KR101823159B1

KR101823159B1 - Pecvd coating using an organosilicon precursor

Info

Publication number: KR101823159B1
Application number: KR1020117028718A
Authority: KR
Inventors: 존 티 펠츠; 토마스 이 피스크; 로버트 에스 아브람스; 로버트 제이 팽본; 피터 제이 사고나
Original assignee: 에스아이오2 메디컬 프로덕츠, 인크.
Priority date: 2009-05-13
Filing date: 2010-05-12
Publication date: 2018-01-29
Also published as: KR20180011350A; WO2010132591A3; WO2010132584A2; WO2010132589A3; KR102003651B1; SG176008A1; WO2010132581A2; KR20120060781A; WO2010132581A9; WO2010132591A2; SG176011A1; WO2010132585A3; WO2010132584A3; WO2010132589A2; WO2010132579A3; WO2010132579A2; WO2010132585A2

Abstract

There is provided a method of coating a substrate surface by PECVD comprising generating a plasma from a gaseous reactant comprising an organosilicon precursor and optionally O2. The lubricity, hydrophobicity and / or barrier properties of the coating are set by setting the ratio of O2 to the organosilicon precursor in the gaseous reactant and / or by setting the power used to generate the plasma. In particular, lubricative coatings prepared by the above method are provided. Also provided is a container coated by the method and the use of the container to protect the coated or contained compound or composition contained in the coated container from mechanical and / or chemical influences of the uncoated container material surface.

Description

[0001] PECVD COATING USING AN ORGANOSILICON PRECURSOR WITH ORGANIC SILICON PRECURSOR [0002]

The present invention relates to the technical field of making biologically active compounds or coated containers for storing blood. In particular, the present invention relates to a container handling system for coating and inspecting containers, which is a container handling system for coating containers, and more particularly to a portable container support for a container handling system, The present invention relates to a chemical vapor deposition apparatus, and more particularly, to a method for coating an inner surface of a vessel, a method for coating and inspecting a vessel, a vessel treatment method, a use of a vessel treatment system, , And program components.

A method of coating a substrate surface by PECVD comprises generating a plasma from gas reactants comprising an organic silicon precursor and, optionally, oxygen (O ₂₎ is provided. The lubricity, hydrophobicity and / or barrier properties of the coating are set by setting the ratio of O ₂ to the organosilicon precursor in the gaseous reactant and / or by setting the power used to generate the plasma. In particular, lubricative coatings prepared by the above method are provided. Also provided is a container coated by the method and the use of the container to protect the coated or contained compound or composition contained in the coated container from mechanical and / or chemical influences of the uncoated container material surface.

The present disclosure also relates to improved methods for the treatment of vessels, for example venous puncture and other medical sample collection, storage and delivery of pharmaceutical preparations, and containers of a plurality of identical vessels used for other purposes. Such containers must be used in large quantities for these purposes, be relatively economical to manufacture, and be highly reliable in storage and use.

For example, vacuum blood collection tubes are used to collect blood from a patient for medical analysis. The tubes are sold in vacuum. The blood of the patient is inserted into the blood vessel of the patient by inserting one end of the hypodermic needle using both sides of the needle into the other end of the needle using the both sides of the vacuum blood collection tube, . Due to the vacuum in the vacuum blood collection tube, blood is drawn through the needle through the vacuum blood collection tube (or more precisely the blood pressure of the patient pushes out the blood), and pressure is increased in the tube Thereby reducing the pressure difference. Typically, blood flow continues until the tube is removed from the needle or the pressure differential is too low to support the flow.

Vacuum blood collection tubes should have a substantial shelf life that facilitates efficient and easy dispensing and storage of the tubes prior to use. For example, a shelf life of one year is preferred, and gradually longer shelf lives, such as 18 months, 24 months or 36 months, are also desirable in some cases. Preferably, the tubes are maintained in a vacuum sufficiently to the extent necessary to draw sufficient blood for at least analysis, during the entire shelf life, with few (if optimally none) of the defective tubes supplied Maintains at least 90% of the volume in which the tube was originally inhaled.

A defective tube is likely to cause the ophthalmologist using the tube to fail to draw sufficient blood. The ophthalmologist then needs to obtain and use one or more other tubes to obtain a sufficient blood sample.

As another example, pre-filled syringes are commonly prepared and sold so that the syringes do not need to be filled before use. As another example, the syringe may be pre-filled with saline, a injectable dye, or a pharmaceutically active agent.

Typically, the pre-filled syringe is capped at its distal end using a cap and closed at its proximal end by the plunger of the syringe. The pre-filled syringe may be packaged in a sterile package prior to use. To use the pre-filled syringe, the package and cap are removed, and optionally a hypodermic needle or other delivery conduit is attached to the distal end of the barrel, and the delivery water or syringe is moved to the use position (Such as by inserting the hypodermic needle into the patient's blood vessel or inserting it into the device for rinsing with the contents of the syringe), the plunger advances in the barrel to inject the contents of the barrel.

One important consideration in making prefilled syringes is that the contents of the syringe preferably have a substantial lifetime which is important to separate it from the barrel wall which contains material filling the syringe during its life, It will avoid filtering out the material with the filled contents or vice versa.

Because many of these containers are expensive and used in large quantities, it may be useful for certain applications to reliably obtain the required shelf life without increasing production costs to prohibited levels. In addition, from a glass container which can be broken for a specific use and costly to manufacture, it is almost never broken in normal use (toward the plastic container, which, if broken, does not form sharp pieces in the residue of the container, such as in a glass tube) It is also preferable to change them preferentially. Glass containers are preferred because the glass is more gas-tight and inert to the pre-filled contents than the untreated plastics. Also, because it has been traditionally used, it is readily accepted because it is known to be relatively harmless when it comes into contact with medical samples or pharmaceutical preparations.

Another consideration when considering syringes is that the plunger can move at a constant speed and constant force when compressed into the barrel. For this purpose, a lubricous coating is preferred for either or both of the barrel and the plunger.

A non-exhaustive list of possible related patents includes U.S. Patent Nos. 6,068,884 and 4,844,986 and the United States. Published Application 20060046006 and 20040267194.

It is an object of the present invention to improve the production of coated containers.

In the following, methods and devices fabricated according to the methods are described, which methods can be performed by a vessel treatment system described further below and the devices can be fabricated by the system.

The present invention provides a method of coating a surface, e. G., An inner surface of a vessel, with an < / RTI > coating made by PECVD from an organosilicon precursor. The present invention also provides the use of coatings produced thereby, coatings coated with such coatings and coatings such as, for example, lubricating coatings, hydrophobic coatings or barrier coatings. In addition, an apparatus and some devices for carrying out the present invention are provided. The present invention also provides an inspection method for the coating, particularly a method of using volatile species gas removal by a coated surface for the inspection.

PECVD coating method

The present invention relates to a method of producing a coating by plasma enhanced chemical vapor deposition (PECVD) and, for example, a method of coating the inner surface of a vessel.

A surface, such as an inner vessel surface, is provided, such as a reaction mixture comprising an organosilicon compound gas, alternatively an oxidizing gas and optionally a hydrocarbon gas.

The surface is in contact with the reaction mixture. A plasma is formed in the reaction mixture. Preferably, the plasma is a non-hollow cathode plasma, or in another expression of the same conditions, the plasma is substantially free of hollow cathode plasma. The coating is deposited on at least a portion of the surface, e.g., a portion of the vessel wall.

The method is performed as follows.

A precursor is provided. Preferably, the precursor is an organosilicon compound (also referred to below as an "organosilicon precursor"), more preferably a linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, alkyltrimethoxy Silane, an azo analog of any of these precursors (e.g., linear siloxazan, monocyclic siloxazan, polycyclic siloxazan, polysilsesquioxazane) and a group of any two or more of these precursors &Lt; / RTI > The precursor is applied to the substrate under conditions effective to form the coating by PECVD. Thus, the precursor may be polymerized, cross-linked, partially or totally oxidized, or any combination thereof.

In one aspect of the invention, the coating is a lubricous coating, i. E., Forms a surface with lower frictional resistance than an uncoated substrate.

In another aspect of the invention, the coating is, for example, a passivation coating, such as a hydrophobic coating, which causes less precipitation of components of the composition in contact with the coated surface. Such hydrophobic coatings are characterized by lower wetting tension than uncoated.

In addition, the lubricous coating of the present invention can be a passivation coating and vice versa.

In another aspect of the invention, the coating is a barrier coating such as, for example, a SiO _x coating. Typically, the barrier is for a gas or liquid, preferably for water vapor, oxygen and / or air. In addition, the barrier may be used to create / maintain / sustain a vacuum inside a container coated with the barrier coating, e.g., within a blood collection tube.

The method of the present invention may also include the application of one or more other coatings made by PECVD from an organosilicon precursor. Another optional addition step is the step of post-treating the SiO _x coating with a process gas essentially consisting of oxygen and essentially free of volatile silicone compounds.

Lubricative coating

In a particular aspect, the present invention provides a lubricous coating.

Advantageously, the coating is made using the PECVD process and the precursors described above.

For example, the present invention provides a method of setting the lubricity of a coating on a substrate surface, comprising the steps of:

(a) providing a gas reactant material comprising an organosilicon precursor and optionally O2 near the surface of the substrate; And

(b) generating a plasma from the gas reactive material and forming a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD)

The lubricity of the coating is set by setting the ratio of O2 and the organosilicon precursor in the gaseous reactant and / or by setting the power used to generate the plasma.

A preferred precursor for the lubricous coating is a monocyclic siloxane, such as octamethylcyclotetrasiloxane (OMCTS).

This causes the coated surface to have a lower frictional resistance than the uncoated substrate. For example, when the coated surface is the interior of a syringe barrel and / or a syringe plunger, the lubricating coating is lower than the breakout force or plunger actuation force, or the corresponding force required in the absence of the lubricating coating It is effective in providing both forces.

The article coated with the lubricous coating may be applied to a wall, preferably an inner wall, with a lubricious coating, such as a syringe barrel, or a container portion or container cap having the coating on a tool in contact with the surface, such as a syringe plunger or a container cap .

X is 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, in one aspect, the lubricating coating is, for example, and, preferably w is 1, x is from about 0.5 to 1, y is from about 2 to about 3, z can have from 6 to 9 of formula _{Si w O x C y H z} .

Passivation, for example, hydrophobic coating

The passivation coating according to the invention is, for example, a hydrophobic coating.

A preferred precursor for the passivation, e. G., Hydrophobic coating, is a linear siloxane, e. G., Hexamethyldisiloxane (HMDSO).

The passivation coating according to the present invention prevents or reduces the mechanical and / or chemical effects of the uncoated surface on the compound or composition contained in the container. For example, sedimentation and / or coagulation or platelet activation of a compound or component of the composition in contact with the surface is prevented or reduced, for example, by coagulation of blood or platelet activation or precipitation of insulin, Wetting is prevented.

A particular aspect of the invention is, for example, that w is 1, x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, z is from about 2 to about 9, preferably w is 1 , x is about 0.5 to 1, y is about 2 to about 3, and z is a surface having a hydrophobic coating having the formula Si _w O _x C _y H _z where z is from 6 to 9.

The article coated with the passivation coating may be a container, such as a container portion having a coating on a wall, preferably an inner wall, such as a tube, or a container with a coating on the wall, for example a tube or a surface contacting a surface.

Coating of Container

When the container is coated by the above method using PECVD, the coating method includes several steps. A container is provided having an open end, a closed end and an inner surface. At least one gas reactant is introduced into the vessel. Plasma is formed in the vessel under conditions effective to form a reaction product, i. E. A coating, of the reactant on the inner surface of the vessel.

Advantageously, the method is performed by placing an open end of the container on a container support as described herein, and providing a sealed communication between the container support and the interior of the container. In this preferred aspect, the gas reactive material is introduced into the vessel through the vessel support. In a particularly preferred aspect of the present invention, a plasma enhanced chemical vapor deposition (PECVD) apparatus comprising a vessel support, internal electrodes, external electrodes and a power supply is used for the coating method according to the present invention.

The container support has a port for receiving the container in a seated position for processing. The inner electrode is positioned to be received in a container that is seated in the container support object. The outer electrode has a medial portion positioned to receive a container seated on the receptacle support. The power supply supplies an alternating current to the inner and / or outer electrodes to form a plasma in the vessel resting on the vessel support. Typically, the power supply supplies an alternating current to the external electrode while the internal electrode is grounded. In this embodiment, the vessel defines a plasma reaction chamber.

In one particular aspect of the present invention, the PECVD apparatus described in the preceding paragraph does not necessarily include a vacuum source for transferring gas from or to the interior of a vessel seated on the port to define a closed chamber And includes a gas drain.

In another specific aspect of the present invention, the PECVD apparatus includes a container support, a first gripper, a seat of the container support, a reactant supply, a plasma generator, and a container discharge device.

The container support is configured to rest on an open end of the container. The first gripper is configured to selectively support and release the closed end of the container and to transfer the container around the container support while holding the closed end of the container. The container support has a seat configured to provide a sealed communication between the container support and the interior space of the first container.

The reactant feeder is operatively connected to introduce at least one gaseous reactant in the first vessel through the vessel support. The plasma generator is configured to form a plasma in the first vessel under conditions effective to form a reaction product of the reactants on the inner surface of the first vessel.

The container discharge device is provided to detach the first container from the container support. The gripper being the first gripper or another gripper is configured to axially transfer the first container from the container support and to discharge the first container.

In a particular aspect of the present invention, the method is for PECVD-coating a container, for example, the inner surface of a generally open limited portion of a tubular container. The container includes an outer surface, an inner surface defining a lumen, a larger opening having an inner diameter, and a restricted opening defined by the inner surface and having an inner diameter smaller than the larger opening inner diameter. A processing vessel having a lumen and a processing vessel opening is provided. The processing vessel opening is in communication with a limited opening of the vessel to allow communication between the processing vessel lumen and the lumen of the vessel being processed through the limited opening. Thereby drawing at least a partial vacuum within the lumen of the vessel to be treated and the vessel lumen being processed. The PECVD reactant flows through the first opening, then through the lumen of the vessel to be processed, and then through the restricted opening to the vessel lumen under processing. Plasma is produced adjacent the confined openings under conditions effective to deposit a coating of the PECVD reaction product on the inner surface of the confined openings.

Coated containers and container portions

The present invention provides a coating by the above-described method, a surface coated with the coating, and a container coated with the coating, for example.

The surface coated with the coating, such as a container wall or portion thereof, is a polymer selected from the group consisting of glass or polymer, preferably a thermoplastic polymer, more preferably a polycarbonate, an olefin polymer, a cyclic olefin copolymer and a polyester. . For example, it is a cyclic olefin copolymer, polyethylene terephthalate or polypropylene.

In one particular aspect of the invention, the vessel wall has an inner polymer layer surrounded by at least one outer polymer layer. The polymers may be the same or different. For example, another polymer layer that is one of the polymer layers of a cyclic olefin copolymer (COC) resin (e.g., defines a water vapor barrier) is a layer of polyester resin. Such a container can be produced by a process of introducing COC and polyester resin layers into the injection mold through concentric injection nozzles.

The coated container of the present invention may be hollow, filled with vacuum, or filled (preliminarily) with a compound or composition.

One particular aspect of the present invention is a passivation coating, e. G., A container having the hydrophobic coating described above.

Another particular aspect of the present invention is a surface having the lubricous coating described above. It may be a lubricious coating on a wall, preferably an inner wall, such as a syringe barrel, or a container with a container portion or container cap, such as a syringe plunger or container cap, having said coating on a container in contact with the surface.

A particular aspect of the present invention is a syringe comprising a plunger, a syringe barrel, and a lubricating coating as defined above on one or both of these syringe portions, preferably on the interior walls of the syringe barrel. The syringe barrel includes a barrel having an inner surface for slidably receiving the plunger. The lubricating coating may be provided on the inner surface of the syringe barrel or on the plunger surface in contact with the barrel or on both of the surfaces. The lubricious coating is effective to reduce breakout forces or plunger activity sufficient to move the plunger within the barrel.

