combination of two or more.Alternately, two or more different bundles can reflect from MCL along different incidence and/or reflection paths, to determine mobile or alteration of form from more than one visual angle.The type of a high energy incident beam specifically considered is a kind of coherent photons bundle, as a kind of laser beam.Discussed in this manual " photon " defines to comprise wave energy together with particle or photon energy itself involvedly.

VI.B. an alternative practical measuring examples make use of some MCL changes resonant frequency characteristic when running into a kind of environmentally conscious materials, and this environmentally conscious materials is in an amount effectively completing resonant frequency and change.Such measurement can be carried out as follows.There is provided at least one micro-cantilever, when a kind of material of releasing exists, this micro-cantilever is with a different frequency resonance.Under the condition of the frequency resonance effectively causing this micro-cantilever different with, this micro-cantilever can be exposed in the material of this releasing.Then this different resonant frequency is detected by any applicable method.

VI.B. as an example, can this micro-cantilever is exposed to before or after venting by by energy input to micro-cantilever to induce its resonance to detect this different resonant frequency.Determine the difference between the resonant frequency being exposed to the MCL before and after venting.Alternately, replacing measuring the difference of resonant frequency, a kind of known MCL with a certain resonant frequency can be provided when there is a kind of material of venting of enough concentration or amount.Use a resonant transducer to have detected this different resonant frequency or show the resonant frequency of the material that there is enough releasings.

As the example using MCL technology to measure venting, can be merged in a silica valve by a MCL equipment, this silica valve is connected on a container and a vacuum pump.A kind of resonant transducer can be built, this sensor use a commercially available fabricated piezoresistive cantilevers beam, multiple Wheatstone bridge circuit, positive regeeration controller, one excite piezo-activator and phase-locked loop (PLL) detuner.See, such as,

·HayatoSone，YoshinoriFujinumaandSumioHosakaPicogramMassSensorUsingResonanceFrequencyShiftofCantilever，Jpn.J.Appl.Phys.43(2004)3648；

·HayatoSone，AyumiIkeuchi，TakashiIzumM，HarukiOkano2andSumioHosakaFemtogramMassBiosensorUsingSelf-SensingCantileverforAllergyCheck，Jpn.J.Appl.Phys.43(2006)2301)。

In order to for the preparation of the MCL detected, the side of micro-cantilever can be applied with gelatin.See, such as HansPeterLang, ChristophGerber, STMandAFMStudieson (Bio) molecularSystems:UnravellingtheNanoworld, TopicsinCurrentChemistry, Volume285/2008.Be combined with gelatin from the water vapour of vacuum coat vessel surface desorption, cause this socle girder to bend and its change of resonant frequency, as by measured by one of this socle girder surperficial laser deflection.Uncoated container is taken into account in the decimal place of second relative to the change of the quality of coating container and is distinguishable and is highly reproducible.Article cited above together with socle girder technology for they may be used for detect and quantize venting kind specific MCL and equipment arrange disclosure be combined in this by reference.

Replace above-described gelatin coating or except above-described gelatin coating, the alternative coating for detection of moisture (phosphoric acid) or oxygen detection can be applied to MCL.

VI.B. it is further contemplated that, any venting test set considered at present can with a SiO _xcoating station combines.In so a kind of layout, measuring cell 362 can be shown as above, employs main vacuum tunnel for PECVD as bypass 386.In one embodiment, usually the measuring cell shown in 362 of such as Figure 30 can 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. measuring cell 362 optionally will allow to carry out venting with this combination of pan straddle 50 and measure, and not destroy the vacuum for PECVD.Optionally, for PECVD vacuum pump by by operation one short, time of preferred standard amount to be to pump some or all of remaining after the coating step residual reactants gas (vacuumize and be less than a holder, another option allows a small amount of air, nitrogen, oxygen or other gas blow-washings (flushout) before vacuum extraction or dilutes these process gass).This will promote the anabolic process of the test of the coating of this container and the existence of this coating and barrier level.

VI.B. after this specification sheets of summary, those of ordinary skill in the art will be further understood that, venting is measured and every other described blocking layer measuring technology may be used for multiple object (be different from the effect of determining a blocking layer or in addition).Give one example, this test can be used on uncoated container or coating container to determine the venting degree of wall of container.Such as, when this test can be less than the gas of a specified quantitative with needing a kind of uncoated polymkeric substance to release wherein.

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 uncoated film, or as a kind of static test or as a kind of on-line testing to measure the change of film when it crosses measuring cell in venting.This test may be used for determining the coutinuity of coating of other types or stops effect, and these coatings are 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 the effect of blocking layer, a film etc. (relative with measuring cell) on the side determining to be applied to a wall of container, as being applied to a blocking layer on the outside of a wall of container and venting for the inside of inquiring after wall of container.In this case, this flowing difference will be used for penetrating through this barrier coat, penetrate through this substrate film or wall subsequently.When substrate film or wall are quite easily infiltrations (film of as very thin in one or porous 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 the effect determining a blocking layer, this blocking layer is interior layer, a film etc. of a wall of container, and this measuring cell will detect the venting being added the blocking layer by one or more layer (farther with the distance on blocking layer with the distance ratio of measuring cell) by any venting of the layer of contiguous measuring cell in this case.

VI.B. these venting are measured and every other described blocking layer measuring technology can also be used to determine the percentage of coverage of a kind of blocking material of pattern to a kind of material of releasing, if the venting degree of material that applied by determining section blocking layer is as the ratio (if not having blocking layer on the material of any part) of the discharge quantity of expection.

VI.B. with any venting test implementation scheme in this specification sheets can a kind of measuring technology that may be used for the speed of the venting increasing a test container be reduce the void volume of container, as by insertion plunger or closure member to this container to reduce the void volume of tested container portions.Reducing void volume allows container to be evacuated down to a given vacuum level quickly, because this reducing test interval.

VI.B., after this specification sheets of summary, venting described is at present measured and other application multiple of every other described blocking layer measuring technology will be obvious for those of ordinary skill.

The container of VII.PECVD process

VII. considered container has a barrier coat 90 (such as shown in Figure 2), and it can be a SiO applied _xcoating, the thickness of applying is at least 2nm or at least 4nm or at least 7nm or at least 10nm or at least 20nm or at least 30nm or at least 40nm or at least 50nm or at least 100nm or at least 150nm or at least 200nm or at least 300nm or at least 400nm or at least 500nm or at least 600nm or at least 700nm or at least 800nm or at least 900nm.This coating can be reach 1000nm, or maximum 900nm or maximum 800nm or maximum 700nm or maximum 600nm or maximum 500nm or maximum 400nm or maximum 300nm or maximum 200nm or maximum 100nm or maximum 90nm or maximum 80nm or maximum 70nm or maximum 60nm or maximum 50nm or maximum 40nm or maximum 30nm or maximum 20nm or maximum 10nm or maximum 5nm is thick.Clearly consider that specific thickness range is by any one minimum thickness above-mentioned, add the thickness composition of any equal or larger above-mentioned maximum ga(u)ge.This SiO can be measured _xor the thickness of other coatings, such as, by transmission electron microscopy (TEM), and the formation that x-ray photoelectron spectroscopy (XPS) measures it can be passed through.

VII. institute it is considered that, be prohibited the selection of the material permeating this coating and the SiO of applying _xthe character of coating can affect its stop effect.Such as, the example being usually intended to forbidden bi-material is oxygen and water/water vapor.Material is normally compared to another kind of better blocking layer for one.This is considered to so at least in part, because oxygen transmission is different from the mechanism that water is conveyed through coating by the mechanism of coating.

VII. oxygen transmission affects by the physical features of this coating, such as other physical details of its thickness, the existence in crack and this coating.On the other hand, to be subject to the impact of chemical factor (namely making the material of coating) larger than the impact being subject to physical factor for the transmission of usual phase menstruation.Ladies and gentlemen contriver also thinks, these chemical factors of at least one are substantial concentration of the OH part in coating, and it result in the transmission rate of higher water by this blocking layer.A kind of SiO _xcoating is usually containing OH part, and physically firm (physicallysound) coating of therefore containing OH part at high proportion one is better blocking layer (compared to for water) for oxygen.The physically firm coating based on carbon, as decolorizing carbon or diamond-like carbon (DLC) are considered to for the better blocking layer of water usually (compared to SiO _xcoating) because this barrier coat based on carbon more generally has the OH part of lower concentration.

VII. however other factors result in for a kind of SiO _xcoating preferred, the oxygen as it stops effect and its close chemical similarity to glass and quartz.Glass and quartz (when being used as the base mateiral of a container) be known for a long time present for the very high barrier properties of oxygen G&W transmission and there is in container the bi-material of the substantive inertia of the many materials usually carried.Therefore, it is generally desirable that optimize water barrier properties as a kind of SiO _xthe water vapor transmission rate (WVTR) of coating, instead of select a kind of coating that is different or type in addition to serve as a water transmission blocking layer.

VII. following some modes are considered for improvement of SiO _xthe WVTR of coating.

VII. the organic moiety (compound of carbon and hydrogen) in the coating of deposition and OH concentration ratio partly can be increased.This can such as have been come (as by the feeding rate increasing oxygen feeding rate or reduce one or more other components) by the ratio increasing the oxygen in feed gas.The influence mode of the OH part reduced is considered to the increase due to oxygen charging and the level of response of hydrogen in silicone is originated thus in PECVD is vented, produces the OH part retained or combine in the coating of more volatile water and lower concentration.

VII. higher energy can be used in PECVD process, or by raising plasma body generation power level or continuing longer time period (or both) by applying power.When be used for coating plastics tubing or other devices time, increase in applied energy must adopt carefully, this is because it also has the tendency (reaching the degree that this pipe bears this plasma body generation power) of the container deformation making be processed.Here it is why preferred RF power within the context of the present application.The distortion of medical device can be reduced or eliminated by the following: by adopting by the energy of the pulse of the two or more series separated cooling time, by cooling these containers while applying energy, by applying coating (therefore usually make it thinner) within the shorter time, by selecting the frequency (this coating is that minimally is absorbed by the coated base mateiral selected) applying coating, and/or by applying more than one coating (applying the time between step at the energy of correspondence).As, high power pulse can be used by the work period of operation 1 millisecond, stopping 99 milliseconds, continue this process gas of feeding simultaneously.Then this process gas is refrigerant, and it keeps flowing between the pulses equally.Another replacement scheme reconfigures power applicator, as by add magnet with limit plasma body thus increase active power apply (in fact cause the power of coating increased, with cause heating or the wasted power of undesired coating contrary).This rights and interests measure causes applying more coating formation energy (every total watt-hour of the energy applied).See such as United States Patent (USP) 5,904,952.

VII. can the oxygen aftertreatment of application of coatings, so as from before deposition coating remove OH part.Also contemplate this process to remove residual volatile organosilicon compound or silicone or to be oxidized this coating to form other SiO _x.

VII. can by this plastic basis material preheating.

VII. different volatility silicon sources, as hexamethyldisilazane (HMDZ) can be used as a part or all silicone chargings.Institute it is considered that, feed gas is changed over HMDZ by solving the problem that provides, because do not have aerobic part in this compound.Institute it is considered that, a source of the OH part in the coating in HMDSO source is the hydrogenation of at least some Sauerstoffatom existed in unreacted HMDSO.

VII. can use a kind of compound coating, as with SiO _xin conjunction with a kind of coating based on carbon.This can such as by change reaction conditions or by feed gas together with a kind of based on add a kind of replacement in organosilyl compound or unsubstituted hydrocarbon (as a kind of alkane, alkene or alkynes) come.See such as United States Patent (USP) 5,904,952, it relevant portion " such as; a kind of lower hydrocarbon as propylene be mingled with provide carbon part and improve most of characteristic (except optical transport) of film of depositing, and binding analysis indicates this film is silicon-dioxide in itself.But it is the film of silicone in itself that the use of methane, methyl alcohol or acetylene creates.In air-flow, a small amount of gaseous nitrogen is mingled with the nitrogen part that provides in the film of deposition and adds deposition, improves transmission on glass and reflecting optical characteristics and in response to the N changed ₂amount changes specific refractory power.In air-flow, add Nitrous Oxide add sedimentation rate and improve optical characteristics, but be tending towards reducing film hardness " middle statement.

VII. diamond-like carbon (DLC) coating can be formed as main or unique deposited coatings.This such as can not have oxygen by changing reaction conditions or completing these reaction feed by feeding methyl alcohol, hydrogen and helium to a PECVD process, thus does not have OH part to be formed.Give one example, can by a SiO _xcoating is applied on the inside of a pipe or a syringe cylinder, and an outside DLC coating can be applied on the outside surface of a pipe or syringe cylinder.Or, this SiO _xcan be applied in as a single or multiple lift of an inner tube or syringe cylinder coating with DLC coating.

VII. with reference to Fig. 2, the coating 90 of this barrier coat or other types reduces atmospheric gas enters container 80 transmission by inner surface of container 88.Or the coating 90 of this barrier coat or other types decreases the content of container 80 and the contact of internal surface 88.The coating of this barrier coat or other types can comprise such as SiO _x, amorphous (such as quasi-diamond) carbon or these combination.

VII. any coating described herein may be used for coating surface, such as a frosting.It can by be further used as a blocking layer, be such as used as one antagonism a kind of gas or liquid, preferably to the blocking layer of vapour resistant, oxygen and/or air.If surface is uncoated, it can also be used for stoping or reduce, and the surface of coating may have for the machinery of a kind of compound or composition and/or chemical action.Such as, it can stop or reduce the precipitation of a kind of compound or composition, such as 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, show container as 80 more details.The container 80 shown can be generally tubular, has an opening 82 at an end of container, relative with a closed end 84.This container 80 also has a wall 86, and this wall defines an internal surface 88.An example of container 80 is medical science stopple coupons, as a vacuum test tube, as usual by a bleeder the heparin tube being used in the venipuncture sample of the blood for receiving a patient in medical laboratory that uses.

VII.A.1. this container 80 can be such as made up of thermoplastic material.Some examples of suitable thermoplastic material are polyethylene terephthalate or a kind of polyolefine (as polypropylene) or a kind of cyclopolyolefin multipolymer.

VII.A.1. container 80 can be made up of any applicable method, as passed through injection moulding, by blow molding, by machining, by the method for assembling from blank or be applicable to by other.PECVD can be used for formation one at SiO _xcoating on internal surface.

If be VII.A.1. intended to be used as a vacuum test tube, when be exposed to external pressure 760 hold in the palm or barometric point and other coating processing conditions time, desirably this container 80 can be sufficiently solid to stand one inner vacuum and not being out of shape in fact in fact completely.This characteristic can be provided in a thermoplastic container 80, by providing a container 80 with applicable size and a second-order transition temperature higher than the treatment temp of coating processes be made up of the material being applicable to, a such as cylindrical wall 86, it has and enough is suitable for its diameter and the wall thickness of material.

VII.A.1. medical container or vessel (as sampling tube and syringe) are less and are injection molding and form thicker wall, and this makes them to be evacuated and not crushed by ambient atmosphere pressure.Therefore they than aerated soft drink bottle or other are larger or wall is thinner plastic ware firmer.Owing to being designed to be used as the sampling tube of vacuum vessel by the perfect vacuum typically constructing to stand during preservation, they can be used as vacuum chamber.

VII.A.1. such adaptation (these containers are they self vacuum chambers) may get rid of the necessity being put into by these containers and being used for PECVD process (this carries out typically under very light pressure) in a vacuum chamber.Container can cause treatment time faster (because load at the vacuum chamber of an isolation and be unnecessary from the time that it unloads these parts) as the application of himself vacuum chamber and can cause the equipment configurations that simplifies.In addition, consider and a kind of pan straddle be used for some embodiment, this support by this device of accommodation (for being registered to gas-filled valve and other devices), seal this device (thus can vacuum be produced by being connected to by this pan straddle on a vacuum pump) and between shaping and subsequent processing steps this device mobile.

VII.A.1. the container 80 being used as a vacuum test tube should stand external pressure, simultaneously under inner pumping reduces pressure to one useful for the application of expection, and the air of essence volume or other atmospheric gases is not had to leak in this pipe (as by the closure member that detours) or penetrate through wall 86 within its quality guaranteed period.If just shaping container 80 can not meet this requirement, it can process by applying this internal surface 88 by the coating 90 of a barrier coat or other types.Desirably process and/or apply the internal surface of these devices (as sampling tube and syringe cylinder) to give different characteristics, these characteristics will provide the advantage of the existing glasswork surpassing existing polymer device and/or imitation.Also make us the different qualities desirably measuring these devices before or after process or coating.

VII.A.1.a. from the coating of a kind of organosilicon precursor deposition manufactured by in-situ polymerization organosilicon precursor

Consider a kind of for a slip coating being applied to the method in a kind of substrate (such as the inside of a syringe cylinder), comprise and apply a kind of described precursor to a kind of substrate or near a kind of substrate with the thickness of 1nm to 5000nm or 10nm to 1000nm, optional 10-200nm, optional 20nm to 100nm, and the optionally crosslinked or polymerization by this coating in a PECVD process (or both) to provide a surface of lubricating.The coating applied by this process is considered to new equally.

VII.A.1.a. one kind meets Si _wo _xc _yh _zcoating, wherein w is 1, in this chemical formula x be from about 0.5 to 2.4, y be from about 0.6 to about 3, and z is from 2 to about 9, preferably wherein w to be 1, x be from about 0.5 to 1, y be from about 2 to about 3, and z is from 6 to about 9, is applied by PECVD, has the application as hydrophobic coating further.Whether such coating is considered hydrophobic, do not rely on them and work as slip coating.Compared with corresponding uncoated surface or untreatment surface, if a kind of coating or process reduce a surperficial wet tension, then it is defined as " hydrophobic ".Therefore hydrophobicity is untreated substrate and a kind of function both process.

By changing the formation of a coating, characteristic or deposition method, its a hydrophobicity degree can be changed.Such as, have seldom or there is no the SiOx coating of hydrocarbon composition than have as in specification sheets the Si of substitution value that defines _wo _xc _yh _zcoating is more hydrophilic.Generally speaking, relative to its silicone content, the C-H of coating _x(such as CH, CH ₂or CH ₃) moiety content (or by weight, volume or molar concentration meter) is higher, then this coating is hydrophilic.

A hydrophobic coating can be very thin, and the thickness had is at least 4nm or at least 7nm or at least 10nm or at least 20nm or at least 30nm or at least 40nm or at least 50nm or at least 100nm or at least 150nm or at least 200nm or at least 300nm or at least 400nm or at least 500nm or at least 600nm or at least 700nm or at least 800nm or at least 900nm.This coating can be up to 1000nm or 900nm or at the most 800nm or 700nm or at the most 600nm or 500nm or at the most 400nm or 300nm or at the most 200nm or 100nm or at the most 90nm or 80nm or at the most 70nm or 60nm or at the most 50nm or 40nm or at the most 30nm or 20nm or at the most 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.Clearly consider that specific thickness range is by any one minimum thickness above-mentioned, add the thickness composition of any equal or larger above-mentioned maximum ga(u)ge.

VII.A.1.a. the one application for such hydrophobic coating is that blood collected in a kind of thermoplasticity tube wall (being such as made up of polyethylene terephthalate (PET)) and this pipe is isolated.This hydrophobic coating can be applied in the hydrophilic SiO of on the internal surface of this pipe one _xon coating.This SiO _xcoating adds the barrier properties of this thermoplastic pipe and this hydrophobic coating changes the surface energy of blood contacting surfaces and this tube wall.This hydrophobic coating can by providing a kind of precursor to make, and this precursor is selected from those that identify in this specification sheets.Such as, this hydrophobic coating precursor can comprise hexamethyldisiloxane (HMDSO) or octamethylcyclotetrasiloxane (OMCTS).

VII.A.1.a. another purposes of hydrophobic coating is that preparation glass cell preparation pipe (glasscellpreparationtube) this pipe has wall, the hydrophobic coating in the internal surface of this glass wall that defines an inner chamber, and comprises a kind of Citrate trianion reagent.This hydrophobic coating can by providing a kind of precursor to make, and this precursor is those that be selected from that other places in this manual identify.Another example, this hydrophobic coating precursor can comprise hexamethyldisiloxane (HMDSO) or octamethylcyclotetrasiloxane (OMCTS).Another kind of source material for hydrophobic layer is a kind of alkyl trimethoxysilane with following formula:

R-Si(OCH ₃) ₃

Wherein R is a hydrogen atom or an organic substituent, such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, vinyl, alkynes, epoxide or other.It is also conceivable to the combination of two or more among these.

VII.A.1.a. the combination (using a kind of alkyl trimethoxysilane precursor as above) of acid or base catalysis and heating can by this precursor condensation (removing ROH by product) to form crosslinked polymkeric substance, and it optionally can be cross-linked further by a kind of alternative method.A concrete example is as Shimojimaet.al.J.Mater.Chem., 2007,17,658-663.

VII.A.1.a. at applying SiO _xafter on barrier coat to the internal surface 88 of container 80, a Si can be applied _wo _xc _yh _zcoating as a follow-up coating to provide a lubricated surface, if when particularly at the end of coating processes, this top coat is a kind of liquid silicone siloxane compound.

VII.A.1.a. optionally, at this Si of applying _wo _xc _yh _zafter coating, it can by after fixing after PECVD process.Radiation-curing method can be used, comprise (free radical or positively charged ion), electron beam (E bundle) and the thermopair of UV initiation, as described in the DevelopmentOfNovelCycloaliphaticSiloxanesForThermalandUV-CurableApplications (RubyChakrabortyDissertation, 2008).

VII.A.1.a. for providing the another kind of method of a slip coating to be use a kind of silicone release agent when injection moulding has during thermoplastic container to be lubricated.Such as, it is considered that can use and any cause the releasing agent and recessive monomer (latentmonomer) that form in-situ heat galvanic couple slip coating in moulding process.Or, above-mentioned monomer can be doped in traditional releasing agent to realize identical effect.

VII.A.1.a. a kind of lubricated surface of the internal surface for a syringe cylinder as described further below is considered especially.The internal surface of one of syringe cylinder lubrication can reduce plunger sliding force (be need for advancing a plunger in the operating process of a syringe in this) or this precharging type syringe plunger pushed open intervention lubricant or after adhering on cylinder (such as due to the lubricant breakdown between this plunger and this) start the starting force of a plunger movement.As illustrated in the other places of this specification sheets, a Si _wo _xc _yh _zcoating, wherein w is 1, and in this chemical formula, 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, can also put on the internal surface 88 of container 80 to improve SiO afterwards _xthe bonding of coating.

VII.A.1.a. therefore, coating 90 can comprise a SiO _xlayer and a Si _wo _xc _yh _zlayer, wherein w is 1, and in this chemical formula, x is from about 0.6 to about 3 from about 0.5 to 2.4, y, and z is from 2 to about 9, preferably wherein w to be 1, x be from about 0.5 to 1, 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 layer and the internal surface of this container.Or, this SiO _xlayer can be deposited on Si _wo _xc _yh _zbetween layer and the internal surface of this container.Or, can replace in these two kinds of coating compositions or use three or more layers progressively equally.Can by this SiO _xbe deposited upon Si _wo _xc _yh _znear layer or away from them, wherein there is at least one intervening layer of another kind of material.This SiO _xlayer can be deposited near the internal surface of this container.Or, 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 that this considers, 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, and in this chemical formula, x is from about 0.6 to about 3 from about 0.5 to 2.4, y, and z is from 2 to about 9, preferably wherein w to be 1, x be 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 _xthe layer (wherein there is transition or the interface of intermediate composition between which) of multiple separation or Si _wo _xc _yh _zand SiO _xthe layer (wherein there is the middle different layers of intermediate composition between which) of multiple separation or an individual layer, this individual layer changes continuously or progressively by following: from Si _wo _xc _yh _za kind of composition to similar SiO _xa kind of composition (with conventional direction through this coating).

VII.A.1.a. the gradient in gradient composites can be passed through by either direction.Such as, Si _wo _xc _yh _zcomposition can be applied directly in this substrate and along with apart from SiO _xthe distance on surface crossfades into a kind of composition.Or, SiO _xcomposition 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 composition.If composition coating is for a when adhering to that in this substrate, specific viscosity is attached to better on other layers, special it is considered that a kind of gradient cladding, the composition of this better adhesion in this case can such as be applied directly in this substrate.Institute it is considered that, gradient cladding further from part can be more inconsistent than the neighbouring part of gradient cladding, because this coating characteristically gradually changes at any some place, thus have almost identical formation at the neighbouring part of the almost identical depth of this coating, and substantially the part of the physical sepn to a greater extent at different depths place can have more various characteristic.It is also contemplated that, the coating layer portion forming a better blocking layer (this blocking layer antagonism material transfer to this substrate or from this substrate transfer) can directly against this substrate, with the pollution preventing the coating layer portion of farther end (formed poor blocking layer) to be subject to being intended to the material forbidden by this blocking layer or stop.

VII.A.1.a. this coating (instead of gradient) optionally can have abrupt change transition between a layer and another layer, and does not have substantial formation gradient.Such coating can such as be made by following steps: by providing gas to produce as a kind of layer being in the steady state flow of non-plasma state, is then encouraged to form a coating on this substrate by this system of short duration plasma discharge.If there is a follow-up coating to be applied, then remove the gas being used for coating above and before this plasma body of excitation, be applied for the gas of next coating with steady state way, and in the coating of the surface of this substrate or its foremost, form a different layer again, there is in interface the gradient transition of seldom (if any).

VII.A.1.b. there is the Citrate trianion heparin tube with depositing from the coated wall of the hydrophobic coating of organosilicon precursor

VII.A.1.b. another embodiment is cell product pipe, and this pipe has the wall providing hydrophobic coating on its inner surface, and this pipe contains a kind of sodium citrate aqueous solution reagent.This hydrophobic coating can also put on the hydrophilic SiO be positioned on the internal surface of pipe _xthe top of coating.This SiO _xcoating adds the barrier properties of thermoplastic pipe, and this hydrophobic coating changes the surface energy with the blood contacting surfaces of tube wall.

VII.A.1.b. this wall is made up of thermoplastic material, has the internal surface of a restriction inner chamber.

VII.A.1.b. according to the SiO that the heparin tube of embodiment VII.A.1.b can have on this pipe internal surface _xlayer, applies as illustrated in this manual, to have effect that oxygen stops and to extend quality guaranteed period of vacuum test tube of being made up of thermoplastic material.Then can by the 2nd Si _wo _xc _yh _zlayer is applied on the blocking layer on the internal surface of this pipe to provide a hydrophobic surface, wherein w is 1, in this chemical formula, x is from about 0.5 to 2.4, 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.Compared with the uncoated wall of same type, this coating effectively reduce cross by Trisodium Citrate additive treating and be exposed to the platelet activation of the blood plasma of this internal surface.

VII.A.1.b.PECVD is used for forming coating on an internal surface, has following structure: Si _wo _xc _yh _z.Different from the Citrate trianion heparin tube of routine, there is a Si _wo _xc _yh _zthe heparin tube of hydrophobic layer does not need as routine applying making the surface of pipe have hydrophobicity and smokes a coating on silicone on the wall.

VII.A.1.b. same precursor (such as HMDSO or OMCTS) and different PECVD reaction conditionss can be used to apply this two layers.

VII.A.1.b. then Trisodium Citrate anti-freezing reagent is placed on and vacuumizes in this pipe and by it and carry out sealing with a closure member thus produce a vacuum test tube.Component and the formula of this reagent are known for those of ordinary skills.By aqueous citric acid sodium reagent with the inner chamber effectively suppressing solidify the amount being introduced in the blood in this pipe to be placed in this pipe.

VII.A.1.c.SiO _xdouble-walled plastic container-the COC of blocking layer coating, PET, SiO _xlayer

VII.A.1.c. another embodiment has at least partly around a kind of container of the wall of inner chamber.This wall have by an external polymer layer around an inner polymeric layer.One of these polymer layers are the layers defining thick cyclic olefine copolymer (COC) resin of at least 0.1mm of a water vapor barrier layer.In these polymer layers, another kind is a layer of the vibrin that at least 0.1mm is thick.

VII.A.1.c. this wall comprises the SiO had from about 10 dusts to the thickness of about 500 dusts _xan oxygen barrier layers.

VII.A.1.c. in one embodiment, as show in Figure 36, container 80 can be (being made up of an identical or different materials accordingly) double-walled container with an inwall 408 and an outer wall 410.Can with by the shaping wall of cyclic olefine copolymer (COC) and specific embodiments, wherein a SiO being manufactured this type by a kind of polyester another shaping wall of (such as polyethylene terephthalate (PET)) _xcoating is as previously mentioned in interior surface 412.When needing, a connection coating or layer can be inserted between inner and outer wall to promote the adhesion between them.An advantage of this wall structure the wall with different qualities can be combined thus form a kind of matrix material with the characteristic of the correspondence of each wall.

VII.A.1.c. as an example, inwall 408 can by being coated with a SiO on internal surface 412 _xthe PET on blocking layer makes, and outer wall 410 can be made up of COC.As in this manual as shown in other places, 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.Such as, consider and be configured to Medical vacuum sampling tube by this, this Medical vacuum sampling tube comprises a kind of aqueous reagent namely had during fabrication, and have the substantial quality guaranteed period, therefore it should be had and to prevent from outwards being transmitted by the water vapour of its composite walls during its quality guaranteed period or a kind of blocking layer that oxygen or other gas inwardly transmit.

VII.A.1.c. as another example, inwall 408 can by interior surface 412 being coated with a SiO _xthe COC on blocking layer makes, and outer wall 410 can be made up of PET.Such as, consider to be configured to precharging type syringe by this, a kind of sterile aqueous fluid had when this syringe contains manufacture.This SiO _xblocking layer is entered preventing oxygen in this syringe by its wall.This COC inwall will prevent entering or flowing out of other materials (such as water), therefore prevent the water in sterile aqueous fluid from being leached by the material from wall material and enter in syringe.Also consider that the water that this COC inwall prevents from coming from this sterile aqueous fluid flows out syringe (therefore undesirably concentrating this sterile aqueous fluid), and will having bacterium water or other fluids to be entered by this injector wall and causing these contents to become to have bacterium of syringe exterior be prevented.Also consider that this COC inwall is for reducing the starting force of plunger on the inwall of syringe or frictional force is useful.

VII.A.1.d. double-walled plastic container-COC, PET, SiO is manufactured _xthe method of layer

VII.A.1.d. another embodiment manufactures to have the method for the container of a wall, this wall have by an external polymer layer around an inner polymeric layer, layer is made up of COC and another is made up of polyester.This container is that by COC and polyester resin layer, a kind of method introduced in an injection mold manufactures by comprising by concentric injection nozzle.

VII.A.1.d. an optional other step is, by PECVD, a kind of amorphous carbon coating is put on this container, as a coated inside, an exterior coating or as the interlayer coating of between these layers.

VII.A.1.d. an optional other step is by a SiO _xblocking layer puts on the inside of this wall of container, wherein SiO _xas previously defined.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. optionally, this SiO can be formed by silazane feed gas at least in part _xcoating.

VII.A.1.d. container 80 as shown in Figure 36 can manufacture from inside to outside, such as, by inwall being injected and molded in first mould cavity, then core and shaping inwall are moved to one second, larger mould cavity from this first mould cavity, then in this second mould cavity on inwall injection moulding outer wall.Optionally, by outer wall Overmolded to articulamentum before, an articulamentum can be provided on the outside surface of this shaping inwall.

VII.A.1.d. or, container 80 shown in Figure 36 can manufacture from outside to inside, such as, by first core is inserted in mould cavity, injection moulding outer wall in this mould cavity, then this first core removed from this shaping first wall and insert one second, less core, being then still present in injection moulding inwall on the outer wall in this mould cavity.Optionally, by Overmolded for this inwall to articulamentum before, an articulamentum can be provided on the internal surface of this shaping outer wall.

VII.A.1.d. or, container 80 as shown in Figure 36 can manufacture in a double-color mold.Such as, this can by being used for the material of inwall and being used for the material of outer wall from concentric external nozzles injection moulding and having come from inwardly projecting orifice injection moulding.Optionally, can from one the 3rd that is disposed between this inwardly projecting orifice and external nozzles, concentric nozzle provides an articulamentum.These nozzles can feed corresponding wall material simultaneously.Useful stopgap measure be by inwardly projecting orifice feeding inner-wall material slightly before start to feed outer wall materials by external nozzles.If there is the concentric nozzle of a centre, the order of flowing from external nozzles, and can continue from this intermediate noxzzle and then from this inwardly projecting orifice according to priority.Or the order starting charging from inwardly projecting orifice, and outwards can be run in reverse order compared with previously described.

VII.A.1.T. the barrier coat be made up of glass

VII.A.1.e. another embodiment is the container comprising a wall of container, a barrier coat and a closure member.This container is roughly tubulose and is made up of thermoplastic material.。This container has an opening and at least partly by the inner chamber that a wall limits, this wall has an internal surface of demarcating with this inner chamber.The internal surface of this wall exists be made up of glass one continuous print barrier coat at least substantially.A closure member covers this opening and is isolated from ambient air by the inner chamber of this container.

VII.A.1.e. container 80 can also be such as made up of the glass (such as soda-lime glass, borosilicate glass or other glass preparations) of any type for medical science or laboratory applications.Also contemplate and other containers with any proterties or size be made up of any material are used in system 20.An effect of coating glass containers can be reduce ion in glass or wittingly or enter into the content (reagent of such as vacuum test tube or blood) of this container as impurity (such as, sodium, calcium or other materials) from this glass.Another effect of all or part of (such as optionally in the surface contacted with sliding relation relative to other parts) coating glass containers provides oilness (such as, for being easy to insert or take out stopper or make a sliding members such as plunger pass through in syringe) to coating.The Another reason again of coating glass containers is the increase of the solidification rate of the blood preventing the sample of the reagent of container or expection (such as blood) to adhere on wall of a container or contact with this wall of a container.

VII.A.1.e.i. relevant embodiment is a kind of container as in the previous paragraph, and wherein this barrier coat is made up of the glass of soda-lime glass, borosilicate glass or another kind of type.

VII.A.2. stopper

VII.A.2. Figure 23-25 describes container 268, and it can be a kind of heparin tube of finding time, and has closure member 270 and isolates to make inner chamber 274 and surrounding environment.Closure member 270 comprise one be exposed to the inner chamber 274 of 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 the embodiment shown in the drawing, closure member 270 is the assemblies with stopper 282 and shield [support 284.

VII.A.2.a. the method for slip coating to the stopper in vacuum chamber is applied

VII.A.2.a. another embodiment is in the upper method applying coating of elastomeric stopper (such as 282).The stopper 282 be separated with container 268 is placed in the room of substantially finding time.The reaction mixture provided comprises the gas forming plasma body, i.e. organic silicon compound gas, optionally oxidizing gas and optionally appropriate hydrocarbon gas.Form plasma body in the reactive mixture, by this plasma body and plug contacts.A deposition Si on stopper at least partially _wo _xc _yh _zcoating, wherein w is 1, and in this chemical formula, x is from about 0.6 to about 3 from about 0.5 to 2.4, y, and z is from 2 to about 9, preferably wherein w to be 1, x be from about 0.5 to 1, y is from about 2 to about 3, and z is from 6 to about 9.

VII.A.2.a. in the embodiment shown in the drawing, the wall surface in contact 276 of closure member 270 is applied with slip coating 286.

VII.A.2.a. in some embodiments, this Si _wo _xc _yh _zcoating effectively penetrates container intracavity with the component (the metal ion component of such as this stopper) or the component of this wall of container that reduce one or more these stoppers.The elastic composition manufacturing some useful type of stopper 282 is contained to one or more metal ions of trace.These ions sometimes can not migrate in inner chamber 274 or become and contact with container contents with the amount of reality, if particularly sampling receptacle 268 is used to collect the sample for trace metal analysis.Consider that such as these coatings contain less organic composition, namely wherein y and z is very low or be zero, is useful especially so in this application as metal ion barrier.Silica is taken as metal ion barrier, see such as AnupamaMallikarjunan, JasbirJuneja, GuangrongYang, ShyamP.Murarka, andTon-MingLu, TheEffectoflnterfacialChemistryonMetalIonPenetrationinto PolymericFilms, Mat.Res.Soc.Symp.Proc, Vol.734, pp.B9.60.1toB9.60.6 (MaterialsResearchSociety, 2003); United States Patent (USP) 5578103 and 6200658 and European application EP0697378A2, be combined in this in full by it by reference.But, consider and have more elastic coating and for adhering to this coating to the surface of elastomer of stopper 282, some organic compositions can be useful for providing.

VII.A.2.a. in some embodiments, this Si _wo _xc _yh _zcoating can be the matrix material of the material with the first layer and the second layer, wherein first or internal layer 288 connect with elastomeric stopper 282, and one or more components effectively reducing stopper 282 penetrate container intracavity.The second layer 286 can connect with the inwall 280 of container and for be positioned at when stopper 282 on container 268 or among time, effectively reduce the friction between stopper 282 and the inwall 280 of container.In the other places of this specification sheets, this matrix material is described to relevant with syringe coating.

VII.A.2.a. or, limit the first layer and the second layer 288 and 286 by the coating with gradient characteristics, wherein in the first layer, the value of y and z is greater than value in the second layer.

VII.A.2.a. Si can be applied _wo _xc _yh _zcoating, such as, by basic PECVD as above.This Si _wo _xc _yh _zcoating can such as 0.5 and 5000nm (5 to 50,000 dust) thick between, or 1 and 5000nm thick between, or 5 and 5000nm thick between, or 10 and 5000nm thick between, or 20 and 5000nm thick between, or 50 and 5000nm thick between, or 100 and 5000nm thick between, or 200 and 5000nm thick between, or 500 and 5000nm thick between, or 1000 and 5000nm thick between, or 2000 and 5000nm thick between, or 3000 and 5000nm thick between, or 4000 and 10,000nm thick between.

VII.A.2.a., compared with the organo-silicic oil applied with the Typical spray of thicker (thick a micron or more) far away, the oilness layer for plasma coated considers some advantage.With spray or silicone resin that micron applies compared with, plasma coating has the lower migration potentiality moved in blood far away, and this is all because the amount of plasma coated material is less far away and because it can be applied to coated surface and more closely better in conjunction with in place.

VII.A.2.a. consider compared with micron coating, for the slip of the stream of adjacently situated surfaces or adjacent fluid, the nano coating as applied by PECVD provides lower resistance, because plasma coating tends to provide more level and smooth surface.

VII.A.2.a. still another embodiment applies Si in elastomeric stopper _wo _xc _yh _zthe method of coating.Such as this stopper may be used for closed said vesse.The method comprises some parts.Stopper is placed in the room of substantially finding time.There is provided the reaction mixture comprising the gas forming plasma body, i.e. a kind of organic silicon compound gas, optionally a kind of oxidizing gas and optionally a kind of appropriate hydrocarbon gas.Form plasma body in the reactive mixture.Stopper contacts with reaction mixture, and stopper at least partially deposits Si _wo _xc _yh _zcoating.

VII.A.2.a. putting into practice in this method, in order to obtain y and z of much higher value, considering that reaction mixture can comprise appropriate hydrocarbon gas, further describing as above and following.Optionally, if consider reduce the value of y and z or improve the value of x, so reaction mixture can contain aerobic.Or particularly in order to reduce oxidation and increase the value of y and z, reaction mixture can substantially containing oxidizing gas.

VII.A.2.a. putting into practice this method to apply in some embodiment (such as stopper 282) of stopper, considering and must not spray reaction mixture in the depression of stopper.Such as, the wall of stopper 282 contacts and is protruding substantially towards interior surface 276 and 272, and therefore easy by batch process process, wherein can locate in the single reaction chamber of substantially finding time and process a large amount of stopper (such as 282).Further contemplate in some embodiments, coating 286 and 288 does not need to show as the barrier for oxygen difficulty the same as the barrier coat on the internal surface 280 of container 268 for water, because the material of stopper 282 can play this function to a great extent.

VII.A.2.a. a lot of changes of stopper and stopper coating method are considered.Stopper 282 can with Plasma contact.Or plasma body can be formed in the upstream of stopper 282, production plasma products, and plasma products can contact with stopper 282.Can by forming plasma body with electromagnetic energy and/or micro-wave energy provocative reaction mixture.

VII.A.2.a. the change of reaction mixture is considered.The gas forming plasma body can comprise a kind of rare gas element.Such as, this rare gas element other gases that can be argon or helium or describe in this disclosure.Any other silicoorganic compound that organic silicon compound gas can be or comprise HMDSO, OMCTS, mentions in this disclosure, or the combination of two or more in these.Oxidizing gas can be other gases of mentioning in oxygen or this disclosure or the combination of two or more in these.Such as appropriate hydrocarbon gas can be methane, methyl alcohol, ethane, ethene, ethanol, propane, propylene, propyl alcohol, acetylene or the combination of two or more in these.

VII.A.2.b. on stopper, III or IV race element and carbon coating is applied by PECVD

VII.A.2.b. another embodiment is a kind of method applying composition coating in elastomeric stopper, and said composition comprises carbon and one or more III or IV race element.In order to carry out the method, a stopper is positioned in a sediment chamber.

VII.A.2.b. in sediment chamber, provide a kind of reaction mixture, comprise the gas of formation plasma body of gaseous source with iii group element, IV race element or the combination of two or more in these.Reaction mixture is optionally containing a kind of oxidizing gas and optionally containing the gaseous compound with one or more c h bond.Form plasma body in the reactive mixture, and stopper contacts with reaction mixture.By an iii group element or compound, IV race element or compound or the painting of the combination of two or more in these be deposited upon at least partially on stopper.

VII.A.3. there are the stopper plastic containers effectively providing 95% vacuum to keep the barrier coat of 24 months

VII.A.3. another embodiment is a container, comprises container, barrier coat and closure member.This container is generally tubulose and is made up of thermoplastic material.This container has mouth and is subject to the inner chamber of wall restriction at least partly.This wall has an internal surface connected with inner chamber.The internal surface of this wall applies the barrier coat of an at least basic continous.This barrier coat is effectively to provide basic quality guaranteed period.Provide the closure member of covering container mouth, and the inner chamber of container and ambient air are isolated.

VII.A.3. with reference to figure 23-25, container 268 (such as a kind of heparin tube of finding time or other containers) is shown.

VII.A.3. in this embodiment, this container is generally a tubular vessel, has at least barrier coat of basic continous and a closure member.This container is made up of thermoplastic material, and the inner chamber having mouth and limited by wall, this wall has the internal surface connected with inner chamber.This barrier coat is deposited on the internal surface of this wall, and effectively keeps the initial vacuum level of the container of at least 95% or at least 90% to continue at least 24 months, quality guaranteed period of optionally at least 30 months, optionally at least 36 months.The mouth of this closure member covering container and the inner chamber of container and ambient air are isolated.

VII.A.3. provide this closure member, the closure member 270 such as illustrated in these figures or the closure member of another type with 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 based at U.S. Patent number 6,602, the figure set 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 contacted with the internal surface 278 of wall of container 280.In the embodiment shown in the drawing, closure member 270 is the assemblies with stopper 282 and shield [support 284.

VII.A.3. in the embodiment shown in the drawing, stopper 282 defines wall surface in contact 276 and internal surface 278, this shield [support major part or complete outside the container 268 of stopper simultaneously, retain and provide the handle for stopper 282, and in mobile closure member 270, people is prevented to be exposed to any content of releasing from container 268 (such as when opening container 268 and air pours or goes out with equilibrium pressure difference, because the external and internal pressure of container 268 is poor).

VII.A.3. further contemplate, the wall surface in contact 276 of these coatings on wall of container 280 and stopper can be incorporated into.This stopper can be applied with oilness silicone layer, and can with harder SiO _xlayer or with SiO below _xlayer and oilness overcoat apply the wall of container 280 be such as made up of PET or glass.

VII.B. syringe

VII.B. the description before has solved on the pipe that to be applied to by a kind of barrier coat and to have a closed permanent end largely, such as a heparin tube or, more generally, a sample reception pipe 80.This device is not limited to so a kind of device.

VII.B. another example (as shown in Figure 20-22) of the container be applicable to is a syringe cylinder 250 for injector for medical purpose 252.This kind of syringe 252 is equipped with pre-filled salt brine solution, a kind of pharmaceutical preparation or analogue in medical technology sometimes.Also contemplate precharging type syringe 252 from the SiO of internal surface 254 _xbenefit in the coating of barrier coat or other types, do not contact with the plastics (syringe cylinder 250 such as between the shelf lives) of this syringe to keep the content of this precharging type syringe 252.The coating of this barrier coat or other types can be used avoid in the content component of these plastics being leached into this by internal surface 254.

VII.B. if usually shaping syringe cylinder 250 is in the rear end 256 for receiving plunger 258 with for both the front ends 260 receiving hypodermic needle, a nozzle or for the content of dispense syringe 252 or can be open for material is received the tubing place entered in syringe 252.But front end 260 optionally can add cap and plunger 258 optionally can assemble in position before use precharging type syringe 252, is closed by cylinder 250 two ends.Or for process syringe cylinder 250 or assembling syringe object or in order to remain on appropriate location between the shelf lives of precharging type syringe 252, a cap 262 can be installed, until cap 262 removed and a hypodermic needle or other delivery catheters to be arranged on front end 260 to prepare use syringe 252 by (optionally) time till.

VII.B.1. assembly

VII.B.1. Figure 42 also show available syringe cylinder as an alternative structure, such as by Figure 21,26,28,30 with 34 embodiment and being adjusted to use together with the pan straddle 450 of those figure.

VII.B.1. Figure 50 is syringe decomposition view and Figure 51 is the view of the assembling of syringe.Can with container process and Fig. 1-2 2,26-28,33-35,37-39,44 and this syringe cylinder of inspection units process of 53-54.

A closed end container in the device described before VII.B.1. mounting cover 262 makes cylinder 250 become, this closed end container can be provided SiO on its internal surface 254 _xthe coating of stop or other types, also optionally provides coating on the inside 264 of lid, and the interface of bridge joint between the inside 264 and the front end 260 of cylinder of lid.Show the suitable device being adjusted to this purposes, such as in figure 21, the similar Fig. 2 of Figure 21, adds a cover syringe cylinder 250 except alternate figures 2VII.B for container 80.

VII.B.1 Figure 52 is the view being similar to Figure 42, but shows processed syringe cylinder and do not have flange or finger stop 440.Have Fig. 1-19,27,33,35, the container process of 44-51 and 53-54 and inspection units, this syringe cylinder is available.

VII.B.1.a. there is the syringe of the cylinder applied from the slip coating of organosilicon precursor by deposition

VII.B.1.a. still another embodiment has SiwO _xc _yh _zslip coating meets the container of the type made by the following method.

VII.B.1.a. a kind of precursor is as defined above provided

VII.B.1.a. under the condition effectively forming a kind of coating, this precursor is applied in a kind of substrate.By this coated polymeric or crosslinked (or both), thus form a kind of surface of lubrication, compared to the surface of untreated this lubrication of substrate, there is lower plunger sliding force or starting force.

VII.B.1.a. about any one and subdivision in example VII, this applying step is carried out optionally by being provided to by this front evacuator body and by it near this substrate.

VII.B.1.a. about any embodiment VII.A.1.a.i, near substrate, optionally form a kind of plasma body, optionally form a kind of non-hollow cathode plasma.Optionally, under the condition of basic anoxic, this precursor is provided.Optionally, under the condition of basic shortage vector gas, this precursor is provided.Optionally, under the condition of basic shortage nitrogen, this precursor is provided.Optionally, under the absolute pressure being less than 1 holder, this precursor is provided.Optionally, provide near this precursor to plasma emission.Optionally, or 10 to 1000nm thick or 10-200nm thick or 20 to 100nm thick thickness thick with 1 to 5000nm, applies its reaction product of this precursor to substrate.Optionally, substrate comprises glass.Optionally, substrate comprises a kind of polymkeric substance, optionally a kind of carbonate polymer, optionally a kind of olefin polymer, optionally a kind of cyclic olefine copolymer, optionally a kind of polyacrylic polymer, optionally a kind of polyester polymers, optionally a kind of polyethylene terephthalate polymer.

Optionally, plasma body is produced by the gaseous reactant containing precursor with the electrode excitation of energy supply, such as by the RF frequency be defined as above, such as with from 10kHz to the frequency being less than 300MHz, more preferably with the frequency from 1 to 50MHz, even more preferably with the frequency of 10 to 15MHz, most preferably with the frequency of 13.66MHz.

Optionally, by with provide 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 the electrode excitation of the power of 7 to 11W, particularly 8W contain precursor gaseous reactant produce plasma body.The ratio of this electrode power and volume of plasma can be less than 10W/ml, preferably from 5W/ml to 0.1W/ml, more preferably from 4W/ml to 0.1W/ml, is most preferably from 2W/ml to 0.2W/ml.These power levels are applicable to applying slip coating to syringe and stopple coupon and the container meeting the similar geometric with 1 to 3mL void volume, produces PECVD plasma body wherein.For greater or lesser object institute it is considered that, this process should be determined in proportion according to the size of this substrate, correspondingly increase or reduce the power that applies.

Another embodiment of VII.B.1.a is the slip coating on syringe cylinder inwall.This coating produces the PECVD method from using following material and condition.A kind of cyclic precursor of preferred employing, is selected from monocycle siloxanes, many cyclosiloxane or these the combination of two or more, as this slip coating other places in the description limit.The example of a suitable cyclic precursor comprises octamethylcyclotetrasiloxane (OMCTS), optionally mixes with other precursor materials in any ratio.Optionally, this cyclic precursor is made up of octamethylcyclotetrasiloxane (OMCTS) substantially, mean that namely other precursors by basic the existing with the amount of the characteristic of novelty of slip coating not changing generation, can which reduce plunger sliding force or the starting force on the surface of coating.

VII.B.1.a does not add oxygen to this process at least substantially.The oxygen in some remaining air can be there is in this syringe cylinder, and in former step charging and the remaining oxygen do not exhausted completely may reside in this syringe cylinder, this is defined as substantially there is not oxygen at this.If do not add oxygen to this process, this is also in the scope of " substantially not having oxygen ".

The plasma generation power that VII.B.1.a input is sufficient, any power level that is that such as provide the one or more operational instances being successfully used to this specification sheets or that describe in this manual is to impel coating formation.

VII.B.1.a relative to uncoated syringe cylinder, the material of employing and condition be effectively be reduced by the syringe plunger sliding force of this syringe cylinder movement or starting force at least 25%, alternately at least 45%, alternately at least 60%, be alternately greater than 60%.The scope considering to reduce plunger sliding force or starting force be from 20% to 95%, alternately from 30% to 80%, alternately from 40% to 75%, alternately from 60% as 70%.

VII.B.1.a. another embodiment is the container on the inwall with following structure with hydrophobic coating: Si _wo _xc _yh _z, wherein w, x, y and z were as defined in the past.As for have analogous composition slip coating explained manufacture this coating, but under effectively being formed, than untreated substrate, there is the condition of the hydrophobic surface of higher contact angle.

VII.B.1.a. about any embodiment VII.A.1.a.ii, this substrate optionally comprises glass or a kind of polymkeric substance.This glass is optionally borosilicate glass.This polymkeric substance is optionally a kind of carbonate polymer, optionally a kind of olefin polymer, optionally a kind of cyclic olefine copolymer, optionally a kind of polyacrylic polymer, optionally a kind of polyester polymers, optionally a kind of polyethylene terephthalate polymer.

VII.B.1.a. another embodiment is the syringe comprising a plunger, a syringe cylinder and a lubricant film.This syringe cylinder comprises the plunger internal surface received for sliding.This lubricant film is arranged on the internal surface of syringe cylinder, and comprises a kind of Si _wo _xc _yh _zlubricant film coating.This lubricant film is that to be less than 1000nm thick and effectively reduce for the necessary starting force of mobile plunger in cylinder or plunger sliding force.Reduce plunger sliding force be alternately expressed as the coefficient of sliding friction of the plunger be reduced in cylinder or reduce plunger force, these terms are regarded as having 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 receiving plunger 546 slidably.The internal surface 552 of syringe cylinder 548 comprises Si further _wo _xc _yh _zslip coating 554.This lubricant film be less than 1000nm thick, be optionally less than 500nm thick, be optionally less than 200nm thick, be optionally less than that 100nm is thick, to be optionally less than 50nm thick, and for the necessary starting force of adhesion reduced for overcoming plunger after storage or after plunger departs from cylinder its necessary plunger sliding force mobile be effective.The feature of this lubricant film is to have less plunger sliding force or starting force compared with uncoated surface.

VII.B.1.a. can individually or use any one in the precursor of above any type to provide a slip coating with the combination of two or more among them.

VII.B.1.a. except utilizing vacuum technology, can also use low-temperature atmosphere-pressure (antivacuum) plasma process preferably in nonoxidizing atmosphere (such as helium or argon) by precursor monomer delivery of vapor come inducing molecule ionization and deposition.Dividually, hot CVD (being deposited by fast pyrogenation) can be considered.

VII.B.1.a. aforesaid method is similar to vacuum PECVD, is that surface-coated and cross-linking mechanism can occur simultaneously.

VII.B.1.a. another stopgap measure again considered for any one described herein or multiple coating is by the coating be applied to unevenly on whole inner 88 of container.Such as, be positioned at closing end 84 this internal tank hemisphere portion compared with, one different or other coating optionally can be applied on the barrel portion of this internal tank, or vice versa.This stopgap measure is considered especially for syringe cylinder as described below or sampling tube, wherein lubricated surface can be provided to this barrel portion part or all of on, this plunger or piston or closure member can slide (but not being elsewhere) herein.

VII.B.1.a. optionally, can exist oxygen, substantially do not exist oxygen or there is not oxygen condition under, exist nitrogen, substantially do not exist nitrogen or there is not nitrogen condition under, or exist vector gas, substantially do not exist vector gas or there is not vector gas condition under this precursor is provided.In an embodiment considered, this precursor to be delivered to individually in this substrate and to stand PECVD to apply and solidify this coating.

VII.B.1.a. optionally, this precursor can be provided under the absolute pressure being less than 1Torr.

VII.B.1.a. optionally, this precursor can be provided near this plasma emission.

VII.B.1.a. optionally, its reaction product of this precursor can be applied to substrate by the thickness of 1 to 5000nm or 10 to 1000nm or 10-200nm or 20-100nm.

VII.B.1.a. in any above-mentioned embodiment, this substrate can comprise glass or a kind of polymkeric substance, one or more of polymkeric substance such as carbonate polymer, polyolefin polymer (such as a kind of cyclic olefine copolymer or a kind of polyacrylic polymer) or polyester polymers (such as, a kind of polyethylene terephthalate polymer).

VII.B.1.a., in any above-mentioned embodiment, produce plasma body by the gaseous reactant containing this precursor with electrode excitation, this electrode with as in this specification sheets the RF frequency that defines carry out energy supply.

VII.B.1.a. in any above-mentioned embodiment, produce plasma body by the gaseous reactant containing this precursor with electrode excitation, this electrode is provided with enough electric power for generation of lubricant film.Optionally, produce plasma body by the gaseous reactant containing this precursor with electrode excitation, this electrode provide 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 the electric power of 7 to 11W, particularly 8W.The ratio of this electrode power and volume of plasma can be less than 10W/ml, and preferably from 5W/ml to 0.1W/ml, being more preferably from 4W/ml to 0.1W/ml, is most preferably from 2W/ml to 0.2W/ml.These power levels are suitable for for applying slip coating to the syringe of the void volume had in 1 to 3mL (wherein creating PECVD plasma body) and stopple coupon and the container with similar geometric.For larger or less object institute it is considered that, this process should be determined in proportion according to the size of this substrate, correspondingly increase or reduce the power that applies.

VII.B.1.a. this coating can be cured, and as by being polymerized or crosslinked (or both) this coating, thus forming a kind of surface of lubrication, having lower plunger sliding force or starting force compared to the surface of untreated this lubrication of substrate.Solidification can occur in this applying process (as PECVD) period, maybe can be undertaken by separating process or complete at least partly.

Although VII.B.1.a. plasma-depositedly prove coating feature being employed herein, alternative deposition method can be used, as long as a kind of solid film is still adhered in this base substrate by retaining as much as possible by the chemical component of parent material simultaneously.

VII.B.1.a. such as, this coating or substrate be impregnated in this coated material and be applied to this syringe cylinder by this coated material (from liquid condition) can be formed, wherein this coating or pure precursor or be a kind of precursor (allowing the mechanical deposit compared with shallow layer) of solvent cut by spraying.Heat energy, UV energy, electron beam energy, plasma physical efficiency or these any combination optionally can be used to carry out this coating crosslinked

VII.B.1.a. also contemplate and silicone precursor as above is applied on a surface, then carry out an independent curing schedule.Apply and solidification condition can be similar to for precoating Polyfluoroalkyl ether atmospheric plasma solidification use those (at trade mark a kind of technique of lower implementation).The more details of this technique can find at http://www.triboglide.com/process.htm.

VII.B.1.a., in so a kind of technique, the region of part to be coated is had optionally can to carry out pre-treatment with atmospheric plasma.This pre-treatment is cleaned and be have activated this surface, makes it be easy to accept for the lubricant sprayed in next step like this.

VII.B.1.a. then this lubricating fluid (being the precursor of one of above multiple precursor or a kind of polymerization in this case) is sprayed on pending surface.Such as, the accurate distribution technique of IVEK can be used to be atomized this fluid exactly and to produce uniform coating.

VII.B.1.a. and then use atmospheric plasma field by this coating combine or be linked on these parts.Both secures coating and improves lubricity.

VII.B.1.a. optionally, can produce this atmospheric plasma in this embodiment from ambient air, in this case, gas feed and vacuum means are standby is unwanted.But preferably, when producing plasma body, this container is closed to be minimized by power demand and to prevent the surface of plasma body and this external container or material from contacting at least substantially.

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 comprising a cylinder, and this defines an inner chamber and has the interior surface that receives a plunger slidably, namely receives the plunger be used for this interior surface sliding contact.

VII.B.1.a.i. this syringe cylinder is made up of thermoplastic base material.

VII.B.1.a.i. optionally, this interior surface be coated with as in this manual elsewhere as described in a SiO _xblocking layer.

VII.B.1.a.i. a lubricant film is applied on this interior surface, this plunger (or both), or is applied to the SiO applied above _xon blocking layer.As in embodiment VII.B.1.a or in this manual elsewhere propose can provide, apply and solidify this lubricant film or coating.

VII.B.1.a.i. such as, this lubricant film can be applied by PECVD in any one embodiment.This lubricant film deposits from a kind of organosilicon precursor, and is that to be less than 1000nm thick.

VII.B.1.a.i. on this lubricant film, surface treatment is carried out effectively to reduce this lubricant film, the leaching of this thermoplastic base material (or both) or an amount of extractable content.Therefore a kind of solute restraining mass (soluteretainer) can be served as in the surface of this process.This surface treatment can cause a skin coat, such as, be less than 1nm thick and be less than that 100nm is thick or to be less than 50nm thick or be less than that 40nm is thick or to be less than 30nm thick or be less than that 20nm is thick or to be less than 10nm thick or be less than that 5nm is thick or to be less than 3nm thick or be less than that 2nm is thick or to be less than 1nm thick or be less than a thick skin coat of 0.5nm.

As used herein, " leaching " refer to that material is transferred out of and enters in the content of container (such as syringe) from substrate (such as wall of container).Normally, can be measured by following steps by extract: by be filled with expection content container store, then these contents are analyzed thus define what material by leached into from this wall of container these expection contents in." extraction " refers to and to be shifted out from substrate by material, to determine having what material can be entered into Extraction medium by shifting out from this substrate under test conditions by introducing a kind of solvent different from the expection content of this container or dispersion medium.

VII.B.1.a.i. surface treatment causes a kind of solute restraining mass, can be optionally a SiO _xor Si _wo _xc _yh _zlayer, respectively defined freely above in the description.In one embodiment, SiO can be passed through _xor Si _wo _xc _yh _zpECVD deposition apply surface treatment.Optionally, can use and apply this surface treatment than for generation of the higher power of this lubricant film or stronger oxidizing condition (or both), because herein is provided a kind of harder, thinner, continuous print solute restraining mass 539.In slip coating surface treatment can be less than 100nm deeply, be optionally less than 50nm deeply, be optionally less than 40nm deeply, be optionally less than 30nm deeply, be optionally less than 20nm deeply, be optionally less than 10nm deeply, be optionally less than 5nm deeply, be optionally less than 3nm deeply, be optionally less than 1nm deeply, be optionally less than 0.5nm deeply, optionally between 0.1 to 50nm is dark.

VII.B.1.a.i. this solute restraining mass is considered provides low solute leaching performance to lubricant film below and other layers (comprising this substrate (as required)).This restraining mass by only it is desirable that a kind of for large solute molecule and oligopolymer (such as, siloxanyl monomers such as HMDSO, OMCTS, they fragment and from the derivative movable oligopolymer of lubricant, such as a kind of " can extract restraining mass ") a kind of solute restraining mass instead of a kind of gas (O ₂/ N ₂/ CO ₂/ water vapour) blocking layer.But a kind of solute restraining mass can also be a kind of barrier layer for gases (such as, according to SiOx coating of the present invention).People can by vacuum or based on the PECVD process of normal pressure produce a kind of well there is no a capacity for air resistance can extract restraining mass.Make us should " can extract restraining mass " will being desirably enough thin, namely when syringe plunger moves, this plunger will easily penetrate this " solute restraining mass ", the stopper head of slip be exposed to regard to lubricant film below thus form a surface of lubricating, compared to the surface of untreated this lubrication of substrate, there is lower plunger sliding force or starting force.