Certain other aspects of the invention are syringe barrels coated with lubricous coatings as defined in the preceding paragraph.

In one particular aspect of the coated syringe barrel, the syringe barrel includes a barrel having an inner surface defining a lumen and slidably receiving the plunger. The syringe barrel is advantageously made of a thermoplastic material. The lubricous coating is applied to the inner surface of the barrel, the plunger, or both by plasma enhanced chemical vapor deposition (PECVD). The solute retainer is applied to the lumen on the lubricous coating in an amount effective to reduce filtration of the lubricating coating, the thermoplastic material, or both by surface treatment. The lubricant coating and solute retainer are constructed and present in a relative amount effective to provide both a breakout force or plunger actuation force, or both forces lower than the corresponding force required in the absence of the lubricant coating and solute retainer.

Yet another aspect of the present invention is a syringe comprising a plunger, a syringe barrel and inner and outer coatings. The barrel has an inner surface and an outer surface for slidably receiving the plunger. Lubricating coating is on the internal surface, x may be added to the barrier coating of from about 1.5 to about 2.9 of SiO _X is provided on the inner surface of the barrel. For example, a barrier coating of resin or other SiO _x coating is provided on the outer surface of the barrel.

Yet another aspect of the present invention is a syringe including a plunger, a syringe barrel, and a Luer fitting. The syringe barrel has an inner surface for slidably receiving the plunger. The luer fitting includes a luer taper having an inner passageway defined by an inner surface. The luer fitting is formed of a component separated from the syringe barrel and is joined to the syringe barrel by coupling. The internal passage of the luer taper is, x has a barrier coating of from about 1.5 to about 2.9 of SiO _X.

Another aspect of the invention is a plunger for a syringe, comprising a piston and a push rod. The piston has side and back portions configured to movably seat within a front, generally cylindrical syringe barrel. The plunger has a lubricative coating according to the invention on its side. The push rod is configured to engage the anterior portion of the piston and advance the piston in a syringe barrel. The plunger may further comprise a SiO _x coating.

Another aspect of the present invention is a container having only one opening, i.e., a container for collecting or storing a compound or composition. In certain aspects, such a container is a tube, e.g., a sample collection tube, such as a blood collection tube. The tube may be closed with a closure, such as a cap or stopper. Such a cap or stopper may include a passivation coating according to the present invention on the surface in contact with the tube and / or on the surface in contact with the lumen of the tube and / or may comprise a lubricative coating according to the present invention. In certain aspects, such a stopper or portion thereof may be made of an elastic material.

Such a stopper may be made as follows: the stopper is located in a substantially vacuum chamber. A reaction mixture comprising an organosilicon compound gas, optionally an oxidizing gas and optionally a hydrocarbon gas, is provided. A plasma is formed in the reaction mixture in contact with the stopper. The coating is deposited on at least a portion of the stopper.

Another aspect of the present invention is a container having a barrier coating according to the present invention. The container is generally tubular and can be made of a thermoplastic material. The container has an inlet and a lumen at least partially bounded by the wall. The wall has an inner surface that interfaces with the lumen. In a preferred aspect, at least one essentially continuous barrier coating, made of SiO _x as defined above, is applied on the inner surface of the wall. The barrier coating is effective to maintain at least 90%, alternatively 95%, of the initial vacuum level in the container for a shelf life of at least 24 months. A closure is provided for covering the inlet of the container and separating the lumen of the container from ambient air.

In addition, the PECVD-produced coatings and PECVD coating methods using the organosilicon precursors described herein are useful for coating barrier coatings, hydrophobic coatings, lubricative coatings, or conduits or cuvettes for forming one or more of them. A cubic tube is a small tube of circular or square cross section, which is sealed at one end and is made of polymer, glass or fused quartz (for ultraviolet rays) and is designed to support spectroscopic test samples. The best cubic is as transparent as possible without impurities that can affect spectroscopic readings. Like a test tube, a cubette can have a cap that is open to the atmosphere or can be sealed. The coatings to which the PECVD of the present invention is applied are very thin, transparent, and optically non-glossy, and may not interfere with optical testing of the cuvettes or their contents.

(Spare) filled coating container

One particular aspect of the present invention is a coated container as described above, which is used to pre-fill or fill with a compound or composition in the lumen. The compound composition may be

(i) a composition comprising a biologically active compound or composition, preferably a medicament, more preferably insulin or insulin; or

(ii) a biological fluid, preferably a body fluid, more preferably a blood or blood fraction (e.g., blood cells); or

(iii) a compound or composition for direct mixing with another compound or composition in said container, such as a citrate or citrate-containing composition, for inhibiting blood clotting or platelet activation in a blood collection tube.

In general, the coated containers of the present invention are particularly useful for collecting or storing compounds or compositions that are sensitive to the mechanical and / or chemical effects of uncoated container material surfaces, Or coagulation or platelet activation of the compound or component of the compound of the invention.

For example, a cell manufacturing tube containing a water-soluble sodium citrate reagent with a wall provided with the hydrophobic coating of the present invention is suitable for collecting blood and preventing or reducing blood aggregation. The aqueous sodium citrate reagent is provided to the lumen of the tube in an amount effective to inhibit the coagulation of blood introduced into the tube.

One particular aspect of the invention is a container or blood containing container for collecting / containing blood. The container having a wall; The wall has an inner surface defining a lumen. The inner surface of the wall at least partially has the hydrophobic coating of the present invention. The coating may be as thin as about monomolecular thickness or as thick as about 1000 nm. The blood collected or stored in the container is preferably viable to return to the vascular system of the patient disposed within the lumen in contact with the coating. The coating is effective to reduce coagulation or platelet activation of blood exposed to the inner surface, as compared to uncoated walls of the same type.

Another aspect of the invention is an insulin-containing container comprising a wall having an inner surface defining a lumen. The inner surface has at least in part the hydrophobic coating of the present invention. The coating may be monomolecular to about 1000 nm thick on the inner surface. A composition comprising insulin or insulin is provided in the lumen in contact with the coating. Alternatively, the coating is effective to reduce precipitation formation from insulin in contact with the inner surface, as compared to the same surface without coating.

Accordingly, the present invention provides the following examples of coating methods, coated products and uses of said products:

(1) a method for setting the lubrication of a coating on a substrate surface, comprising the steps of:

(2) a process for producing a hydrophobic coating on a substrate, comprising the steps of:

The hydrophobic character of the coating is set by setting the ratio of O2 to the organosilicon precursor in the gaseous reactant and / or by setting the power used to generate the plasma.

(3) The method of (1) or (2) wherein the atomic ratio C: O is increased and / or the atomic ratio Si: O is reduced as compared to the formula of the organosilicon precursor,

(4) The method according to any one of (1) to (3), wherein the oxygen (O2) is used in a volume to volume ratio of from 0: 1 to 5: 1, To 1: 1, alternatively from 0: 1 to 0.5: 1, alternatively from 0: 1 to 0.1: 1, preferably at least essentially no oxygen in the gaseous reactant.

(5) The method according to any one of (1) to (4), wherein the gas reactive material comprises less than 1 vol% O2, especially less than 0.5 vol% O2, most preferably O2 &Lt; / RTI >

(6) The method according to any one of (1) to (5), wherein the plasma is a non-ball-borne cathode plasma.

(7) The method according to any one of items (1) to (6), wherein the substrate is used at 0.5 to 50 mL, preferably 1 to 10 mL, more preferably 0.5 to 5 mL, &Lt; / RTI > to about 3 mL of lumen volume.

(8) The method according to any one of (1) to (7).

(i) the plasma comprises electrodes supplied with sufficient power to form a coating on the substrate surface, 0.1 to 25 W, preferably 1 to 22 W, more preferably 3 to 17 W, Is generated using 5 to 14 W, most preferably 7 to 11 W, especially 8 W powered electrodes; And / or

(ii) the ratio of the power to the plasma volume is 10 W / ml, preferably 5 W / ml to 0.1 W / ml, more preferably 4 W / ml to 0.1 W / ml, most preferably 2 W / ml to 0.2 W / ml.

(9) A method of making a coating on a substrate surface, comprising the steps of:

(b) generating a non-pore anodic plasma from said gaseous reactant under reduced pressure to form a coating on said substrate surface by plasma enhanced chemical vapor deposition (PECVD)

The physical and chemical properties of the coating are set by setting the ratio of O2 to the organosilicon precursor in the gaseous reactant and / or by setting the power used to generate the plasma.

(10) For example, the present invention provides a method of setting the lubricity of a coating on a substrate surface, comprising the steps of:

(a) providing a gas reactive material comprising an organosilicon precursor and O2 near the substrate surface; And

The barrier properties of the coating are set by setting the ratio of O2 to the organosilicon precursor in the gaseous reactant and / or by setting the power used to generate the plasma.

(11) The method according to paragraph (10)

(i) the plasma comprises electrodes supplied with sufficient power to form a coating on the substrate surface, preferably 8 to 500 W, preferably 20 to 400 W, more preferably 35 to 350 W, More preferably between 44 and 300 W, and most preferably between 44 and 70 W; And / or

(ii) the ratio of the power to the plasma volume is 5 W / ml or less, preferably 6 W / ml to 150 W / ml, more preferably 7 W / ml to 100 W / W / ml to 20 W / ml.

(12) The method according to (10) or (11), wherein the O2 has a volume to volume ratio of from 1: 1 to 100: 1 for the gas reactant, 1 to 30: 1, more preferably from 1: 20 to 1: 20, more preferably 15: 1.

(13) The method of any one of (1) to (12) above, wherein the organosilicon precursor is a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysesquioxane, a linear silazane, A silane coupling agent, a silane coupling agent, a silane coupling agent, a silane coupling agent, a silane coupling agent, a silane coupling agent, a silane coupling agent, a silane coupling agent, to be.

(14) The method according to (1) or (2), wherein the organosilicon precursor is a monocyclic siloxane, preferably OMCTS.

(15) The method according to (2) or (10), wherein the organosilicon precursor is a linear siloxane, preferably HMDSO.

(16) The method of any one of (1) to (15) above, wherein the PECVD is performed at a rate of 6 sccm or less, preferably 2.5 sccm or less, more preferably 1.5 sccm, and most preferably 1.25 sccm or less &Lt; / RTI > is carried out at a flow rate of the organosilicon precursor.

(17) The substrate according to any one of (1) to (16), wherein the substrate is a polymer selected from the group consisting of polycarbonate, olefin polymer, cyclic olefin copolymer and polyester, Olefin copolymer, a polyethylene terephthalate or a polypropylene.

(18) The method of any one of (1) to (17) above, wherein the substrate surface is part or all of the inner surface of the container having at least one opening and an inner surface, Filling the inner lumen of the vessel and wherein the plasma is generated in some or all of the inner lumen of the vessel.

(19) The plasma processing method according to any one of items (1) to (18), wherein the plasma is preferably at a radio frequency, preferably from 10 kHz to less than 300 MHz, more preferably from 1 to 50 MHz, Is generated using electrodes powered at a frequency of 10 to 15 MHz and most preferably of 13.56 MHz.

(20) The method according to any one of (1) to (19), wherein the plasma is produced under reduced pressure and the reduced pressure is less than 300 mTorr, preferably less than 200 mTorr, more preferably less than 100 mTorr Lt; / RTI >

(21) The method according to any one of (1) to (20), wherein the PECVD deposition time is 1 to 30 seconds, preferably 2 to 10 seconds, more preferably 3 to 9 seconds How to.

(22) The method according to any one of (1) to (21), wherein the resulting coating has a thickness in the range of 1 to 100 nm, preferably 20 to 50 nm.

(23) A coating obtainable by the method of any one of the preceding claims.

(24) The coating according to (23), wherein the coating is a lubricating and / or hydrophobic coating.

(25) The coating according to (24), wherein the atomic ratio of carbon to oxygen is increased relative to the organosilicon precursor and / or the atomic ratio of oxygen to silicon is reduced relative to the organosilicon precursor.

(26) The method of any one of (23) to (25), wherein the precursor is octamethylcyclotetrasiloxane and the coating has a density greater than the density of the coating made from HMDSO under the same PECVD reaction conditions &Lt; / RTI >

(27) The method according to any one of (24) to (26)

(i) has a lower frictional resistance than the uncoated surface, and preferably the frictional resistance is at least 25%, more preferably at least 45%, even more preferably at least 60% %. &Lt; / RTI >

(28) The coating composition according to any one of (24) to (27)

(i) a wet tension lower than the uncoated surface, preferably a wet tension of 20 to 72 dyne / cm, more preferably a wet tension of 30 to 60 dyne / cm, more preferably a wet tension of 30 to 40 dyne / / RTI > cm, preferably 34 dyne / cm;

(iv) is more hydrophobic than the uncoated surface.

(29) A coating according to any one of (23) to (28), which is coated on at least a part of the inner surface thereof, preferably a container

(i) sample collection tubes, especially blood collection tubes; or

(ii) a vial; or

(iii) a syringe or syringe portion, particularly a syringe barrel or syringe plunger; or

(iv) a pipe; or

(v) Quvet.

(30) The method of (29), further comprising at least one layer of SiOx wherein x is from 1.5 to 2.9,

(i) the coating is located between the SiOx layer and the substrate surface, or vice versa,

(ii) the coating is located between two SiOx layers or vice versa,

(iii) SiOx and the layers of said coating are inclined functional composites of SiwOxCyHz to SiOx or vice versa.

(31) The method of any one of (29) to (30), further comprising at least one other layer on its outer surface, preferably another layer of plastic or SiOx, 2.9. &Lt; / RTI >

(32) The method according to any one of (29) to (31), wherein the lumen contains a compound or composition, preferably a biologically active compound or composition or biological fluid, more preferably (i) Salt or citrate containing composition, (ii) a medicament, in particular an insulin or insulin containing composition, or (iii) blood or blood cells.

(33) The method according to any one of (29) to (32), wherein the precursor is a siloxane, more preferably a monocyclic siloxane, even more preferably octamethylcyclotetrasiloxane Wherein the gas reactant material is substantially free of any O2 gas in step (a), and the force to move the plunger through the coated barrel Is reduced by at least 25%, more preferably by at least 45%, even more preferably by at least 60%, relative to uncoated syringe barrels.

(34) The use of a coating having the formula SiwOxCyHz wherein w is 1, x is 0.5 to 2.4, y is 0.6 to 3, and z is 2 to 9

(i) a lubricative coating having a lower frictional resistance than an uncoated surface; And / or

(ii) a hydrophobic coating that is more hydrophobic than the uncoated surface.

(35) The use according to (34), wherein the coating is a coating as defined in any one of (24) to (28).

(36) A method according to (34) or (35), wherein the coating is characterized by the fact that, compared to the surface coated with the uncoated surface and / or HMDSO as a precursor, Characterized in that it prevents or reduces the precipitation of the components of the compound or composition in contact with the coating and, in particular, prevents or reduces insulin precipitation or blood coagulation.

Also provided is a container coated by the method and the use of the container to protect the coated or contained compound or composition contained in the coated container from mechanical and / or chemical influences of the uncoated container material surface.

(38) The compound or composition according to (37), wherein the compound or composition is

(i) a composition comprising a biologically active compound or composition, preferably a medicament, more preferably insulin or insulin in which insulin precipitation is reduced or prevented; or

(ii) a blood or blood fraction in which biological fluid, preferably body fluid, more preferably blood coagulation and / or platelet activation is reduced or prevented.