VII.B.1.a.i. in another embodiment, this surface treatment can be carried out by the surface (oxygen as by being exposed on this surface in plasma environment) being oxidized the lubricant film applied above.The plasma environment described in this specification sheets can be used to form SiO _xcoating.Or, atmospheric plasma concrete conditions in the establishment of a specific crime can be applied in oxygen-enriched environment.

VII.B.1.a.i. but, optionally can solidify formed lubricant film and solute restraining mass simultaneously.In another embodiment, this lubricant film can be solidified, is optionally solidified completely at least partly, after this, can provide, applies surface treatment and can solidify this solute restraining mass.

VII.B.1.a.i. lubricant film and solute restraining mass are configured and effectively to provide starting force, the relative quantity of plunger sliding force or both (this power is less than and is lacking under lubricant film and surface treatment required corresponding power) and existing.In other words, the thickness of this solute restraining mass and form and be such thus decrease material and leach into the content of syringe from lubricant film, allows lubricant film below to lubricate this plunger simultaneously.It is considered that this solute restraining mass will be easy to depart from and be enough thin to such an extent as to this lubricant film will still work to lubricate this plunger when it being moved.

VII.B.1.a.i., in an embodiment considered, swabbing and surface treatment can be applied on tube inner surface.In the embodiment that another is considered, swabbing and surface treatment can be applied on plunger.In embodiment of another consideration again, swabbing and surface treatment can be applied on tube inner surface and plunger.In these embodiments any, the optional SiO on the inside of this syringe cylinder _xblocking layer can be exist or lack.

VII.B.1.a.i. a considered embodiment is a multilayer (the such as 3 layers) configuration be applied on the internal surface of syringe cylinder.。Layer 1 can be the SiO be made up of the PECVD of HMDSO, OMCTS (or both) under oxidizing atmosphere _xbarrier layer for gases.As described in this description, such as so a kind of atmosphere can be provided by HMDSO and oxygen being fed in a PECVD coating unit.Layer 2 can be a kind of lubricant film using the OMCTS put in nonoxidizing atmosphere.As described in this description, such as so a kind of nonoxidizing atmosphere (optionally substantially or completely lacking oxygen) can be provided by being fed into by OMCTS in a PECVD coating unit.OMCTS and/or HMDSO can be used to use higher power and oxygen, and by a process, (this process forms a thin SiO _xor SiwO _xc _yh _zepidermal area, as solute restraining mass) form solute restraining mass subsequently.

VII.B.1.a.i. some in these laminated coatings is considered has one or more following optional advantage at least to a certain extent.They can solve the organosilyl difficulty of reported process, because this solute restraining mass can restricted internal silicone and prevent it from moving in the content of syringe or other places, which results in less silicone particles and less interactional chance between slip coating and the content of syringe in the content sent of syringe.They can also solve lubricant film or coating moves the problem left from oiling point, improve the oilness at the interface between syringe cylinder and plunger.Such as, breakaway force (break-freeforce) can be reduced, the towing force (drag) on mobile plunger can be reduced, or optionally both.

VII.B.1.a.i. institute is it is considered that when solute restraining mass is destroyed, and this solute restraining mass will continue to adhere on this slip coating and syringe cylinder, and this can forbid any particle entrainment in the content sent of this syringe.

VII.B.1.a.i. in these coatings certain some also will provide manufacture advantage, if when this barrier coat, slip coating and surface treatment are applied in same device (such as described PECVD device) especially.Optionally, this SiO _xbarrier coat, slip coating and surface treatment can be applied in a PECVD device, therefore significantly reduce required treatment capacity.

Form this barrier coat, slip coating and solute restraining mass can obtain further advantage by using identical precursor and changing this technique.Such as, a SiO can be applied by following steps _xbarrier layer for gases: at superpower/high O ₂using a kind of OMCTS precursor under condition, then by using a kind of OMCTS precursor in low power and/or substantially or completely lacking an applying lubricant film under oxygen, finally using a kind of OMCTS precursor to carry out surface treatment under middle power and oxygen.

VII.B.1.b has SiO _xthe syringe of the cylinder of the outside of the inside of coating and blocking layer coating

VII.B.1.b. shown in Figure 50, still another embodiment is the syringe 544 comprising plunger 546, cylinder 548 and inside and outside barrier coat 554 and 602.Cylinder 548 can be made up of thermoplastic based material and limit an inner chamber 604.Cylinder 548 can have the internal surface 552 and outside surface 606 that receive plunger 546 slidably.Can by a kind of SiO _xbarrier coat 554 be provided on the internal surface 552 of cylinder 548, wherein x is from 1.5 to about 2.9.A kind of barrier coat 602 of resin can be provided on the outside surface 606 of cylinder 548.

VII.B.1.b. in any embodiment, this thermoplastic base material typically can comprise a kind of polyolefines if polypropylene or a kind of cyclic olefine copolymer are (such as at trade mark the material of lower sale), a kind of polyester (such as polyethylene terephthalate), a kind of polycarbonate (such as a kind of bisphenol-a polycarbonate thermoplastics) or other materials.Consider matrix material syringe cylinder, they have any one in these materials as the identical or different one in outer and these materials as internal layer.Any combination of materials of matrix material syringe cylinder in this manual described in other places or stopple coupon can also be used.

VII.B.1.b. in any embodiment, this resin optionally can comprise the polyvinylidene dichloride being in homopolymer or multipolymer form.Such as, United States Patent (USP) 6 can be adopted, 165, the PvDC homopolymer (popular name: saran) described in 566 (being combined in this by reference) or multipolymer.This resin optionally can be applied on this outer surface with the form of latex or other dispersions.

VII.B.1.b. in any embodiment, this syringe cylinder 548 optionally can comprise a slip coating, and this slip coating is placed in this plunger and SiO _xbarrier coat between.Other places describe suitable slip coating in this manual.

VII.B.1.b. in any embodiment, this slip coating preferably can be applied by PECVD, and optionally can comprise and have composition Si _wo _xc _yh _zmaterial.

VII.B.1.b. in any embodiment, this syringe cylinder 548 optionally can comprise one cover this slip coating with the surface treatment effectively reducing this slip coating, component (or the both) amount in inner chamber 604 that leaches into of this thermoplastic base material is carried out.

VII.B.1.c manufactures has SiO _xthe method of the syringe of the cylinder of the outside of the inside of coating and blocking layer coating

VII.B.1.c. even another embodiment be manufacture a kind of syringe as described in any embodiment of part VII.B.1.b method, this syringe comprises a plunger, a cylinder and inside and outside barrier coat.Provide a kind of cylinder, this has for receiving plunger interior surface for sliding and an outer surface.By PECVD by a SiO _xbarrier coat be provided in this interior surface.A kind of barrier coat of resin is provided on this outer surface.This plunger and cylinder are carried out assembling thus provides a kind of syringe.

VII.B.1.c. in order to the coating of use latex effectively (moistening equably) this plastic article, it is considered that it is useful for making the surface tension of this latex and this plastic-substrates match.This can be realized by independently or in combination several methods, such as, reduce the surface tension (with tensio-active agent or solvent) of this latex, and/or corona pre-treatment is carried out to this plastic article, and/or Chemical Pretreatment (priming) is carried out to this plastic article.

VII.B.1.c. this resin optionally can by by latex dip-coating to this outer surface, (or both) in this latex spray to this outer surface is applied in, thus provide the article based on plastics, provide gas and the vapor barrier performance of improvement.Can manufacture polyvinylidene chloride plastic and laminate article, compared with no lamination plastic article, these article provide significantly improved capacity for air resistance.

VII.B.1.c. in any embodiment, optionally can this resin thermosets.Optionally by solidifying this resin except anhydrating.Can by by resin thermosets, resin being exposed to partial vacuum or low-humidity environment, catalytically solidifying this resin or other stopgap measures except anhydrating.

VII.B.1.c. consider an effective thermofixation scheme to provide final drying, thus allow PvDC crystallization, this provide barrier properties.At high temperature (such as between 180 °F to 310 °F (82 DEG C to 154 DEG C)) can carry out primary curing reaction, this depends on the thermotolerance of this thermoplastic base material certainly.About 85% of the final barrier properties that barrier properties optionally after primary curing reaction realizes after can being final curing.

VII.B.1.c. final curing can be carried out under the temperature range of lasting short time (as four hours) that continues long time (such as 2 weeks) from envrionment temperature (as about 65 °F to 75 °F (18 DEG C to 24 DEG C)) to high temperature (as 122 °F (50 DEG C)).

VII.B.1.c. the PvDC plastic lamination article (except the barrier properties of excellence) optionally considered are with the performance providing one or more to wish (such as water white transparency, good gloss, wear resistance, impressionability and mechanical strain resistance).

VII.B.2. plunger

VII.B.2.a. have blocking layer coating piston before

VII.B.2.a. another embodiment is a kind of plunger for syringe, comprises a piston and a push rod.This piston has before one, the side of a substantial cylindrical and a rear section, and this side is configured to be seated within syringe cylinder movably.Before being somebody's turn to do, there is a barrier coat.This push rod engages this rear section and is configured to piston is advanced in syringe cylinder.

VII.B.2.b. there is the slip coating meeting boundary with side

VII.B.2.b. another embodiment is a kind of plunger for syringe again, comprises a piston, a slip coating and a push rod.This plunger has before one, the side of a substantial cylindrical and a rear section.This side is configured to be seated in syringe cylinder movably.This slip coating and side meet boundary.This push rod engages the rear section of this plunger and is configured to piston is advanced in syringe cylinder.

VII.B.3. two-piece type syringe and female Luer

VII.B.3. another embodiment is the syringe comprising a plunger, a syringe cylinder and a female Luer.This syringe comprises the cylinder with the internal surface receiving plunger slidably.Female Luer comprises a Luer taper, and this Luer taper has the internal passages limited by an internal surface.This female Luer is formed with the form of the separation member be separated with this syringe cylinder and is connected on this syringe cylinder by a junctor.The internal passages of this Luer taper has a SiO _xbarrier coat.

VII.B.3. with reference to figure 50-51, syringe 544 optionally can comprise a female Luer 556, and it comprises a Luer taper 558 to receive an intubate (not shown, routine) be contained in attached Luer taper.Luer taper 558 has an internal passages limited by internal surface 562 560.Female Luer 556 is optionally formed as the separation member be separated with this syringe cylinder 548 and is connected on syringe cylinder 548 by a junctor 564.As shown in Figure 50 and 51, junctor 564 in this example has a convex part 566 and a female component 568, and they are fastened togather thus the female Luer existed in the mode of at least basic sealing is fixed to cylinder 548.The internal surface 562 of this Luer taper comprises a SiO _xbarrier coat 570.It is thick and effectively reduce the internal passages that oxygen enters this female Luer that this barrier coat can be less than 100nm.Barrier coat can be applied before this female Luer is connected to syringe cylinder.The syringe of Figure 50-51 also has the female locking collar 572 of arbitrary tool, and the attached Luer taper being used for locking this intubate on cone 558 is in place.

VII.B.4. lubricating composition-deposition is from the slip coating of the organosilicon precursor made by in-situ polymerization organosilicon precursor

VII.B.4.a. the product processing and lubricate

VII.B.4.a. another embodiment is a kind of slip coating again.This coating can be the type made by following process.

VII.B.4.a. these precursors any mentioned elsewhere in this manual can individually or combinationally use.Under the condition effectively forming a kind of coating, precursor is applied in substrate.By this coated polymeric or crosslinked (or both), thus form a kind of surface of lubrication, compared to the surface of untreated this lubrication of substrate, there is lower plunger sliding force or starting force.

VII.B.4.a. another embodiment is a kind of method applying lubricant film.Under the condition effectively forming a kind of coating, a kind of organosilicon precursor is applied in a substrate.By this coated polymeric or crosslinked (or both), thus form a kind of surface of lubrication, compared to the surface of untreated this lubrication of substrate, there is lower plunger sliding force or starting force.

VII.B.4.b. the product of technique and analytical characteristics

VII.B.4.b. even another aspect of the present invention is a slip coating by depositing from the PECVD of feed gas, this feed gas comprises a kind of Organometallic precursor, preferably a kind of organosilicon precursor, 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 cyclosilazanes or any combination of two or more among these.As there is 1.25 and 1.65g/cm by X ray reflection rate (XRR) this coating determined ³between, optionally 1.35 and 1.55g/cm ³between, optionally 1.4 and 1.5g/cm ³between, optionally 1.44 and 1.48g/cm ³between density.

VII.B.4.b. another aspect again of the present invention is a slip coating by depositing from the PECVD of feed gas, this feed gas comprises a kind of Organometallic precursor, preferably a kind of organosilicon precursor, 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 cyclosilazanes or any combination of two or more among these.As by vapor-phase chromatography/mass spectroscopy determined, this coating have as a kind of component of exitting containing repeat-(Me) ₂one or more oligopolymer of SiO-part.Optionally, this coating meets the restriction of any embodiment VII.B.4.a or VII.B.4.b.Optionally, if component of being exitted by vapor-phase chromatography/mass spectroscopy this coating determined is not containing trimethyl silanol substantially.

VII.B.4.b. as by vapor-phase chromatography/mass spectroscopy determined, this coating venting component can be at least 10ng/ often test containing repeat-(Me) ₂the oligopolymer of SiO-part, this vapor-phase chromatography/mass spectroscopy uses following test condition:

GC post: 30mX0.25mmDB-5MS (J & WScientific), the film thickness of 0.25 micron

Flow velocity: 1.0ml/ minute, constant current mode

Detector: mass selective detector (MSD)

Injection way: split stream sampling (10: 1 splitting ratio)

Venting condition: 1 ¹/ ₂" (37mm) room, 85 DEG C of cleanings three hours, flow rate 60ml/min

Oven temperature: 40 DEG C (5 minutes), rise to 300 DEG C with the speed of 10 DEG C/min; 5 minutes are maintained at 300 DEG C.

VII.B.4.b. optionally, this venting component can comprise that at least 20ng/ often tests containing repeat-(Me) ₂the oligopolymer of SiO-part.

VII.B.4.b. optionally, this feed gas comprises a kind of monocycle siloxanes, a kind of monocycle silazane, a kind of many cyclosiloxane, a kind of many cyclosilazanes or two or more any combination among these, such as monocycle siloxanes, a kind of monocycle silazane or any combination of two or more among these, such as octamethylcyclotetrasiloxane.

VII.B.4.b. the slip coating of any embodiment can have between 1 and 500nm the thickness measured by transmission electron microscopy (TEM), optionally between 20 and 200 nm, optionally between 20 and 100nm, optionally between 30 and 100nm.

VII.B.4.b. another aspect of the present invention is a slip coating by depositing from 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 cyclosilazanes or any combination of two or more among these.As determined by x-ray photoelectron spectroscopy (XPS), this coating can have the atomic percent being normalized to the carbon of 100%, the carbon of oxygen and silicon, and this concentration is greater than the atomic percent of carbon in the atomic formula of feed gas.Optionally, this coating meets the restriction of embodiment VII.B.4.a or VII.B.4.b.A.

VII.B.4.b. optionally, the atomic percent of carbon from 1 atom % be increased to 80 atom % (as calculate and XPS condition Case-based Reasoning 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 a lubricant film by depositing from 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 cyclosilazanes or any combination of two or more among these.This coating has as determined by x-ray photoelectron spectroscopy (XPS), and be normalized to the atomic percent of a silicon of the carbon of 100%, oxygen and silicon, this concentration is less than the atomic percent of silicon in the atomic formula of feed gas.Optionally, this coating meets the restriction of embodiment VII.B.4.a or VII.B.4.b.

VII.B.4.b. optionally, the atomic percent of silicon from 1 atom % be increased to 80 atom % (as calculate and XPS condition Case-based Reasoning 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. the slip coating of the combination with two or more characteristics any quoted as proof in part VII.B.4 is also considered especially.

VII.C. container summary

VII.C. the as described herein and/or container of coating prepared according to method described herein or vessel can be used to receive and/or store and/or send a kind of compound or composition.This compound or composition can be responsive, such as air-sensitive, oxygen sensitive, to humidity sensitive and/or to mechanical influence sensitivity.It can be a kind of bioactive compound or composition, such as a kind of medicament, as Regular Insulin or the composition comprising Regular Insulin.In yet another aspect, it can be a kind of biofluid, preferably a kind of body fluid, such as blood or a kind of blood ingredient.Of the present invention in some in, this compound or composition have to be applied to a kind of product in its subject in need, such as a kind of have product to be injected, such as blood (as in the process of transfusing blood from donor to acceptor, or blood is introduced from patient again turn back in this patient body) or Regular Insulin.

As described herein and/or the container of coating prepared according to method described herein of VII.C.A or vessel can be further used in protection package and be contained in a kind of compound in its internal space or composition from the machinery on the surface of this uncoated container material and/or chemical action.Such as, it may be used for preventing or reducing the compound of said composition or a kind of precipitation of component and/or solidify or platelet activation, such as insulin precipitation or blood coagulation or platelet activation.

VII.C. it can be further used for protection package and be contained in a kind of compound in its inside or the composition external environment influence from this container, such as, by preventing or reducing one or more compounds to enter into this container internal space from the environment of this container surroundings.This kind of environmental compound can be a kind of gas or solution, such as a kind of atmospheric gas or liquid containing oxygen, air and/or water vapour.

VII.C. the container of coating as described herein can also be evacuated and store with vacuum state.Such as, this coating allows better vacuum to maintain compared with corresponding uncoated container.In of this embodiment, the container of this coating is a kind of heparin tube.Described pipe can also containing a kind of reagent for preventing blood coagulation or platelet activation, such as EDTA or heparin.

VII.C. such as container by providing from about 1cm to about 200cm, optionally from about 1cm to about 150cm, optionally from about 1cm to about 120cm, optionally from about 1cm to about 100cm, optionally from about 1cm to about 80cm, optionally from about 1cm to about 60cm, optionally from about 1cm to about 40cm, optionally long from about 1cm to about 30cm pipe length, and use as described below probe electrode processes it, can make any above-mentioned embodiment.Particularly for the longer length in above-mentioned scope, should it is considered that the relative movement during forming coating between probe and container may be useful.Such as, this can by carrying out mobile containers or carry out mobile probe relative to container to have come relative to probe.

VII.C. in these embodiments, it is considered that with can preferably compared with barrier coat this coating can be thinner or more incomplete because this container high barrier integrity that will vacuum test tube do not needed to have in some embodiments.

VII.C. as one of any above-mentioned embodiment optional feature, this container has a central axis.

VII.C. as one of any above-mentioned embodiment optional feature, this wall of container is enough pliable and tough for bending (stride across and not destroy wall from least substantially straight to the scope of 100 times being not more than the external diameter equaling this container in central axis bending radius) at least one times at 20 DEG C.

VII.C. as one of any above-mentioned embodiment optional feature, be not more than 90 times of the external diameter equaling this container (or to be not more than and to equal 80 times in the bending radius at central axis place, or be not more than and equal 70 times, or be not more than and equal 60 times, or be not more than and equal 50 times, or be not more than and equal 40 times, or be not more than and equal 30 times, or be not more than and equal 20 times, or be not more than and equal 10 times, or be not more than and equal 9 times, or be not more than and equal 8 times, or be not more than and equal 7 times, or be not more than and equal 6 times, or be not more than and equal 5 times, or be not more than and equal 4 times, or be not more than and 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 feature, this wall of container can be the surface of a kind of contacting with fluid be made up of pliable material.

VII.C. as one of any above-mentioned embodiment optional feature, this container intracavity can be a kind of fluid flowing passage of pump.

VII.C. as one of any above-mentioned embodiment optional feature, this container can be that a kind of being adapted keeps blood to be in the blood bag of the good condition for medical use.

VII.C, VII.D. as one of any above-mentioned embodiment optional feature, this macromolecular material can be a kind of silicone elastomer or a kind of thermoplastic polyurethane (as two examples) or be suitable for and blood or any material of contacting with Regular Insulin.

VII.C, VII.D. are in an optional embodiment, and this container has the internal diameter of at least 2mm or at least 4mm.

VII.C. as one of any above-mentioned embodiment optional feature, this container is a kind of pipe.

VII.C. as one of any above-mentioned embodiment optional feature, this inner chamber has at least two open end.

VII.C.1. contain active blood, there is the container of a deposition from the coating of organosilicon precursor

VII.C.1. even another embodiment is a kind of container containing blood.A kind of so some limiting examples of container are transfusion bags, the Blood Sample Collection container wherein having collected sample, the pipeline of cardiopulmonary machine, the blood collection bag of flexible wall or at surgery for collecting blood samples of patients and blood being reintroduced back to the pipeline of patient's vascular system.If this container comprises a pump for pump blood, so a specially suitable pump is impeller pump or peristaltic pump.This container has a wall; This wall has the internal surface that limits inner chamber.The internal surface of this wall has an at least part of Si _wo _xc _yh _zcoating, wherein preferably w to be 1, x be from about 0.5 to 2.4, y is from about 0.6 to about 3, and z is from 2 to about 9, more preferably wherein w to be 1, x be 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 as thin as monomolecular thickness or thick to this container of about 1000nm. contain activated for the vascular system returning patient, be arranged in inner chamber and Si _wo _xc _yh _zthe blood of coating layer touch.

VII.C.1. an embodiment is the Sheng blood container comprising a wall and have the internal surface limiting inner chamber.This internal surface has an at least part of Si _wo _xc _yh _zcoating.This coating can also comprise or basic by SiO _xcomposition, wherein x is as defined in this specification sheets.On an internal surface, the thickness of this coating is in the scope thick to about 1000nm from monomolecular thickness.This container contain activated for the vascular system returning patient, be arranged in inner chamber and Si _wo _xc _yh _zthe blood of coating layer touch.

VII.C.2. deposit and reduce solidifying or platelet activation of blood in this embodiment from a kind of coating of organosilicon precursor

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 an at least part of Si _wo _xc _yh _zcoating, wherein preferably w, x, y and z are from about 0.5 to about 2.4, y if above definition: W is 1, x is from about 0.6 to about 3, and z is from 2 to about 9, more preferably wherein w to be 1, x be from about 0.5 to 1, y is from about 2 to about 3, and z is from 6 to about 9.On an internal surface, the thickness of this coating is thick to about 1000nm from monomolecular thickness.With identical type do not use Si _wo _xc _yh _zthe wall of coating is compared, and this coating effectively reduces solidifying of the blood being exposed to internal surface or platelet activation.

VII.C.2. as with it with unmodified polymkeric substance or SiO _xthe characteristic of surface contact compare, consider in conjunction with Si _wo _xc _yh _zcoating will reduce the attachment of blood or solidify formation trend.Consider that this characteristic maybe may be eliminated for the needs by heparin processing blood to reduce, as during cardiac operation, such when using cardiopulmonary machine, need to shift out blood from patient and the required haemoconcentration then returning heparin in the operating patient of patient standing a class by reducing.Consider that this will reduce the operating complication of the blood channel related to by such container, by reducing by the hemorrhage complication using heparin to cause.

VII.C.2. another embodiment comprises a wall and has the container that limits the internal surface of inner chamber.This internal surface has at least part of Si _wo _xc _yh _zcoating, in this interior surface, the thickness of this coating is thick to about 1000nm from monomolecular thickness, and this coating effectively reduces the blood coagulation or platelet activation that are exposed to this internal surface.

VII.C.3. containing active blood, the container with the coating of an III or IV race element

VII.C.3. another embodiment is the Sheng blood container with a wall, and this wall has the internal surface that limits inner chamber.This internal surface has the coating of at least part of composition, and said composition comprises one or more iii group elements, one or more IV race elements or two or more combination in these.In this interior surface, the thickness of this coating is between monomolecular thickness and about 1000nm thick (being included).This container contains has activity for the vascular system returning patient, be arranged in and the blood in the inner chamber of coating layer touch.

VII.C.4. the coating of III or IV race element decreases solidifying or platelet activation of blood in this embodiment

VII.C.4. optionally, in the container in earlier paragraphs, the coating of III or IV race element effectively reduces solidifying of the blood of the internal surface being exposed to this wall of container or platelet activation.

VII.D. drug delivery container

VII.D. as said, the container of a coating or vessel may be used for stoping or reduce the compound that comprises in the above-described container or composition and to escape the environment entered around this container.

Also consider as said this coating of further use and container, they illustrate from these and any part of claim is clearly.

VII.D.1. the container containing Regular Insulin, has the coating of deposition from organosilicon precursor

VII.D.1. another embodiment is the Sheng insulin reservoir comprising a wall, and this wall has the internal surface limiting inner chamber.This internal surface has an at least part of Si _wo _xc _yh _zcoating, preferably wherein w, x, y and z are be from about 0.6 to about 3 from about 0.5 to 2.4, y if above definition: w is 1, x, and z is from 2 to about 9, more preferably wherein w to be 1, x be from about 0.5 to 1, y is from about 2 to about 3, and z is from 6 to about 9.In this interior surface, this coating can be thick to about 1000nm from monomolecular thickness, and Regular Insulin is disposed in inner chamber and Si _wo _xc _yh _zcoating layer touch.

VII.D.1. still another embodiment is the Sheng insulin reservoir comprising a wall and have the internal surface limiting inner chamber.This internal surface has an at least part of Si _wo _xc _yh _zcoating, the thickness of coating is thick to about 1000nm from monomolecular thickness in this interior surface.Regular Insulin, such as FDA approval is used for the drug insulin of people, is disposed in inner chamber and Si _wo _xc _yh _zcoating layer touch.

VII.D.1. a Si is considered _wo _xc _yh _zthe combination of coating by be reduced in insulin pump delivery tube in the attachment of Regular Insulin or precipitation formation trend when the Property comparison contacted with unmodified polymer surfaces () with it.Consider this characteristic to reduce maybe may eliminate for the Regular Insulin through delivery tube being filtered thus the needs of removing solid precipitation.

VII.D.2. the precipitation reducing Regular Insulin in a reservoir from the coating of organosilicon precursor is deposited

VII.D.2., optionally, in the container of earlier paragraphs, and Si is lacked _wo _xc _yh _zthe similar face of coating is compared, this Si _wo _xc _yh _zcoating effectively reduces and forms precipitation from insulin exposure internal surface.

VII.D.2. even another embodiment is the container again comprising a wall and have the internal surface limiting inner chamber.This internal surface comprises an at least part of Si _wo _xc _yh _zcoating.In this interior surface, the thickness of coating is in the scope thick to about 1000nm from monomolecular thickness.This coating effectively reduces and forms precipitation from insulin exposure internal surface.

VII.D.3. the container containing Regular Insulin, has III or unit of IV race element coating

VII.D.3. another embodiment is the Sheng insulin reservoir comprising a wall, and this wall has the internal surface that limits inner chamber.This internal surface has at least part of composition coating, and said composition comprises carbon, one or more iii group elements, one or more IV race elements or the combination of two or more in these.In this interior surface, this coating can be thick to about 1000nm from monomolecular thickness.Regular Insulin is disposed in inner chamber and coating layer touch.

VII.D.4. III or unit of IV race element coating reduce the precipitation of Regular Insulin in container

VII.D.4. optionally, in the container described in earlier paragraphs, compared with the similar face lacking coating, comprise carbon, one or more elements of III-th family, one or more elements of IV race or in these a kind of coating of composition of combination of two or multinomial effectively reduce and form precipitation from insulin exposure internal surface.

Operational instances

Example 0: for the formation of the basic experiment scheme also applying pipe and syringe cylinder

Form and be coated in the container tested in operational instances subsequently according to exemplary experiment scheme (except indicating in addition in independent example) below.The concrete parameter value (such as electric power and process gas flow rate) provided in following basic experiment scheme is representative value.Compared with these representative values, when parameter value changes, this indicates in operational instances subsequently.Same principle is applied to type and the formation of process gas.

For the formation of the experimental program of COC pipe (such as using in example 1,19)

Have the shape and size being typically used as vacuum test tube cyclic olefine copolymer (COC) pipe (" COC pipe ") be from 8007-04 cyclic olefine copolymer (COC) resin carrys out injection moulding, this resin can obtain from the HoechstAG company in Frankfurt, Germany city, and these COC pipes have the length of these sizes: 75mm below, the external diameter of 13mm, and the wall thickness of 0.85mm, there is about 7.25cm separately ³volume and closed, a circular end.

For the formation of the experimental program of PET pipe (such as using in example 2,4,8,9,10)

Polyethylene terephthalate (PET) pipe that is typically used as the type of the heparin tube (" PET pipe ") of finding time is injection moulding in the equal dies of the experimental program for the formation of COC pipe, there is these sizes: the length of 75mm, the external diameter of 13mm, and the wall thickness of 0.85mm, there is about 7.25cm separately ³volume and closed, a circular end.

For with SiO _xthe experimental program of the inside of (such as using in example 1,2,4,8,9,10,18,19) coating pipe

Use and have the device as shown in Figure 2 of the sealing mechanism of Figure 45, this is the embodiment of a special consideration.Pan straddle 50 be by derlin is made (can obtain from E.I.duPontdeNemoursandCo company of Delaware, USA Wilmington city), has the external diameter of 1.75 inches (44mm) and the height of 1.75 inches (44mm).Pan straddle 50 is accommodated in in structure, device is allowed to move into and shift out electrode (160).

Electrode 160 is by having the copper shielded becomes. shielding comes 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 pipe being used as container 80 is inserted with the outside (Figure 45) around this pipe o shape circle 490,504 pan straddle 50 sealed bottom ( the trade mark of U.S. DupontPerformanceElastomersLLC, WilmingtonDelaware).Pipe 80 is carefully moved to sealing station, and this position on (static) 1/8-inch (3-mm) diameter brass probe extended or counter electrode 108, and pushes a copper plasma body net to.

Copper plasma body net 610 is copper foil material (U.S. KandSEngineering that are porose, that cut the external diameter to be applicable to this pipe, ChicagoIllinois, Part#LXMUW5 copper mesh), and clamped (see Figure 45) in place by radial abutment surface 494 that extend, that serve as the stopper inserted for this pipe.Two pieces copper mesh is fitted snugly in this brass probe or counter electrode 108 around, to guarantee good electrical contact.

Brass probe or counter electrode 108 extend about 70mm and enter the inside of this pipe and have the array of a #80 wire (diameter=0.0135 inch or 0.343mm).Brass probe or counter electrode 108 extend through one and are positioned at bottom pan straddle 50 joint (can obtain from U.S. SwagelokCo., SolonOhio), extends 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 be 12 holes in the probe or counter electrode 108 of the length along this pipe (mutually directed 90 degree four limits every one side on three) and two holes in the aluminium lid of the end of jam-pack gas delivery port one 10.Gas delivery port one 10 is connected to stainless steel assembly, and this assembly comprises and combines for the manual manipulation ball valve of exitting joint, a thermopair pressure warning unit and one are connected to the by-pass valve of vacuum exhaust pipeline.In addition, this gas system is connected to gas delivery port one 10, allows process gas, oxygen and hexamethyldisiloxane (HMDSO) to flow through gas delivery port one 10 (under processing pressure) and enters this pipe inside.