(39) a drug or diagnostic agent contained in the coated container; And / or hypodermic needles, needles with either ends, or other delivery water; And / or instructions. &Lt; Desc / Clms Page number 13 >

The present invention further provides the following embodiments:

I. Container processing system with multi-processing station and multi-vessel supports

According to an aspect of the present invention, there is provided a container handling system for coating a container, the system comprising a first processing station, a second processing station, a container support and a conveyor arrangement. The first processing station is configured to perform a first process, for example, inspection or coating of the inner surface of the vessel. The second processing station is configured to perform a second process based on the first process station and being, for example, an inspection or coating of the inner surface of the container. The container support receives an opening of the container for processing (inspecting and / or coating and / or inspecting) the inner surface of the seated container through the container port at the first processing station and the second processing station And a container port configured to be seated. The conveyor arrangement transfers the container support and the seated container from the first processing station to a second processing station for a second process of the inner surface of the seated container at the second processing station after the first processing station .

As used herein, containers include sample tubes for collecting or storing blood, urine or other samples, syringes for storing or delivering biologically active compounds or compositions, vials for storing biologically or biologically active compounds or compositions Including, but not limited to, catheters that support biological materials or biologically active compounds or compositions and conduits that carry biological materials or biologically active compounds or compositions, Is broadly defined.

All of the containers described below are processed using one of the processing systems or devices described below. That is, the features described below for the device or processing system can also be performed as method steps and can affect the treated containers.

A cubic tube is a small or round cross section tube, sealed at one end, made of plastic, glass or fused quartz (for ultraviolet light) and designed to support specimens for spectroscopic testing. The best cubic is as transparent as possible without impurities that can affect spectroscopic readings. Like a test tube, a cubette can have a cap that is open to the atmosphere or can be sealed.

The term "interior of the container" refers to a hollow space inside a container that can be used to store blood or store biologically active compounds or compositions, according to other exemplary embodiments.

The term treatment includes a series of coating and testing steps, such as a coating step and / or an inspection step or, for example, a coating is performed after the initial inspection step and then a second or even third or fourth inspection is performed . The second, third, and fourth checks may be performed simultaneously.

According to an exemplary embodiment of the present invention, a container support includes a vacuum duct for withdrawing gas from an interior space of the seated container, wherein the container support is configured to receive the gas, such that no other vacuum chamber is required to process the container To maintain a vacuum inside the container. That is, the container support together with the seated container forms a vacuum chamber adapted to provide a vacuum in the interior space of the container. This vacuum is important for certain processing steps such as plasma enhanced chemical vapor deposition (PECVD) or other chemical vapor deposition steps. In addition, the vacuum inside the container can be particularly important for performing a specific inspection of the vessel wall, such as coating the inner surface of the vessel wall, for example by measuring the rate of gas removal of the wall or the electrical conductivity of the wall .

According to another exemplary embodiment of the present invention, the first process is performed in 30 seconds or less. Further, the second process is performed in 30 seconds or less.

Thus, a vessel treatment system for vessel coating, which enables rapid production of vessels, is provided.

According to another exemplary embodiment of the present invention, the first process and / or the second process includes performing a coating of the inner space after inspecting the inner space of the container.

According to another exemplary embodiment of the present invention, the container support includes a gas inlet port for delivering gas into the interior of the container.

According to another exemplary embodiment of the present invention, the system is adapted to automatically reprocess the container when coating defects are detected. For example, the vessel treatment system and in particular the vessel support may comprise an array of different detectors, such as, for example, optical detectors, pressure probes, gas detectors, electrodes for electrical measurement, .

Further, according to another embodiment of the present invention, for example, the processing system, which is one or more of the processing stations, includes one or more grippers for transporting the container or the container support and / or removing the container from the container support do.

According to another exemplary embodiment of the present invention, the vessel treatment system is adapted to automatically reprocess the vessel if coating defects are detected.

The gas delivered to the interior space of the vessel may be useful for PECVD coating the interior space of the vessel.

According to another exemplary embodiment of the present invention, the first treatment and / or the second treatment includes coating the inner space of the container.

According to another exemplary embodiment of the present invention, the first processing station and / or the second processing station include a PECVD apparatus for coating the inner space of the vessel.

According to another exemplary embodiment of the present invention, the system further comprises an outer electrode surrounding at least an upper portion of the seated vessel.

According to another exemplary embodiment of the present invention, there is provided an electrical conduction probe for providing a counter electrode in the container.

According to another exemplary embodiment of the present invention, the first process and / or the second process includes inspecting the inner surface of the container to determine whether it is defective.

According to another exemplary embodiment of the present invention, the system can be inserted into the container through the container port of the first process station and / or the second process station for inspecting the inner space of the container to check for defects. The first detector is further adapted to be positioned.

According to another exemplary embodiment of the present invention, the vessel treatment system further comprises a second detector located outside the vessel for inspecting the inner surface of the vessel to determine whether it is defective.

According to another exemplary embodiment of the present invention, the first detector and / or the second detector are mounted in the container.

According to another exemplary embodiment of the present invention, the support includes a forming die for forming the container.

According to another aspect of the present invention there is provided a system for the treatment of vessels as described above and below, comprising a syringe for storing a biologically active compound or composition, a vial for storing a biologically active compound or composition, For use in a pipette for pipetting a conduit or biologically active compound or composition for transferring a composition.

In addition, the vessel treatment system may be configured for inspection of the vessel, in particular, to perform a first inspection of the vessel to determine whether it is defective, to apply the first coating to the inner surface of the vessel, To perform a second inspection of the inner surface of the coated container. In addition, the system may be tailored to evaluate the data acquired during the different tests, and the second tests and the data evaluation take less than 30 seconds.

In accordance with another aspect of the present invention there is provided a method of inspecting a substrate for a first inspection of the vessel to perform the application of the first coating to the inner surface of the vessel, Wherein the second inspection and data evaluation is less than 30 seconds, characterized in that the second inspection and data evaluation is less than 30 seconds, and the second inspection and data evaluation is less than 30 seconds. A container handling system for inspection is provided.

The application of the first coating may also be referred to as a first or second treatment, and performing the second inspection of the inner surface of the coated container may be referred to as a second treatment.

According to another exemplary embodiment of the present invention, the processing station arrangement comprises a first processing station for performing the first inspection, an application of the first coating to the inner surface of the seated vessel, And a second processing station. The processing station arrangement may also include a container port having a container port configured to receive and seat the opening of the container for inspecting and applying a first coating of the inner surface of the seated container through the container port at the first processing station, Lt; / RTI >

According to another exemplary embodiment of the present invention, the processing station arrangement is spaced from the first processing station, performing the second inspection, applying a second coating, and performing a third inspection after the second coating And a second processing station configured to process the received data. In addition, the processing system may be configured to transfer the first coating from the first processing station to the inner surface of the seated vessel at the second processing station after application of the first coating to the second processing station And a conveyor arrangement for conveying the container support and the seated container. The container port of the container support is configured to receive and seat the opening of the container to coat and inspect the interior surface of the container seated through the container port at the first processing station and the second processing station.

According to another exemplary embodiment of the present invention, the container support includes a vacuum duct for withdrawing gas from the interior space of the seated container, wherein the container support does not require any other vacuum chamber to coat and inspect the container So as to maintain a vacuum inside the container.

According to another exemplary embodiment of the present invention, each test is performed in 30 seconds or less.

According to another exemplary embodiment of the present invention, the first processing station and / or the second processing station include a PECVD apparatus for coating the inner surface of the vessel.

According to another exemplary embodiment of the present invention, the coating is a barrier coating, the system being adapted to check for the presence of a barrier.

According to another exemplary embodiment of the present invention, the second coating is a lubricating coating, the system being adapted to determine the presence of the lubricating coating (i.e., lubricating layer).

According to another exemplary embodiment of the present invention, the first coating is a barrier coating, the system being adapted to determine the presence of the barrier and lubricating coating.

According to another exemplary embodiment of the present invention, the system is adapted to confirm the presence of the barrier and the lubricating layer at least at the 6-sigma level.

According to another exemplary embodiment of the present invention, the first inspection and / or the second inspection may include measuring the gas removal rate of the gas from the coated container, performing coating of the coating with optical monitoring, Measuring optical parameters of the inner surface of the coated container, and measuring the electrical properties of the coated container.

The measurement data can then be analyzed by the processor.

According to another exemplary embodiment of the invention, the treatment system comprises a first detector for measuring the gas removal rate and / or a second detector for measuring the diffusion rate and / or a third detector for measuring the optical parameters and / And a fourth detector for measuring electrical parameters.

According to another exemplary embodiment of the present invention, the first coating and / or the second coating is less than 100 nm thick.

According to another exemplary embodiment of the present invention, the vessel treatment system further comprises a processor obtained during the inspection.

One aspect of the invention is a container handling system comprising a first processing station, a second processing station, a plurality of container supports, and a conveyor. The first processing station is adapted to process a vessel having an opening and a wall defining an interior surface. The second processing station is spaced from the first processing station and is adapted to process a vessel having an opening and a wall defining an interior surface.

At least a portion of the container support, and optionally all of the container ports, comprises a container port configured to receive and seat the opening of the container that processes the interior surface of the container seated through the container port in the first process . The conveyor is configured to transfer a series of the container supports and the seated containers from a first processing station to a second processing station for processing of an interior surface of the seated container at the second processing station.

II. Container support

II.A. Container support that does not cite a specific enclosure

Wherein the inner surface of the vessel is coated and inspected for defects and the vessel is transferred from a first processing station to a second processing station of the vessel processing system, Is configured to seat the opening of the vessel and the vessel support for treating the interior surface of the vessel seated through the vessel port at the first processing station and the second processing station may be adapted to support the vessel.

According to another exemplary embodiment of the present invention, the portable container support includes a second port for receiving an external gas supply or discharge port and a duct for passing gas between the opening of the container seated on the container port and the second port, .

According to another exemplary embodiment of the present invention, the portable container support weighs less than 2.25 kg.

According to another exemplary embodiment of the present invention, the container support includes a vacuum duct and an external vacuum port for withdrawing gas from the interior of the seated container through the container port, And is arranged to maintain a vacuum inside the seated container so that no other vacuum chamber is required.

According to another exemplary embodiment of the present invention, the external vacuum port also incorporates a gas input port contained in the vacuum port that delivers gas into the interior of the seated container.

According to another exemplary embodiment of the present invention, the treatment of the vessel comprises coating the inner surface of the seated vessel.

According to another exemplary embodiment of the present invention, the container support is made essentially of a thermoplastic material.

According to another exemplary embodiment of the present invention, the portable container support includes a cylindrical inner surface for receiving a cylindrical wall of the container, a first annular groove coaxial with the cylindrical inner surface in the cylindrical inner surface, And a first O-ring disposed within the container support and providing a seal between the seated containers within the container support.

According to another exemplary embodiment of the present invention, the portable container support further comprises a radially extending abutment adjacent a round cylindrical inner surface on which the open end of the seated container can be supported.

According to another exemplary embodiment of the present invention, the portable container support further comprises a second annular groove coaxial with and axially spaced from the first annular groove within the cylindrical inner surface. The container support also includes a second O-ring disposed in the second annular groove providing a seal between the seated containers in the container support.

According to another exemplary embodiment of the present invention, the container support further comprises a first detector for inspecting an interior space of the container through a container port for inspection of the inner surface of the container seated in the container to determine whether the container is defective.

According to another exemplary embodiment of the present invention, the container support includes a forming die for forming the container.

According to another exemplary embodiment of the present invention, said vessel treatment system for coating a vessel comprises a vessel support as described above and below.

According to another exemplary embodiment of the present invention, the portable container support includes a container port, a second port, a duct, and a movable housing. The container port is configured to seat the container opening which is in communication with each other. The second port is configured to receive an external gas supply or an outlet. And to pass at least one gas between the container opening seated on the container port and the second port. The vessel port, the second port and the duct are substantially rigidly attached to the movable housing. Optionally, the portable container support weighs less than 5 pounds.

Another aspect of the invention is a portable container support comprising a container port, a vacuum duct, a vacuum port and a movable housing. The container port is configured to receive a container opening in a sealed, communicating relationship. The vacuum duct is configured to recover gas from a container seated on the vessel port. The vacuum port is configured to communicate between the vacuum duct and an external vacuum source. The vacuum source may be a lower pressure pump or gas cylinder or a ballast tank than the vacuum duct. The container port, the vacuum duct and the vacuum port are substantially rigidly attached to the movable housing. Optionally, the portable container support weighs less than 5 pounds.

II.B. A container support comprising a sealing arrangement.

Yet another aspect of the present invention is a container support for receiving an open end of a container having a substantially cylindrical wall adjacent its open end. The container support may have a generally cylindrical inner surface (e.g., a round cylindrical inner surface), an annular groove, and an O-ring. It will be understood that containers designated as having round or circular openings or cross sections throughout this specification are illustrative only and are not intended to limit the scope of the disclosure or the claims. If the container has, for example, a non-circular opening or cross-section that is not typical of the container where the container is a cube, the "round" cylindrical surface of the container support may not be circular, , It can be sealed using a non-circular sealing component such as a gasket or a seal shaped to seal on the non-circular cross-section. In addition, "cylindrical" does not require a circular cross-section cylinder, and includes other cross-sectional shapes such as, for example, a square with rounded corners.

The general cylindrical inner surface is sized to receive the container cylindrical wall.

The annular groove is coaxially disposed within the substantially cylindrical inner surface. The first annular groove has an opening in the substantially cylindrical inner surface and a bottom wall radially spaced from the substantially cylindrical inner surface.

The O-ring is disposed in the first annular groove. With respect to the first annular groove, the O-ring is sized to extend radially through the opening and radially outwardly pressed by the container received by the generally cylindrical inner surface. This arrangement forms a seal between the container and the first annular groove.

According to another aspect of the present invention, there is provided a method of coating and inspecting a container, wherein a first inspection of the inner surface of the container is performed after the coating is applied to the inner surface of the container to check for defects. Thereafter, a second inspection of the inner surface of the coated container is performed to see if there is a defect, then an evaluation of the data obtained during the first and second inspection is performed, and the second inspection and the data evaluation It takes less than 30 seconds.

According to another aspect of the present invention there is provided a container treatment method wherein the opening of the container is seated on a container port of the container support after the inner surface of the container is coated through the container port. Thereafter, the coating is inspected for defects in the coating through the vessel port. After performing this, the vessel is transferred from the first processing station to the second processing station, and the seated vessel is supported during coating, inspection and transport by the vessel support.

III. Container transfer method - Container placed on the container support

III.A. Transporting the vessel support to the processing station

Another aspect of the present invention is a container treatment method. A first processing station and a second processing station spaced from the first processing station are provided for vessel processing. A container is provided having a wall defining an opening and an interior surface. A container support comprising a container port is provided. An opening of the container is seated on the container port. The inner surface of the seated vessel is processed through the vessel port at the first processing station. The container support and the seated container are transported from the first processing station to the second processing station. The inner surface of the seated vessel is processed through the vessel port at the second processing station.

III.B. Transporting the treatment device to the container support or vice versa.

Another aspect of the present invention is a method of treating a vessel comprising parts. The first processing apparatus and the second processing apparatus are provided for the container processing. A container is provided having a wall defining an opening and an interior surface. A container support comprising a container port is provided. An opening of the container is seated on the container port.

The first treatment device is operably engaged with the container support and vice versa. The inner surface of the seated vessel is treated through the vessel port using the first processing apparatus.

Thereafter, the second processing device is operably engaged with the container support and vice versa. And an inner surface of the seated vessel through the vessel port using the second processing apparatus.

III.C. Using a gripper to transport the tube back and forth to the processing station

Yet another aspect of the present invention is a plasma enhanced chemical vapor deposition (PECVD) processing method of a first vessel, including some steps. A first container is provided having an open end, a closed end and an inner surface. At least the first gripper is configured to selectively hold and release the closed end of the first container. The closed end of the first container is gripped using the first gripper and is conveyed to the vicinity of the container support configured to seat with the open end of the first container using the first gripper. The first gripper is then used to axially advance the first container and seat its open end on the container support so as to provide a sealed communication between the interior of the container support and the first container.

At least one gas reactant is introduced into the first vessel through the vessel support. A plasma is formed in the first vessel under conditions effective to form a reaction product of the reactants on the inner surface of the first vessel.