This gas system comprises one gFC17 mass flowmeter (U.S. Part#EW-32661-34, Cole-ParmerInstrumentCo., BarringtonIllinois) polyether-ether-ketone (" the PEEK ") kapillary (external diameter " OD " 1/16 inch (1.5mm), internal diameter " ID " 0.004 inch (0.1mm)) of (it enters this process for making oxygen with 90sccm (or being used for the specific flow rates of specific examples with report) controllable flow) and a length 49.5 inches (1.26m).This PEEK capillary end is inserted liquid hexamethyldisiloxane (" HMDSO ", Alfa parts number L16970, NMR level, can obtain from JohnsonMattheyPLC, London) within.Because the pressure in pipe during processing is lower, this liquid HMDSO is attracted by this kapillary.Then in the exit of this kapillary, when HMDSO enters area of low pressure, HMDSO is evaporated into as steam.

In order to ensure there is no liquid HMDSO through this point after condensation, do not flow into this pipe at it inner for warp during 3 logical valve process, this gas stream (comprising oxygen) is diverted to pumping line.Once this pipe is mounted, the inside of vacuum pump valve to pan straddle 50 and this pipe is opened.

An Alcatel rotary vane vacuum pump and gas blower form this vacuum pump system.When process gas flows with the speed of specifying, this pump system allows the inside of this pipe to be reduced to the pressure being less than 200mTorr.

Once arrive base vacuum level, pan straddle 50 assembly is moved in electrode 160 assembly.This gas stream (oxygen and HMDSO steam) flows into the gas delivery port one 10 (by regulating 3 logical valves from pumping line to gas delivery port one 10) of this brass.Measured by the capacitance manometer (MKS) near the valve controlling vacuum by being arranged on this pumping line, the pressure of this pipe inside is about 300mTorr.Except pipe pressure, the thermocouple gauge be connected on this gas system is used also to measure the internal pressure of this gas delivery port one 10 and gas system.This pressure is less than 8Torr typically.

Once this gas stream is inner to this pipe, RF power supply is opened into its constant power level.One ENIACG-6600 watt RF power supply (with 13.56MHz) is used with the constant power level of about 50 watts.Between the working life of this coating unit, model 43RF watt, the Bird company in RF outputs of power supply of being connected to is used to count in this and whole following experimental program and Multi-instance alignment output rating.Dial card on power supply arranges and finds following relation between output rating: RF power stage=55x dial card is arranged.In the earlier application of the application, usage factor 100, this is incorrect.This RF power supply is connected on a COMDELCPMX1000 automatic adapter, and the complex impedance of plasma body (needing to be produced in the tube) and 50 ohm output impedance of ENIACG-6RF power supply match by this matching box.Forward power is 50 watts (or for specific amounts that a specific examples is reported) and reflective power is 0 watt, makes applied power be delivered to the inside of pipe like this.This RF power supply be controlled by a laboratory timing register and 5 seconds (or for specific time period that specific examples is reported) will be set as conduction time.When starting RF power supply, among the inside of this pipe, establish uniform plasma body.This plasma body maintains whole 5 seconds until this RF power supply is timed device termination.Plasma body creates a thick silica coating of about 20nm (or the specific thickness reported in specific examples) in this pipe interior surface.

After coating, this gas stream is gone back to this vacuum pipeline and is closed this vacuum valve.Then purging valve is opened, make the inside of pipe turn back to normal atmosphere (about 760Torr).Then this pipe is removed carefully from pan straddle 50 assembly (after pan straddle 50 assembly is shifted out electrode 160 assembly).

For the experimental program with hydrophobic coating (such as using in example 9) coating pipe inside

Use and have the device as shown in Figure 2 of the sealing mechanism of Figure 45, this is the embodiment of a special consideration.Pan straddle 50 by derlin is made (can obtain from E.I.duPontdeNemoursandCo company of Delaware, USA Wilmington city), has the external diameter of 1.75 inches (44mm) and the height of 1.75 inches (44mm).Pan straddle 50 is accommodated in in structure, device is allowed to move into and shift out electrode (160).

Electrode 160 is by having the copper shielded becomes. shielding comes 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 pipe being used as container 80 is inserted with the outside (Figure 45) around this pipe o shape circle 490,504 pan straddle 50 sealed bottom ( the trade mark of U.S. DupontPerformanceElastomersLLC, WilmingtonDelaware).Pipe 80 is carefully moved to sealing station, and this position on (static) 1/8-inch (3-mm) diameter brass probe extended or counter electrode 108, and pushes a copper plasma body net to.

Copper plasma body net 610 is copper foil material (U.S. KandSEngineering that are porose, that cut the external diameter to be applicable to this pipe, ChicagoIllinois, Part#LXMUW5 copper mesh), and clamped (see Figure 45) in place by radial abutment surface 494 that extend, that serve as the stopper embedded for this pipe.Two pieces copper mesh is fitted snugly in this brass probe or counter electrode 108 around, to guarantee good electrical contact.

Brass probe or counter electrode 108 extend about 70mm and enter the inside of this pipe and have the array of a #80 wire (diameter=0.0135 inch or 0.343mm).Brass probe or counter electrode 108 extend through one and are positioned at bottom pan straddle joint (can obtain from U.S. SwagelokCo., SolonOhio), extends 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 be 12 holes in the probe or counter electrode 108 of the length along this pipe (mutually directed 90 degree four limits every one side on three) and two holes in the aluminium lid of the end of jam-pack gas delivery port one 10.Gas delivery port one 10 is connected to stainless steel assembly, and this assembly comprises and combines for the manual manipulation ball valve of discharging joint, a thermopair pressure warning unit and one are connected to the by-pass valve of vacuum exhaust pipeline.In addition, this gas system is connected to gas delivery port one 10, allows process gas, oxygen and hexamethyldisiloxane (HMDSO) to flow through gas delivery port one 10 (under processing pressure) and enters this pipe inside.

This gas system comprises one gFC17 mass flowmeter (U.S. Part#EW-32661-34, Cole-ParmerInstrumentCo., BarringtonIllinois) (this process is flowed into for controllably making oxygen with 60sccm (or being used for specific flow rates of specific examples with report)) and polyether-ether-ketone (" the PEEK ") kapillary of a kind of length 49.5 inches (1.26m) (external diameter " OD " 1/16 inch (1.5mm), internal diameter " ID " " 0.004 inch (0.1mm)).This PEEK capillary end is inserted liquid hexamethyldisiloxane (" HMDSO " Alfa parts number L16970, NMR level, can obtain from JohnsonMattheyPLC, London).Because the pressure in pipe during processing is lower, this liquid HMDSO is attracted by this kapillary.Then in the exit of this kapillary, when HMDSO enters area of low pressure, HMDSO is evaporated into as steam.

In order to ensure there is no liquid HMDSO through this point after condensation, do not flow into this pipe at it inner for warp during 3 logical valve process, this gas stream (comprising oxygen) is turned into pumping line.Once this pipe is mounted, the inside of vacuum pump valve to pan straddle 50 and this pipe is opened.

An Alcatel rotary vane vacuum pump and gas blower form this vacuum pump system.When process gas flows with the speed of specifying, this pump system allows the inside of this pipe to be reduced to the pressure being less than 200mTorr.

Once arrive base vacuum level, pan straddle 50 assembly just moves into electrode 160 assembly.This gas stream (oxygen and HMDSO steam) flows into brass gas delivery port one 10 (by adjusting 3 logical valves from pumping line to gas delivery port one 10).Measured by the capacitance manometer (MKS) near the valve controlling vacuum by being arranged on this pumping line, the pressure of this pipe inside is about 270mTorr.Except pipe pressure, the thermocouple gauge be connected on this gas system is used also to measure the internal pressure of this gas delivery port one 10 and gas system.This pressure is less than 8Torr typically.

Once this gas stream is inner to this pipe, RF power supply is opened to its fixing power level.The constant power level of about 39 watts uses one ENIACG-6600 watt RF power supply (with 13.56MHz).This RF power supply is connected on a COMDELCPMX1000 automatic adapter, and the complex impedance of plasma body (needing to be produced in the tube) and 50 ohm output impedance of ENIACG-6RF power supply match by this matching box.Forward power is 39 watts (or for specific amounts that a specific examples is reported) and reflective power is 0 watt, makes applied power be delivered to the inside of pipe like this.This RF power supply be controlled by a laboratory timing register and 7 seconds (or for specific time period that specific examples is reported) will be set as conduction time.When starting RF power supply, among the inside of this pipe, establish uniform plasma body.This plasma body maintains whole 7 seconds until this RF power supply is timed device termination.Plasma body creates a thick silica coating of about 20nm (or the specific thickness reported in specific examples) in this pipe interior surface.

After coating, this gas stream is gone back to this vacuum pipeline and is closed this vacuum valve.Then purging valve is opened, make the inside of pipe turn back to normal atmosphere (about 760Torr).Then this pipe is removed carefully from pan straddle 50 assembly (after pan straddle 50 assembly is shifted out electrode 160 assembly).

For the formation of COC syringe cylinder (such as example 3,5, use in 11-18,20) experimental program

From 8007-04 cyclic olefine copolymer (COC) resin injection molding syringe cylinder (" COC syringe cylinder "), CV hold assembly 11447 (each has the cumulative volume (not comprising female Luer) of 2.8ml and the delivery volume of 1ml or plunger free air delivery), female Luer type, from German HoechstAG, FrankfurtamMain can obtain, there is these sizes: at the total length of the about 51mm of cylindrical part, the inner injectors cylinder diameter of 8.6mm and the wall thickness of 1.27mm, there is the needle-like hair tubule female Luer of entirety 9.5 millimeters long being molded over one end, and two the finger-type flanges be molded near the other end.

For with SiO _xthe experimental program of (such as using in example 3,5,18) coating COC syringe cylinder inside

Use SiO _xthe inside of the COC syringe cylinder of coating injection moulding.Modification has the device as shown in Figure 2 of the sealing mechanism of Figure 45, and the bottom being used for being clamped in COC syringe cylinder has the COC syringe cylinder of joint packing.In addition, a lid (shown in Figure 26) is made by the polypropylene cap of end of stainless steel female Luer and this COC syringe cylinder of sealing, the inside of this COC syringe cylinder that allows to find time.

Pan straddle 50 by make, there is the external diameter of 1.75 inches (44mm) and the height of 1.75 inches (44mm).Pan straddle 50 is incorporated in in structure, this structure allows device move into and shift out electrode 160.

Electrode 160 is by having the copper shielded becomes. shielding comes 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.COC syringe cylinder is inserted pan straddle 50, and bottom is used seal with O ring.

COC syringe bucket is carefully moved to sealing station, and this position on (static) 1/8-inch (3-mm) diameter brass probe extended or counter electrode 108, and pushes a copper plasma body net to.Copper plasma body net is copper foil material (KandSEngineeringPart#LXMUW5 copper mesh) that is porose, that cut the external diameter to be applicable to this COC syringe cylinder, and clamps in place by the abutment surface 494 of serving as the stopper inserted for this COC syringe cylinder.Two pieces copper mesh is fitted snugly in this brass probe or counter electrode 108 around, to guarantee good electrical contact.

This probe or counter electrode 108 extend about 20mm enter this COC syringe cylinder inside and in its open-ended.Brass probe or counter electrode 108 extend through one and are positioned at bottom pan straddle 50 joint, extends 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 stainless steel assembly, and this assembly comprises and combines for the manual manipulation ball valve of exitting joint, a thermopair pressure warning unit and one are connected to the by-pass valve of vacuum exhaust pipeline.In addition, this gas system is connected to gas delivery port one 10, allows process gas, oxygen and hexamethyldisiloxane (HMDSO) to flow through gas delivery port one 10 (under processing pressure) and enters this COC syringe cylinder inside.

This gas system comprises one gFC17 mass flowmeter (U.S. Part#EW-32661-34, Cole-ParmerInstrumentCo., BarringtonIllinois) polyether-ether-ketone (" the PEEK ") kapillary (OD1/16 inch (3mm), ID0.004 inch (0.1mm)) of (it flows into this process for controllably making oxygen with 90sccm (or being used for the specific flow rates of specific examples with report)) and a kind of length 49.5 inches (1.26m).This PEEK capillary end is inserted liquid hexamethyldisiloxane (Alfa parts number L16970, NMR level).Because the pressure in this COC syringe cylinder during processing is lower, this liquid HMDSO is attracted by this kapillary.Then in the exit of this kapillary, when HMDSO enters area of low pressure, HMDSO is evaporated into as steam.

In order to ensure there is no liquid HMDSO through this point after condensation, do not flow into this COC syringe cylinder at it inner for warp during 3 logical valve process, this gas stream (comprising oxygen) is turned into pumping line.

Once this COC syringe cylinder is mounted, the inside of vacuum pump valve to pan straddle 50 and this COC syringe cylinder is opened.An Alcatel rotary vane vacuum pump and gas blower form this vacuum pump system.When process gas flows with the speed of specifying, this pump system allows the inside of this COC syringe cylinder to be reduced to the pressure being less than 150mTorr.Contrary with this pipe, a lower pumping pressure can be reached, because this COC syringe cylinder has less internal volume far away with COC syringe cylinder.

After arriving base vacuum level, pan straddle 50 assembly just moves in electrode 160 assembly.This gas stream (oxygen and HMDSO steam) flows into brass gas delivery port one 10 (by adjusting 3 logical valves from pumping line to gas delivery port one 10).By being arranged on measured by the capacitance manometer (MKS) near the valve controlling vacuum on this pumping line, the pressure of this COC syringe cylinder inside is about 200mTorr.Except COC syringe cylinder pressure, the thermocouple gauge be connected on this gas system is used also to measure the internal pressure of this gas delivery port one 10 and gas system.This pressure is less than 8Torr typically.

When this gas stream is inner to this COC syringe cylinder, RF power supply is opened to its constant power level.One ENIACG-6600 watt RF power supply (with 13.56MHz) is used with the constant power level of about 30 watts.This RF power supply is connected on a COMDELCPMX1000 automatic adapter, and the complex impedance of plasma body (needing to be produced in this COC syringe cylinder) and 50 ohm output impedance of ENIACG-6RF power supply match by this matching box.Forward power is 30 watts (or for any values that an operational instances is reported) and reflective power is 0 watt, makes this power be delivered to the inside of this COC syringe cylinder like this.This RF power supply be controlled by a laboratory timing register and 5 seconds (or for specific time period that specific examples is reported) will be set as conduction time.

When starting RF power supply, among the inside of this COC syringe cylinder, establish uniform plasma body.This plasma body maintains whole 5 seconds (or other coating times indicated in particular instances) until this RF power supply is timed device termination.Plasma body creates the thick silica coating (or thickness reported in particular instances) of about 20nm in this COC syringe cylinder interior surface.

After coating, this gas stream is gone back to this vacuum pipeline and is closed this vacuum valve.Then purging valve is opened, make the inside of this COC syringe cylinder turn back to normal atmosphere (about 760Torr).Then this COC syringe cylinder is removed carefully from pan straddle 50 assembly (after pan straddle 50 assembly is shifted out electrode 160 assembly).

For with OMCTS slip coating (such as example 11,12, use in 15-18,20) experimental program of coating COC syringe cylinder inside

Inner, as differentiated in the past COC syringe cylinder is applied with slip coating.To have the device modification as shown in Figure 2 of the sealing mechanism of Figure 45, the bottom being used for being clamped in COC syringe cylinder has the COC syringe cylinder of joint packing.In addition, a lid (shown in Figure 26) is made by stainless steel female Luer and the polypropylene cap of the end of this COC syringe cylinder of sealing.Be mounted to the Buna-NO shape circle permission vacuum-packed sealing in this female Luer, allow the inside of this COC syringe cylinder to be evacuated.

Pan straddle 50 by make, there is the external diameter of 1.75 inches (44mm) and the height of 1.75 inches (44mm).Pan straddle 50 is incorporated in in structure, this structure allows device move into and shift out electrode 160.

Electrode 160 is by having the copper shielded becomes. shielding comes 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 bottom is with the bottom of the antelabium around these finger-type flanges and this COC syringe cylinder seal with O ring.

COC syringe bucket is carefully moved to sealing station, and this position on (static) 1/8-inch (3-mm) diameter brass probe extended or counter electrode 108, and pushes a copper plasma body net to.Copper plasma body net 610 is copper foil materials (KandSEngineeringPart#LXMUW5 copper mesh) that are porose, that cut the external diameter to be applicable to this COC syringe cylinder, and clamps in place by the abutment surface 494 of serving as the stopper inserted for this COC syringe cylinder.Two pieces copper mesh is fitted snugly in this brass probe or counter electrode 108 around, to guarantee good electrical contact.

This probe or counter electrode 108 extend about 20mm (except as otherwise noted) enter this COC syringe cylinder inside and in its open-ended.Brass probe or counter electrode 108 extend through one and are positioned at bottom pan straddle joint, extends 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 stainless steel assembly, and this assembly comprises and combines for the manual manipulation ball valve of exitting joint, a thermopair pressure warning unit and one are connected to the by-pass valve of vacuum exhaust pipeline.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 through gas delivery port one 10 (under processing pressure) and enters this COC syringe cylinder inside.

This gas system comprises the mass flow vapo(u)rization system that commercially available HoribaVC1310/SEF8240OMCTS10SC4CR heats, and this system heating OMCTS is to about 100 DEG C.This Horiba system by have the internal diameter of 1/16 inch (1.5mm), the PFA pipe of 1/8 inch of (3mm) external diameter is connected to liquid octamethylcyclotetrasiloxane (Alfa parts number A12540,98%).By OMCTS flow rate set to 1.25sccm (or report is used for the particular silicone precursor flow rate of specific examples).In order to ensure there is no the OMCTS evaporated through this point after condensation, do not flow into the inside of this COC syringe cylinder for warp at it during 3 logical valve process, this gas stream (comprising oxygen) is turned into pumping line.

Once this COC syringe cylinder is mounted, the inside of vacuum pump valve to pan straddle 50 and this COC syringe cylinder is opened.An Alcatel rotary vane vacuum pump and gas blower form this vacuum pump system.When process gas flows with the speed of specifying, this pump system allows the inside of this COC syringe cylinder to be reduced to the pressure being less than 100mTorr.Compare with above COC syringe cylinder example with this pipe, lower pressure can be obtained in this case, because total process gas flow velocity is lower in this case.

Once arrive base vacuum level, pan straddle 50 assembly just moves into electrode 160 assembly.This gas stream (OMCTS steam) flows into brass gas delivery port one 10 (by adjusting 3 logical valves from pumping line to gas delivery port one 10).Measured by the capacitance manometer (MKS) near the valve controlling vacuum by being arranged on this pumping line, the pressure of this COC syringe cylinder inside is about 140mTorr.Except COC syringe cylinder pressure, the thermocouple gauge be connected on this gas system is used also to measure the internal pressure of this gas delivery port one 10 and gas system.This pressure is less than 6Torr typically.

Once this gas stream is inner to this COC syringe cylinder, RF power supply is opened to its constant power level.One ENIACG-6600 watt RF power supply (with 13.56MHz) is used with the constant power level of about 7.5 watts (or other power levels indicated in particular instances).This RF power supply is connected on a COMDELCPMX1000 automatic adapter, and the complex impedance of plasma body (needing to be produced in this COC syringe cylinder) and 50 ohm output impedance of ENIACG-6RF power supply match by this matching box.Forward power is 7.5 watts and reflective power is 0 watt, and the power (or the different power level sent in the example provided) of such 7.5 watts is delivered to the inside of this COC syringe cylinder.This RF power supply be controlled by a laboratory timing register and is set as 10 seconds (or the different time of stating in the example provided) conduction time.

When starting RF power supply, among the inside of this COC syringe cylinder, establish uniform plasma body.This plasma body maintains whole coating time, stops until this RF power supply is timed device.Plasma body produces a slip coating in this COC syringe cylinder interior surface.

After coating, this gas stream is gone back to this vacuum pipeline and is closed this vacuum valve.Then purging valve is opened, make the inside of this COC syringe cylinder turn back to normal atmosphere (about 760Torr).Then this COC syringe cylinder is removed carefully from pan straddle 50 assembly (after pan straddle 50 assembly is shifted out electrode 160 assembly).

For the experimental program with HMDSO coating (such as using in example 12,15,16,17) coating COC syringe cylinder inside

Except replacing OMCTS with HMDSO, for being also used to applying HMDSO coating with the experimental program of OMCTS slip coating coating COC syringe cylinder inside.

Example 1

V. as described in the experimental program for the formation of COC pipe, in following test, hexamethyldisiloxane (HMDSO) is used as the organosilicon (" O-Si ") of the PECVD device being fed to Fig. 2 to apply a SiO _xcoating is on the internal surface of cyclic olefine copolymer (COC) pipe.For with SiO _xmode of deposition is outlined in the experimental program of coating pipe inside and table 1.Contrast is the pipe of the identical type not applying barrier coat.Then test is coating with uncoated pipe, penetrates speed (WVTR) about their oxygen transfer rate (OTR) and their water vapor.

V. reference table 1, uncoated COC pipe has the OTR in a 0.215cc/ pipe/sky.Pipe A and B of experience PECVD14 second has the average OTR in a 0.0235cc/ pipe/sky.These results illustrate SiO _xcoating provides the oxygen transmission BIF that exceedes uncoated pipe 9.1 times.In other words, SiO _xbarrier coat by be reduced to by the transmission of the oxygen of this pipe be less than it does not have 1/9th of cated value.

V. the pipe C experiencing PECVD7 second has the OTR of 0.026.This result illustrates SiO _xcoating provides the OTRBIF that exceedes uncoated pipe 8.3 times.In other words, the SiO applied in 7 seconds _xbarrier coat by be reduced to by the transmission of the oxygen of this pipe be less than it does not have 1/8th of cated value.

V. the multiple relevant WVTR of the identical barrier coat be coated on COC pipe is also measured.Uncoated COC pipe has the WVTR in a 0.27mg/ pipe/sky.Pipe A and B of experience PECVD14 second has a 0.10mg/ pipe/sky or less average WVTR.The pipe C of experience PECVD7 second has the WVTR in a 0.10mg/ pipe/sky.This result illustrates SiO _xcoating provides the water vapor exceeding uncoated pipe about 2.7 times and penetrates barrier improvement factor (WVTRBIF).This is a surprising result, because uncoated COC pipe has had a low-down WVTR.

Example 2

V. a series of PET pipe, makes according to the experimental program for the formation of PET pipe, under the condition that table 2 is reported, according to for SiO _xthe experimental program SiO of coating pipe inside _xcoating.Contrast is made according to the experimental program for the formation of PET pipe, but uncoated.OTR and the WVTR sample of these pipes is prepared by open end to aluminium adapter of each pipe of epoxy sealing.

In a test separated, use the PET of the coating of identical type to manage, guide the mechanical scraper with different lengths by coated inside with a draw point, and test OTRBIF.Contrast or uncoated or not have the pipe of coating of identical type of scraper of guiding.While minimizing, this OTRBIF is still modified exceed uncoated pipe (table 2A).

V. according to the OTR of following testing tube.Each sample/adapter assembly is installed to one on Oxtran2/21 oxygen permeability instrument.Under following test condition, sample is allowed 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 DEG C (73.4 °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 table 2.

V. according to the WVTR of following testing tube.Sample/adapter assembly is installed to one permatran-W3/31 water vapor permeability instrument.Under following test condition, sample is allowed 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

Test gas temperature: 37.8 (DEG C) 100.0 (°F)

Vector gas: dry nitrogen

Vector gas humidity: 0% relative humidity

This WVTR is reported as the average of two measured values in table 2.

Example 3

According to the experimental program for the formation of COC syringe cylinder, make a series of syringe cylinder.Or use SiO _xstop these syringe cylinders of coating, or not for SiO _xunder the condition reported in the experimental program of coating COC syringe cylinder inside, modification as indicated in table 3.

OTR and the WVTR sample of these syringe cylinders is prepared by open end to aluminium adapter of each syringe cylinder of epoxy sealing.In addition, with the Capillary of this syringe cylinder of epoxy sealing.Test OTR or WVTR of these syringe adapter assemblies in the mode identical with PET pipe sample, reuse oxtran2/21 oxygen permeability instrument and permatran-W3/31 water vapor permeability instrument.Report result in table 3.

Example 4

The plasma-coated formation of x-ray photoelectron spectroscopy (the XPS)/electron spectroscopy for chemical analysis (ESCA), surface analysis is used to measure

V.A. by according to make for the formation of the experimental program of PET pipe and according to being used for SiO _xthe PET pipe of the experimental program coating of coating pipe inside cuts in half the internal surface exposing pipe, then uses x-ray photoelectron spectroscopy (XPS) to analyze this surface.

V.A. model quantitatively these XPS data of relative sensitivity factor and a supposition homogeneous layer are used.This analysis volume is the product analyzing area (spot size or hole size) and information depth.In X-ray penetration depth (typically a lot of micron), produce photoelectron, but the photoelectron in the photoelectron escaped depth of three, top only detected.Select the degree of depth to exist rank, this causes about analysis depth.Typically, the signal source of 95% is in this degree of depth.

V.A. table 5 provides the atomic ratio of the element detected.Analytical parameters for XPS is as follows:

Instrument PHIQuantum2000

X-ray source MonochromatedAlk _α1486.6eV

Accept angle ± 23 °

Emission angle 45 °

Analyzed area 600 μm

Charged correction C1s284.8eV

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) using the element detected, the value provided is standardized to Si=1, and calculate and example for uncoated polyethylene terephthalate, the value provided is standardized to O=1.Limit of detection is about 0.05 to 1.0 atomic percent.The value provided alternately is normalized to 100%Si+O+C atom.

V.A. example of the present invention has 2.4 times of SiO indicated _xthe Si/O ratio of composition, has the remaining carbon of the incomplete oxidation from coating.This analytical proof to be applied to the SiO of polyethylene terephthalate pipe according to the present invention _xthe formation on blocking layer.

V.A. table 4 shows SiO _xthe thickness of sample, uses and determines according to the TEM of following methods.The sample of these sample preparations is applied for focused ion beam (FIB) section gauge by using the platinum (50-100nm is thick) of a K575XEmitech application system jetted layers.These samples applied are placed in FEIFIB200FIB system.Deposited the platinum of an extra play by injection organic metal gas FIB, use the interested region of gallium ion beam raster scanning of 30kV simultaneously.Select the interested region of each sample, be used for the half of the length being positioned at this pipe.Measuring thin cross section, to be about 15 μm (" micron ") long, 2 μm wide and 15 μm dark, use proprietary original position FIB lift technique to take out from die surface.The platinum of FIB deposition is used this interface to be attached to 200 sieve mesh copper TEM grids.One or two window measured in each interface is about 8 μm wide, uses the gallium ion beam of FEIFIB that window is thinned to electron lucent.

V.C. transmission electron microscope (TEM) is utilized to carry out the cross-sectional image analysis of the sample that these are prepared.These view data of digital recording.

Sample grid is transferred to a HitachiHF2000 transmission electron microscope.Transmitted electron image is obtained with suitable ratio of enlargement.The pertinent instruments setting used during being given in IMAQ below.

Example 5

Plasma uniformity

V.A. make COC syringe cylinder according to the experimental program for the formation of COC syringe cylinder, use SiO _xthis syringe cylinder of experimental program process of coating COC syringe cylinder inside, has following change.Syringe cylinder for coating (such as has SiO _x250 of film), test three kinds of different plasma generation patterns.V.A. in mode 1, in inlet mouth 310, restricted areas 292 and processing vessel inner chamber 304, produce hollow cathode plasma igniting, and in the remainder of container intracavity 300, produce plasma body that is common or non-hollow cathode.

V.A. in mode 2, in restricted areas 292 and processing vessel inner chamber 304, produce hollow cathode plasma igniting, and produce plasma body that is common or non-hollow cathode in the remainder of container intracavity 300 and inlet mouth 310.

V.A., in mode 3, in whole container intracavity 300 and inlet mouth 310, plasma body that is common or non-hollow cathode is produced.This has been come to any hollow cathode igniting of quencher by hoisting power.Table 6 shows the condition for reaching 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)chloride hydrates is made.By 0.2gRu ^(III)chloride hydrates puts into medicine bottle.Add 10ml SYNTHETIC OPTICAL WHITNER and fully mix until Ru (III) chloride hydrates dissolves.

V.A. seal each syringe cylinder with plastic Luer sealing member, and be infected with mixture by 3 and be added into each syringe cylinder.Then use aluminium these syringe cylinders of rubber belt sealing and allow to leave standstill 30-40 minute.In each group syringe cylinder of test, be at least infected with a uncoated syringe cylinder.Restricted areas 292 is faced up and stores these syringe cylinders.

V.A. be infected with based on this, draw to draw a conclusion:

V.A.1., within the open-assembly time of 0.25 hour, this is infected with and starts to attack uncoated (or applying very poor) region.

V.A.2. the igniting in restricted areas 292 causes the SiO of restricted areas 292 _xcoating.

V.A.3. by or produce best syringe cylinder at inlet mouth 310 or the test that do not use hollow cathode plasma to light a fire in restricted areas 292.Only restricted opening 294 is infected with, and most probable is due to the seepage of dyestuff.

V.A.4. being infected with is the good qualitative instrument guiding homogeneity work.

V.A. based on all above contents, we conclude:

V.A.1. the homogeneity under test conditions, or at inlet mouth 310 or the hollow cathode plasma in restricted areas 292 causing this coating very poor.

V.A.2. or at inlet mouth 310 or do not use hollow cathode plasma thus reach best homogeneity in restricted areas 292.

Example 6

From the jamming pattern-predictive example of reflection measurement

VI.A. a UV visible source (OceanOpticsDH2000-BALDeuteriumTungsten200-1000nm) is used, fiber optic reflection probe (projector/collector OceanOpticsQR400-7SR/BX be combined with about 3mm probe area), small detector (OceanOpticsHR4000CGUV-NIRSpectrometer), and spectrograph signal is converted into the software of the transparence/wavelength graph picture on notebook computer, simultaneously around the internal circumference of this pipe and inwall longitudinally along this pipe scan (use launch and collection radially from the probe of the light of the medullary ray of this pipe, therefore perpendicular to the surface of coating) a uncoated PET manage (BectonDickinson (U.S. FranklinLakes, NewJersey) production number 366703, 13 × 75mm, (there is no additive)), this probe is used to observe visible jamming pattern.Then as SiO _xdescribed in the experimental program of coating pipe inside, with the SiO of 20 nanometer thickness ₂coating coating SiO _xbD366703 pipe (BectonDickinson production number 366703,13 × 75mm, (not having additive)) of plasma coated.This pipe is scanned by the mode of similar uncoated pipe.Observe jamming pattern clearly with the pipe of this coating, wherein strengthen some wavelength and in circulation pattern, eliminate other wavelength, show to there is coating on this PET pipe.

Example 7

From the optical transport of the enhancing that integrating sphere detects

VI.A. the equipment used is an xenon light source (OceanOpticsHL-2000-HP-FHSA-20W output halogen lamp source (185-2000nm)), an integrating sphere detector (OceanOpticsISP-80-8-I) entering its inside for accepting PET pipe through machining, and HR2000+ES strengthens sensitivity UV.VIS spectrograph, there is optical transport source and optical receiver fiber optic cosmogony (QP600-2-UV-VIS-600umPremium optical fiber, UV/VIS, 2m), and signal transform software (SPECTRASUITE-intersection-platform spectroscopy function software).The uncoated PET pipe made according to the experimental program for the formation of PET pipe is inserted on TEFZEL tube support (disk), and inserts this integrating sphere.Use the Spectrasuite software of absorbance patterns, (at 615nm) will be absorbed and be set as zero.Then by according to make for the formation of the experimental program of PET pipe and according to being used for SiO _xthe SiO of the experimental program coating of (except what change in table 16) coating pipe inside _xthe pipe of coating is installed on this disk, inserts integrating sphere and is recorded in the absorbancy of 615nm wavelength.Data are recorded in table 16.

Use SiO _xthe pipe of coating, observes relative to uncoated article, the increase on absorbing; The coating number of times increased causes the absorption increased.The time that this measurement cost is less than 1 second.

VI.A. these spectrographies should not be considered to be applied collection mode (such as reflection contrast transparence contrast absorbancy), frequency or radiation type or other parameters restriction.

Example 8

Venting about PET is measured

VI.B. adapt from United States Patent (USP) 6, what Figure 15 of 584,828, Figure 30 showed is the schematic diagram of setting for the test of operational instances, and this operational instances is used for measurement and passes through SiO _xthe venting of barrier coat 348, according to for SiO _xthe experimental program of coating pipe inside applies coating 348, above-mentioned SiO _xbeing positioned on the inside of wall 346 of PET pipe 358, making PET pipe 358 according to the experimental program for the formation of PET pipe, managing with generally sealing this PET at 362 sealing members 360 on the upstream extremity of microfluidic technology measuring cell indicated.

VI.B. (one has leakage tester device model M E2, has the intelligent gas leaking substance of the s-generation IMFS sensor vacuum pump 364 to be connected to commercially available measuring cell 362, (10 μ/minute whole process), absolute pressure transducer scope: 0-10Torr, flow measurement is uncertain: the +/-5% of reading, at calibration range, adopt the Leak-Tek program being used for automatic data acquisition (with PC), and the mark of seepage stream/drawing reduced time.There is provided this equipment by ATCInc.) downstream end, and detecting by the arrow of measuring cell 362 for determining that the steam of exitting enters the mass rate of flow of container 358 from its wall, configuring this vacuum pump and being used for from the inside sucking-off gas of pet container 358.

VI.B. to describe according to diagram and the measuring cell 362 illustrated is understood to basic by following content efforts at this, although from the actual use angle of operation and equipment, this information may some depart from.Pond 362 has a conical passage 368, guides this bleed flow by this passage.Lateral aperture 370 and 372 drain pressure separated along two longitudinal directions of passage 368, and be fed to the room 374 and 376 partly formed by barrier film 378 and 380 respectively.The pressure deflection barrier film 378 and 380 of these correspondences of accumulation in the room 374 and 376 of correspondence.Measure these deflection in an appropriate manner, as the change by measuring between barrier film 378 and the conductive surface of 380 and near conductive surface (such as 382 and 384) electric capacity.A bypass 386 optionally can be provided thus accelerate initially to find time until reach the vacuum level for carrying out the hope tested by walking around measuring cell 362.

The PET wall 350 of the container VI.B. used in this test is in the thick rank of 1mm, and coating 348 is in the thick rank of 20nm (nanometer).Therefore, wall 350 is 50 with the Thickness Ratio of coating 348, the rank of 000: 1.

VI.B. in order to determine the flow velocity by measuring cell 362, this pond comprises container seal 360, substantially identical in size and the Glass Containers building up to container 358 is placed in container seal 360 continuously by 15, be pumped to the internal pressure of 1Torr, then collect capacitance data with measuring cell 362 and be converted into " venting " flow velocity.About each container, this test is carried out twice.After carrying out first time, proceeding second time before, with nitrogen release vacuum and these containers allow time of recovery to reaching balance.Because Glass Containers is considered to have very little venting, and it is substantially impermeable by its wall, this measurement is understood to the amount of the seepage at least pointing out this container and the connection in measuring cell 362, and if there is any real venting or infiltration, so reflection really seldom.These results in table 7.

The family of the drawing 390 VI.B. in Figure 31 shows " venting " flow velocity of independent pipe, also represents with microgram per minute, and this flow velocity corresponds to the secondary data in above-mentioned table 7.Because these flow velocitys of drawing do not increase substantially in time, and well below the flow velocity shown in other, so this flow velocity should 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, makes these pipes according to the experimental program for the formation of PET pipe.

VI.B. these data of uncoated pipe illustrate larger flow velocity far away: these increase owing on the interior region of wall of container or within the bleed flow of gas that catches.Between these containers, there are some gaps, the fine difference that these containers are shown in and/or they be how to be placed on test set, it is the instruction of 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, according to for using SiO on the inside of the wall 346 of PET pipe _xthe experimental program of coating PET pipe inside applies coating 348, makes this PET manage according to the experimental program for the formation of PET pipe.

VI.B. the SiO of this example _xthe family of the curve 394 of PET pipe that apply, injection moulding illustrates SiO _xcoating plays for the effect of restriction from the barrier of pet container wall venting, because compared with uncoated PET pipe, the flow velocity in this test is lower all the time.(this SiO _xit is considerably less that coating self is considered to venting.) separation between the curve 394 of corresponding container shows that this test is for the SiO of difference on different pipes _xslightly differentiated stop effect of coating is enough responsive.With the change in the venting between pet container wall or settle the change in integrity (it has the curve family 392 more sealed far away) contrary, this gap in family 394 is mainly owing at SiO _xbe coated with the change in the air seal degree of interlayer.As following proof, two curves 396 of sample 2 and 4 are outliers, and they are considered to from the difference of other data the SiO that these pipes are shown _xcoating is defective.This illustrates this test and very clearly can separate sample by different treatment or damage.

VI.B. with reference to above-mentioned table 8 and 9 and Figure 32, these data of statistical study with find out average and on average (mean value) and under first and the 3rd value of standard deviation.These values are plotted in Figure 32.

VI.B. first this statistical study illustrates that the sample 2 and 4 of table 9 of the PET pipe of representative coating is outlier clearly, departs from average more than the standard deviation of+3 times.But these outliers illustrated have some stop effects because their flow velocity still clearly differentiate with those values of uncoated PET pipe (lower than).

VI.B. this statistical study also illustrate for very fast and accurately analyze nano thickness barrier coat and be used for distinguish coating pipe and uncoated pipe (at this coat-thickness, if the sensation of end user, this cup is thought indistinguishable) venting measure ability.With reference to Figure 32, venting level shown in the pet container three times standard deviations higher than average of coating, shown in the bar of top group, have the venting less than uncoated pet container, venting level shown in this uncoated container three times standard deviations lower than average, shown in the bar of low group.These data illustrate that for more than 6 σ (six sigma) qualitative level really, data do not have overlap.

VI.B. based on the success of this test, consider to detect SiO on these pet containers far away in the test shorter than this operational instances _xthe presence or absence of coating, particularly because produce the statistical value of the sample being used for larger quantity.This is obvious, and such as, from the sample for 15 containers, even in time T=12 second, the family that is smooth, sharp separation of drawing, represents the test time of about a second after the starting point of about T=11 second.

VI.B. also consider, based on these data, by optimizing SiO _xcoating, can obtain close to glass or the SiO equaling glass _xstop effect of the pet container of coating.

Example 9

The PET pipe example of wet tension-plasma coated

VII.A.1.a.ii. wet tension method is the amendment of the method described in ASTMD2578.Wet tension is for a surperficial hydrophobicity or hydrophilic one is specific measures.The method uses standard wet tension solution (being called dyne solution) to determine the solution continuing two seconds exactly closest to a moistening Plastic film surface.Here it is film wet tension.

VII.A.1.a.ii. this step change utilized is from ASTMD2578, wherein these substrates are not flat plastics films, but make according to the experimental program for the formation of PET pipe and (except contrast) according to the pipe of the experimental program coating with hydrophobic coating coating pipe inside.The glass syringe being also tested for silicone-coated (has most advanced and sophisticated BectonDickinson the pre-encapsulated injector of PRTC glass) (1mL).The results are shown in Table 10 in this test.

Surprisingly, by changing plasma process conditions, the plasma coating (40 dyne/cm) of uncoated PET pipe can reach or the surface of the identical hexamethyldisiloxane of use (HMDSO) feed gas of higher (more hydrophilic) or lower (more hydrophobic) energy.According to for SiO _xthin (about 20-40 nanometer) SiO that the experimental program applying pipe inside is made _xcoating (in these tables not shown data) provides the similar wettability as hydrophilic bulk glass substrate.The similar non-wettability (in these tables not shown data) as hydrophobic siloxanes liquid is provided according to thin (being less than the about 100 nanometers) hydrophobic coating for making with the experimental program of hydrophobic coating coating pipe inside.

Example 10

Vacuum via the pipe of accelerated deterioration keeps research

VII.A.3 accelerated deterioration provides identifying sooner of prolonged shelf life product.At United States Patent (USP) 5, the 792,940, the 1st hurdle, the accelerated deterioration of the heparin tube that 11-49 line description keeps for vacuum.

VII.A.3 tests the shaping pipe of polyethylene terephthalate (PET) 13 × 75mm (wall that 0.85mm is thick) of three types:

BectonDickinson production number 36670313 × 75mm (not having additive) manages (545 days or 18 months quality guaranteed period), uses the stopper of system redness and uncoloured protection [commercial contrast] are closed;

The PET pipe made according to the experimental program for the formation of PET pipe, by identical type the stopper of system redness and uncoloured protection are closed; And

PET13 × 75mm pipe of injection moulding, makes according to the experimental program for the formation of PET pipe, according to for SiO _xthe experimental program coating of coating pipe inside, by identical type the stopper of system redness and uncoloured protection [sample of invention] are closed.

VII.A.3 uses the commercial contrast of BD as received.Find time internal contrast and invention sample and with blind system cover for sealing after, the partial pressure (vacuum) of hope is provided in the inside of pipe.All samples is placed in one the three gallons wide mouth pressurized vessels (SterlitechNo.740340) of (3.8L) 304SS.This pressurized vessel is forced into 48psi (3.3atm, 2482mm.Hg).3-5 sample is moved by the timed interval that (a) is increasing, b () allows water to suck the pipe of finding time from the Plastic Bottle holder of a liter by 20 gauge blood collecting adapters, (c) and the quality change measured before and after water inspiration carries out volume of water suction change detection.

VII.A.3 shows result on table 11.

VII.A.3 sucks the average decay rate of [quality change/(number of days x initial mass)] normalized divided by supercharging number of days and initial mass by the time variations in quality.Also calculate the pick-up period (moon number) to 10% loss.Both data are all listed in table 12.

These data of VII.A.3 show that commercial contrast and uncoated internal contrast all have identical vacuum leak speed, and surprisingly, in conjunction with SiOx coating to PET inwall with 2.1 the factor improve the vacuum hold-time.

Example 11

Slip coating

VII.B.1.a. in this test, following material is used:

Have most advanced and sophisticated (ca1mL) commercial ( pRTC) glass pre-encapsulated injector

According to the COC syringe cylinder that the experimental program for the formation of COC syringe cylinder is made;

There is the commercialization plastic injector plunger (obtaining as being full of the syringe of salt solution in advance) of the elastomer tips taking from BectonDickinson production number 306507;

Normal salts solution (taking from the syringe that Becton-Dickinson production number 306507 is full of in advance);

There is the Dillon test-bed (model AFG-50N) of advanced ergometer

Syringe rack and draining guide plate (manufacture is used for installing Dillon test-bed)

VII.B.1.a. in this test, following steps are used.

VII.B.1.a. guide plate is installed on Dillon test-bed.Adjustment platform probe moves to 6 inch per minute clocks (2.5mm/ second) and sets upper and lower closed position.Sky syringe and cylinder is used to change these closed positions.The syringe being full of salt solution of marked articles, removing plunger, and in order to reuse, salts solution is discharged in the open end via these syringe cylinders.Obtain extra plunger in an identical manner, for using together with glass infuser with COC.

VII.B.1.a. that syringe plunger is inserted COC syringe cylinder, the second horizontal form point of each plunger even together with syringe cylinder tip (end at distance tip is about 10mm) like this.Use another syringe and needle assemblies, be filled with the salts solution of 2-3 milliliter via kapillary to test injection device, keep capillary end the highest.Any bubble to remove the bubble at plunger/fluid interface and any size along these walls, and is carefully released syringe by the side of knocking syringe, keeps plunger at its vertical orientation simultaneously.

VII.B.1.a. syringe cylinder/the plunger assembly each be full of is installed in syringe fixture.By moving towards plunger with the metal hammer of ahead running by the downward switch be pressed on test-bed, thus start test.When the metal hammer moved moves within the top 5mm of distance contact plunger, repeatedly the data button of knocking in Dillon module is recorded in the power of the time that data button is each time depressed, from before this syringe plunger initial contact until by contacting with the antetheca of syringe cylinder thus stopping this plunger.

VII.B.1.a. the syringe cylinder of all reference points and coating carries out five repetitions (reusing new plunger and cylinder each time).

VII.B.1.a. with the COC syringe cylinder that the coating of OMCTS slip coating is made according to the experimental program for the formation of COC syringe cylinder, according to the OMCTS coating for the experimental program coating COC syringe cylinder with OMCTS slip coating coating COC syringe cylinder inside, install and be full of salt solution, and as above this for slip coating example as described in test.OMCTS steam (and oxygen is allowed according to the polypropylene room for using with the experimental program of OMCTS slip coating coating COC syringe cylinder inside, if add-see table 13) flow into polypropylene room (although in this example, may not slip coating be needed in the capillary tube segment of this syringe) by syringe cylinder and by syringe kapillary.Test some different coated conditions, as shown in above-mentioned table 13.All depositions are completed from the COC syringe cylinder of identical production batch.

Then according to the experimental program of this example, use the test of plunger sliding force to carry out the test of the sample applied, the result of generation, in table 13, uses made in Great Britain and metric system unit of force.For the COC syringe of COC and coating, illustrate to these clear data that low power and anaerobic provide minimum plunger sliding force.Notice that plunger sliding force is increased to 2.27Ib, 1.03Kg from 1.09Ib, 0.49Kg (with power=11W) when when more low power (6W) (lower power is favourable) interpolation oxygen.This shows to reach minimum possible plunger sliding force, may not wish to add oxygen.

VII.B.1.a. best plunger sliding force (power=11W is also noted that, plunger sliding force=1.09lb, 0.49Kg) industrial standards (plunger sliding force=0.58lb, 0.26Kg) that closely glass of silicone-coated is present, avoid the problem (such as friability and more expensive manufacturing process) of glass syringe simultaneously.Use extra optimization, with the present glassy phase ratio with silicone resin performance, expect to reach the value be parity with or superiority over.

VII.B.1.a. according to the experimental program be used for OMCTS slip coating coating COC syringe cylinder inside, these samples are applied by coating COC syringe cylinder.The alternative embodiment of a technology at this, will at another film coating (such as SiO _x) on apply slip coating, such as, according to being used for SiO _xthe experimental program of coating COC syringe cylinder inside applies.

Example 12

The syringe cylinder slip coating improved

VII.B.1.a. for inwall coating syringe, determine use plug made of plastics material by capillary apertures from syringe discharge useful load 0.9 percentage brine needed for power.

VII.B.1.a. the COC syringe cylinder of the three types made according to the experimental program for the formation of COC syringe cylinder is tested: a type does not have coated inside [uncoated contrast], another type has the inside coating [HMDSO contrast] of hexamethyldisiloxane (HMDSO) base plasma coated, this coating is according to the experimental program be used for HMDSO coating coating COC syringe cylinder inside, and the 3rd type there is the inside coating of octamethylcyclotetrasiloxane [OMCTS invention example] base plasma coated, this coating is applied according to the experimental program for applying COC syringe cylinder inside with OMCTS slip coating.There is the fresh plug made of plastics material of the elastomer tips taking from BD product B ecton-Dickinson production number 306507 for all examples.Also use the salt solution from production number 306507.

VII.B.1.a. in other experimental sections of the application, describe the plasma coated scheme for applying syringe cylinder inwall and device.For the experimental program with HMDSO coating coating COC syringe cylinder inside, for by the specific coating parameters listed in the OMCTS slip coating coating experimental program of COC syringe cylinder inside and table 14 for HMDSO base and OMCTS base coating.

VII.B.1.a. plunger being inserted this syringe cylinder about 10 millimeters, the syringe kapillary subsequently by opening, vertically filling experiment syringe with the syringe/needle system being full of salt solution separately.When this experiment syringe has been filled in capillary apertures, this syringe of knocking to allow to discharge any bubble adhering to inwall, and allows them to be elevated through this capillary apertures.

VII.B.1.a. the experiment syringe cylinder/plunger assembly this be full of vertically is placed in homemade hollow metal fixture, this injector assembly is supported in the finger-type flange on fixture.This fixture has the water shoot in bottom, and is set on the Dillon test-bed with advanced ergometer (model AFG-50N).This test-bed has a metal hammer, with the speed vertical downward movement of six inches of (152 millimeters) per minutes.The plunger that the contact of this metal hammer extends, discharges salts solution by this kapillary.Once this plunger has contacted this syringe cylinder/kapillary interface, stop experiment.

VII.B.1.a. move downward period at the plunger of metal hammer/extension, on electrical form, record is as the resistance be delivered on this hammer measured on this ergometer.From the data of this form, differentiate each maximum power of testing.

VII.B.1.a. table 14 lists for each example, from the mean value of the maximum power of the COC syringe cylinder of repetitive coatings, and by standardized maximum power that the mean value of the maximum power of the syringe cylinder of coating is determined divided by the mean value of uncoated maximum power.

VII.B.1.a. these data show, the COC syringe cylinder (invention example C, E, F, G, H) of all OMCTS base inwall plasma coated proves the plunger sliding force well below 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 in gas barrier coating keeps fabulous low plunger sliding force (invention example F).Best plunger sliding force is example C (power=8, plunger sliding force=1.1lb, 0.5Kg).The industrial standards (plunger sliding force=0.581b, 0.26Kg) that the glass of its closely silicone-coated is present, avoids the problem (such as friability and more expensive manufacturing process) of glass syringe simultaneously.Use extra optimization, with the present glassy phase ratio with silicone resin performance, expect to reach the value be parity with or superiority over.

Example 13

Processing has the example of the COC syringe cylinder-prophesy of exterior coating

VII.B.1.c. with the disposable COC syringe cylinder closing at two ends sealing and formed according to the experimental program for the formation of COC syringe cylinder.The COC syringe cylinder of adding a cover is passed through 8100 saran latex (OwensboroSpecialtyPlastics) baths.The Virahol that this latex contains 5 percent is used for reducing surface tension to the 32 dyne/cm of said composition.The outside of this latex composition this COC syringe cylinder completely moistening.After putting dry 30 seconds, the COC syringe cylinder of this coating is exposed to table heat-up time, this timetable is included in 275 °F (135 DEG C) 25 seconds (latex coalescence) and 122 °F (50 DEG C) four hours (terminating solidification) in corresponding high wind stove.The PvDC film generated is that 1/10mil (2.5 microns) is thick.A MOCON board Oxtran2/21 oxygen permeability instrument and this COC syringe cylinder of Permatran-W3/31 water vapor permeability apparatus measures and PvDC-COC is used to laminate OTR and WVTR of COC syringe cylinder respectively.

VII.B.1.C. OTR and the WVTR value predicted is listed in table 15, and the stacking material barrier improvement factor (BIF) that it illustrates expectation will be 4.3 (OTR-BIF) and 3.0 (WVTR-BIF) respectively.

Example 15

Apply the atomic building of the PECVD of OMCTS and HMDSO coating

VII.B.4. provide and make COC syringe cylinder sample according to the experimental program for the formation of COC syringe cylinder, apply (according to for the experimental program with OMCTS slip coating coating COC syringe cylinder inside) with OMCTS or apply according to the experimental program HMDSO for applying COC syringe cylinder inside by HMDSO coating.Use x-ray photoelectron spectroscopy (XPS) expression derived from the feature of the atomic building of the coating of OMCTS or HMDSO.

VII.B.4. the quantitative XPS data of model of relative sensitivity Summing Factor supposition homogeneous layer are used.This analysis volume is the product of analyzed area (spot size or hole size) and information depth.In X-ray penetration depth (typically a lot of micron), produce photoelectron, but the photoelectron in the photoelectron escaped depth of three, top only detected.Select the degree of depth to exist rank, this causes about analysis depth.Typically, the signal source of 95% is in this degree of depth.

VII.B.4. following analytical parameters is used:

Instrument PHIQuantum2000

X-ray source MonochromatedAlk α 1486.6eV

Accept angle ± 23 °

Emission angle 45 °

Analyzed area 600 μm

Charged correction C1s284.8eV

Ion gun condition Ar ⁺, 1keV, 2 × 2mm grating

Injection rate / min (SiO ₂equivalent)

VII.B.4. table 17 provides the atomic percent of the element detected.XPS does not detect hydrogen or helium.Use the element detected, the value provided is standardized to 100%.Limit of detection is about 0.05 to 1.0 atomic percent.

VII.B.4.b. the initial monomers precursor elements per-cent of result and calculating is formed from the coating shown in table 17, simultaneously relative to initial HMDSO free carbon atomic percent, the atomic percent carbon of HMDSO base coating reduces (being down to 44.4% from 54.1%), surprisingly, relative to OMCTS free carbon atomic percent, OMCTS base coating atomic percent carbon increases (rising to 48.4% from 34.8%), adds 39 atom %, is calculated as follows:

100% [(48.4/34.8)-1]=39 atom %.

And, relative to initial HMDSO monomer atomic percent silicon, while the atomic percent silicon of HMDSO base coating does not almost change (21.8% to 22.2%), surprisingly, relative to OMCTS monomer atomic percent silicon, OMCTS base coating atomic percent silicon significantly reduces (42.0% is down to 23.6%), decreases 44 atom %.Carbon and silicon all change, and the OMCTS monomer of coating behavior is not identical with the trend observed in usual precursor monomer (such as HMDSO).See such as HansJ.Griesser, RonaldC.Chatelier, ChrisMartin, ZoranR.Vasic, ThomasR.Gengenbach, GeorgeJessupJ.Biomed.Mater.Res. (ApplBiomater) 53:235-243,2000.

Example 16

From plasma-coated volatile constituent (" venting ")

VII.B.4. provide and make COC syringe cylinder sample according to the experimental program for the formation of COC syringe cylinder, apply (according to for the experimental program with OMCTS slip coating coating COC syringe cylinder inside) with OMCTS or apply (according to for the experimental program with HMDSO coating coating COC syringe cylinder inside) with HMDSO.Venting vapor-phase chromatography/mass spectrum (GC/MS) is used to analyze the volatile matter measured from OMCTS or HMDSO coating.

VII.B.4. syringe cylinder sample (the COC syringe cylinder that four length aspects cut in half) is placed in one 1 of dynamic head space sampling system (CDS8400 automatic sampler) ¹/ ₂" in the room of (37mm) diameter.Before sample analysis, analytical system is blank.Analytic sample on an Agilent7890A gas chromatograph/Agilent5975 mass spectrograph, uses following parameter, illustrates the data of generation in table 18:

GC post: 30mX0.25mmDB-5MS (JandWScientific),

The film thickness of 0.25 micron

Flow velocity: 1.0ml/ minute, constant current mode

Detector: mass selective detector (MSD)

Injection pattern: Split Injection (10: 1 splitting ratio)

Venting condition: 1 ¹/ 2 " (37mm) room, 85 DEG C of cleanings three hours, flow rate 60ml/ minute

Furnace temperature: 40 DEG C (5 minutes) are warming up to 300 DEG C with 10 DEG C/min; 5 minutes are maintained at 300C.

Gassing results from table 18 clearly shows the formation difference between the HMDSO base and OMCTS base lubricating coat of test.HMDSO composition venting trimethyl silanol [(Me) ₃siOH], and do not exit containing repeating-(Me) ₂the higher oligomers of measurement of SiO-part, OMCTS based composition and use thereof in packaging is not exitted trimethyl silanol [(Me) simultaneously ₃siOH], and venting is containing repeating-(Me) ₂the higher oligomers of SiO-part.Consider this test may for difference HMDSO base coating and OMCTS base coating useful.

Not do not limit the present invention according to the scope of following theory or accuracy, consider that this result can by considering that the ring structure of OMCTS is explained, only have two methyl groups to be connected to each Siliciumatom, relative to the acyclic portion of HMDSO, wherein each Siliciumatom connects three methyl groups.Consider to be formed by ring opening OMCTS reaction that there is repetition-(Me) ₂siO-part divalent group, this has been oligopolymer, and can condensation to form higher oligomers.On the other hand, consider that HMDSO is by incision O-Si key reaction, stays containing, for example (Me) ₃a fragment of single O-Si key of the same condensation again of SiOH, and not containing, for example [(Me) ₃si] ₂other fragments of the same O-Si key of condensation again.

The character of the ring of OMCTS be considered to cause ring opening and these there is the condensation of the ring opening moiety 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 of the lower molecular weight from HMDSO.

Example 17

Use the plasma-coated density measurement of X ray reflection rate (XRR)

Sapphire evidence sample (0.5 × 0.5 × 0.1cm) is pasted the inwall of PET pipe separately, make these pipes according to the experimental program for the formation of PET pipe.Manage (all according to being used for, with the experimental program of OMCTS slip coating coating COC syringe cylinder inside, all departing from 2x power) with the PET of OMCTS or HMDSO coating containing sapphire evidence.Then remove the sapphire samples of coating and obtain X ray reflection rate (XRR) data on PANalyticalX ' Pert diffractometer that is equipped with parabolic multilayer incident light monochromator and parallel plate diffracted beam collimator.Use two-layer Si _wo _xc _yh _zthe coating density from critical angle measuring result determined by model.Consider to provide with this model to be separated real Si _wo _xc _yh _zthe best approach of coating.These results shown in table 19.

From the result of the example 15 shown in table 17, compared with HMDSO, the lower oxygen (28%) of OMCTS and higher carbon (48.4%) are formed should have lower density, due to atomic mass reason and valency (oxygen=2; Carbon=4).Surprisingly, XRR density result shows to observe contrary result, and that is exactly that OMCTS density is higher than HMDSO density.

Not do not limit the present invention according to the scope of following theory or accuracy, considering being formed in corresponding HMDSO base and OMCTS base coating, in reaction mechanism, there is basic difference.HMDSO fragment may easier nucleation or reaction to form intensive nano particle, then these particle depositions are from the teeth outwards and react from the teeth outwards further, and the gas phase nano particle that the very more impossible formation of OMCTS is intensive.OMCTS active ingredient very more may condensation from the teeth outwards, to be more similar to the form of initial OMCTS monomer far away, causes overall more not intensive coating.

Example 18

The thickness evenness of the coating that PECVD applies

The COC syringe cylinder made according to the experimental program for the formation of COC syringe cylinder is provided to sample, and respectively according to being used for SiO _xthe experimental program SiO of coating COC syringe cylinder inside _xcoating, or according to the experimental program OMCTS base lubricating coat coating for applying COC syringe cylinder inside with OMCTS slip coating.Return sample and provide the PET made according to the experimental program for the formation of PET pipe pipe, respectively according to being used for SiO _xthe experimental program of coating pipe inside applies or does not apply, and experiences accelerated aging tests.Transmission electron microscopy (TEM) is used to measure the thickness of the coating that PECVD on these samples applies.Use the TEM step of the example 4 of above statement.By the SiO used in this example _xdemonstrate as the uniform coating as shown in table 20 with the method and apparatus that slip coating experimental program describes.

Example 19

Venting on COC is measured

VI.B. COC pipe is made according to the experimental program for the formation of COC pipe.Some pipes provide according to for SiO _xthe SiO of the experimental program of coating pipe inside _xinner barrier coat, and other COC uncoated manage.Also as foregoing provided the commercialization BectonDickinson13x75mm glass heparin tube with similar size.In the room of the ambient air containing 45% relative humidity and 70 °F (21 DEG C), store this pipe about 15 minutes, and carry out following test with equivalent environment relative humidity.According to ATC miniflow measuring process and (one has leakage tester device model M E2, has the intelligent gas leaking substance of s-generation IMFS sensor with the equipment of example 8, (10 μ/minute gamut), according to pressure transmitter scope: 0-10Torr, flow-rate measurement is uncertain: the +/-5% of reading, at calibration range, adopt and be used for the Leak-Tek program (with PC) of automaticdata data gathering and the mark/drawing of seepage stream relative time) test the venting of this pipe.In the present case, the body moisture steps of exhausting of 22 second of each pipe experience under the pressure of 1mmHg, with nitrogen pressurization 2 seconds (to 760 mm Hg), then emptying nitrogen, and carries out miniflow measuring process about 1 minute under 1 mm Hg pressure.

VI.B. result shown in Figure 57, this is similar to the Figure 31 produced in example 8.In Figure 57, the drawing of uncoated COC pipe is at 630, SiO _xthe drawing of COC pipe of coating 632, and with the drawing of the Glass tubing compared 634.Again, about 4 seconds time, start venting measure, and after several second, the drawing 630 of uncoated COC pipe and SiO _xstop the drawing 632 clearly bifurcated of the pipe of coating, again prove to stop the difference sharply between the pipe of coating and uncoated pipe.Recognize uncoated COC (60 seconds time > 2 microgram) and SiO _xthe consistent separation that the COC (being less than 1.6 micrograms 60 seconds time) applied compares.

Example 20

Slip coating

VII.B.1.a. slip coating (according to for the experimental program with OMCTS slip coating coating COC syringe cylinder inside) is used to apply COC syringe cylinder (making according to the experimental program for the formation of COC syringe cylinder).These results are supplied in table 21.These results illustrate in oxygen-free situation, increase the trend of power level, be increased to 14 watts to improve the oilness of coating from 8 watts.The further experiment with power and flow velocity can provide the further enhancing of oilness.

Example 21

The example of slip coating-supposition

Cyclic olefine copolymer (COC) the plastic injector cylinder of injection moulding is made according to the experimental program for the formation of COC syringe cylinder.Some uncoated (" contrasts ") and other bases are used for carrying out PECVD lubrication coating (" syringe of lubrication ") with the experimental program of OMCTS slip coating coating COC syringe cylinder inside.Use the automatic injection device Force meansurement device of a Genesis packaging, model AST tests the syringe of lubrication and contrasts the power (starting force) measured and cause the motion of plunger in this, and the power (plunger sliding force) keeping plunger to move in this.