Thereafter, the first container is detached from the container support, and the first container is axially transported from the container support using the first gripper or other gripper. Thereafter, the first container is released from the gripper used to axially transfer from the container support.

IV. PECVD apparatus for container manufacturing

IV.A. A PECVD apparatus including a container support, internal electrodes, and a vessel as a reaction chamber

According to another aspect of the present invention, a plasma enhanced chemical vapor deposition (PECVD) mechanism is provided for coating an inner surface of a vessel. The PECVD apparatus may be part of the vessel treatment system and includes a vessel configured to receive and seat a first opening of a vessel for treating an interior surface of a vessel seated through the vessel port, And a container support including a port. The PECVD apparatus also includes an outer electrode having an inner electrode arranged in the inner space of the seated vessel and an inner portion receiving the seated vessel. A power supply is also provided for generating plasma in the vessel, characterized in that the seated vessel and the vessel support are adapted to define a plasma reaction chamber.

According to another exemplary embodiment of the present invention, the PECVD apparatus further comprises a vacuum source for evacuating the interior space of the seated vessel, the vessel port and the seated vessel being adapted to define a vacuum chamber.

According to another exemplary embodiment of the present invention, the PECVD apparatus further comprises a gas supplier for supplying the reaction gas from the reactant gas source to the inner space of the vessel.

According to another exemplary embodiment of the present invention, the gas supply is located in the distal portion of the inner electrode.

According to another exemplary embodiment of the present invention, the inner electrode is a probe having a distal portion positioned to extend concentrically to the seated container.

According to another exemplary embodiment of the present invention, the outer electrode has a cylindrical section and extends concentrically around the seated container.

According to another exemplary embodiment of the present invention, the PECVD apparatus includes a gripper for selectively supporting and discharging the closed end of the container, and for grabbing the closed end of the container to transport the container to the vicinity of the container support, .

According to another exemplary embodiment of the present invention, the PECVD apparatus is adapted to form a plasma in the interior space of a vessel substantially free of hollow cathode plasma.

According to another exemplary embodiment of the present invention, the PECVD apparatus further comprises a detector for irradiating the interior space of the vessel through the inspection vessel port of the inner surface of the vessel to determine whether it is defective.

According to another exemplary embodiment of the present invention, the PECVD apparatus has a processing vessel opening for connecting with a second limited opening of the vessel, wherein a reaction gas flows from the inner space of the vessel to the processing vessel And the processing vessel is provided with a processing vessel.

According to another exemplary embodiment of the present invention, the distal end of the inner electrode is located less than a half of the distance from the first larger opening to the second restricted opening of the seated container.

According to another exemplary embodiment of the present invention, the distal end of the inner electrode is located outside the first larger opening of the seated vessel.

Also provided is a method of coating an interior surface of a container that receives and seats an opening of the container on a container port of a container support for treating an interior surface of the container. The inner electrode is then arranged in the inner space of the seated vessel after the gas feeder is positioned in the distal portion of the inner electrode. Further, the seated container is accommodated in the inner portion of the outer electrode. The seated vessel in the vessel support is adapted to define a plasma reaction chamber.

In particular, a vacuum chamber may be defined by the vessel port and gas is withdrawn from the interior space of the seated vessel such that no external vacuum chamber is required for the coating.

In another step, a plasma is formed in the interior space of the seated vessel and a coating material is deposited on the interior surface of the seated vessel.

According to another exemplary embodiment of the present invention, a processing vessel opening is connected to a limited opening of the vessel to allow reaction gas to flow from the inner space of the vessel to the processing vessel.

According to another aspect of the present invention there is provided a system for the treatment of vessels as described above and below, comprising a syringe for storing a biologically active compound or composition, a vial for storing a biologically active compound or composition, The use of a conduit for transferring a composition or a cuvette for supporting a biologically active compound or composition.

Another aspect of the present invention is a PECVD apparatus including a container support, an inner electrode, an outer electrode, and a power supply.

The container support has a port for receiving the container in a seated position for processing. The inner electrode is positioned to be received in a container that is seated in the container support object. The outer electrode has a medial portion positioned to receive a container seated on the receptacle support. The power supply supplies an alternating current to the inner and outer electrodes to form a plasma in a container seated on the container support. The vessel defines a plasma reaction chamber.

Yet another aspect of the present invention is a PECVD apparatus as described in the preceding paragraph which does not necessarily include a vacuum source for transferring gas into or out of a vessel seated on the port to define a closed chamber And a gas exhaust port.

IV.B. PECVD apparatus using a gripper to transport the tube back and forth to the coating station

Another aspect of the present invention is an apparatus for PECVD processing of a first vessel having an open end, a closed end and an internal space. The apparatus includes a container support, a first gripper, a sheet of the object to be supported, a reactant supply, a plasma generator, and a container discharge device.

V. PECVD methods

According to another aspect of the present invention there is provided a method of coating (and / or inspecting) an inner surface of a container that receives and seats an opening of the container in a container support for treating an inner surface of the container. The term treatment may refer to a coating step or some coating steps or even a series of coating and inspecting steps.

Further, a first treatment of the inner surface of the seated vessel is performed through the vessel port of the vessel support at the first treatment station. The container support and the seated container are then transported to a second processing station after the first processing at the first processing station. Thereafter, at the second processing station, a second treatment of the inner surface of the seated vessel is performed through the vessel port of the vessel support.

V.A. SiO2 using plasma with substantially no hollow cathode plasma _x PECVD to apply barrier coatings

Another aspect of the present invention is a method of applying a barrier coating of SiO _x on a surface, preferably on the interior of a vessel, wherein x is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, 2, a barrier coating application method. The method includes some steps.

For example, a surface, e.g., a vessel wall, is provided as a reaction mixture comprising a plasma-forming gas comprising an organosilicon compound gas, alternatively an oxidizing gas and optionally a hydrocarbon gas.

The plasma is formed in the reaction mixture substantially free of cathode hollow plasma. The vessel wall is contacted with the reaction mixture and a coating of SiO _x is deposited on at least a portion of the vessel wall.

V.B. PECVD coating a limited opening of the vessel (syringe capillary)

Another aspect of the present invention is a method of coating an inner surface of a limited opening of a generally tubular container that is treated by PECVD. The method includes these steps.

Tubular containers are generally provided and treated. The container includes an outer surface, an inner surface defining a lumen, a larger opening having an inner diameter, and a restricted opening defined by the inner surface and having an inner diameter smaller than the larger opening inner diameter.

A processing vessel having a lumen and a processing vessel opening is provided. The processing vessel opening is in communication with a limited opening of the vessel to allow communication between the processing vessel lumen and the lumen of the vessel being processed through the limited opening.

Thereby drawing at least a partial vacuum within the lumen of the vessel to be treated and the vessel lumen being processed. The PECVD reactant flows through the first opening, then through the lumen of the vessel to be processed, and then through the restricted opening to the vessel lumen under processing. Plasma is produced adjacent the confined openings under conditions effective to deposit a coating of the PECVD reaction product on the inner surface of the confined openings.

V.C. Method of applying a lubricous coating

Another aspect of the invention is a method of applying a lubricous coating on a substrate. The method is performed as follows.

A precursor is provided. The precursor is preferably an organosilicon compound, more preferably a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, or a combination of two or more of these precursors. Other precursors are also contemplated, including organometallic precursors including Group III and Group IV metals of the Periodic Table of the Elements. The precursor is applied to the substrate under conditions effective to form the coating. The coating is polymerized, cross-linked, or both to form a lubricating surface with a "plunging force" or "breakout force" lower than that of the untreated substrate, as defined herein.

VI. Container inspection

VI.A. Container processing including precoating and postcoat inspection

Yet another aspect of the present invention is a container treatment method for treating a container having an opening and a wall defining an interior surface. Said method comprising the steps of: inspecting an interior surface of said container provided for detecting defects; Applying the coating to an inner surface of the container after inspecting the provided container; And inspecting the coating to see if it is defective.

Another aspect of the present invention relates to a method of treating a container, wherein the container is coated with a barrier coating after the molded container is inspected, and after application of the barrier coating, the inner surface of the container is inspected for defects Method.

V.I.B. For example, a container inspection performed by detecting gas removal of the container wall through a barrier

Another aspect of the invention is a method of inspecting coatings by measuring volatile species that have been degassed by the coated article ("degassing method"). The method can be used to test the product of a coating process in which the coating is applied to the surface of the substrate to form a coated surface. In particular, the method can be used as an in-line process control for coating processes to distinguish and remove coated products or damaged coating products that do not meet certain criteria.

In general, a "volatile species" is a gas or vapor under test conditions and is preferably selected from the group consisting of air, nitrogen, oxygen, water vapor, volatile coating components, volatile substrate components and combinations thereof, Air, nitrogen, oxygen, water vapor or a combination thereof. The method may be used to measure only one or more volatile species and preferably all volatile species measured in a plurality of different volatile species step (c), and more preferably substantially all of the volatile species discharged from the subject, ).

The gas removal method includes the following steps:

(a) providing a product as an object to be inspected;

(c) measuring the release of at least one volatile species from the object to be inspected into the gas space adjacent to the coated surface; And

(d) comparing the result of step (c) with the result of step (c) for at least one reference object measured under the same test conditions to determine the presence or absence of said coating and / or the physical and / Measuring properties.

In the gas removal method, the physical and / or chemical properties of the coating to be measured are selected from the group consisting of blocking effect, wet tension and composition thereof, preferably a blocking effect.

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

Preferably, the reference object (i) is an uncoated substrate; Or (ii) a substrate coated with a reference coating. This may be achieved, for example, by the fact that, compared to a coating with known properties, for example, if the degassing process is used to determine the presence or absence of a coating (which may then be a non-coated substrate) . In order to determine the identity of the coating as a specific coating, the reference coating may also be a conventional choice.

In addition, the degassing process may be carried out at atmospheric pressure in a gas space adjacent to the coated surface so that a mass flow rate or volume flow rate of the volatile species, which is provided with a pressure differential across the coated surface and higher than when there is no pressure differential, (B) as an additional step between steps (a) and (c). In this case, the volatile species will move in the direction of the lower side of the pressure differential. If the coated object is a container, a pressure differential between the container lumen and the exterior is set to measure the gas removal status of the volatile species from the coated vessel wall. The pressure differential may be provided, for example, by at least partially evacuating the gas space in the vessel. In this case, volatile species that are degassed into the lumen of the vessel can be measured.

If a vacuum is applied to produce a pressure differential, the measurement may be performed using a measurement cell interposed between the coated surface of the substrate and a vacuum source.

In one aspect, the object to be inspected is a volatile species of step (a), preferably air, nitrogen, nitrogen or a mixture thereof, in order to enable the adsorption or absorption of the volatile species into or into the volatile species, , Oxygen, water vapor, and combinations thereof. Subsequent emissions of the volatile species from the subject are then measured in step (c). Since different materials (e.g., the coating and the substrate, etc.) have different adsorption and absorption characteristics, this can simplify the determination of the presence and characteristics of the coating.

The substrate is a polymeric compound, preferably a polyester, a polyolefin, a cyclic olefin copolymer, a polycarbonate, or a combination thereof.

In the context of the present invention, the coatings characterized by the degassing process are, for example, coatings prepared by conventional PECVD from the organosilicon precursors described herein. In a particular aspect of the present invention (i) The coating barrier coating, preferably x is from about 1.5 to about 2.9 and the SiO _x film; And / or (ii) the coating is a coating modifying the lubricity and / or surface tension of the coated substrate, preferably w is 1, x is from about 0.5 to 2.4, y is from about 0.6 to about 3 , and z is a film of Si _w O _x C _y H _z of 2 to about 9.

If the coating process in which the product is inspected by the degassing process is a PECVD coating performed under vacuum conditions, subsequent degassing measurements may be performed without breaking the vacuum used for PECVD.

The measured volatile species may be volatile species discharged from the coating, volatile species discharged from the substrate, or a combination of both. In one aspect, the volatile species is a volatile species, preferably a volatile coating component, discharged from the coating, and the inspection is performed to determine the presence, nature, and / or composition of the coating. In another aspect, the volatile species are volatile species discharged from the substrate, and the inspection is performed to determine the presence of the coating and / or the blocking effect of the coating.

The degassing method of the present invention is particularly suitable for measuring the presence and characteristics of coatings on the vessel walls. Thus, the coated substrate can be a container having walls at least partially coated on its inner or outer surface during the coating process. For example, the coating is provided on the inner surface of the vessel wall.

Conditions effective to distinguish the presence of the coating and / or to measure the physical and / or chemical properties of the coating include conditions less than 1 hour, or less than 1 minute, or less than 50 seconds or less than 40 seconds, or less than 30 seconds, or less than 20 seconds Or less than 15 seconds, or less than 10 seconds, or less than 8 seconds, or less than 6 seconds, or less than 4 seconds, or less than 3 seconds, or less than 2 seconds, or less than 1 second .

In order to increase the difference between the reference object and the inspected object with respect to the discharge rate and / or the type of the measured volatile species, the discharge rate of the volatile species may be changed by changing ambient pressure and / or temperature and / .

In a particular aspect, the degassing is measured using a microcantilever measurement technique. For example, the measurement may be performed by:

(i) providing at least one microcantilever having characteristics that (a) when the degassed material is present, is moved or changed to a different shape;

(b) exposing the microcantilever to the degassed material under conditions effective to cause the microcantilever to move or change to a different shape; And

(c) Preferably, an energy incident beam, such as, for example, a laser beam is reflected from a part of the microcantilever which changes its shape before and after the microcantilever is exposed to the gas removal, and at a point apart from the cantilever Measuring the deflection of the reflected beam; Or detecting a moving or different shape as follows

(ii) providing (a) providing at least one microcantilever resonating at a different frequency when the degassed material is present;

(b) exposing the microcantilever to the degassed material under conditions effective to cause the microcantilever to resonate at different frequencies; And (c) detecting a different resonant frequency using the harmonic vibration sensor.

Further, an apparatus for carrying out the gas removing method, for example, an apparatus including the above-described micro cantilever is considered.

Using the degassing method of the present invention, for example, a barrier film on a vapor removing material is inspected, which has several steps. A sample of material is provided which has been degassed and has at least one partial barrier film. In one particular aspect of the present invention, a pressure differential is provided across the blocking membrane such that at least a portion of the degassing material is on the high pressure side of the blocking membrane. The degassed gas passing through the barrier is measured. If a pressure differential is present, the measurement is performed selectively on the lower pressure side of the barrier.

VII. PECVD treated vessels

VII.A.1.a.i. Hydrophobic coating deposited from an organosilicon precursor

Another aspect of the invention is, for example, a hydrophobic coating deposited from an organosilicon precursor in a vessel having a hydrophobic coating on the inner wall. The coating is of the type produced by the following steps.

Organometallic compounds, preferably organosilicon compounds, more preferably linear siloxanes, monocyclic siloxanes, polycyclic siloxanes, polysilsesquioxanes, alkyltrimethoxysilanes, linear silazanes, monocyclic silazanes, , A polycyclic silazane, a polysilsesquiazane, or a compound selected from the group consisting of any combination of any two or more of these precursors. In addition, organometallic compounds including metals of group III or IV can be considered as precursors.

The precursor is applied to the substrate under conditions effective to form the coating. The coating is polymerized, cross-linked, or both to form a hydrophobic surface having a higher contact angle than the substrate not treated herein.

The resulting coating may have the formula: w is 1, x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, z is from about 2 to about 9, preferably w is 1 and, x is from about 0.5 to 1, y is from about 2 to about 3, z is from 6 to 9, _{Si w O x C y H z} .

The values of w, x, y, and z used throughout this specification should be understood in proportion to empirical formulas (e.g., for coatings) rather than as a limitation on the number of atoms in a molecule. For example, octamethylcyclotetrasiloxane having a molecular formula of Si ₄ O ₄ C ₈ H ₂₄ is obtained by dividing each of w, x, y and z in the molecular formula by the maximum common factor of 4 Can be described by empirical formula: Si ₁ O ₁ C ₂ H ₆ . Also, the values of w, x, y, and z are not limited to integers. For example, (acyclic) octamethyltrisiloxane, the molecular formula of Si ₃ O ₂ C ₈ H ₂₄ , can be reduced to Si ₁ O _0.67 C _2.67 H ₈ .