This test is the revision of ISO7886-1:1993 test.Following steps are used for each test.The fresh plug made of plastics material (obtaining as being full of the syringe of salt solution in advance) with the elastomer tips taking from BectonDickinson production number 306507 is shifted out from injector assembly.By this elastomer tips of compressed air drying of clean drying.Then elastomer tips is inserted COC syringe cylinder, test together with the plunger placed, even test together with the bottom of syringe cylinder.Then regulate the syringe that is full of to reaching tested state as required.Such as, if test target finds to store this syringe after three months, about the effect of the slip coating of the starting force of syringe, so just store these syringes three months to reach the state of hope.

Automatic injection device Force meansurement device syringe being installed into Genesis packaging, according to the specification sheets of manufacturers, calibrates this tstr when starting this test.This tstr input variable is speed=100mm/ minute, scope=10,000.Start button pressed by this tstr.When completing this test, measure starting force (moving in this cylinder to cause plunger) and plunger sliding force (being used for keeping motion), and the data being found in contrast syringe are compared, the data of the syringe of lubrication are substantially lower.

Figure 59 shows the container processing systems 20 according to an exemplary embodiment of the present invention.Container processing systems 20 especially comprises, first treatment station 5501 and second treatment station 5502.Example for this type for the treatment of station is the reference number 24,26,28,30,32 and 34 be such as described in Fig. 1.

Although the first container processing systems 5501 pan straddle 38. Figure 59 containing the container 80 gripped describes heparin tube 80, this container can be a syringe body, a medicine bottle or a such as transfer pipet.Such as this container can be made up of glass or plastics.In the case of a plastic receptacle, this first treatment station can also comprise a mould for these plastic containers shaping.

After the first treatment station processes for the first time (current process can comprise container molding, initial examination container defect, the internal surface of coating container and inspection container defect (particularly coated inside) for the second time), pan straddle 38 is transported to second container treatment station 5502 together with container 82.Arrange that 70,72,74 transport by transfer roller.Such as, a clamp or some clamps can be provided for clamping this pan straddle 38 and/or container 80 thus this container/holder combination being moved to next treatment station 5502.Alternately, can only move this container and not move this support.But maybe advantageously moved together with this container by this support, in this case, this support is adapted thus makes it can be arranged by this transfer roller and transports.

Figure 60 shows the container processing systems 20 according to another exemplary embodiment of the present invention.Again, two container handling stations 5501,5502 are provided.In addition, provide extra container handling stations 5503,5504, they are arranged in order, and can processing vessel in them, namely check and/or apply.

Container can be moved to left treatment station 5504 from a kind of raw material.Alternately, can container molding at the first treatment station 5504.Under any circumstance, a first container process is carried out in treatment station 5504, as shaping, check and/or coating, one second inspection can be carried out after which.Then, via transfer roller, container is arranged that 70,72,74 move to next treatment station 5501.Typically, this container moves together with this pan straddle.One second process is carried out in the second treatment station 5501, and thereafter, this container and support are moved in next treatment station 5502, carry out the 3rd process here.Then moved by this container in (again together with this support) to the 4th treatment station 5503 and process for one the 4th, it is transported in a storer thereafter.

Before and after the step of each coating step or forming step or any other operation vessel, once can check, check overall container, partial containers and particularly inner surface of container.Via data bus 5507, the result checked each time can be passed to central processing unit 5505.Each treatment station is connected to data bus 5507.Treater 5505, it can be adapted to be center-control and regulate the form of unit, and process checks data, analyzes these data and determine whether last treatment step is successful.

If determine that the treatment step after group is not successful, because such as coating comprise hole or because determine the surface of coating be rule or level and smooth not, so container can not enter next treatment station, but or shift out from this production technique at (see transfer roller station 7001,7002,7003,7004), or conveying goes back to carry out reprocessing.

Treater 5505 is connected to user interface 5505, for input control or regulating parameter.

Figure 61 shows the container handling stations 5501 according to exemplary embodiment of the present invention.This station comprises a PECVD device 5701 for applying an internal surface of this container.In addition, some detector 5702-5707 are provided for container inspection.This type of detector can be such as carrying out electrometric electrode, photodetector, as CCD camera, gas detector or pressure detector.

Figure 62 shows the pan straddle 38 according to an exemplary embodiment of the present invention, illustrates together with having the electrode of gas entry ports 108,110 with some detectors 5702,5703,5704.

When container is settled on the bracket 38, electrode and detector 5702 can be adapted for the internal space moving into container 80.

Optical check can be carried out especially, such as, under the help of the fluorescence detector 5703,5704 outside the container 80 being arranged in arrangement, or under the help of fluorescence detector 5705 even in the internal space being arranged in container 80 during coating step.

These detectors can comprise color filter, different wavelength can be detected like this during coating procedure.This processing unit 5505 is analyzed optical data and is determined that whether this coating is successfully to the determinacy of a predeterminated level.If determine that this coating is most possibly unsuccessful, then the container of correspondence be separated from this treatment system or carry out reprocessing.

Although the present invention in accompanying drawing and above-mentioned explanation by detailed diagram and description, these diagrams and illustrate and will be considered to illustrative or exemplary, instead of restrictive; The present invention is not limited to disclosed embodiment.By studying these accompanying drawings, disclosure and appending claims, those of ordinary skill in the art and putting into practice the personnel of claim that the present invention proposes and be appreciated that and carry out other changes for disclosed embodiment.In these claims, word " comprises " does not get rid of other key elements or step, and indefinite article " " or " one " are not got rid of multiple.Only fact is, some measure of quoting as proof in mutually different dependent claims does not show that the combination of these measures can not be used for producing advantage.Any reference symbol should not be construed as and limit its scope in the claims.

Table 1: OTR and WVTR of the COC pipe of coating measures

Table 2: OTR and WVTR of the PET pipe of coating measures

Table 2 continues

Table 2A. has the OTR of the PET pipe of the coating of mechanical abrasion defect

* two pipes average

Table 4: the SiO detected by TEM _xcoat-thickness (nanometer)

Table 5: the atom ratio (in bracket, use per-cent indicated concentration, be normalized to the element detected of 100%) of the element detected

Table 6: the scope of hollow cathode plasma igniting

Table 7: the flow velocity using Glass tubing

Table 8: the flow velocity using PET pipe

Table 9:SiO _xthe flow velocity of the PET pipe of coating

Table 10: measuring with the wet tension of uncoated pipe of coating

Table 11: water suction quality (gram)

Table 12: the standardized average-volume decay rate of calculating and the time to 10% VOLUME LOSS

Table 13: the syringe cylinder with slip coating, English unit

Table 13: the syringe cylinder with slip coating, metric unit

Table 15:OTR and WVTR measures (prophesy)

Table 16.SiO _xthe optical absorption (being normalized to uncoated PET pipe) of the PET pipe of coating

Table 17: atomic percent (in bracket: precentagewise, being normalized to the element detected of 100%)

Table 18: from the volatile matter of syringe cylinder

Table 19: the plasma coating density measured from XRR

Table 20: by the PECVD coat-thickness of TEM

Table 21:OMCTS slip coating performance (English unit)

* that repeats for 4 times is average

Table 21:OMCTS slip coating performance (metric unit)

Above power measurement is the mean value of 4 samples.

In below listing, such as, with reference to Figure 59 to 62, describe exemplary embodiment of the present invention.Although employ term " claim " or " omnibus claims " in following listing, it should be noted that following list refer to exemplary embodiment and do not refer to claims.

I has the container processing systems of multiple treatment station and multiple pan straddle

1. a container processing systems 20, comprising:

First treatment station 5501,24,26,28,30, the container that this first treatment station is arranged to having an opening and a wall defining an interior surface processes;

Second treatment station 5502,24,26,28,30, this second treatment station and the spaced apart and container be arranged to having an opening and a wall defining an interior surface of this first treatment station process;

Multiple pan straddle 38, each pan straddle comprises a container port 92, and this container port is arranged to and receives and the opening fixing a container processes for the interior surface of the container port by being positioned at this first treatment station to a fixed container; And

A handling machinery 70,72,74, this transfer roller is used for that a series of pan straddle and fixing container are transported to from this first treatment station the interior surface of container port to a fixed container that this second treatment station is used for by being positioned at this second treatment station and processes.

2. invent as claimed in claim 1, comprise the 3rd treatment station 5503 further, 3rd treatment station and this first and second treatment station spaced apart, and to be configured to for processing (see such as Figure 60) the container of the wall that there is an opening and define an interior surface.

3. invent as claimed in claim 2, wherein this transfer roller is configured to process for a series of pan straddle and the container of taking a seat are transported to from this second treatment station the interior surface of container port to the container that is taken a seat that the 3rd treatment station is used for via being positioned at the 3rd treatment station.

4. the invention as described in any one of claims 1 to 3, wherein one or more pan straddles comprise a vacuum pipe further, and this vacuum pipe is for withdrawing gas from the container be seated on one or more container port.

5. the invention as described in any one of Claims 1-4, wherein one or more pan straddles are included in a vacuum ports be communicated with between this vacuum pipe and an external vacuum source of vacuum further.

6. the invention as described in any one of claim 1 to 5, wherein one or more vacuum ports have an O type circle to receive and the sealing be formed on an external vacuum source.

7. the invention as described in any one of claim 1 to 6, wherein one or more pan straddles comprise a gas entry ports further, and this gas entry ports is for delivering into a kind of gas in the container be seated on one or more container port.

8. the invention as described in any one of claim 1 to 7, the vacuum ports that wherein one or more pan straddles comprise a composite gas input port further and are connected with one or more container port, these ports are accordingly for deliver into a kind of gas in the container be seated on one or more container port and from wherein extracting a kind of gas out.

9. wherein one or more pan straddles of the invention as described in any one of claim 1 to 8 are manufactured by thermoplastic material.

10. the invention as described in any one of claim 1 to 9, wherein one or more container ports have for receiving and forming a sealing element sealed in this vessel port.

10a invents as claimed in claim 10, and wherein sealing element is an O type circle.

11. as claim 1 to 10a any one as described in invention, one of them treatment station is configured to check for the interior surface of defect to a container.

12. inventions as described in any one of claim 1 to 11, one of them treatment station is configured to a coating to be applied in the interior surface of a container.

13. inventions as described in any one of claim 1 to 12, one of them treatment station is configured to check a coating for defect.

14. inventions as described in any one of claim 1 to 13, one of them treatment station is configured to measure the atmospheric pressure lost by a wall of container.

15. inventions as described in any one of claim 1 to 14, one of them treatment station comprises an area supported, and this area supported is used for supporting one or more pan straddle in predetermined position, processes the interior surface of the container of taking a seat at this treatment station simultaneously.

16. inventions as described in any one of claim 1 to 15, wherein another treatment station comprises second area supported, this second area supported is used for supporting one or more pan straddle in predetermined position, processes the interior surface of the container of taking a seat at other treatment station simultaneously.

17. inventions as described in any one of claim 1 to 16, wherein another treatment station comprises the 3rd area supported, 3rd area supported is used for supporting one or more pan straddle in predetermined position, simultaneously via the interior surface of one or more these containers of taking a seat of container port process at other treatment station.

18. inventions as described in any one of claim 1 to 17, comprise the 3rd treatment station further, the 3rd treatment station and this first and second treatment station spaced apart for the treatment of multiple container.

19. invent as claimed in claim 18, comprise the 4th treatment station further, the 4th treatment station and this first, second and the 3rd treatment station spaced apart for the treatment of multiple container.

20. invent as claimed in claim 19, comprise the 5th treatment station further, the 5th treatment station and this first, second, third and the 4th treatment station spaced apart for the treatment of multiple container.

21. invent as claimed in claim 20, comprise the 6th treatment station further, the 6th treatment station and this first, second, third, fourth and the 5th treatment station spaced apart for the treatment of multiple container.

22. inventions as described in any one of claim 1 to 21, comprise a transfer roller further, and this transfer roller is used for one or more pan straddle and the container of taking a seat to be transported to the 3rd treatment station from this second treatment station.

23. invent as claimed in claim 22, comprise a transfer roller further, and this transfer roller is used for one or more pan straddle and the container of taking a seat to be transported to the 4th treatment station from the 3rd treatment station.

24. inventions as described in any one of claim 1 to 23, comprise a transfer roller further, and this transfer roller is used for one or more pan straddle and the container of taking a seat to be transported to the 5th treatment station from the 4th treatment station.

25. inventions as described in any one of claim 1 to 24, comprise a transfer roller further, and this transfer roller is used for one or more pan straddle and the container of taking a seat to be transported to the 6th treatment station from this May 4th treatment station.

26. inventions as described in any one of claim 1 to 25, comprise a spreader further, this spreader for forming a coating via the one or more container ports at a treatment station on the inside of a container.

27. inventions as described in any one of claim 1 to 26, one of them treatment station comprises PECVD device.

28. invent as claimed in claim 27, and wherein this PECVD device comprises:

An interior electrode, this interior electrode is located with to be received as to be in fluid connection with the inside of the container be seated on a pan straddle;

An outer electrode, this outer electrode has an internal portion, and this internal portion is located to receive the container be seated on this pan straddle;

A power supply, alternating-current to be input in these on electrode and outer electrode to form plasma body being seated within the container on this pan straddle by this power supply;

A vacuum source, this vacuum source is used for the inner pumping of container, the container defines a vacuum chamber;

A reactant gas source; And

A gas feed device, a kind of reactant gas is fed in the container be seated at this pan straddle from this reactant gas source by this gas feed device.

29. invent as claimed in claim 28, and wherein this interior electrode extends in this container.

30. invent as claimed in claim 28, and wherein this interior electrode is positioned in the outside of this container.

31. inventions as described in claim 28 or 30, wherein this interior electrode is positioned within this pan straddle.

32. invent as claimed in claim 28, and wherein this interior electrode is a probe with a distal portions, and this distal portions is located to extend into roughly concentrically in a container being seated on this pan straddle.

33. inventions as described in claim 28 or 32, wherein this gas feed device is the distal portions at this interior electrode.

34. inventions as described in claim 28,32 or 33, comprise a reactant gas source and a passage within this interior electrode further, and this passage is used for the distal portions this reactant gas being delivered to this interior electrode from this reactant gas source.

35. invent as claimed in claim 34, and wherein the distal portions of this interior electrode comprises a long and narrow porous sidewall, and this sidewall is centered around the passage within this interior electrode, and this passage is used for laterally discharging this reactant gas at least partially from this passage.

36. invent as claimed in claim 35, and wherein the external diameter of this interior electrode is equivalent at least 50% of the contiguous internal diameter of side direction of this container.

37. invent as claimed in claim 35, and wherein the external diameter of this interior electrode is equivalent at least 60% of the contiguous internal diameter of side direction of this container.

38. invent as claimed in claim 35, and wherein the external diameter of this interior electrode is equivalent at least 70% of the contiguous internal diameter of side direction of this container.

39. invent as claimed in claim 35, and wherein the external diameter of this interior electrode is equivalent at least 80% of the contiguous internal diameter of side direction of this container.

40. invent as claimed in claim 35, and wherein the external diameter of this interior electrode is equivalent at least 90% of the contiguous internal diameter of side direction of this container.

41. invent as claimed in claim 35, and wherein the external diameter of this interior electrode is equivalent at least 95% of the contiguous internal diameter of side direction of this container.

42. inventions as described in any one of claim 28 to 34, comprise a carrier gas source and a passage within this interior electrode further, and this passage is used for the distal portions this carrier gas being delivered to this interior electrode from this carrier gas source.

43. inventions as described in any one of claim 28 to 42, comprise an interior electrode stretcher and retractor further, for be inserted by this interior electrode in this pan straddle and to remove from it.

44. inventions as described in any one of claim 28 to 43, comprise an array of at least two interior electrodes further, and wherein this interior electrode stretcher and retractor are configured to for be inserted by this array interior electrode in this pan straddle and to remove from it.

45. invent as claimed in claim 44, and wherein this interior electrode stretcher and retractor are configured to for making interior electrode move relative between the position of propelling completely of pan straddle, mid-way and retracted position.

46. inventions as described in claim 44 or 45, comprise the interior electrode driver that interior electrode stretcher and retractor with this are operatively connected further, this driving mechanism is used for retracted position electrode in first being moved to it from its extended position, replace this electrode in first with a second inner electrode, and advance this second inner electrode to its extended position.

47. inventions as described in claim 28,32,33,34 or 42, wherein this outer electrode is substantial cylindrical and is located to extend roughly concentrically around the container be seated on this pan straddle.

48. inventions as described in any one of claim 28 to 47, wherein this outer electrode comprises an end cap.

49. invent as claimed in claim 48, wherein at this end cap and to be seated at the gap limited between the far-end of a container on this pan straddle be basically identical.

50. inventions as described in any one of claim 28 to 49, the gap wherein limited between this outer electrode and the container being seated on this pan straddle is basically identical.

51. inventions as described in any one of claim 1 to 50, comprise a detector further, this detector is configured to be inserted in this container for detecting the situation on this internal tank surface via the one or more container ports at a treatment station.

52. inventions as described in any one of claim 1 to 51, comprise a kind of detector further, this detector is positioned on a treatment station of this external container.

53. inventions as described in any one of claim 1 to 52, comprise a kind of energy being positioned at a treatment station further, this treatment station be used for guiding energy inwardly by this wall of container and internal tank surface to be detected by detector.

54. inventions as described in any one of claim 1 to 53, comprise a kind of energy being positioned at a treatment station further, this treatment station for energy to be directed on wall of container and reflection from the energy one of at least in the coating of on this wall surface and this wall surface.

55. inventions as described in any one of claim 1 to 54, comprise a kind of energy being positioned at a treatment station further, and this treatment station is used for guiding energy and passes outwardly this wall of container and internal tank surface to be detected by detector.

56. inventions as described in any one of claim 1 to 55, comprise a kind of energy, this energy is arranged to and inserts in a container via a vessel port.

57. inventions as described in any one of claim 51 to 56, wherein this detector is configured to the situation on the internal tank surface for detecting the position at multiple tight spacing on this internal tank surface.

58. inventions as described in any one of claim 51 to 57, wherein this detector is by the energy locating to receive from this energy.

59. inventions as described in any one of claim 1 to 58, are included in a collector of a treatment station further, for being removed from one or more pan straddle by this container after the interior surface of the container of taking a seat of this second treatment station in process.

II.VESSELHOLDERS

II.A. pan straddle

60. 1 kinds of carry-case supports, for keeping when processing container and carrying the container with an opening, this pan straddle comprises:

A container port, this container port is configured to for making a vessel port take a seat with the relation interconnected;

Second port, this second port is configured to receive extraneous gas supply or ventage;

A pipeline, this pipeline passes through being seated between on this container port vessel port and this second port for making one or more gases; And

Can carry housing for one, this container port, the second port and pipeline are attached on it with the relation of rigidity in fact.

The weight of this carry-case support is less than five pounds.

II.B

61. 1 kinds of carry-case supports, for keeping when processing container and carrying the container with an opening, this pan straddle comprises:

A container port, this container port be configured to for sealing, the relation that interconnects receives a vessel port;

A vacuum pipe, for via the withdrawing gas from the container be seated at this container port of this container port;

A vacuum ports, this vacuum ports is configured between this vacuum pipe with an external vacuum source and is communicated with; And

Can carry housing for one, this container port, vacuum pipe and vacuum ports are attached on it with the relation of rigidity in fact;

The weight of this carry-case support is less than five pounds.

62. invent as claimed in claim 61, and wherein this container port has reception vessel port and forms a sealing element of a sealing thereon.

62a invents as claimed in claim 61, and wherein sealing element is an O type circle.

63. as claim 61 to 62a any one as described in invention, wherein this vacuum ports there is reception external vacuum source and thereon formed one sealing an O type circle.

64. inventions as described in any one of claim 61 to 63, wherein this gas entry ports has reception inlet mouth and forms an O type circle of a sealing thereon.

65. inventions as described in any one of claim 61 to 64, wherein this vacuum ports is further configured thus works as a gas entry ports be communicated with this container port, for being transported to by a kind of gas in the container be seated on this container port.

66. inventions as described in any one of claim 61 to 65, wherein this housing is made up of thermoplastic material.

67. inventions as described in any one of claim 61 to 66, comprise a gas entry ports further, this gas entry ports is attached to this in fact rigidly and can carries on housing and to be configured to for being transported to by a kind of gas in the container be seated on this container port.

II.C. the pan straddle of sealing arrangement is comprised.

68. 1 pan straddles, the adjacent open end for being received in it has an opening end of the container of the wall of a substantial cylindrical, comprising:

The internal surface of a substantial cylindrical, this internal surface is made into a certain size for receiving the cylindrical wall of this container;

Be arranged in the internal surface of this substantial cylindrical and a coaxial with it first ring connected in star, the diapire that this first ring connected in star has an opening and separates with the inner surface radial direction of this substantial cylindrical on the internal surface of this substantial cylindrical; And

First sealing element, this first sealing element to be disposed in this first ring connected in star and relative to this O type circle of this first ring connected in star be made into a certain size for normally extend radial through this opening and the container that receives by the internal surface by this substantial cylindrical radially to external pressure, thus between this container and the diapire of this first ring connected in star, form one seal.

68a. container as recited in claim 68, wherein sealing element is an O type circle.

69. pan straddles as recited in claim 68, comprising further can by the opening end of this container docking near the internal surface of this substantial cylindrical radial bearing extended thereon.

70. pan straddles as described in claim 68 or 69, comprise the first upper side wall and lower wall further, between the opening that these sidewalls are disposed in this first ring connected in star and diapire, when an O type circle is radially outward pressed by a container, these the first side walls are located thus are docked on an O shape circle.

71. pan straddles as described in any one of claim 68 to 70, wherein an O type circle has the diameter of section of the radial depth of the groove being greater than this first general toroidal when unstressed.

72. pan straddles as described in any one of claim 68 to 71, comprise further

In the internal surface of this substantial cylindrical and coaxial with it and axially spaced with this first ring connected in star second annular recesses, this second annular recesses has an opening and a diapire isolated with the inner surface radial direction of this substantial cylindrical on the internal surface of this substantial cylindrical; And

A 2nd O type circle, 2nd O type circle to be disposed in this second annular recesses and relative to this second annular recesses make a certain size be used for normally extending radially through this opening and need a container receiving by the internal surface by this substantial cylindrical radially outward press, thus form a sealing between this container and diapire of this annular recesses.

73. pan straddles as described in claim 72, comprise the first upper side wall and lower wall further, between the opening that these sidewalls are disposed in this second annular recesses and diapire, when the 2nd O type circle is radially outward pressed by a container, these second sidewalls are located thus are docked on the 2nd O shape circle.

74. pan straddles as described in any one of claim 72 to 73, wherein the 2nd O type circle has the diameter of section of the radial depth of the groove being greater than this first general toroidal when unstressed.

75. pan straddles as described in any one of claim 69 to 74, be included in a vacuum source in this bearing further, this vacuum source is positioned for a container vacuum-pumping to being seated in pan straddle, and wherein the opening of this container is towards this bearing.

76. pan straddles as described in any one of claim 69 to 75, be included in a process gas source in this bearing further, this process gas source is positioned for being communicated with the inside of the container be seated in this pan straddle, and wherein the opening of this container is towards this bearing.

III is landed in the method for the container on pan straddle for conveying containers-process

III..A. conveying containers support is to treatment station.

77. for the treatment of a kind of method of container, and the method comprises:

There is provided one for the treatment of the first treatment station of container;

There is provided one and isolated second treatment station of this first treatment station, for the treatment of these containers;

There is provided a kind of container, this container has an opening and defines a wall of an interior surface;

There is provided a pan straddle, this pan straddle comprises a container port;

The opening of this container is made to be seated on this container port;

By the interior surface via this container of taking a seat of container port process at 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 interior surface of this container of taking a seat of container port process at this second treatment station.

78. inventions as described in claim 77, wherein this container is generally tubular.

79. inventions as described in any one of claim 77 or 78, wherein this opening is positioned at an end of this container.

80. inventions as described in any one of claim 77 to 79, wherein this container is made up of thermoplastic material.

81. inventions as described in any one of claim 77 to 80, wherein this container is made up of polyethylene terephthalate.

82. inventions as described in any one of claim 77 to 80, wherein this container is made up of polyolefine.

83. inventions as described in any one of claim 77 to 80, wherein this container is made up of polypropylene.

84. inventions as described in any one of claim 77 to 83, wherein this container is made up of glass.

85. inventions as described in any one of claim 77 to 84, wherein this container is made up of borosilicate glass.

86. inventions as described in any one of claim 77 to 85, wherein this container is manufactured by soda-lime glass.

87. inventions as described in any one of claim 77 to 86, wherein this container is made up of silica glass.

88. inventions as described in any one of claim 77 to 87, wherein when being exposed to the external pressure of one 760 holder, this container can be sufficiently solid to stand one inner vacuum and not being out of shape in fact in fact completely.

89. inventions as described in any one of claim 77 to 88, wherein by injection moulding, it provides this container.

90. inventions as described in any one of claim 77 to 88, wherein by blow molding, it provides this container.

91. inventions as described in any one of claim 77 to 90, wherein this container is provided by the end of a closed pipe.

92. inventions as described in any one of claim 77 to 91, wherein this pan straddle comprises a vacuum pipe further, and this vacuum pipe is for withdrawing gas from the container be seated on this container port.

93. inventions as described in claim 92, wherein this pan straddle comprises a vacuum ports further, and this vacuum ports is communicated with between this vacuum pipe with an external vacuum source.

94. inventions as described in claim 93, wherein this vacuum ports has one and receives and the O type circle being formed in a sealing on an external vacuum source.

95. inventions as described in any one of claim 77 to 94, wherein this pan straddle comprises a gas entry ports further, and this gas entry ports is for delivering the gas in the container be seated on this container port.

96. inventions as described in any one of claim 77 to 95, wherein this pan straddle vacuum ports of comprising a composite gas input port and being communicated with this container port, these ports are accordingly for delivering into gas in the container be seated on this container port and therefrom extracting a kind of gas out.

97. inventions as described in any one of claim 77 to 96, wherein this pan straddle is made up of thermoplastic material.

98. inventions as described in any one of claim 77 to 97, wherein this pan straddle is included in the upper part and a base that a joint links together.

99. inventions as described in claim 98, are included in joint further and are captured in the O type circle for sealing this joint between this upper part and this base.

100. inventions as described in any one of claim 77 to 99, the O type circle be wherein trapped between this upper part and this base also receives this container and around this vessel port, forms one and seals.

101. inventions as described in any one of claim 77 to 100, wherein this container port has the first and second axially spaced O type circles, each O type circle have make a certain size with the external diameter of receiving vessel internal diameter, for sealing between this container port and a container.

102. inventions as described in any one of claim 77 to 101, wherein this container port has and to be positioned near these O type circles and around a radial abutment surface extended of this vacuum pipe.

103. inventions as described in any one of claim 77 to 102, one of them treatment station is configured to check for the interior surface of defect to a container.

104. inventions as described in any one of claim 77 to 103, one of them treatment station is configured to a coating to be applied in the interior surface of a container.

105. inventions as described in any one of claim 77 to 104, one of them treatment station is configured to the coating of a barrier coat or other types to be applied in the interior surface of a container.

106. inventions as described in any one of claim 77 to 105, one of them treatment station is configured to check a coating for defect.

107. inventions as described in any one of claim 77 to 106, one of them treatment station is configured to check a barrier coat for defect.

108. inventions as described in any one of claim 77 to 107, one of them treatment station is configured to measure the atmospheric pressure lost by a wall of container.

109. inventions as described in any one of claim 77 to 108, one of them treatment station comprises an area supported, and this area supported is used for supporting that this pan straddle processes the interior surface of the container of taking a seat at this treatment station simultaneously in a predetermined position.

110. inventions as described in claim 109, wherein, after being seated on this container port by the opening of this container, this pan straddle is transported the joint entered with this area supported.

111. inventions as described in any one of claim 77 to 110, wherein another treatment station comprises second area supported, and this second area supported is used for supporting that this pan straddle processes the interior surface of the container of taking a seat at other treatment station simultaneously in a predetermined position.

112. inventions as described in claim 110, wherein, after being seated on this container port by the opening of this container, this pan straddle is transported the joint entered with this second area supported.

113. inventions as described in any one of claim 77 to 112, wherein another treatment station comprises the 3rd area supported, and the 3rd area supported is used for supporting in a predetermined position interior surface of container of this pan straddle simultaneously by taking a seat in the container port process of other treatment station.

114. inventions as described in claim 113, wherein, after being seated on this container port by the opening of this container, this pan straddle is transported the joint entered with the 3rd area supported.

115. inventions as described in any one of claim 77 to 114, comprise further:

3rd treatment station is provided, the 3rd treatment station and this first and second treatment station spaced apart, for the treatment of container;

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 interior surface of this container of taking a seat of container port process at the 3rd treatment station.

116. inventions as described in any one of claim 77 to 115, are included in a treatment station further and the opening of this container are seated on this container port.

117. inventions as described in any one of claim 77 to 116, are included in a treatment station further and in the interior surface of a container, form a coating via this container port.

118. inventions as described in any one of claim 77 to 117, wherein comprise in the process at a treatment station place and checking for the interior surface of defect to a container.

119. inventions as described in claim 118, wherein this inspection is by a detection probe to be inserted in this container via this container port and the situation using this probe to detect this internal tank surface is carried out.

120. inventions as described in claim 119, to comprise energy further inwardly by this wall of container and internal tank surface and by this detected energy of popping one's head in.

121. inventions as described in claim 119 or 120, are included in the situation of the position detection receptacle interior surface of the multiple tight spacings on this internal tank surface further.

122. inventions as described in any one of claim 118 to 121, wherein check it is by be inserted in this container via this container port by a source of radiation and carried out with the condition of detection receptacle interior surface by the radiation using a detector to detect this source of radiation from the beginning.

123. inventions as described in any one of claim 118 to 122, comprise further and make the outside radiation of energy by this internal tank surface and detect this energy with the detector being positioned at this external container.

124. inventions as described in any one of claim 120 to 123, comprise reflection further from the radiation on internal tank surface and detect this energy with the detector being positioned at this internal tank.

125. inventions as described in any one of claim 118 to 124, are included in the situation of the position detection receptacle interior surface of the multiple tight spacings on this internal tank surface further.

126. inventions as described in any one of claim 77 to 125, wherein comprise in the process at a treatment station place and a coating being applied in the interior surface of a container.

127. inventions as described in any one of claim 77 to 126, wherein comprise in the process at a treatment station place and being applied in the interior surface of a container by a barrier coat.

128. inventions as described in any one of claim 77 to 127, wherein comprise in the process at a treatment station place and a liquid obscures coating being applied in the interior surface of a container.

129. inventions as described in any one of claim 77 to 128, wherein comprise in the process at a treatment station place and checking the coating in the interior surface of a container for defect.

130. inventions as described in any one of claim 77 to 129, wherein comprise in the process at a treatment station place and checking the barrier coat in the interior surface of a container for defect.

131. inventions as described in any one of claim 77 to 130, wherein comprise in the process at a treatment station place and checking the coating applied as a kind of liquid in the interior surface of a container for defect.