VII.A.1.b. Citrate salts with walls coated with a hydrophobic coating deposited from an organosilicon precursor Blood tubes

Another aspect of the invention is a cell manufacturing tube containing a water soluble sodium citrate reagent having a wall provided with a hydrophobic coating.

The wall is made of a thermoplastic material having an inner surface defining a lumen.

The hydrophobic coating is provided on the inner surface of the tube. The hydrophobic coating may comprise an organometallic compound, preferably an organosilicon compound, more preferably a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, an alkyltrimethoxysilane, a linear silazane, a mono A cyclic silazane, a polycyclic silazane, a polysilsesquiazane, or an organometallic compound that is a compound selected from the group consisting of combinations of any two or more of these precursors. PECVD is used to form the coating on the inner surface. The resulting coating may have the following structure: w is 1, x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, z is from about 2 to about 9, preferably 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 9. Si _w O _x C _y H _z .

The aqueous sodium citrate reagent is provided to the lumen of the tube in an amount effective to inhibit the coagulation of blood introduced into the tube.

VII.A.1.c. SiO _x Barrier-coated double-walled plastic containers -COC, PET, SiO _x Layers

Another aspect of the invention is a container having a wall at least partially enclosing the lumen. The wall has an inner polymer layer surrounded by an outer polymer layer. One of the polymer layers is a layer that is at least 0.1 mm thick of a cyclic olefin copolymer (COC) resin that defines a water vapor barrier. One of the polymer layers is a layer that is at least 0.1 mm thick of the polyester resin.

Wherein said wall comprises an oxygen barrier film of Si _{x having} an oxygen barrier film wherein x is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, or from about 2 to about 500 angstroms .

VII.A.1.d. How to make double-walled plastic containers -COC, PET, SiO _x Layers

Another aspect of the present invention is a method of making a container having a wall having an inner polymer layer surrounded by an outer polymer layer, one layer made of COC and another layer made of polyester. The container is fabricated by a process comprising introducing COC and polyester resin layers into the injection mold through concentric injection nozzles.

Another optional step is to apply an amorphous carbon coating to the vessel by PECVD with an inner coating and an outer coating or an interlayer coating located between the coatings.

An optional additional step is to define the SiO _x as before and to apply the SiO _x barrier to the interior of the vessel wall. Another optional additional step is the step of post-treating the SiO _x film with a process gas essentially consisting of oxygen and essentially free of volatile silicone compounds.

Optionally, the SiO _x coating may be at least partially formed from a silazane feed gas.

VII.A.1.e. Barrier coating made of glass

Another aspect of the invention is a container comprising a container, a barrier coating and a closure. The container is generally tubular and made of a thermoplastic material. The container has a lumen that is at least partially bounded by a wall having an inlet and an interior surface that interfaces with the lumen. There is at least one essentially continuous barrier coating made of glass on the inner surface of the wall. A closure covers the inlet and separates the lumen of the vessel from ambient air.

A related aspect of the present invention is the container described in the preceding paragraph, wherein the barrier coating is made of soda lime glass or borosilicate glass or other type of glass.

VII.A.2. Stoppers

VII.A.2.a. Method of applying a lubricous coating to a stopper in a vacuum chamber

Another aspect of the invention is a method of applying a coating, e. G., A lubricous coating, as defined above, on an elastic stopper. For example, the stopper is located in a substantially vacuum chamber. A reaction mixture comprising a plasma forming gas, such as an organosilicon compound gas, optionally an oxidizing gas and optionally a hydrocarbon gas, is provided. A plasma is formed in the reaction mixture in contact with the stopper. Where x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, z is from 2 to about 9, preferably w is 1, and x is from about 0.5 is to 1, y is from about 2 to about 3, z is from 6 to 9 in the coating of Si _w O _x C _y H _z, is deposited on at least a portion of the stopper.

VII.A.2.b. Applying a coating of Group III or Group IV elements and carbon onto the stopper by PECVD

Another aspect of the invention is a method of applying a coating of a composition comprising carbon and one or more elements of group III or IV on an elastic stopper. To perform the method, the stopper is located in a vacuum chamber.

A reaction mixture comprising a plasma-forming gas having a Group III element (e.g., Al), a Group IV element (e.g., Si, Sn), or a combination of two or more thereof is provided in the deposition chamber. Optionally, the reaction mixture comprises an oxidizing gas and optionally a gaseous compound having at least one C-H bond. A plasma is formed in the mixture, and the stopper contacts the reaction mixture. A coating of a Group III element or compound, a Group IV element or compound, or a combination of at least two of the foregoing, is deposited on at least a portion of the stopper.

VII.A.3. A stoppered plastic container with a barrier coating effective to maintain a 95% vacuum for 24 months.

Another aspect of the invention is a container comprising a container, a barrier coating and a closure. The container is generally tubular and made of a thermoplastic material. The container has an inlet and a lumen at least partially bounded by the wall. The wall has an inner surface that interfaces with the lumen. At least one essentially continuous barrier coating is applied on the inner surface of the wall. The barrier coating is effective to maintain at least 90%, alternatively 95%, of the initial vacuum level in the container for a shelf life of at least 24 months. A closure is provided for covering the inlet of the container and separating the lumen of the container from ambient air.

VII.B.1.a A syringe having a barrel coated with a lubricous coating deposited from an organometallic precursor

Another aspect of the present invention is a container having a lubricous coating made from an organosilicon precursor. In addition, other organometallic precursors as defined herein may be contemplated.

The coating may be of the type produced by the following process.

The organometallic precursor, preferably an organosilicon precursor, more preferably a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, a linear silazane, a monocyclic silazane, a polycyclic silazane, , Polysilsesquiazane, or a precursor that is any combination of two or more of these precursors.

The precursor is applied to the substrate under conditions effective to form the coating. The coating is polymerized, cross-linked, or both to form a lubricating surface with lower plunger force or breakout force than the untreated substrate.

Yet another aspect of the present invention is a syringe comprising a plunger, a syringe barrel and a lubricity layer. The syringe barrel has an inner surface for slidably receiving the plunger. The lubricating layer comprises a coating of a Si _w O _x C _y H _z lubricity layer provided on the inner surface of the syringe barrel and made from the organosilicon precursor as defined herein. The lubricity layer is less than 1000 nm thick and is effective to reduce the breakout force or plunger force required to move the plunger within the barrel.

Another aspect of the invention is a lubricous coating on the inner wall of a syringe barrel. The coating is produced from a PECVD process using the following materials and conditions. A cyclic siloxane, a monocyclic siloxane, a polycyclic siloxane, or a combination of two or more thereof. At least essentially no oxygen is added to the process. Plasma generating power input sufficient to induce coating formation is provided. The materials and conditions employed herein are effective to reduce the syringe plunger activity or breakout force moving through the syringe barrel by at least about 25% for uncoated syringe barrels.

The resulting coating may have the following formula: w is 1, x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, z is from about 2 to about 9, preferably w is 1, x is from about 0.5 to 1, y is from about 2 to about 3, z is from 6 to 9, _{Si w O x C y H z} .

VII .B.1.a.i. Lubricity coating: SiO _x Barrier, Lubricity Layer, surface treatment.

Another aspect of the invention is a syringe comprising a barrel defining a lumen and receiving the plunger in a glide-able manner. The syringe barrel may be made of a thermoplastic material. The lubricous coating is applied to the inner surface of the barrel, plunger, or both, for example, by PECVD. The lubricous coating may be fabricated from an organosilicon precursor and may be less than 1000 nm thick. The surface treatment is performed on the lubricative coating in an amount effective to reduce filtration of the lubricous coating, the thermoplastic series material, or both into the lumen, i. E., To form a solute retainer on the surface. The lubricant coating and solute retainer are constructed and present in a relative amount effective to provide both a breakout force or plunger actuation force, or both forces lower than the corresponding force required in the absence of the lubricant coating and solute retainer.

VII.B.1.b SiO _X A syringe having an outer barrel coated with a coated inner and a barrier

Yet another aspect of the present invention is a syringe comprising a plunger, a barrel, and inner and outer barrier coatings. The wall is made of a thermoplastic material that defines the lumen. The barrel has an inner surface and an outer surface for slidably receiving the plunger. Wherein a barrier coating of SiO _x , wherein x is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, or about 2, is provided on the inner surface of the barrel. A barrier coating of the resin is provided on the outer surface of the barrel.

VII.B.1.c SiO _x Method of making a syringe having coated inner and outer barrier coated barrels

Yet another aspect of the invention is a method of making a syringe comprising a plunger, a barrel and inner and outer barrier coatings. There is provided a barrel having an inner surface and an outer surface for slidably receiving the plunger. Wherein a barrier coating of SiO _x , wherein x is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, or about 2, is provided on the inner surface of the barrel by PECVD. A barrier coating of the resin is provided on the outer surface of the barrel. The plunger and barrel are assembled to provide a syringe.

VII.B.2 Plunger

VII.B.2.a Using a piston-coated front face

Another aspect of the invention is a plunger for a syringe, comprising a piston and a push rod. The piston has side and back portions configured to movably seat within a front, generally cylindrical syringe barrel. The front face has a barrier coating. The push rod engages the posterior portion and is configured to advance the piston in a syringe barrel.

VII.B.2.b. Use a lubricous coating that contacts the sides with each other

Yet another aspect of the present invention is a plunger for a syringe, comprising a piston, a lubricous coating, and a pushrod. The piston has a front side, a generally cylindrical side and a back side. The side surface is configured to movably seat within the syringe barrel. The lubricant coating is in contact with the side surface. The push rod is configured to engage the anterior portion of the piston and advance the piston in a syringe barrel.

VII.B.3. Two-part syringe and luer fitting

Yet another aspect of the present invention is a syringe including a plunger, a syringe barrel, and a Luer fitting. The syringe barrel has an inner surface for slidably receiving the plunger. The luer fitting includes a luer taper having an inner passageway defined by an inner surface. The luer fitting is formed of a component separated from the syringe barrel and is joined to the syringe barrel by coupling. The internal passageway of the luer taper has a barrier coating of SiO _x , wherein x is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, or about 2.

VII.B.4. Lubricating Coatings Made with In Situ Polymerized Organic Silicon Precursors

VII.B.4.a. Process products and lubricity

Another aspect of the invention is a lubricous coating made from an organosilicon precursor. This coating comes from a type produced by the following process.

The organometallic precursor, preferably an organosilicon precursor, preferably a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, a linear silazane, a monocyclic silazane, a polycyclic silazane, Polysilsesquiazane or a precursor selected from any combination of two or more of these precursors is provided. The precursor is applied to the substrate under conditions effective to form the coating. The coating is polymerized, cross-linked, or both to form a lubricating surface with lower plunger force or breakout force than the untreated substrate.

The resulting coating may have the following structure: w is 1, x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, z is from about 2 to about 9, preferably 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 9. Si _w O _x C _y H _z .

VII.B.4.b. Process and product characterization

Another aspect of the present invention is to provide an organic metal precursor, preferably an organic silicon precursor, more preferably a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, a linear silazane, A polynuclear silazane, a polysilsesquiazane, or a precursor which is any combination of two or more of these precursors. The coating has a density between 1.25 and 1.65 g / cm < ³ > as measured by X-ray reflectance (XRR).

It is also possible to use a metal containing a metal of group III such as boron, aluminum, gallium, indium, thallium, scandium, yttrium or lanthanum or silicon, germanium, tin, lead, titanium, zirconium, half, thorium or any combination of two or more thereof The use of an organometallic precursor can also be considered. Other volatile organic compounds may also be considered. However, organosilicon compounds are preferred for carrying out the present invention.

Another aspect of the present invention is to provide an organic metal precursor, preferably an organic silicon precursor, more preferably a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, a linear silazane, A polynuclear silane, a polysilsesquiazane, or any combination of two or more of these precursors. The use of precursors comprising metals of group III or IV can also be considered.

The coating has one or more oligomers as repeating (Me) ₂ SiO-moieties as a degassing component, as measured by a gas chromatography / mass spectrometer. Optionally, the coating meets the limitations of any of the embodiments VII.B.4.a or VII.B.4.b.

Another aspect of the present invention is to provide an organic metal precursor, preferably an organic silicon precursor, more preferably a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, a linear silazane, A polynuclear silane, a polysilsesquiazane, or any combination of two or more of these precursors. The coating has an atomic concentration normalized to 100% carbon, oxygen and silicon, less than 50% carbon and more than 25% silicon, as measured by X-ray photoelectron spectroscopy (XPS). Optionally, the coating meets the limitations of any of the embodiments VII.B.4.a or VII.B.4.b.

The use of an organometallic precursor comprising a Group III or IV metal may also be considered.

Another aspect of the present invention relates to a process for the preparation of a feed gas comprising an organosilicon precursor, preferably a monocyclic siloxane, a monocyclic silazane, a polycyclic siloxane, a polycyclic silazane, or any combination of two or more of these precursors Lt; RTI ID = 0.0 > PECVD < / RTI > Wherein the coating is normalized to 100% of carbon, oxygen and silicon as measured by X-ray photoelectron spectroscopy (XPS), and wherein the atomic concentration of carbon, in atomic form relative to the feed gas, . Optionally, the coating meets the limitations of Example VII.B.4.a or VII.B.4.b.

Another aspect of the present invention relates to a process for the preparation of a feed gas comprising an organosilicon precursor, preferably a monocyclic siloxane, a monocyclic silazane, a polycyclic siloxane, a polycyclic silazane, or any combination of two or more of these precursors Lt; RTI ID = 0.0 > PECVD < / RTI > Wherein the coating is normalized to 100% of carbon, oxygen and silicon as measured by X-ray photoelectron spectroscopy (XPS), and wherein the atomic concentration of silicon, less than the atomic concentration of silicon in the atomic form for the feed gas, . Optionally, the coating meets the limitations of Example VII.B.4.a or VII.B.4.b.

VII.C.1. A container comprising a viable blood having a coating deposited from an organosilicon precursor

Another aspect of the present invention is a blood containing container. The container having a wall; The wall has an inner surface defining a lumen. The inner surface of the wall is at least one partial hydrophobic coating as described above, preferably a hydrophobic coating of Si _w O _x C _y H _z , preferably w is 1, wherein x is from about 0.5 to about Y is from about 2 to about 3, y is from about 0.6 to about 3, z is from 2 to about 9, more preferably w is 1, x is from about 0.5 to 1, About 9, hydrophobic coating. The coating may be as thin as about monomolecular thickness or as thick as about 1000 nm. The container comprises a viable blood capable of returning to the vasculature of the patient placed in the lumen in contact with the Si _w O _x C _y H _z coating.

VII.C.2. Coatings deposited from the organosilicon precursors reduce coagulation or platelet activation on the vessel walls

Another aspect of the invention is a container having a wall. The wall has an inner surface defining the lumen and is coated with at least one partial passivation, such as a hydrophobic coating made from an organosilicon precursor by PECVD, preferably a coating of Si _w O _x C _y H _z , and w is 1, wherein x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, z is from 2 to about 9, more preferably w is 1, x is from about 0.5 to 1 , y is from about 2 to about 3, and z is from 6 to about 9. The thickness of the coating is from monomolecular thickness to about 1000 nm thickness on the inner surface. The coating is effective to reduce platelet activation of plasma treated with sodium citrate additive and exposed to the inner surface, compared to uncoated walls of the same type. The coating is effective to reduce the coagulation of blood exposed to the inner surface, compared to uncoated walls of the same type.

VII.C.3. A vessel containing a viable blood and having a coating of a Group III or Group IV metal element

Another aspect of the invention is a blood containing container having a wall having an inner surface defining a lumen. The inner surface has at least a partial coating of a composition comprising carbon, one or more Group III metals, one or more Group IV metals, or a combination of two or more thereof. The thickness of the coating is on the inner surface from not less than monomolecular thickness to less than about 1000 nm. The container includes viable blood that can return to the vasculature of the patient disposed within the lumen in contact with the coating.

VII.C.4 Coating of Group III or Group IV elements reduces coagulation or platelet activation of blood in the vessel

Optionally, in the container of the preceding paragraph, the coating of Group III or Group IV elements is effective to reduce coagulation or platelet activation of blood exposed to the inner surface of the container wall.

VII.D.1. A container comprising an insulin, having a coating deposited from an organosilicon precursor

Another aspect of the invention is an insulin-containing container comprising a wall having an inner surface defining a lumen. The inner surface is an at least partial passivation coating made from an organosilicon precursor by PECVD, preferably a coating of Si _w O _x C _y H _z , preferably w is 1, wherein x is about 0.5 to about Y is from about 2 to about 3, y is from about 0.6 to about 3, z is from 2 to about 9, more preferably w is 1, x is from about 0.5 to 1, About 9 passivation coatings. The coating may be monomolecular to about 1000 nm thick on the inner surface. Insulin is placed in the lumen in contact with the Si _w O _x C _y H _z coating.

VII.D.2. Coatings deposited from the organosilicon precursors reduce insulin deposition in the container

Alternatively, as compared in the vessel of the previous paragraph, with the same surface coating of Si _w O _x C _y H _z is not a coating of Si _w O _x C _y H _z, in reducing the precipitation from the insulin in contact with the inside surface effective.

VII.D.3. A container comprising an insulin, having a coating of Group III or Group IV elements

Another aspect of the invention is an insulin-containing container comprising a wall having an inner surface defining a lumen. The inner surface has at least a partial coating of a composition comprising carbon, one or more Group III elements, one or more Group IV elements, or a combination of two or more thereof. The coating may be monomolecular to about 1000 nm thick on the inner surface. Insulin is provided in the lumen in contact with the coating.

Optionally, in the container of the preceding paragraph, the coating of a composition comprising carbon, one or more Group III elements, one or more Group IV elements, or a combination of two or more thereof, It is effective to reduce the formation of precipitate from the contacting insulin.

VII.E. Cuvette

In addition, the PECVD coating methods and the like described herein are useful for coating barrier coatings, hydrophobic coatings, lubricating coatings or cuvettes for forming one or more of these. A cubic tube is a small or round cross section tube, sealed at one end, made of plastic, glass or fused quartz (for ultraviolet light) and designed to support specimens for spectroscopic testing. The best cubic is as transparent as possible without impurities that can affect spectroscopic readings. Like a test tube or a sample collection tube, a cubette can have a cap that is open to the atmosphere or can be sealed. The coatings to which the PECVD of the present invention is applied are very thin, transparent, and optically non-glossy, and may not interfere with optical testing of the cuvettes or their contents.

VII.F. Vial

In addition, the PECVD coating methods and the like described herein are useful for coating vials to form a coating, for example, a barrier coating or a hydrophobic coating, or a combination of these coatings. Vials are particularly small containers or bottles used to store medicaments such as liquid, powder or lyophilized powder. They may also be sample vessels for use in automatic sample injector devices, for example, in analytical chromatography. The vial may have a tubular or necked bottle shape. The bottle is mainly flat, unlike a test tube or a sample collection tube having a round bottom. The vial may be made of, for example, plastic (e.g., polypropylene, COC, COP).

Computer-readable media and program components

Also provided is a computer-readable medium having stored thereon a computer program for coating and / or inspecting a container, wherein the process, when executed by a processor of the container handling system, causes the method to perform the method steps described above or below do.

Also provided is a program component for coating and / or inspecting a container that when executed by a processor of a container handling system causes the process to perform the method steps described above or below.

Other aspects of the invention will be apparent from this disclosure and the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic diagram illustrating a vessel treatment system in accordance with one embodiment of the present disclosure.
Figure 2 is a simplified cross-sectional view of the container support in a coating station in accordance with one embodiment of the present disclosure.
Figure 3 is a view similar to Figure 2 in accordance with another embodiment of the present disclosure;
4 is a schematic plan view of another embodiment of the container support.
Figure 5 is a schematic plan view of another embodiment of the container support.
Figure 6 is a view similar to Figure 2 of the container inspection apparatus.
Fig. 7 is a view similar to Fig. 2 of another container inspection apparatus.
8 is a cross section taken along the section line AA in Fig.
Fig. 9 is another embodiment of the structure shown in Fig.
Figure 10 is a view similar to Figure 2 of the container support in a coating station according to another embodiment of the present disclosure, employing a CCD detector.
FIG. 11 is a detail view similar to FIG. 10 of the light source and detector inverted compared to the corresponding portions of FIG.
12 is a view similar to FIG. 2 of the container support in a coating station according to another embodiment of the present disclosure, employing microwave energy to generate a plasma.
Figure 13 is a view similar to Figure 2 of the container support in a coating station according to another embodiment of the present disclosure, wherein the container can be seated in the process station at the container support.
14 is a view similar to FIG. 2 of the container support in a coating station according to another embodiment of the present disclosure, wherein the electrodes may be constructed as coils.
Figure 15 is a view similar to Figure 2 of the container support in a coating station according to another embodiment of the present disclosure, employing a tube transport that reciprocates the container in the coating station.
Fig. 16 is a schematic view showing the operation of a container transport system such as that shown in Fig. 15, for positioning and supporting containers in a process station.
17 is a schematic view showing a mold frame and a mold cavity for forming a container according to one aspect of the present disclosure;
Figure 18 is a schematic view showing the mold cavity of Figure 17, provided with a container coating apparatus according to one aspect of the present disclosure.
Figure 19 is a view similar to Figure 17, provided with another container coating apparatus according to one aspect of the present disclosure.
20 is an exploded longitudinal cross-sectional view of a syringe and cap adapted for use with a pre-filled syringe;
Figure 21 is a view generally similar to Figure 2 showing a capped syringe barrel and a container support in a coating station according to one aspect of the present disclosure.
22 is a view generally similar to FIG. 21 showing a non-capillary syringe barrel and container support for a coating station in accordance with another embodiment of the present invention.
23 is a perspective view of a blood collection tube assembly having a closure in accordance with another embodiment of the present invention.
24 is a fragmentary section of the blood collection tube and closure assembly of FIG. 23. FIG.
25 is an isolated section of the elastic insert of the closure of Figs. 23 and 24. Fig.
Figure 26 is a view similar to Figure 22 of another embodiment of the present invention for treating syringe barrels and other containers.
Fig. 27 is an enlarged detail view of the processing container of Fig. 26;
28 is a schematic view of another processing container.
29 is a schematic diagram showing gas removal of material through a coating.
Figure 30 is a simplified cross-sectional view showing a set-up in which a measurement cell interposed between a vessel and a vacuum source is used to perform a gas-removal and a degass-removal measurement from the vessel to the interior of the vessel.
Figure 31 is a plot of the gas removal mass flow rate measured on the test set-up of Figure 30 for a plurality of vessels.
32 is a bar graph showing the statistical analysis of the end point data shown in FIG.
33 is a longitudinal cross-section showing a combination of a syringe barrel and a gas receiving volume according to another embodiment of the present invention.
34 is a view similar to FIG. 34 of another embodiment of the present invention including an electrode extension.
35 is a view taken from section line 35-35 of Fig. 34 showing the distal gas supply openings and extension electrodes of Fig. 34;
Figure 36 is a perspective view of another double-walled blood collection tube assembly in accordance with another embodiment of the present invention.
37 is a view similar to Fig. 22 showing another embodiment.
Fig. 38 is a view similar to Fig. 22 showing yet another embodiment.
Figure 39 is a view similar to Figure 22 showing yet another embodiment.
Figure 40 is a view similar to Figure 22 showing yet another embodiment.
41 is a plan view of the embodiment of Fig.
Figure 42 is a cross-sectional view of another embodiment of the seal arrangement for use with the embodiments of Figures 1, 2, 3, 6-10, 12-16, 18, 19, 33 and 37-41, Section in the longitudinal direction. Also shown at 42 is another syringe barrel structure that may be used with the embodiments of Figures 2,3, 6-10, 12-22, 26-28, 33-34, and 37-41, for example.
Figure 43 is another enlarged detail view of the sealing arrangement shown in Figure 42;
FIG. 44 is a block diagram of an embodiment of the present invention for use with embodiments of FIGS. 1, 2, 3, 8, 9, 12-16, 18-19, 21-22, 33, 37-43, 46-49, and 52-54 Figure 2 is a view similar to Figure 2 of another possible gas delivery tube / inner electrode.
Figure 45 is a cross-sectional view of an embodiment of the present invention, for example, with the embodiments of Figures 1, 2, 3, 6-10, 12-16, 18, 19, 21, 22, 26, 28, 33-35, It is another structure for the support.
46 is a schematic cross-sectional view of a series of gas delivery tubes and a mechanism for inserting and removing the gas delivery tubes into the vessel support, showing the gas delivery tube in a fully advanced position;
Figure 47 is a view similar to Figure 46 showing the gas delivery tube in an intermediate position.
Figure 48 is a view similar to Figure 46 showing the gas delivery tube in the retracted position. The series of gas delivery tubes of Figures 46-48 and internal electrode drive 530, for example, Figures 1, 2, 3, 8, 9, 12-16, 18-19, 21-22, 26-28, 33 -35, 37-45, 49 and 52-54. The mechanism of Figs. 46-48 may be applied to, for example, the probes of the container inspection apparatus of Figs. 6 and 7 as well as the probes of Figs. 2, 3, 8, 9, 12-16, 18-19, 21-22, 26-28, 33-35, 37-45, 49, and 52-54.
Figure 49 shows the vessels being treated in Figure 16 of the container inspection apparatus and the mechanism for transferring the cleaning reactor to the PECVD coating apparatus. The mechanism of Fig. 49 can be used, for example, with the container inspection apparatus of Figs. 1, 9, 15 and 16.
50 is an exploded view of a two-part syringe barrel and a luer lock fitting. The syringe barrel may be used with the vessel handling and inspection apparatus of Figs. 1-22, 26-28, 33-35, 37-39, 44, and 53-54.
51 is an assembly view of the two-part syringe barrel and Luer lock fitting of FIG. 50;
52 is a view similar to FIG. 42, showing a syringe barrel being processed, without flange or flanger stops 440. FIG. The syringe barrel may be used with the vessel handling and inspection apparatus of Figs. 1-22, 26-28, 33-35, 37-39, 44, and 53-54.
53 is a schematic view of an assembly for treating vessels; The assembly is usable with the devices of Figs. 1-3, 8-9, 12-16, 18-22, 26-28, 33-35, and 37-49.
54 is a schematic view of the embodiment of FIG.
Figure 55 is a schematic view similar to Figure 2 of an embodiment of the present invention including a plasma screen.
56 is a simplified cross-sectional view of a series of gas delivery tubes having their own gas feeders and mechanisms for inserting and removing gas delivery tubes into the vessel support.
57 is a plot of the degassing mass flow rate measured in Example 19. FIG.
Figure 58 shows a linear rack similar to Figure 4;
Figure 59 is a simplified illustration of a vessel treatment system in accordance with an exemplary embodiment of the present invention.
60 schematically illustrates a container handling system according to an exemplary embodiment of the present invention.
61 illustrates a processing station of a vessel treatment system in accordance with an exemplary embodiment of the present invention.
Figure 62 illustrates a portable container support according to an exemplary embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will now be described in more detail with reference to the accompanying drawings, in which several embodiments are shown. However, the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are examples of the present invention having a full range represented by the language used in the claims. Like numbers refer to like elements throughout the specification.

In the context of the present invention, the following definitions and abbreviations are used:

RF is radio frequency; sccm is the standard cubic centimeter per minute.

The term "at least" in the context of the present invention means "equal to or greater than" The word "comprising" does not exclude other elements or steps, and "a" or "an" does not exclude plural forms unless the context clearly dictates otherwise.

The terms " first "and" second "or similar references, e.g., processing stations or processing devices, refer to the smallest number of processing stations or devices present but do not necessarily represent the order or total number of processing stations and devices. These terms do not limit the number of processing stations or the specific processing performed on the individual stations.

For purposes of the present invention, "organosilicon precursor" is a tetravalent silicon atom that is bonded to an oxygen atom and an organic carbon atom (an organic carbon atom that is a carbon atom bonded to at least one hydrogen atom)

&Lt; / RTI > The volatile organosilicon precursors, which are defined as precursors that can be fed to water vapor in PECVD equipment, are the preferred organosilicon precursors. Preferably, the organosilicon precursor is selected from the group consisting of linear siloxanes, monocyclic siloxanes, polycyclic siloxanes, polysilsesquioxanes, alkyltrimethoxysilanes, linear silazanes, monocyclic silazanes, Polysilsesquiazane, a combination of two or more of these precursors.

In the context of the present invention, "essentially oxygen free" or (synonymously) "substantially oxygen free" is added to the gas reactant in some embodiments. This may be present in the reaction space where some residual atmospheric oxygen may be present in the reaction space and the remaining oxygen supplied in the preceding step and not completely consumed is defined herein as essentially free of oxygen. Especially where the gaseous reactant is less than 1 vol% O ₂ , more preferably 0.5 vol% O ₂ , and even more preferably the gaseous reactant is not O ₂ , essentially no oxygen is present in the gaseous reactant, If oxygen is not added to the gaseous reactant or if oxygen is not present at all during PECVD, this is also in the range "essentially oxygen free ".

"Container" in the context of the present invention may be any type of container having at least one opening, and a wall defining an interior surface. The term "at least" in the context of the present invention means "equal to or greater than" Thus, in the context of the present invention, the container has one or more openings. One or two openings are preferred, such as the openings of a sample tube (one opening) or a syringe barrel (two openings). If the container has two openings, they may be the same or different sizes. If there is more than one opening, one opening may be used for the gas inlet for the PECVD coating method according to the present invention, while the remaining openings are capped or open. The container according to the present invention may be, for example, a sample tube for collecting or storing biological fluids such as blood or urine, a biologically active compound or composition such as a syringe (or a part thereof, e.g., For example, a syringe barrel), such as a vial containing a biological material or a biologically active compound or composition, such as a conduit for transporting a biological material or a biologically active compound or composition, or a biological material or biologically Or it may be a cubette that supports fluids, such as supporting an active compound or composition.

The container may be of any type and is preferably a container having a substantially cylindrical wall adjacent to at least one of its open ends. Generally, the inner wall of the vessel is of a cylindrical shape, such as in a sample tube or syringe barrel. Sample tubes and syringes or parts thereof (e.g., syringe barrels) are particularly preferred.

"Hydrophobic coating" in the context of the present invention means lowering the wet tension of the surface coated with the coating, compared to the surface on which the coating is not coated. Thus, hydrophobicity is a function of both uncoated substrate and coating. The same applies to other contexts where the term "hydrophobic" is used as appropriate. The term "hydrophilic" means the opposite, i.e. the wet tension is increased relative to the reference sample. Certain hydrophobic coatings in the context of the present invention are those of Si _w O _x C _y H _z where w is 1, x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, and z is from 2 to about 9 Or a coating having a chemical formula.

The "wet tension" is a specific measure of the hydrophobicity or hydrophilicity of a surface. A preferred wet tension measurement method in the context of the present invention is ASTM D 2578 or a variation of the method described in ASTM D 2578. This method uses standard wet tension solutions (called dyne solutions) to measure the closest solution to wetting the surface of the plastic film for exactly 2 seconds. This is the wet tension of the film. The procedure used here is that the substrates are not flat plastic films but are tubes (other than the control) coated according to a protocol for fabricating PET tubes and for coating the interior of the tubes with a hydrophobic coating, ASTM D 2578 (see Example 9).