132. inventions as described in any one of claim 126 to 131, comprise and a detection probe to be inserted in this container via this container port and to use this probe to detect the situation of this coating.

133. inventions as described in any one of claim 127 to 132, to comprise energy further and inwardly detect this energy by this wall of container with this probe.

134. inventions as described in any one of claim 127 to 133, the situation of this coating is detected in the position being included in the multiple tight spacings on this internal tank surface further.

135. inventions as described in any one of claim 129 to 134, be included in the step of carrying out this inspection throughout the position of enough numbers on internal tank surface further, to determine that this coating is greater than 20% of ambient atmosphere pressure by effectively preventing the pressure of within this container (when it is initially evacuated and its wall is exposed under ambient atmosphere) to be increased to during the quality guaranteed period of 1 year.

136. inventions as described in any one of claim 129 to 135, wherein this inspection step is carried out within each container 30 seconds or shorter elapsed time.

137. inventions as described in any one of claim 129 to 135, wherein this inspection step is carried out within each container 25 seconds or shorter elapsed time.

138. inventions as described in any one of claim 129 to 135, wherein this inspection step is carried out within each container 20 seconds or shorter elapsed time.

139. inventions as described in any one of claim 129 to 135, wherein this inspection step is carried out within each container 15 seconds or shorter elapsed time.

140. inventions as described in any one of claim 129 to 135, wherein this inspection step is carried out within each container 10 seconds or shorter elapsed time.

141. inventions as described in any one of claim 129 to 135, wherein this coating and check that step is carried out within each container 5 seconds or shorter elapsed time.

142. inventions as described in any one of claim 129 to 135, wherein this coating and check that step is carried out within each container 3 seconds or shorter elapsed time.

143 inventions as described in any one of claim 129 to 135, wherein this coating and check that step is carried out within each container 2 seconds or shorter elapsed time.

144. inventions as described in any one of claim 129 to 135, wherein this coating and check that step is carried out within each container 1 second or shorter elapsed time.

145. inventions as described in any one of claim 129 to 135, wherein this coating and check that step is carried out within each container 30 seconds or shorter elapsed time.

146. inventions as described in any one of claim 129 to 135, wherein this coating and check that step is carried out within each container 25 seconds or shorter elapsed time.

147. inventions as described in any one of claim 129 to 135, wherein this coating and check that step is carried out within each container 20 seconds or shorter elapsed time.

148. inventions as described in any one of claim 129 to 135, wherein this coating and check that step is carried out within each container 15 seconds or shorter elapsed time.

149. inventions as described in any one of claim 129 to 135, wherein this coating and check that step is carried out within each container 10 seconds or shorter elapsed time.

150. inventions as described in any one of claim 129 to 135, wherein this coating and check that step is carried out within each container 8 seconds or shorter elapsed time.

151. inventions as described in any one of claim 129 to 135, wherein this coating and check that step is carried out within each container 7 seconds or shorter elapsed time.

152. inventions as described in any one of claim 129 to 135, wherein this coating and check that step is carried out within each container 6 seconds or shorter elapsed time.

153. inventions as described in any one of claim 129 to 135, wherein this coating and check that step is carried out within each container 5 seconds or shorter elapsed time.

154. inventions as described in any one of claim 129 to 135, wherein this coating and check that step is carried out within each container 4 seconds or shorter elapsed time.

155. inventions as described in any one of claim 129 to 135, wherein this coating and check that step is carried out within each container 3 seconds or shorter elapsed time.

156. inventions as described in any one of claim 129 to 135, be included in the step of carrying out this detection throughout the position of enough numbers on internal tank surface further, to determine that this container is greater than 20% of ambient atmosphere pressure by being increased to during the quality guaranteed period effectively preventing the pressure of within this container (when it is initially evacuated and its wall is exposed under ambient atmosphere) at least 18 months.

157. inventions as described in any one of claim 129 to 135, be included in the step of carrying out this detection throughout the position of enough numbers on internal tank surface further, to determine that this container is greater than 20% of ambient atmosphere pressure by being increased to during the quality guaranteed period effectively preventing the pressure of within this container (when it is initially evacuated and its wall is exposed under ambient atmosphere) at least two years.

158. inventions as described in any one of claim 129 to 135, be included in the step of carrying out this detection throughout the position of enough numbers on internal tank surface further, to determine that this container is greater than 15% of ambient atmosphere pressure by effectively preventing the pressure of within this container (when it is initially evacuated and its wall is exposed under ambient atmosphere) to be increased to during the quality guaranteed period of 1 year.

159. inventions as described in any one of claim 129 to 135, be included in the step of carrying out this detection throughout the position of enough numbers on internal tank surface further, to determine that this container is greater than 10% of ambient atmosphere pressure by effectively preventing the pressure of within this container (when it is initially evacuated and its wall is exposed under ambient atmosphere) to be increased to during the quality guaranteed period of 1 year.

160. inventions as described in any one of claim 129 to 159, wherein this inspection is by be inserted in this container via this container port by a source of radiation and use a detector to be undertaken by the situation radiation from this source of radiation being detected to this coating.

161. inventions as described in any one of claim 129 to 160, comprise further and make the outside radiation of energy by this coating and wall of container and detect this energy with the detector being positioned at this external container.

162. inventions as described in any one of claim 129 to 161, comprise reflection further from the radiation of this coating and wall of container and detect this energy with the detector being positioned at this internal tank.

163. inventions as described in any one of claim 129 to 162, the situation of this coating is detected in the position being included in the multiple tight spacings on this internal tank surface further.

To the air pressure that the coating inspection in the interior surface of container is wall of container by measuring blocking layer coating, 164. inventions as described in any one of claim 129 to 163, wherein stop that effect is carried out for defect.

165. inventions as described in any one of claim 117 to 164, wherein be The coating reduces atmospheric gas and are entered in this container by its interior surface transmission.

166. inventions as described in any one of claim 117 to 165, wherein The coating reduces the content of container and the contact of interior surface.

167. inventions as described in any one of claim 117 to 166, wherein this coating comprises SiO _x, elemental carbon or the combination of these one, wherein in this formula, x is from about 1.5 to about 2.9, alternately from about 1.5 to about 2.6, alternately about 2.

168. inventions as described in any one of claim 77 to 167, remove this container from this pan straddle after being included in the interior surface of the container that this second treatment station process is taken a seat further.

169. inventions as described in claim 168, comprise further:

After removing step, provide a second container, this second container has an opening and defines a wall of an interior surface; And

The opening of this second container is seated on this container port.

170. inventions as described in any one of claim 168 to 169, are included in the interior surface of the second container that this first treatment station is taken a seat via this container port process further.

171. inventions as described in any one of claim 168 to 170, comprise further and pan straddle and the second container of taking a seat are transported to this second treatment station from this first treatment station.

172. inventions as described in any one of claim 168 to 171, are included in this second treatment station further via this second container of taking a seat of this container port process.

173. inventions as described in any one of claim 77 to 172, comprise further and form this container in a mold, removed by container from mould, and after being removed from mould by container within 60 seconds, vessel port is seated on this container port.

174. inventions as described in any one of claim 77 to 173, comprise further and form this container in a mold, removed by container from mould, and after being removed from mould by container within 30 seconds, vessel port is seated on this container port.

175. inventions as described in any one of claim 77 to 174, comprise further and form this container in a mold, removed by container from mould, and after being removed from mould by container within 25 seconds, vessel port is seated on this container port.

176. inventions as described in any one of claim 77 to 175, comprise further and form this container in a mold, removed by container from mould, and after being removed from mould by container within 20 seconds, vessel port is seated on this container port.

177. inventions as described in any one of claim 77 to 176, comprise further and form this container in a mold, removed by container from mould, and after being removed from mould by container within 15 seconds, vessel port is seated on this container port.

178. inventions as described in any one of claim 77 to 177, comprise further and form this container in a mold, removed by container from mould, and after being removed from mould by container within 10 seconds, vessel port is seated on this container port.

179. inventions as described in any one of claim 77 to 178, comprise further and form this container in a mold, removed by container from mould, and after being removed from mould by container within 5 seconds, vessel port is seated on this container port.

180. inventions as described in any one of claim 77 to 179, comprise further and form this container in a mold, removed by container from mould, and after being removed from mould by container within 3 seconds, vessel port is seated on this container port.

181. inventions as described in any one of claim 77 to 180, comprise further and form container in a mold, removed by container from mould, and after being removed from mould by container within 1 second, vessel port is seated on this container port.

III.B. treatment facility is transported on pan straddle or vice versa.

182. one kinds of methods for the treatment of container, the method comprises:

There is provided one for the treatment of the first treatment facility of container;

There is provided one for the treatment of the second treatment facility of these containers;

There is provided a kind of container, this container has an opening and defines a wall of an interior surface;

There is provided a pan straddle, this pan straddle comprises a container port;

The opening of this container is made to be seated on this container port;

In this first treatment facility being moved into engage with the operability of this pan straddle, or vice versa;

Use this first treatment facility via the interior surface of this this container of taking a seat of container port process;

In this second treatment facility being moved into engage with the operability of this pan straddle, or vice versa; And

Use this second treatment facility via the interior surface of this this container of taking a seat of container port process.

183. inventions as described in claim 182, comprise further:

There is provided one for the treatment of the 3rd treatment facility of container;

In 3rd treatment facility being moved into engage with the operability of this pan straddle, or vice versa;

Use the 3rd treatment facility via the interior surface of this this container of taking a seat of container port process;

184. inventions as described in claim 182 or 183, wherein this container is generally tubular.

185. inventions as described in any one of claim 182 to 184, wherein this opening is positioned at an end of this container.

186. inventions as described in any one of claim 182 to 185, wherein this container is made up of thermoplastic material.

187. inventions as described in any one of claim 182 to 186, wherein this container is made up of polyethylene terephthalate.

188. inventions as described in any one of claim 182 to 187, wherein this container is made up of polyolefine.

189. inventions as described in any one of claim 182 to 186, wherein this container is made up of polypropylene.

190. inventions as described in any one of claim 182 to 189, wherein when being exposed to the external pressure of one 760 holder, this container can be sufficiently solid to stand one inner vacuum and not being out of shape in fact in fact completely.

191. inventions as described in any one of claim 182 to 190, wherein this container is by carrying out injection moulding to provide to it.

192. inventions as described in any one of claim 182 to 191, wherein this container is by carrying out blow molding to provide to it.

193. inventions as described in any one of claim 182 to 192, wherein this pan straddle comprises a vacuum pipe further, and this vacuum pipe is for withdrawing gas from the container be seated on this container port.

194. inventions as described in claim 193, wherein this pan straddle comprises a vacuum ports further, and this vacuum ports is communicated with between this vacuum pipe with an external vacuum source.

195. inventions as described in claim 194, wherein this vacuum ports has reception external vacuum source and forms an O type circle of a sealing thereon.

196. inventions as described in any one of claim 182 to 195, wherein this pan straddle comprises a gas entry ports further, and this gas entry ports is for delivering gas in the container be seated on this container port.

197. inventions as described in any one of claim 182 to 196, wherein this pan straddle vacuum ports of comprising a composite gas input port and being communicated with this container port, these ports are accordingly for delivering into a kind of gas in the container be seated on this container port and therefrom extracting a kind of gas out.

198. inventions as described in any one of claim 182 to 197, wherein this pan straddle is made up of thermoplastic material.

199. inventions as described in any one of claim 182 to 198, wherein this container port has reception vessel port and forms an O type circle of a sealing thereon.

200. inventions as described in any one of claim 182 to 199, one of them treatment facility is configured to check for the interior surface of defect to a container

201. inventions as described in any one of claim 182 to 200, one of them treatment facility is configured to a coating to be applied in the interior surface of a container.

202. inventions as described in any one of claim 182 to 201, one of them treatment facility is configured to check a coating for defect.

203. inventions as described in any one of claim 182 to 202, one of them treatment facility is configured to measure the atmospheric pressure lost by a wall of container.

204. inventions as described in any one of claim 182 to 203, one of them treatment facility comprises an area supported, and this area supported is used for supporting this pan straddle simultaneously by the interior surface of this this container of taking a seat for the treatment of facility process in a predetermined position.

205. inventions as described in claim 204, wherein, after being seated on this container port by the opening of this container, this pan straddle is transported in the joint entered with this area supported.

206. inventions as described in any one of claim 182 to 205, wherein another treatment facility comprises second area supported, and this second area supported is used for supporting this pan straddle simultaneously by the interior surface of other these containers of taking a seat for the treatment of facility process in a predetermined position.

207. inventions as described in claim 206, wherein, after being seated on this container port by the opening of this container, this pan straddle is transported and enters with the joint of this second area supported.

208. inventions as described in any one of claim 182 to 207, wherein another treatment facility comprises the 3rd area supported, and the 3rd area supported is used for supporting in a predetermined position interior surface of the container that this pan straddle is taken a seat via this container port process with other treatment facilities simultaneously.

209. inventions as described in claim 208, wherein, after being seated on this container port by the opening of this container, this pan straddle is transported and enters with the joint of the 3rd area supported.

210. inventions as described in any one of claim 182 to 209, comprise further:

3rd treatment facility is provided, the 3rd treatment facility and this first and second treatment facility spaced apart, for the treatment of container;

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 via the interior surface of this this container of taking a seat of container port process.

211. inventions as described in any one of claim 182 to 210, are included in a treatment facility place further and are seated on this container port by the opening of this container.

212. inventions as described in any one of claim 182 to 211, are included in a treatment facility place further and on the inside of a container, form a coating via this container port.

213. inventions as described in any one of claim 182 to 212, wherein comprise in the process at a treatment facility place and checking for the interior surface of defect to a container.

214. inventions as described in claim 213, wherein this inspection is by a detection probe to be inserted in this container via this container port and the situation using this probe to detect this internal tank surface is carried out.

215. inventions as described in claim 214, to comprise energy further inwardly by this wall of container and internal tank surface and by this detected energy of popping one's head in.

216. inventions as described in claim 214 or 215, are included in the situation of the position detection receptacle interior surface of the multiple tight spacings on this internal tank surface further.

217. inventions as described in any one of claim 213 to 216, wherein check it is by be inserted in this container via this container port by a source of radiation and carried out with the condition of detection receptacle interior surface by the radiation using a detector to detect this source of radiation from the beginning.

218. inventions as described in any one of claim 213 to 217, comprise further and make the outside radiation of energy by this internal tank surface and detect this energy with the detector being positioned at this external container.

219. inventions as described in any one of claim 215 to 216, comprise reflection further from the radiation on internal tank surface and detect this energy with the detector being positioned at this internal tank.

220. inventions as described in any one of claim 213 to 219, are included in the situation of the position detection receptacle interior surface that the multiple tight spacings on this internal tank surface are opened further.

221. inventions as described in any one of claim 182 to 220, the process at one of them treatment facility place comprises and a coating being applied in the interior surface of a container.

222. inventions as described in any one of claim 182 to 221, the process at one of them treatment facility place comprises and a coating being applied in liquid form in the interior surface of a container.

223. inventions as described in any one of claim 182 to 222, wherein comprise in the process at a treatment facility place and checking the coating in the interior surface of a container for defect.

224. inventions as described in any one of claim 221 to 223, comprise and a detection probe to be inserted in this container via this container port and to use this probe to detect the situation of this coating.

225. inventions as described in any one of claim 221 to 224, to comprise energy further and inwardly detect this energy by this wall of container with this probe.

226. inventions as described in any one of claim 221 to 225, the situation of this coating is detected in the position being included in the multiple tight spacings on this internal tank surface further.

227. inventions as described in any one of claim 223 to 131, be included in the step of carrying out this inspection throughout the position of enough numbers on internal tank surface further, to determine that this container is greater than 20% of ambient atmosphere pressure by effectively preventing the pressure of within this container (when it is initially evacuated and its wall is exposed under ambient atmosphere) to be increased to during the quality guaranteed period of 1 year.

228. inventions as described in any one of claim 223 to 227, wherein this inspection step is carried out within each container 30 seconds or shorter elapsed time.

229. inventions as described in any one of claim 223 to 227, wherein this inspection step is carried out within each container 25 seconds or shorter elapsed time.

230. inventions as described in any one of claim 223 to 227, wherein this inspection step is carried out within each container 20 seconds or shorter elapsed time.

231. inventions as described in any one of claim 223 to 227, wherein this inspection step is carried out within each container 15 seconds or shorter elapsed time.

232. inventions as described in any one of claim 223 to 227, wherein this inspection step is carried out within each container 10 seconds or shorter elapsed time.

233. inventions as described in any one of claim 223 to 227, wherein this coating and check that step is carried out within each container 30 seconds or shorter elapsed time.

234. inventions as described in any one of claim 223 to 227, wherein this coating and check that step is carried out within each container 25 seconds or shorter elapsed time.

235. inventions as described in any one of claim 223 to 227, wherein this coating and check that step is carried out within each container 20 seconds or shorter elapsed time.

236. inventions as described in any one of claim 223 to 227, wherein this coating and check that step is carried out within each container 15 seconds or shorter elapsed time.

237. inventions as described in any one of claim 223 to 227, wherein this coating and check that step is carried out within each container 10 seconds or shorter elapsed time.

238. inventions as described in any one of claim 223 to 227, be included in the step of carrying out this detection throughout the position of enough numbers on internal tank surface further, to determine that this coating is greater than 20% of ambient atmosphere pressure by being increased to during the quality guaranteed period effectively preventing the pressure of within this container (when it is initially evacuated and its wall is exposed under ambient atmosphere) at 18 months.

239. inventions as described in any one of claim 224 to 227, be included in the step of carrying out this detection throughout the position of enough numbers on internal tank surface further, to determine that this coating is greater than 20% of ambient atmosphere pressure by being increased to during the quality guaranteed period effectively preventing the pressure of within this container (when it is initially evacuated and its wall is exposed under ambient atmosphere) at least two years.

240. inventions as described in any one of claim 223 to 227, be included in the step of carrying out this detection throughout the position of enough numbers on internal tank surface further, to determine that this coating is greater than 15% of ambient atmosphere pressure by effectively preventing the pressure of within this container (when it is initially evacuated and its wall is exposed under ambient atmosphere) to be increased to during the quality guaranteed period of 1 year.

241. inventions as described in any one of claim 223 to 227, be included in the step of carrying out this detection throughout the position of enough numbers on internal tank surface further, to determine that this coating is greater than 10% of ambient atmosphere pressure by effectively preventing the pressure of within this container (when it is initially evacuated and its wall is exposed under ambient atmosphere) to be increased to during the quality guaranteed period of 1 year.

242. inventions as described in any one of claim 223 to 241, wherein this inspection is by be inserted in this container via this container port by a source of radiation and use a detector to be undertaken by the situation radiation from this source of radiation being detected to this coating.

243. inventions as described in any one of claim 223 to 242, comprise further and make the outside radiation of energy by this coating and wall of container and detect this energy with the detector being positioned at this external container.

244. inventions as described in any one of claim 223 to 243, comprise reflection further from the radiation of this coating and wall of container and detect this energy with the detector being positioned at this internal tank.

245. inventions as described in any one of claim 223 to 244, the situation of this coating is detected in the position being included in the multiple tight spacings on this internal tank surface further.

To the air pressure that the coating inspection in the interior surface of container is wall of container by measuring coating, 246. inventions as described in any one of claim 223 to 245, wherein stop that effect is carried out for defect.

247. inventions as described in any one of claim 212 to 246, wherein be The coating reduces atmospheric gas and are entered in this container by its interior surface transmission.

248. inventions as described in any one of claim 212 to 247, wherein The coating reduces the content of container and the contact of interior surface.

249. inventions as described in any one of claim 212 to 248, wherein this coating comprises SiO _x, wherein in this formula, x is from about 1.5 to about 2.9, alternately from about 1.5 to about 2.6, alternately about 2, elemental carbon, a kind of material based on fluorine, Si _wo _xc _yh _z, to be wherein 1, x be w from about 0.5 to 2.4, y is from about 0.6 to about 3, and z is from 2 to about 9, or these one combination.

250. inventions as described in any one of claim 182 to 249, remove container from pan straddle after being included in the interior surface of the container of taking a seat with the second treatment facility process further.

251. inventions as described in claim 250, comprise further:

After this removes step, provide a second container, this second container has an opening and defines a wall of an interior surface; And

The opening of this second container is seated on this container port.

252. inventions as described in any one of claim 250 to 251, comprise the interior surface of the second container of taking a seat via this container port process with the first treatment facility further.

253. inventions as described in any one of claim 250 to 252, comprise further and this pan straddle and the second container of taking a seat are transported to this second treatment facility from this first treatment facility.

254. inventions as described in any one of claim 250 to 253, comprise the second container of taking a seat via this container port process with the second treatment facility further.

255. inventions as described in any one of claim 182 to 254, comprise further and form this container in a mold, removed by container from mould, and after being removed from mould by container within 60 seconds, vessel port is seated on this container port.

256. inventions as described in any one of claim 182 to 255, comprise further and form this container in a mold, removed by container from mould, and after being removed from mould by container within 30 seconds, vessel port is seated on this container port.

257. inventions as described in any one of claim 182 to 256, comprise further and form this container in a mold, removed by container from mould, and after being removed from mould by container within 25 seconds, vessel port is seated on this container port.

258. inventions as described in any one of claim 182 to 257, comprise further and form this container in a mold, removed by container from mould, and after being removed from mould by container within 20 seconds, vessel port is seated on this container port.

259. inventions as described in any one of claim 182 to 258, comprise further and form this container in a mold, removed by container from mould, and after being removed from mould by container within 15 seconds, vessel port is seated on this container port.

260. inventions as described in any one of claim 182 to 259, comprise further and form this container in a mold, removed by container from mould, and after being removed from mould by container within 10 seconds, vessel port is seated on this container port.

261. inventions as described in any one of claim 182 to 260, comprise further and form this container in a mold, removed by container from mould, and after being removed from mould by container within 5 seconds, vessel port is seated on this container port.

262. inventions as described in any one of claim 182 to 261, comprise further and form this container in a mold, removed by container from mould, and after being removed from mould by container within 3 seconds, vessel port is seated on this container port.

263. inventions as described in any one of claim 182 to 260, comprise further and form this container in a mold, removed by container from mould, and after being removed from mould by container within 1 second, vessel port is seated on this container port.

III.C. clamp is used to be used for pipe to transport enter or leave coating station

264. one kinds are carried out the method for PECVD process to first container, and the method comprises:

There is provided first container, this first container has an opening end, a closing end and an interior surface;

There is provided at least one first clamp, this first clamp is configured to for optionally keeping and discharging the closing end of this first container;

The closing end of this first container is clamped with this first clamp;

Use this first clamp, be transported to by this first container near a pan straddle, this pan straddle is configured to the opening end of this first container is taken a seat;

Use this first clamp, this first container axially advanced and its opening end is seated on this pan straddle, being based upon being communicated with of the sealing between this pan straddle and the inside of this first container;

By this pan straddle, at least one gaseous reactant is introduced in this first container;

The interior surface of this first container forms plasma body under the condition of a kind of reaction product of effective forming reactions thing in 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 and leaves this pan straddle; And

This first container is discharged from being used for axially it being transported from this pan straddle in the clamp that leaves.

265. inventions as described in claim 264, comprise further:

There is provided a reaction vessel different from this first container, 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 the sealing between this pan straddle and internal space of this reaction vessel;

A PECVD reactant conduit is provided in this internal space;

In the internal space of reaction vessel, plasma body is formed under effective sedimental condition at least partially removing PECVD reaction product from reactant conduit;

This reaction vessel is disseated from this pan straddle; And

Transport this reaction vessel and leave this pan straddle.

266. inventions as described in claim 264 or 265, comprise further:

At least one second clamp is provided;

Operationally at least the first and second clamps are connected on the transfer roller of a series connection;

Provide a second container, this second container has an opening end, a closing end and an interior surface.

There is provided a clamp, this clamp is configured to for optionally keeping and discharging the closing end of this second container;

The closing end of this second container is clamped with this clamp;

Use this clamp, be transported to by this second container near a pan straddle, this pan straddle is configured to this opening end to this second container is taken a seat;

Use this clamp, this second container axially advanced and its opening end is seated on this pan straddle, being based upon being communicated with of the sealing between this pan straddle and inside of this second container;

By this pan straddle, at least one gaseous reactant is introduced in this second container;

The interior surface of this second container forms plasma body under the condition of a kind of reaction product of effective forming reactions thing in 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 from this pan straddle in the clamp that leaves.

IV. for the manufacture of the PECVD device of container

IV.A. pan straddle, interior electrode, PECVD device as the container of reaction chamber is comprised

267. one kinds of PECVD devices, comprising:

A pan straddle, this pan straddle has a port, this port by a container reception in the position of taking a seat to process;

An interior electrode, this interior electrode is located thus is received in the container be seated on a pan straddle;

An outer electrode, this outer electrode has an internal portion, and this internal portion is located to receive the container be seated on this pan straddle; And

A power supply, this power supply alternating-current is input to this inside and outer electrode one of at least in thus form plasma body being seated in the container on pan straddle, the container define a plasma-reaction-chamber;

268. inventions as described in claim 267, wherein this interior electrode is a probe with distal portions, and this distal portions is located thus extended into roughly concentrically in the container be seated on this pan straddle.

The invention of 268a. as described in claim 267 or 268, comprise a reactant gas source and a kind of gas feed device further, a kind of reactant gas is seated in a container this pan straddle from the feeding of this reactant gas source by this gas feed device.

269. inventions as described in claim 268a, wherein this gas feed device is the distal portions being positioned at this electrode.

270. inventions as described in claim 268a or 269, are included in a passage within this interior electrode further, and this passage is used for the distal portions this reactant gas being delivered to this interior electrode from this reactant gas source.

271. inventions as described in any one of claim 267 to 270, comprise a carrier gas source and a passage within this interior electrode further, and this passage is used for the distal portions a kind of carrier gas being delivered to this interior electrode from this carrier gas source.

272. inventions as described in any one of claim 267 to 271, wherein this outer electrode is substantial cylindrical and is located to extend roughly concentrically around the container be seated on this pan straddle.

273. inventions as described in any one of claim 267 to 272, wherein this outer electrode comprises an end cap.

274. inventions as described in claim 273, wherein at this end cap and to be seated at the gap limited between the far-end of a container on this pan straddle be basically identical.

275. inventions as described in any one of claim 267 to 274, the gap wherein limited between this outer electrode and the container being seated on this pan straddle is basically identical.

276. as claim 117 to 167 or 212 to 168 any one as described in invention, wherein this coating comprises a SiO _xlayer and a Si _wo _xc _yh _zlayer, wherein w is 1, and in this formula, 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.

278. inventions as described in claim 276 or 277, wherein this Si _wo _xc _yh _zlayer is deposited on a SiOx layer, this SiO _xlayer is deposited in the interior surface of this container.

279. inventions as described in claim 276 or 277, wherein this SiO _xlayer is deposited over this Si _wo _xc _yh _zbetween layer and the interior surface of container.

280. inventions as described in any one of claim 276 to 279, wherein this SiO _xlayer is deposited over Si _wo _xc _yh _znear layer.

281. inventions as described in any one of claim 276 to 280, wherein this SiO _xlayer is deposited near the interior surface of container.

282. inventions as described in any one of claim 276 to 280, wherein this Si _wo _xc _yh _zlayer is deposited near the interior surface of this container.

283. inventions as described in any one of claim 280 to 282, wherein SiO _xwith Si _wo _xc _yh _zlayer is a kind of Si _wo _xc _yh _zto SiO _xgraded composite thing.

284. inventions as described in any one of claim 267 to 283, wherein this container comprises a closure member further.

285. inventions as described in claim 284, wherein this closure member comprises the surface towards inside that is exposed to the inner chamber of container.

286. inventions as described in claim 284 or 285, wherein this closure member comprises the surface of a contact wall, and this surface contacts with the interior surface of this wall of container.

287. inventions as described in any one of claim 284 to 286, wherein this closure member comprises a stopper.

288. inventions as described in claim 287, wherein this closure member comprises a shield [support, and this stopper is clamped among this shield [support.

289. inventions as described in claim 287 or 288, wherein this stopper comprises the surface of a contact wall, and this surface contacts with the internal surface of this wall of container

290. inventions as described in any one of claim 284 to 289, wherein this stopper comprises a surface towards inside, and this surface is exposed to the inner chamber of container.

The invention of 290a. as described in any one of claim 267 to 290, comprise a vacuum source for removing gas from the container be seated on pan straddle further, this container of taking a seat defines a vacuum chamber.

291. as claim 284 to 290a any one as described in invention, a part for the wall of container wherein contacted with the surface of the contact wall of this closure member is coated with a Si _wo _xc _yh _zslip coating

301. inventions as described in any one of claim 284 to 300, wherein this Si _wo _xc _yh _zcoating is applied by PECVD.

302. inventions as described in any one of claim 291 to 301, wherein this Si _wo _xc _yh _zcoating has the thickness between 0.5nm and 5000nm.

303. inventions as described in any one of claim 291 to 301, wherein this Si _wo _xc _yh _zcoating has the thickness between 100nm and 5000nm.

304. inventions as described in any one of claim 291 to 301, wherein this Si _wo _xc _yh _zcoating has the thickness between 200nm and 5000nm.

305. inventions as described in any one of claim 291 to 301, wherein this Si _wo _xc _yh _zcoating has the thickness between 500nm and 5000nm.

306. inventions as described in any one of claim 291 to 301, wherein this Si _wo _xc _yh _zcoating has the thickness between 1000nm and 5000nm.

307. inventions as described in any one of claim 291 to 301, wherein this Si _wo _xc _yh _zcoating has the thickness between 2000nm and 5000nm.

308. inventions as described in any one of claim 291 to 301, wherein this Si _wo _xc _yh _zcoating has the thickness between 3000nm and 5000nm.

309. inventions as described in any one of claim 291 to 301, wherein this Si _wo _xc _yh _zcoating there is thickness between 4000nm and 10,000nm.

310.PECVD device, comprising:

A pan straddle, this pan straddle have a port with by a container reception in the position of taking a seat to process;

An interior electrode, this interior electrode is located thus is received in the container be seated on a pan straddle;

An outer electrode, this outer electrode has an internal portion, and this internal portion is located to receive the container be seated on this pan straddle,

A power supply, alternating-current to be input on inner and outer electrode thus to form plasma body being seated in the container on this pan straddle by this power supply;

An eduction pipe, this eduction pipe is for being transferred to the inside of the container be seated on port or leaving from its transfer thus limit a closed-chamber by gas;

A reactant gas source; And

A gas feed device, a kind of reactant gas is seated in a container this pan straddle from the feeding of this reactant gas source by this gas feed device.