A "lubricous coating" according to the present invention is a coating having a lower frictional resistance than an uncoated surface. That is, it reduces the frictional resistance of the coated surface compared to the uncoated reference surface. "Friction resistance" may be static friction resistance and / or kinetic friction resistance. One of the preferred embodiments of the present invention is a syringe component coated with a lubricous coating, such as a syringe barrel or plunger. In the presently preferred embodiment, the appropriate static friction resistance in the context of the present invention is the breakout force defined herein, and the appropriate dynamic friction resistance in the context of the present invention is the plunger force defined herein. For example, the plunger activity force, as defined and measured herein, determines the presence and lubrication characteristics of the lubricous coating in the context of the present invention when the coating is applied to the inner wall of any syringe or syringe component, e.g., a syringe barrel It is suitable. The breakout force is applied to the syringe, which may be stored for a period of time, e. G., Several months or even years, before the pre-filled syringe, i. E., Filled after coating and the plunger must be moved again ("broken out & Which is particularly suitable for evaluating the effect of the coating.

In the context of the present invention, "plunging force" is the force required to maintain movement of the plunger within the syringe barrel during aspiration or dispensing. This can be advantageously measured using the ISO 7886-1: 1993 test described herein and known in the art. The synonym for "plunger activity", which is often used in the industry, is "plunger force" or "pushing force".

In the context of the present invention, the "breakout force" is the initial force required to move the plunger in a syringe, for example, in a pre-filled syringe.

The "plunging force" and "breakout force" as well as their measurement methods are described in more detail later in this description.

"Scalable" means that the plunger is sliding in the syringe barrel.

In the context of the present invention, "substantially rigid" means that assembled members (ports, ducts, and housings, as will be further discussed below) are not displaced significantly with respect to the rest of the assembled members , It means that it can be moved in one unit by operating the housing. In particular, none of the members are connected by a hose or the like that allows a substantial relative movement between the components during normal use. Providing a substantially rigid relationship of these components allows the position of the container seated on the container support to be known and accurate to the positions of these components secured to the housing.

In the following, an apparatus for carrying out the present invention will be described first, followed by coating methods, coatings and coated containers and applications according to the present invention.

I. Container handling systems including a first processing station, a second processing station, a plurality of vessel supports, and a conveyor are contemplated. The first processing station is adapted to process a vessel having an opening and a wall defining an interior surface. The second processing station is spaced from the first processing station and is adapted to process a vessel having an opening and a wall defining an interior surface.

I. At least a portion of the container support, and optionally all of the container ports are connected to a container port configured to receive and seat the opening of the container for processing the interior surface of the container seated through the container port in the first process . The conveyor is configured to transfer a series of the container supports and the seated containers from a first processing station to a second processing station for processing of an interior surface of the seated container at the second processing station.

I. Priority Referring to Figure 1, there is shown a vessel treatment system generally designated 20. The vessel treatment system may include processing stations that are more widely considered as processing devices. The vessel treatment system 20 of the illustrated embodiment includes an injection molding machine 22, additional processing stations or devices 24, 26, 28, 30, 32, and 34 (which may be considered as a processing station or device) And an output 36 (which may be considered a processing station or device). At a minimum, the system 20 has at least a first processing station, for example a station 28, and a second processing station, for example 30, 32 or 34.

I. In the illustrated embodiment, one of the processing stations 22-36 may be a first processing station, and any other processing station may be a second processing station or the like.

I. The embodiment shown in FIG. 1 may include the following eight processing stations or devices: 22, 24, 26, 28, 30, 32, 34 and 36. The exemplary vessel handling system 20 Coating inspection station 22, an injection molding machine 22, a post-molding inspection station 24, a pre-coating inspection station 26, a coating station 28, a post-coating inspection station 30, 32, an optical source transfer station 34 and an output station 36 for inspecting the coating for defects.

I. The system 20 may include a transfer mechanism 72 for transferring containers from the injection molding machine 22 to the container support 38. The delivery mechanism 72 may for example detect, move, pick, convey, orient, seat and discharge the containers 80 to remove them from the container forming machine 22 (38) And a robot arm for mounting them on the container supports.

I. In addition, the system may include a delivery mechanism (not shown) at the processing station 74 to remove the vessel from one or more vessel supports, such as 66, after processing the interior surface of the anchored vessel, (Fig. 1). Accordingly, the containers 80 are movable from packaging support 66 to packaging, storage or other suitable areas or process steps, generally indicated at 36. The transfer mechanism 72 may be used to detect, move, pick, convey, orient, seat and eject the containers 80, for example, to remove them from the container supports 38, 36 may be configured with robotic arms for mounting them on other equipment.

I. The processing stations or devices 32, 34 and 36 shown in FIG. 1 may be used in the coating and inspection system 20 (FIG. 1) after the individual containers 80 are removed from the container supports, such as 64 Lt; RTI ID = 0.0 > 1 < / RTI > Some non-limiting examples of functions of the stations or devices 32, 34 and 36 include the following steps:

Placing the processed and inspected containers on a conveyor and moving them to another processing device;

Adding chemicals to the containers;

Capping the vessels;

Placing the containers in suitable processing racks;

Packaging the containers; And

Sterilizing the packaged containers

1, the vessel handling system 20 also includes a plurality of vessel supports (or "pucks" because they resemble hockey pucks in some embodiments) each having a size of 38 to 68, 24, 26, 28, 30, 32, 34, and 36, labeled with a band 70 without a plurality of blanks, such as one or more container supports 38-68, As shown in FIG.

I. The processing station or device 22 may be a device forming the containers 80. One device 22 considered is an injection molding machine. Another contemplated device 22 may be a blow molding machine. Also contemplated are vacuum drawers, drawers, cutters or millers, glass drawers or other types of container-forming machines that draw glass or other drawable materials. Alternatively, the container forming station 22 can obtain already-formed containers and thus can be omitted.

II. Container support

II.A. Portable container supports 38-68 are provided to support and move the container with the opening while the container is being processed. The vessel includes a vessel port, a second port, a duct, and a moveable housing.

II.A. The container port is configured to seat the container opening which is in communication with each other. The second port is configured to receive an external gas supply or an outlet. And to pass at least one gas between the container opening seated on the container port and the second port. The vessel port, the second port and the duct are substantially rigidly attached to the movable housing. Optionally, the portable container support weighs less than 5 pounds. The advantage of lightweight container supports is that they can be more easily transported from one processing station to another.

II.A. In certain embodiments of the container support, the duct is specifically a vacuum duct and the second port is specifically a vacuum port. The vacuum duct is configured to recover gas from a container seated on the vessel port. The vacuum port is configured to communicate between the vacuum duct and an external vacuum source. The container port, the vacuum duct and the vacuum port are substantially rigidly attached to the movable housing.

II.A. The container supports of Examples II.A. and II.A.1. Are shown, for example, in FIG. The container support 50 has a container port 82 configured to receive and seat the opening of the container 80. The inner surface of the seated container 80 can be processed through the container port 82. [ The vessel support 50 may include a duct, for example, a vacuum duct 94, which recovers gas from a vessel seated on the vessel port 92. The container support may include a second port, for example, a vacuum port 96, which communicates between the vacuum duct 94 and an external vacuum source, such as the vacuum pump 98. The vessel port 92 and the vacuum port 96 are located between the inner or outer cylindrical wall of the vessel port 82 and the inner or outer cylindrical wall of the vessel 80, , And 100 and 102, respectively, to receive and form the vessel (80) or external vacuum source (98) and the seal while allowing communication through the port. Gasket or other sealing methods may also be used.

II.A. The container support, such as container 50, may be made of any material, such as thermoplastic and / or electrically non-conductive material. In addition, a container support, such as 50, may be partially or predominantly made of an electrically conductive material and may be electrically and electrically conductive in passageways defined by the container port 92, vacuum duct 94 and vacuum port 96, , It can counteract nonconducting adult substances. Examples of materials suitable for the container support 50 include: polyacetals, for example Delrin® acetal materials sold by E. I. Du Pont de Nemours, Inc., Wilmington, DE; Polytetrafluoroethylene (PTFE), such as Teflon (R) PTFE sold by EI DuPont de Nemours & Co., Wilmington, Delaware; Ultra high molecular weight polyethylene (UHMWPE); High density polyethylene (HDPE); Or other materials known or newly discovered in the industry.

II.A. 2 also may have a ring 116 which centers the container 80 when, for example, a container support 50, which is in close proximity to or seated in the port 92,

An array of container supports

II.A. Another approach to processing, inspecting, and / or moving components through a production system may be to use an array of container supports. The arrays may be comprised of individual pucks, or may be solid arrays in which the devices are loaded. The array may allow one or more devices, optionally many devices, to be tested, moved, or processed / coated simultaneously. The arrays may be one-dimensional, for example, grouped together to form a linear rack, or may be two-dimensional, similar to a tub or tray.

II.A. Figures 4, 5 and 58 illustrate three array approaches. Figure 4 shows a solid array 120 in which the devices or containers 80 are loaded. In this case, the devices or containers 80 can move through the production process as a solid array, even though they may be moved through the production process and moved to individual container supports. The single vessel support 120 has a plurality of vessel ports, such as 122 for moving an array of seated vessels, such as 80, moving as a unit. In this embodiment, a plurality of separate vacuum ports, such as 96, may be provided to receive the array of vacuum sources 98. Also, a single vacuum port connected to all vessel ports, such as 96, may be provided. A plurality of gas input probes, such as 108, may also be provided in the array. Arrays of gas input probes or vacuum sources may be mounted and moved as a unit to process multiple vessels, such as 80, simultaneously. Also, a plurality of vessel ports, such as 122, may be processed in the processing station one or more lines at a time, or individually. The number of devices in the array may be related to the number of devices being molded in a single step or other tests or steps that may enable efficiency during operation. When processing / coating the array, the electrodes can be coupled together (forming one large electrode) or individual electrodes with their own power air. All of these approaches may still be applicable (in terms of electrode geometry, frequency, etc.).

II.A. In FIG. 5, the individual pucks or container supports (discussed above) are brought together into the array by enclosing them in the outer frame 130. This arrangement provides the advantages of the solid array of FIG. 4, if desired, and also allows the array to be disassembled for other processing steps in which the vessels 80 are processed in different arrays or solely.

II.A. Figure 58 shows a linear rack similar to Figure 4; If a linear rack is used, in addition to those described above, another option transports the rack in a single file format through a processing station to process the containers in series.

II.B. Container support with O-ring arrangement

II.B. Figures 42 and 43 show alternative embodiments of a container support embodiment of Figures 2, 3, 6, 7, 19, 12, 13, 16, 18, 19, 30 and 43, Sectional side view and detail view of a container support 450 provided in a sealing arrangement. 42, the container, e. G., A syringe barrel 438, resting on the container support 450, includes generally cylindrical sidewalls 454 as well as generally annular (and generally corrugated or rounded) And a rear opening 442 defined by a lip 452. The medical fluid collection tubes commonly have the same type of lip 452, but without the flange 440, and instead can be seated on the container support 450.

II.B. In the illustrated embodiment, the container support 450 includes a generally cylindrical inner surface 456 that serves as a guide surface in the illustrated embodiment to accommodate the generally cylindrical sidewall 454 of the syringe barrel 438 do. The wall is also defined by a generally annular abutment 458 to which the annular lip 452 is joined when the syringe barrel 438 is seated on the container support 450. A generally annular pocket or groove 460 formed in the interior surface 456 is provided to support a sealing component, for example, an O-ring 462. The radial depth of the pocket 460 is smaller than the radial section of the sealing component, e.g., O-ring 462 (shown in FIG. 42), and preferably the inner diameter of the O- Is slightly smaller than the outer diameter of the annular lip 452.

II.B. These relative dimensions are at least equal to the relative dimensions of the outer wall 464 of the pocket 460 and the outer wall 464 of the syringe barrel 438 as shown in Figure 42 when the container such as 438 is seated, Allowing the radial section of the O-ring 462 to compress horizontally between the cylindrical side walls 454. This compression flattens the bearing surfaces of the O-ring 462 to create a seal between at least the outer wall 464 of the pocket 460 and the substantially cylindrical side wall 454 of the syringe barrel 438 .

II.B. The pockets 460 may optionally have upper and lower walls 468 and 466 spaced apart by a respective radial cross-sectional diameter of the O-ring 462 relative to the values of the O- May be fabricated to form two or more chambers between the bottom and top walls 466 and 468 and the sidewall 454. When the O-ring 462 is squeezed between the outer wall 464 and the substantially cylindrical sidewall 454 of the pocket 460, the O-ring 462 expands up and down as shown in FIG. 43 due to its restoring force The upper and lower walls 466 and 464, and become flat against them. Alternatively, the O-ring 462 may be deformed vertically and horizontally to normally taper the round cross-section to a square. In addition, the annular lip 452 seated in the abutment 458 will limit the flow of PECVD process reactants and other gases introduced through or adjacent to the rear opening 442.

II.B. As a result of this selective structure, only the gap at the lower right corner of the O-ring 462 is outside the O-rings, as shown in Figure 43, Or is exposed to process gases, plasma, etc., generated internally. This structure protects the O-ring 462 and adjacent surfaces (as the outer surface of the sidewall 438) from undesired accumulation of PECVD deposits and attack by activated species in the plasma. In addition, the container 438, unlike the elastic surfaces provided by butt seats of the annular lip 452 directly to the O-ring, as shown in some of the other figures, Lt; RTI ID = 0.0 > 458 < / RTI > Also, forces acting on respective portions around the major circumference of the O-ring 462 may be more uniformly distributed as the container 438 is tightened against any substantial rocking, do.

II.B. In addition, the pocket 460 may be formed with a bottom wall 466 on the abutment 458 shown in Fig. In another embodiment, the axially spaced apart at least one pocket 460 is provided to provide a double or higher level of seal and to further tighten the container 438 against locking when seated against the abutment 458 .

II.B. Figure 45 is a cross-sectional view of an embodiment of the present invention, for example, with the embodiments of Figures 1, 2, 3, 6-10, 12-16, 18, 19, 21, 22, 26, 28, 33-35, Is another structure for support 482. The container support 482 includes an upper portion 484 and a base 486 joined together at the joint 488. [ Ring 490 (the right side of which is cut so that the pockets that support it are described) is located between the upper portion 484 and the base 486 at the joint 488. A sealing component, e. . In the illustrated embodiment, the O-ring 490 is received within the annular pocket 492 and is located in the O-ring when the upper portion 484 is connected to the base 486.

II.B. In this embodiment, the O-ring 490 is captured and, when the upper portion 484 and the base 486 are connected, in this case, the joints radially extending by the screws 498 and 500, Extending radially extending wall 496 that partially defines the surface 494 and the pocket 492. Thus, the O-ring 490 rests between the upper portion 484 and the base 486. Also, an O-ring 490 trapped between the upper portion 484 and the base 486 receives the container 80 (which is removed for clarity if other features are shown in this figure) Ring seals of the container port 502 around the opening of the container 80, similar to the O-ring sealing arrangement around the container rear opening 442 in FIG.

II.B. In this embodiment, although not required, the vessel port 502 has both the first O-ring 490 chamber and the second axially spaced O-ring 504 chamber, And has an inner diameter such as sized 506 to accommodate the outer diameter (similar to sidewall 454 in FIG. 43) of the container, such as 80, for sealing between containers such as ports 502 and 80. The space between the O-rings 490 and 504 provides support for a container such as 80 at two axially spaced points such that a container such as 80 is positioned between the O-rings 490 and 504 ) Or against the container port (502). In this embodiment, although not essential, a radially extending abutment surface 494 is located near the O-ring 490 and 506 chambers and surrounds the vacuum duct 508.

III.A. Transporting the vessel support to the processing station

III.A. Figures 1, 2, and 10 illustrate how to treat the vessel 80. The above method can be performed as follows.