IV.B. clamp is used to be used for being transported to by pipe or leaving the PECVD device of coating station

311. for carrying out the device of PECVD process to first container, this first container has an opening end, a closing end and an internal space, and this device comprises:

A pan straddle, this pan straddle is configured to for making the opening end of container take a seat;

First clamp, this first clamp is configured to for optionally keeping and discharging the closing end of container, and clamps the closing end of container simultaneously, is transported to by this container near this pan straddle;

A seat on this pan straddle, this is configured to for being based upon being communicated with of sealing between this pan straddle and the internal space of this first container;

A reactant feeding mechanism, this reactant feeding mechanism is operably connected for being incorporated in this first container by this pan straddle by least one gaseous reactant;

A plasma generator, in the interior surface that this plasma generator is configured in this first container effective a kind of reaction product of forming reactions thing condition under in this first container, form plasma body;

A kind of container releasing device, this container releasing device is used for this first container is disseated from this pan straddle; And

A clamp, this clamp is this first clamp or another clamp, and this clamp is configured to leave this pan straddle for axially transporting this first container, and then discharges this first container.

312. inventions as described in claim 311, comprise further:

A reaction vessel different from this first container, this reaction vessel has an opening end and an internal space and to be configured to its opening end to be seated on this pan straddle and to be based upon being communicated with of the sealing between this pan straddle and internal space of this reaction vessel; And

A PECVD reactant conduit, when this reaction vessel is seated on this pan straddle, this conduit is located thus is located within the internal space of reaction vessel;

Wherein this plasma generator can be configured to for forming plasma body under effective sedimental condition at least partially removing PECVD reaction product from reactant conduit in the internal space of reaction vessel.

313. inventions as described in claim 311 or 312, comprise further:

The transfer roller of a series connection, the transfer roller of this series connection is configured to for transporting clamp; And

Second clamp, this second clamp is configured to, for optionally keeping and discharging the closing end of container, clamp the closing end of container simultaneously, be transported near this pan straddle by this container.

The transfer roller that this first and second clamp is operably connected to this series connection is configured to for being in turn transported near this pan straddle by least two containers a series, the opening end of these containers is made to be seated on this pan straddle, be based upon being communicated with of the sealing between this pan straddle and inside of this second container, these containers are axially transported and leaves this pan straddle, and discharge these containers from these clamps.

V.B. the opening (capillary injector) of the PECVD coating restriction of container

316. one kinds for applied by PECVD a generally tubular have the interior surface of the opening of the restriction of pending container method, the method comprises:

What provide a generally tubular has pending container, this container comprises an outside surface, defines an internal surface of an inner chamber, has one of an internal diameter compared with big uncork and an opening limited, and the opening of this restriction is limited by an internal surface and has the internal diameter less compared with the internal diameter of big uncork compared to this.

There is provided a processing vessel, this container has an inner chamber and a processing vessel opening;

This processing vessel opening to be connected with the opening of the restriction having pending container thus opening via this restriction is based upon the inner chamber of pending container and being communicated with between processing vessel inner chamber;

At least part of vacuum is pumped into by having in the inner chamber of pending container and processing vessel inner chamber;

Making PECVD reagent flow by this first opening, then by there being the inner chamber of pending container, then by the opening of this restriction, then entering processing vessel inner chamber; And

Near the opening of this restriction, plasma body is produced under condition on the internal surface of the opening coating of a PECVD reaction product being effectively deposited on restriction.

317. methods as described in claim 316, wherein have pending container to be a syringe cylinder.

318. methods as described in claim 316 or 317, wherein the opening of this restriction has first joint, and this processing vessel opening has second joint, this second joint to be adapted to be seated on this first joint thus to be based upon this processing vessel inner chamber and to have being communicated with between the inner chamber of pending container.

319. methods as described in claim 318, wherein this first and second joint is luer lock joint.

320. methods as described in claim 319, wherein one of being at least made up of electro-conductive material of this first and second joint.

321. methods as described in claim 299,319 or 320, wherein one of being at least made up of electro-conductive material of this first and second joint.

322. methods as described in claim 299,319,320 or 299a2, wherein one of being at least made up of stainless steel of this first and second joint.

323. methods as described in claim 319, the first and second wherein corresponding luer lock joints are outer luer lock joint and interior luer lock joint.

324. methods as described in claim 299,319 or 323, comprise the sealing member be positioned between this first and second joint further.

325. as described in claim 324 method, wherein the seal comprises an O type circle.

326. methods as described in claim 319,323,324 or 325, wherein when these joints are engaged, one of these joints comprise a lock collar, this lock collar there is a kind of screw thread and define an axial plane to, the first bearing of general toroidal, and other joints comprise one towards this first bearing axial plane to, the second bearing of general toroidal.

327. methods as described in claim 326, comprise the lip ring be bonded between this first and second bearing further.

328. methods as described in any one of claim 316 to 318, being wherein based upon the inner chamber of pending container with being communicated with between processing vessel inner chamber via the opening of this restriction is leakproof at least substantially.

329. methods as described in any one of claim 316 to 328, wherein make a kind of PECVD reagent flow by there being being undertaken by following steps compared with big uncork of pending container:

There is provided the interior electrode of a generally tubular, this electrode has an internal passages, a near-end, a far-end and this far-end contiguous and the distal openings be communicated with this internal passages;

This electrode distal end is inserted with pending container compared with near big uncork or wherein; And

Feeding reactant gas is with in the inner chamber of pending container by the distal openings of electrode.

330. methods as described in claim 329, wherein when feeding reactant gas, the far-end of electrode has locating to the half of the distance of the opening of this restriction compared with big uncork of pending container to be less than from this.

331. methods as described in claim 329, wherein when feeding reactant gas electrode far-end be less than from have pending container compared with big uncork to the opening of this restriction distance 40% and locate.

332. methods as described in claim 329, wherein when feeding reactant gas electrode far-end be less than from have pending container compared with big uncork to the opening of this restriction distance 30% and locate.

333. methods as described in claim 329, wherein when feeding reactant gas electrode far-end be less than from have pending container compared with big uncork to the opening of this restriction distance 20% and locate.

334. methods as described in claim 329, wherein when feeding reactant gas electrode far-end be less than from have pending container compared with big uncork to the opening of this restriction distance 15% and locate.

335. methods as described in claim 329, wherein when feeding reactant gas electrode far-end be less than from have pending container compared with big uncork to the opening of this restriction distance 10% and locate.

336. methods as described in claim 329, wherein when feeding reactant gas electrode far-end be less than from have pending container compared with big uncork to the opening of this restriction distance 8% and locate.

337. methods as described in claim 329, wherein when feeding reactant gas electrode far-end be less than from have pending container compared with big uncork to the opening of this restriction distance 6% and locate.

338. methods as described in claim 329, wherein when feeding reactant gas electrode far-end be less than from have pending container compared with big uncork to the opening of this restriction distance 4% and locate.

339. methods as described in claim 329, wherein when feeding reactant gas electrode far-end be less than from have pending container compared with big uncork to the opening of this restriction distance 2% and locate.

340. methods as described in claim 329, wherein when feeding reactant gas electrode far-end be less than from have pending container compared with big uncork to the opening of this restriction distance 1% and locate.

341. methods as described in claim 329, wherein when feeding reactant gas, the far-end of electrode is positioned in this and has in the comparatively big uncork of pending container.

342. methods as described in claim 329, wherein when feeding reactant gas, the far-end of electrode is positioned in the outside compared with big uncork that this has pending container.

343. methods as described in any one of claim 329 to 342, the far-end of this electrode is positioned in the far-end of the opening of this restriction.

344. methods as described in any one of claim 329 to 343, wherein during deposition PECVD reaction product, this electrode is moved axially.

345. methods as described in any one of claim 316 to 344, wherein this plasma body fills the air the opening throughout syringe inner chamber and this restriction substantially.

346. methods as described in any one of claim 316 to 345, wherein this plasma body fills the air opening throughout this syringe inner chamber, this restriction and this processing vessel inner chamber substantially.

347. methods as described in any one of claim 316 to 346, wherein this plasma body has basically identical color throughout the opening of syringe inner chamber and this restriction.

348. methods as described in any one of claim 316 to 347, wherein this plasma body has basically identical color throughout the opening of this syringe inner chamber, this restriction and this processing vessel inner chamber substantially.

349. methods as described in any one of claim 316 to 348, wherein this plasma body is substantially stable throughout the opening of this syringe inner chamber and this restriction.

350. methods as described in any one of claim 316 to 349, wherein this plasma body is substantially stable throughout the opening of this syringe inner chamber, this restriction and this processing vessel inner chamber.

351. methods as described in any one of claim 316 to 350, wherein the vessel port of this processing vessel is unique opening.

352. methods as described in any one of claim 316 to 351, wherein the volume of this processing vessel inner chamber is less than 3 times that this has the volume of the inner chamber 300 of pending container 250.

353. methods as described in any one of claim 316 to 352, wherein the volume of this processing vessel inner chamber is less than 2 times that this has the cavity volume of pending container.

354. methods as described in any one of claim 316 to 353, wherein the volume of this processing vessel inner chamber is less than the volume that this has the inner chamber of pending container.

355. methods as described in any one of claim 316 to 354, wherein the volume of this processing vessel inner chamber be less than that this has the volume of the inner chamber 300 of pending container 250 50%.

356. methods as described in any one of claim 316 to 355, wherein the volume of this processing vessel inner chamber is be less than that this has the volume of the inner chamber 300 of pending container 250 25%.

357. methods as described in any one of claim 316 to 356, be included in further by have in the inner chamber 300 of pending container 250 be pumped at least part of vacuum before make this have the comparatively big uncork of pending generally tubular container to be seated on pan straddle.

358. methods as described in claim 357, comprise further and make being seated on a port of this pan straddle compared with big uncork of pending container.

359. methods as described in claim 357 or 358, comprise an interior positioning of electrode further being seated at having in pending container on this pan straddle.

360. methods as described in claim 357,358 or 359, comprise further and will pending container be had to locate relative to an outer electrode, this outer electrode has an internal portion, this internal portion located to receive pending while be seated at container on pan straddle.

361. methods as described in claim 357,358,359 or 330, comprise further with this outer electrode of power feed alternating current driver thus form plasma body being seated at having within pending container on this pan straddle.

362. methods as described in claim 361, comprise further and make this interior electrode ground connection.

363. methods as described in claim 357,358,359,360 or 361, comprise further and provide a vacuum source with the inside of pending container of finding time, this has pending container to define a vacuum chamber.

364. methods as described in claim 363, comprising further providing has second vacuum chamber of pending container around this.

365. methods as described in claim 364, under wherein the inside of this container is maintained at the vacuum level lower than this second vacuum chamber.

366. methods as described in claim 363, wherein this processing vessel is the conduit be communicated with the vacuum ports of in pan straddle.

367. methods as described in any one of claim 357 to 366, comprise a reactant gas source and a gas feed device further, a kind of reactant gas is seated at having in pending container this pan straddle from the feeding of this reactant gas source by this gas feed device.

VI. container inspection

V1.A. the container process of precoating and rear coating inspection is comprised

399. one kinds of container-treatments for processing shaping plastic containers, this container comprises an opening and defines a wall of an interior surface, and the method comprises:

Check for the interior surface of defect to shaping container;

After shaping container is checked, a coating is applied in the interior surface of this container; And

For defect, this coating is checked.

400. one kinds of container-treatments for processing shaping plastic containers, this container comprises an opening and defines a wall of an interior surface, and the method comprises:

Check for the interior surface of defect to shaping container;

After shaping container is checked, a barrier coat is applied on this container; And

After this barrier coat of applying, check for the interior surface of defect to container.

401. inventions as described in claim 400, the interior surface of position to shaping container of the multiple tight spacings wherein in the interior surface of this container checks.

402. inventions as described in claim 400 or 401, the interior surface of position to this container of the multiple tight spacings wherein after applying this barrier coat on this internal tank surface checks.

403. inventions as described in claim 400,401 or 402, the position of the multiple tight spacings wherein on this internal tank surface is by location and check on shaping container, apply with barrier coat, and reexamine after this barrier coat of applying.

VI.B. container inspection is carried out by detecting by the venting of the wall of container on blocking layer

404. one kinds for checking the method on the blocking layer on the material of letting off steam, the method comprises:

There is provided and release gas and the material sample with blocking layer at least partially; And

Measure the gas of this releasing.

405. methods as described in claim 404, wherein the material of this releasing gas comprises a kind of polymer compound.

406. methods as described in claim 404 or 405, wherein the material of this releasing gas comprises a kind of thermoplastic compound.

407. methods as described in any one of claim 404 to 406, wherein the material of this releasing gas comprises a kind of polyester.

408. methods as described in any one of claim 404 to 407, wherein the material of this releasing gas comprises polyethylene terephthalate.

409. methods as described in any one of claim 404 to 408, wherein the material of this releasing gas comprises a kind of polyolefine.

410. methods as described in any one of claim 404 to 409, wherein the material of this releasing gas comprises polypropylene.

411. methods as described in any one of claim 404 to 410, wherein the material of this releasing gas comprises a kind of cyclic olefine copolymer.

The method of 411a. as described in any one of claim 404 to 411, makes this blocking layer contact with water before being included in the gas measured and release further.

The method of 411b. as described in any one of claim 404-411, makes blocking layer contact with steam before being included in the gas measured and release further.

The method of 411c. as described in any one of claim 404 to 411, makes this blocking layer contact with the air under the relative humidity of 35% to 100% before being included in the gas measured and release further.

The method of 411d. as described in any one of claim 404 to 411, makes this blocking layer contact with the air under the relative humidity of 40% to 100% before being included in the gas measured and release further.

The method of 411e. as described in any one of claim 404 to 411, makes this blocking layer contact with the air under the relative humidity of 40% to 50% before being included in the gas measured and release further.

The method of 411f. as described in any one of claim 404 to 411, makes blocking layer contact with oxygen before being included in the gas measured and release further.

The method of 411g. as described in any one of claim 404 to 411, makes blocking layer contact with nitrogen before being included in the gas measured and release further.

The method of 411h. as described in any one of claim 411a to 411g, wherein this duration of contact is from 10 seconds to one hour.

The method of 411i. as described in any one of claim 411a to 411g, wherein this duration of contact is from one minute to 30 minutes

The method of 411j as described in any one of claim 411a to 411g, wherein this duration of contact is from 5 minutes to 25 minutes

The method of 411k. as described in any one of claim 411a to 411g, wherein this duration of contact is from 10 minutes to 20 minutes.

411l. as claim 404 to 411k any one as described in method, the gas of wherein this releasing is measuring to the pressure of 100 holders from 0.1 holder.

411m. as claim 404 to 411k any one as described in method, the gas of wherein this releasing is measuring to the pressure of 50 holders from 0.2 holder.

411n. as claim 404 to 411k any one as described in method, the gas of wherein this releasing is measuring to the pressure of 40 holders from 0.5 holder.

411o. as claim 404 to 411k any one as described in method, the gas of wherein this releasing is measuring to the pressure of 30 holders from 1 holder.

411p. as claim 404 to 411k any one as described in method, the gas of wherein this releasing is measuring to the pressure of 100 holders from 5 holders.

411q. as claim 404 to 411k any one as described in method, the gas of wherein this releasing is measuring to the pressure of 80 holders from 10 holders.

411r. as claim 404 to 411k any one as described in method, the gas of wherein this releasing is measuring to the pressure of 50 holders from 15 holders.

411s. as claim 404 to 411r any one as described in method, the gas of wherein this releasing is measuring at the temperature of 0 DEG C to 50 DEG C.

411t. as claim 404 to 411r any one as described in method, the gas of wherein this releasing is measuring at the temperature of 0 DEG C to 21 DEG C.

411u. as claim 404 to 411r any one as described in method, the gas of wherein this releasing is measuring at the temperature of 5 DEG C to 20 DEG C.

412. as claim 404 to 411u any one as described in method, wherein provide with the form of the container with a wall and release the material of gas, this wall has an outside surface and an internal surface, and this internal surface is around an inner chamber.

413. methods as described in claim 412, wherein this blocking layer is disposed on the internal surface of this wall of container.

414. methods as described in claim 412 or 413, wherein provide by inner chamber of finding time at least in part the pressure difference that crosses this blocking layer.

415. methods as described in any one of claim 412 to 414, comprise further and being connected on a vacuum source with this inner chamber of finding time at least in part via pipeline by inner chamber.

416. methods as described in claim 415, comprise further and provide a measuring cell of exitting be communicated with between this inner chamber and this vacuum source.

417. methods as described in any one of claim 404 to 416, wherein measuring is undertaken by the volume of the material determining the releasing that each timed interval is exitted by this blocking layer.

418. methods as described in any one of claim 404 to 417, wherein measure and use microfluidic technology to carry out.

419. methods as described in any one of claim 404 to 418, wherein measuring is undertaken by the mass flow rate measuring the material of releasing.

420. methods as described in any one of claim 404 to 419, wherein measure and carry out with molecule flowing operation scheme.

The method of 420a. as described in any one of claim 404 to 420, wherein measure and undertaken by following steps:

There is provided at least one micro-cantilever, this micro-cantilever has and to move when a kind of material of releasing exists or to change over difform characteristic;

Under effectively causing this micro-cantilever to move or change over difform condition, this micro-cantilever is exposed in the material of this releasing; And

Then detect this to move or different shapes.

The method of 420b as described in claim 420a, wherein micro-cantilever is exposed to the different shapes before or after venting can by reflection from change shape micro-cantilever part high energy incident beam and measure and the deflection of reflected beam that produces of the some place at this micro-cantilever interval detect.

The method of 420c. as described in claim 420b, wherein this energy-incident bundle is selected from a kind of photon beam, a kind of electron beam or these the combination of two or more.

The method of 420d. as described in claim 420b, wherein this high energy incident beam is a kind of photon beam.

The method of 420e. as described in claim 420b, wherein this high energy incident beam is a kind of laser beam.

The method of 420f. as described in any one of claim 404 to 420, wherein measure and undertaken by following steps:

Provide at least one micro-cantilever, when a kind of material of releasing exists, this micro-cantilever is with a different frequency resonance;

Under the condition of the frequency resonance effectively causing this micro-cantilever different with, can this micro-cantilever be exposed in the material of this releasing; And

Detect the resonant frequency that these are different.

The method of 420g. as described in claim 420f, wherein this different resonant frequency detected in energy input to micro-cantilever to induce its to resonate before or after being exposed to venting at this micro-cantilever.

The method of 420h. as described in claim 420g, wherein this different resonant frequency is that use resonant transducer detects.

421. methods as described in claim 404, wherein the material of this releasing gas provides in the form of a film.

422. methods as described in any one of claim 404 to 421, wherein this blocking layer is on the surface of the material of venting one coating wholly or in part.

425. methods as described in any one of claim 404 to 424, wherein this blocking layer comprises SiO _x, wherein x is from about 1.5 to about 2.9.

426. methods as described in any one 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. methods as described in any one of claim 404 to 426, to be wherein less than 500nm thick on this blocking layer.

428. methods as described in any one of claim 404 to 427, to be wherein less than 300nm thick on this blocking layer.

429. methods as described in any one of claim 404 to 428, to be wherein less than 100nm thick on this blocking layer.

430. methods as described in any one of claim 404 to 429, to be wherein less than 80nm thick on this blocking layer.

431. methods as described in any one of claim 404 to 430, to be wherein less than 60nm thick on this blocking layer.

432. methods as described in any one of claim 404 to 431, to be wherein less than 50nm thick on this blocking layer.

433. methods as described in any one of claim 404 to 432, to be wherein less than 40nm thick on this blocking layer.

434. methods as described in any one of claim 404 to 433, to be wherein less than 30nm thick on this blocking layer.

435. methods as described in any one of claim 404 to 434, to be wherein less than 20nm thick on this blocking layer.

436. methods as described in any one of claim 404 to 435, to be wherein less than 10nm thick on this blocking layer.

437. methods as described in any one of claim 404 to 436, to be wherein less than 5nm thick on this blocking layer.

438. methods as described in any one of claim 404 to 437 are wherein carry out effectively distinguishing under the existence on this blocking layer or the condition of shortage to the measurement of the gas of releasing.

439. methods as described in any one of claim 438, the condition of the existence or shortage of wherein effectively distinguishing this blocking layer comprises the test time being less than a minute.

440. methods as described in claim 438, the condition of the existence or shortage of wherein effectively distinguishing this blocking layer comprises the test time being less than 50 seconds.

441. methods as described in claim 438, the condition of the existence or shortage of wherein effectively distinguishing this blocking layer comprises the test time being less than 40 seconds.

442. methods as described in claim 438, the condition of the existence or shortage of wherein effectively distinguishing this blocking layer comprises the test time being less than 30 seconds.

443. methods as described in claim 438, the condition of the existence or shortage of wherein effectively distinguishing this blocking layer comprises the test time being less than 20 seconds.

444. methods as described in claim 438, the condition of the existence or shortage of wherein effectively distinguishing this blocking layer comprises the test time being less than 15 seconds.

445. methods as described in claim 438, the condition of the existence or shortage of wherein effectively distinguishing this blocking layer comprises the test time being less than 10 seconds.

446. methods as described in claim 438, the condition of the existence or shortage of wherein effectively distinguishing this blocking layer comprises the test time being less than 8 seconds.

447. methods as described in claim 438, the condition of the existence or shortage of wherein effectively distinguishing this blocking layer comprises the test time being less than 6 seconds.

448. methods as described in claim 438, the condition of the existence or shortage of wherein effectively distinguishing this blocking layer comprises the test time being less than 4 seconds.

449. methods as described in claim 438, the condition of the existence or shortage of wherein effectively distinguishing this blocking layer comprises the test time being less than 3 seconds.

450. methods as described in claim 438, the condition of the existence or shortage of wherein effectively distinguishing this blocking layer comprises the test time being less than 2 seconds.

451. methods as described in claim 438, the condition of the existence or shortage of wherein effectively distinguishing this blocking layer comprises the test time being less than 1 second.

452. methods as described in any one of claim 438-451, the observed value that wherein whether blocking layer exists is proved the determinacy reaching at least six σ levels.

453. methods as described in any one of claim 438 to 452, wherein this observed value has the determinacy of at least six σ levels.

454. methods as described in any one of claim 404 to 453, the measurement of the gas of the releasing of the low-tension side wherein on this blocking layer carries out under the condition of the barrier improvement factor effectively determining this blocking layer compared to the same material without blocking layer.

455. methods as described in any one of claim 404 to 454, wherein measure the venting of multiple gas with various.

456. methods as described in any one of claim 404 to 455, wherein measure the venting of the gas of releasings all in fact.

457. methods as described in any one of claim 404 to 456, wherein measure the venting of the gas of releasings all in fact simultaneously.

458. methods as described in any one of claim 404 to 457, wherein measure the venting of the gas of releasings all in fact simultaneously.

Claims (50)

1., for setting a method for the lubricity of coating on the surface of the substrate, the method comprises the following steps

(a) near this substrate surface providing package containing organosilicon precursor and optionally O ₂gaseous reactant; And

B () produces plasma body from this gaseous reactant, form coating thus by the chemical vapour deposition (PECVD) of plasma enhancing on this substrate surface,

Wherein said coating is measured by X-ray photoelectron spectroscopic (XPS) has following atomic ratio: Si _wo _xc _y, wherein w be 1, x in the scope of 0.5-2.4, and y is in the scope of 0.6 to 3,

Wherein the lubricating property of this coating is by setting O in this gaseous reactant ₂with the ratio of organosilicon precursor with to be set by the electric power set for generation of this plasma body, wherein O ₂exist with the amount that the volume-volume ratio with gaseous reactant is 0:1 to 0.5:1, and wherein said plasma body is produced by the electrode of the electric power being supplied to 0.1 to 25W.

2. method according to claim 1, the method causes being characterised in that the coating of wherein total formula that atomic ratio C:O increases and/or atomic ratio Si:O reduces compared with total formula of described organosilicon precursor.

3. the method described in claim 1 or 2, wherein O ₂exist with the amount that the volume-volume ratio with gaseous reactant is 0:1 to 0.1:1.

4. the method described in claim 1 or 2, wherein said gaseous reactant comprises the O being less than 1 volume % ₂.

5. method according to claim 4, wherein said gaseous reactant comprises the O being less than 0.5 volume % ₂.

6. method according to claim 4, wherein said gaseous reactant is not containing O ₂.

7. the method described in claim 1 or 2, wherein said plasma body is non-hollow cathode plasma.

8. the method described in claim 1 or 2,

I () wherein said plasma body electrode of the power being provided 1 to 22W produces; And/or

(ii) wherein the ratio of electrode power and volume of plasma is less than 10W/ml.

9. method according to claim 8,

I () wherein said plasma body electrode of the power being provided 3 to 17W produces; And/or

(ii) wherein the ratio of electrode power and volume of plasma is 5W/ml to 0.1W/ml.

10. the method described in claim 1 or 2, wherein said organosilicon precursor is selected from the group be made up of the following: two or more combination any of linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, alkyl trimethoxy siloxane and these compounds.

Method described in 11. claims 1 or 2, wherein said organosilicon precursor is monocycle siloxanes.

12. methods according to claim 11, wherein said organosilicon precursor is octamethylcyclotetrasiloxane.

Method described in 13. claims 1 or 2, wherein said substrate is selected from the polymkeric substance of lower group: polycarbonate, olefin polymer, cyclic olefine copolymer and polyester.

Method described in 14. claims 1 or 2, the electrode that wherein said plasma body is used in energy supply from 10kHz to the frequency be less than within the scope of 300MHz produces.

15. methods according to claim 14, the electrode that wherein said plasma body is used in energy supply from the frequency in 1 to 50MHz scope produces.

16. 1 kinds for preparing the method for hydrophobic coating in substrate, the method comprises the following steps

(a) near this substrate surface providing package containing organosilicon precursor and optionally O ₂gaseous reactant; And

B () produces plasma body from this gaseous reactant, form coating thus by the chemical vapour deposition (PECVD) of plasma enhancing on this substrate surface,

Wherein said coating is measured by X-ray photoelectron spectroscopic (XPS) has following atomic ratio: Si _wo _xc _y, wherein w be 1, x in the scope of 0.5-2.4, and y is in the scope of 0.6 to 3,

Wherein the hydrophobic property of this coating is by O in setting gaseous reactant ₂with the ratio of organosilicon precursor with to be set by the electric power set for generation of this plasma body, wherein O ₂exist with the amount that the volume-volume ratio with gaseous reactant is 0:1 to 0.5:1, and wherein said plasma body is produced by the electrode of the electric power being supplied to 0.1 to 25W.

17. methods according to claim 16, the method causes being characterised in that the coating of wherein total formula that atomic ratio C:O increases and/or atomic ratio Si:O reduces compared with total formula of described organosilicon precursor.

Method described in 18. claims 16 or 17, wherein O ₂exist with the amount that the volume-volume ratio with gaseous reactant is 0:1 to 0.1:1.

Method described in 19. claims 16 or 17, wherein said gaseous reactant comprises the O being less than 1 volume % ₂.

20. methods according to claim 19, wherein said gaseous reactant comprises the O being less than 0.5 volume % ₂.

21. methods according to claim 19, wherein said gaseous reactant is not containing O ₂.

Method described in 22. claims 16 or 17, wherein said plasma body is non-hollow cathode plasma.

Method described in 23. claims 16 or 17,

I () wherein said plasma body electrode of the power being provided 1 to 22W produces; And/or

(ii) wherein the ratio of electrode power and volume of plasma is less than 10W/ml.

24. methods according to claim 23,

I () wherein said plasma body electrode of the power being provided 3 to 17W produces; And/or

(ii) wherein the ratio of electrode power and volume of plasma is 5W/ml to 0.1W/ml.

Method described in 25. claims 16 or 17, wherein said organosilicon precursor is selected from the group be made up of the following: two or more combination any of linear siloxane, monocycle siloxanes, many cyclosiloxane, polysilsesquioxane, alkyl trimethoxy siloxane and these compounds.

Method described in 26. claims 16 or 17, wherein said organosilicon precursor is monocycle siloxanes.

27. methods according to claim 26, wherein said organosilicon precursor is octamethylcyclotetrasiloxane.

28. methods according to claim 16, wherein said organosilicon precursor is linear siloxane.

29. methods according to claim 28, wherein said organosilicon precursor is hexamethyldisiloxane.

Method described in 30. claims 16 or 17, wherein said substrate is selected from the polymkeric substance of lower group: polycarbonate, olefin polymer, cyclic olefine copolymer and polyester.

Method described in 31. claims 16 or 17, the electrode that wherein said plasma body is used in energy supply from 10kHz to the frequency be less than within the scope of 300MHz produces.

32. methods according to claim 31, the electrode that wherein said plasma body is used in energy supply from the frequency in 1 to 50MHz scope produces.

33. 1 kinds of coatings, this coating obtains by the method described in any one of the preceding claims.

34. coatings according to claim 33, this coating is slip coating and/or hydrophobic coating.

35. coatings according to claim 34, wherein this coating

I () has the friction resistance being reduced by least 25% than uncoated surface.

36. coatings according to claim 34, this coating

I () has the wetting tension of 20 to 72 dyne/cm.

The 37. upper at least partially containers with the coating coating according to any one of claim 33 to 36 surperficial therein.

The container of 38. coatings according to claim 37, it is selected from following container:

(i) sample collection tube; Or

(ii) bottle; Or

(iii) syringe or syringe part; Or

(iv) pipe; Or

(v) cuvette.

The container of 39. coatings according to claim 37, it comprises at least one SiO in addition _xlayer, wherein x is 1.5 to 2.9, wherein

I () described coating is positioned at described SiO _xbetween layer and described substrate surface, or described SiO _xlayer between described coating and described substrate surface, or wherein

(ii) described coating is positioned at two SiO _xbetween layer, or wherein

(iii) multiple SiO _xlayer and described coating are Si _wo _xc _yh _zto SiO _xgradient composites.

The container of 40. coatings according to claim 37, this container holds compound or composition in chamber within it.

The container of 41. coatings according to claim 37, this container holds bioactive compounds or composition or biofluid within it in chamber.

The container of 42. coatings according to claim 37, this container holds (i) Citrate trianion or the composition containing Citrate trianion in chamber within it, (ii) medicament, or (iii) blood or hemocyte.

The container of 43. coatings according to claim 37, this container holds Regular Insulin or the composition containing Regular Insulin within it in chamber.

The container of 44. coatings according to claim 37, the container of this coating is the syringe cylinder that method according to claim 1 manufactures, and wherein said precursor is siloxanes, and in step (a), be wherein less than the O of 1 volume % ₂be provided in described gaseous reactant, wherein compared with uncoated syringe cylinder, be reduced by least 25% for mobile plunger by the power of the syringe cylinder of described coating.

The purposes of the container of the coating according to any one of 45. claims 37 to 44, for preventing or reducing the components precipitate of compound or the composition contacted with the interior surface of this container and/or solidify.

46. purposes according to claim 45, wherein said compound or composition are bioactive compounds or composition.

47. purposes according to claim 45, wherein said compound or composition are medicaments.

48. purposes according to claim 45, wherein said compound or composition are Regular Insulin or the composition comprising Regular Insulin.

49. purposes according to claim 45, wherein said compound or composition are biofluids.

50. purposes according to claim 45, wherein said compound or composition are blood.