III.A. A container 80 having a wall 86 defining an opening 82 and an interior surface 88 may be provided. In one embodiment, the container 80 may be formed in a mold such as 22 and then removed therefrom. Optionally, within 60 seconds, or within 30 seconds, or within 25 seconds, or within 20 seconds, or within 15 seconds, or within 10 seconds, or within 5 seconds, or within 3 seconds after removal of the container from the mold (Assuming it is made at high temperature and is gradually cooled therefrom) so that the container 80 can be moved within a second or without twisting it during processing of the container 80, the container opening 82 May be seated on the container port 92. By quickly moving the container 80 from the forming mold 22 to the container port 92 it is possible to reduce dust or other impurities that may reach the surface 88 and prevent the barrier coating or other types of coatings 90 from being adhered or prevented. In addition, the quicker the vacuum is drawn on the container 80 after the container 80 is fabricated, the lower the likelihood that the fine particle impurities will adhere to the inner surface 88.

III.A. A container support such as 50 including a container port 92 may be provided. The opening 82 of the vessel 80 may be seated on the vessel port 92. The container support (e. G., FIG. 6), such as 40, is transported one by one before, during, or after seating the opening 82 of the container 80 on the container port 92, And may be positioned in the container support 40 with respect to a processing device or station such as 24 that is engaged with the bearing surfaces 220-240.

III.A. One or more or all of the processing stations, such as (24-34), as illustrated by the station 24 shown in FIG. 6, may be located in a processing station or apparatus, such as (24) One or more of the bearing surfaces 220, 222, 224, 226, 228, 230, 232, 234, 236 (e.g., , 238, or 240). These bearing surfaces may be part of a stationary or moving structure, such as, for example, tracks or guides that guide and position the container support, such as 40, while the container is being processed. For example, the downwardly facing bearing surfaces 222 and 224 are located in the container support 40 so that when the probe 108 is inserted into the container support 40, Acting as a reaction surface to prevent movement in the upward direction. The reaction surface 236 is located in the vessel support while the vacuum source 98 (Fig. 2) is seated on the vacuum port 96 and prevents the vessel support 40 from moving to the left. The bearing surfaces 220, 226, 228, 232, 238, and 240 similarly reside in the container support 40 to prevent horizontal movement during processing. The bearing surfaces 230 and 240 are likewise located in the container support, such as 40, to prevent them from moving out of position vertically. Thus, the first bearing surface, the second bearing surface, the third bearing surface, etc. may be provided in each of the processing stations, such as 24-34.

III.A. The inner surface 88 of the seated container 80 may be processed through the container port 92 at the first processing station, which may be, for example, a barrier application or another type of coating station 28 shown in FIG. . The vessel support 50 and the seated vessel 80 are transported from the first processing station 28 to the second processing station, for example, the processing station 32. The interior surface 88 of the seated vessel 80 may be processed through the vessel port 92 at the second processing station, such as 32.

III.A. One of the methods may include removing the vessel 80 from a vessel support such as 66 after processing the inner surface 88 of the vessel 80 seated in the second processing station or apparatus .

III.A. One of the methods may further comprise, after the removing step, providing a second container (80) having an opening (82) and a wall (86) defining an inner surface (88). The opening 82 of the second container, such as 80, may be seated on the container port 92 of another container support, such as (38). The interior surface of the seated vessel 80 may be treated through the vessel port 92 in the first processing station or apparatus, such as (24). The container support and the seated second container 80, such as the first container 38, may be transported from the first processing station or device 24 to the second processing station, such as 26. The seated second vessel (80) can be processed through the vessel port (92) by the second processing station or device (26).

III.B. Further, the processing stations may be more broadly processing devices, and the container supports may be communicated to the processing devices, and the processing devices may be moved relative to the container supports, Some may be provided to a given system. In another arrangement, the container supports may be moved to one or more stations, and one or more processing devices may be disposed at or near at least one of the stations. Therefore, there is not always a one-to-one correspondence between the processing devices and the processing stations.

III.B. Container handling methods involving some portions are contemplated. A first processing device, such as probe 108 (FIG. 2) and a second processing device, such as light source 170 (FIG. 10), are provided for processing vessels such as 80. A container 80 having a wall 86 and an opening 82 defining an interior surface 88 is provided. A container support (50) is provided that includes a container port (92). The opening 82 of the container 80 is seated on the container port 92.

III.B. The first processing device, such as the probe 108, may be operably engaged with the container support 50 and vice versa. The inner surface 88 of the seated vessel 80 is processed through the vessel port 92 using the first processing device or probe 108.

III.B. (FIG. 10), such as the first container 170, may be operably engaged with the container support 50 and vice versa. The inner surface 88 of the seated vessel 80 is treated through the vessel port 92 using a second processing apparatus, such as a light source 170.

III.B. Optionally, any number of different processing steps may be provided. For example, the third processing device 34 may be provided for processing the containers 80. The third processing device 34 may be operatively engaged with the container support 50 and moved in the opposite direction. The inner surface of the seated container 80 can be processed through the container port 92 using the third processing device 34. [

III.B. In another method of treating the container, a container 80 having a wall 86 defining an opening 82 and an interior surface 88 may be provided. A container support such as 50 including a container port 92 may be provided. The opening 82 of the vessel 80 may be seated on the vessel port 92. The inner surface 88 of the seated vessel 80 may be treated through the vessel port 92 at the first processing station, which may be, for example, a barrier or other type of coating apparatus 28 shown in FIG. 2 . The container support 50 and the seated container 80 are transported from the first processing device 28 to the second processing device, for example, the processing device 34 shown in Figs. 1 and 10. The inner surface 88 of the seated vessel 80 may then be processed through the vessel port 92 by a second processing unit, such as 34.

III.C. Using a gripper to transport the tube back and forth to the coating station

III.C. Yet another embodiment is a method of treating a PECVD of a first vessel comprising some steps. A first container is provided having an open end, a closed end and an inner surface. At least the first gripper is configured to selectively hold and release the closed end of the first container. The closed end of the first container is gripped using the first gripper and is conveyed to the vicinity of the container support configured to seat with the open end of the first container using the first gripper. The first gripper is then used to axially advance the first container and seat its open end on the container support so as to provide a sealed communication between the interior of the container support and the first container.

III.C. At least one gas reactant is introduced into the first vessel through the vessel support. A plasma is formed in the first vessel under conditions effective to form a reaction product of the reactants on the inner surface of the first vessel.

III.C. Thereafter, the first container is detached from the container support, and the first container is axially transported from the container support using the first gripper or other gripper. Thereafter, the first container is released from the gripper used to axially transfer from the container support.

III.C. Referring to Figures 16 and 49, a serial conveyor 538 may be used to support and transport a plurality of grippers, such as 204, through the apparatus and process as described herein. The gripper 204 is operably connected to the serial conveyor 538 and continuously delivers a series of at least two containers 80 in the vicinity of the container support 48 As well as other steps of the cleaning method.

IV. PECVD apparatus for container manufacturing

IV.A. A PECVD apparatus including a container support, internal electrodes, and a vessel as a reaction chamber

IV.A. Another embodiment is a PECVD apparatus comprising a container support, an inner electrode, an outer electrode, and a power supply. The container seated in the container support defines a plasma reaction chamber, which may alternatively be a vacuum chamber. Alternatively, a vacuum source, a reactant gas source, a gas supply or a combination of two or more of these may be supplied. Optionally, to define a closed chamber, a gas vent that is not necessarily a vacuum source is provided to transfer gas from or into the interior of the vessel seated on the port.

IV.A. The PECVD apparatus can be used for atmospheric pressure PECVD in the case where the plasma reaction chamber does not need to serve as a vacuum chamber.

IV.A. In the embodiment shown in FIG. 2, the container support 50 includes a gas input port 104 that delivers gas to a container that is seated on the container port. The gas input port 104 may include at least one O-ring 106 or an O-ring 106 that is seated against the cylindrical probe 108 when the probe 108 is inserted through the gas input port 104 And has a sliding chamber provided by two O-rings connected in series or by three O-rings connected in series. The probe 108 may be a gas input that extends from the distal end 110 to the gas delivery port. The distal end 110 of the illustrated embodiment can be deeply inserted into the vessel 80 providing one or more PECVD reactants and other process gases.

IV.A. Alternately, in the embodiment shown in FIG. 2, or more generally in FIGS. 1-5, 8, 9, 12-16, 18, 19, 21, 22, 26-28, 33-35, 37-49 , Or any of the disclosed embodiments, such as embodiments of 52-55, and the plasma screen 610 specifically described in Figure 55, the plasma formed in the vessel 80 is generally transferred to the plasma screen 610). &Lt; / RTI > The plasma screen 610 is a conductive, porous material, some examples of which are porous films made of a ceramic wool, porous sintered metal, or a ceramic material coated with a conductive material or a metal (e.g., brass) or other conductive material Disk. One example is center-to-center holes with 0.02 inch (0.5 mm) 0.04 inch (1 mm) spaced center holes sized to pass through the gas inlet 108, Lt; RTI ID = 0.0 > 22% < / RTI > open area.

IV.A. In particular, for embodiments in which the probe 108 functions as a counter electrode, the plasma screen 610 may be positioned within or near the opening 82 of the tube, syringe barrel or other container 80 being processed, It is possible to make intimate contact with the gas inlet 108. Also, the plasma screen 610, which preferably has a potential in common with the gas inlet 108, may be grounded. The plasma screen 610 is positioned adjacent to the vessel support 50 and in the vicinity of, for example, the vacuum duct 94, the gas input port 104, the O-ring 106, the vacuum port 96, Reducing or eliminating the plasma in the O-ring 102 and other devices adjacent to the gas inlet 108. At the same time, the porosity of the plasma screen causes gases, air, and the like to flow out of the vessel 80 into the vacuum port 96 and the downstream device.

IV.A. In the coating station 28 shown in FIG. 3, the container supports 112 each deliver gas (via the probe 108) to a container 80 seated on the container port 92, And a combined gas inlet port and a vacuum port 96 in communication with the vessel port 92 for withdrawing gas from the vessel placed on the vessel 92 (via the vacuum source 98). In this embodiment, the gas input probe 108 and the vacuum source 98 may be provided as a composite probe. The two probes can be advanced as a unit or separated if desired. This arrangement eliminates the need for the third chamber 106 and allows the use of support seals throughout. The support chamber may be configured to securely place the vessel 80 and the vacuum source 98 by, for example, extracting a vacuum within the vessel 80 and applying an axial force to deform the O- To close any gaps left on the opposite side of the ring due to the presence of any foreign matter on the sealing surface. In the embodiment of Figure 3 the axial forces exerted on the container support 112 by the container 80 and the vacuum source 98 are facing away and the container 80 and the container support 112 Hold it together and keep each support chamber.

IV.A. Figure 13 is a view similar to Figure 2 of the container support 48 in a coating station according to another embodiment of the present disclosure in which the container 80 can be seated on the container support 48 in the process station. to be. 2 of the container support 48 in the coating station according to another embodiment of the present disclosure in which the container 80 can be seated on the container support 48 at the processing station 48, Such as 48 prior to being moved to the other apparatus by the system 20, or to prevent the container 80 from being seized first, May be used for other types of coating stations 28. [

IV.A. Figure 13 shows a cylindrical electrode 160 suitable for frequencies of 50 Hz to 1 GHz as an alternative to the U-shaped electrodes of Figures 2 and 9. The container support (or electrode) may be moved into place prior to activation by moving the electrode down or moving the container support up. In addition, movement of the vessel supports and electrodes in the vertical plane is facilitated by the use of an electrode 160 of the same construction as the shell shell (two cylinders that can come together from the opposite side when the vessel support is ready to be treated / coated in place) Can be prevented. IV.A. Alternatively, in the coating station 28, the vacuum source 98 is a continuous process in which the tube is moved through a coating station, such as 28, while the vacuum is removed and gas is introduced through the probe 108 , A puck or container support 50 that can be retained during movement of the container support. The puck or container support 50 is also moved to a rest position in which the probe 108 is pushed into the device and then the pump or vacuum source 98 is coupled and activated in the vacuum port 96 A stopping step for generating a vacuum can be used. Once the probe 108 is in place and a vacuum is generated, the external fixed electrode 160, independent of the puck or container support 50 and the tube or other container 80, and the interior of the tube or container 80 A plasma can be established.

IV.A. FIG. 53 is a block diagram illustrating an embodiment of the present invention, for example, with the embodiments of FIGS. 1, 2, 3, 6-10, 12-16, 18, 19, 21, 22, 26-28, 30, 33-35, 37-44, Lt; RTI ID = 0.0 > 28 < / RTI > In addition, the coating station 28 may have a main vacuum valve 574 in a vacuum line 576 leading to a pressure sensor 152. A manual bypass valve 578 is provided in the bypass line 580. The exhaust valve 582 controls the flow at the exhaust port 404.

IV.A. The flow rate from the PECVD gas source 144 is controlled by the main reactant gas valve 584, which regulates the flow rate through the main reactant supply line 586. One component of the gas source 144 is the organosilicon liquid reservoir 588. The contents of the reservoir 588 are recovered via an organosilicon capillary line 590 provided at an appropriate length to provide the desired flow rate. The flow rate of the organosilicon vapor is controlled by the organosilicon shutoff valve 592. The pressure may be, for example, a pressure source 616, such as compressed air, connected to the space portion 614 by a pressure line 618 to establish a repetitive organosilicon liquid transfer that does not depend on (and fluctuates within) ) Is applied to the space portion 614 of the liquid reservoir 588 in the range of 0 to 15 psi (0 to 78 cm. Hg). The reservoir 588 is sealed and the capillary connection 620 is connected to the capillary tube 590 only at the bottom of the reservoir 588 by pure organic silicon liquid (not compressed gas from the space portion 614) . The organosilicon liquid may optionally be heated above ambient temperature if it is necessary or desired to vaporize the organosilicon liquid to form organosilicon vapor. Oxygen is provided from an oxygen tank 594 provided with an oxygen shutoff valve 600 through an oxygen feed line 596 controlled by a mass flow controller 598.

IV.A. 7, the station or device 26 includes a vacuum source 98 adapted to rest on the vacuum port 96, a side channel 134 connected to the probe 108, or both Lt; / RTI > In the illustrated embodiment, the side channel 134 includes a shutoff valve 136 that regulates the flow rate between the probe port 138 and the vacuum port 140. In the illustrated embodiment, the selection valve 136 has at least two states: the ports 138 and 140 are connected such that two parallel passages for gas flow (thus increasing the pumping speed Or reducing the pumping effort) and disconnected states in which the ports 138 and 140 are separated. Optionally, the select valve 136 may have a third port, such as a PECVD gas input port 142, for introducing PECVD reaction and process gases from a gas source 144. This means allows the same vacuum supply and probe 108 to be used for both leakage or penetration testing and blocking or other types of coating applications.

IV.A. In the illustrated embodiments, the vacuum line, such as 146 to the vacuum source 98, may also include a shutoff valve 148. The shutoff valves 136 and 148 may be closed if the probe 108 and the vacuum source 98 are not connected to a container support such as 44 so that the side channel 134 and the vacuum line 146 need not be vacuum evacuated on the sides of the valves 136 and 148 from the vessel 80 when moved from one vessel support 44 to another. An axial movement of the probe 108 independent of the position of the vacuum line 146 relative to the port 96 is required to facilitate axial removal of the probe 108 from the gas input port 104. [ The flexible line 150 can be provided.

IV.A. 7 also shows another optional feature that can be used with the vent 404 to the ambient air controlled by any embodiment-valve 406. FIG. The valve 406 may be configured to eject the container 80 from the container support 44 or eject the container support 44 from the vacuum port 96 at the vacuum port 96, Anyway, the valve 406 may be opened to break the vacuum quickly after processing the vessel 80.

IV.A. The probe 108 may also be connected to a pressure gauge 152 and may communicate with the interior 154 of the vessel 80 and within the vessel 80 Allow the pressure to be measured.

IV.A. In the device of Figure 1, the container coating station 28 is, for example, a coating 90 of SiO _x barrier coating or other type on the inner surface 88 of the container 80 as shown in Figure 2, May be a PECVD apparatus, described below, that operates under conditions suitable for deposition

IV.A. 1 and 2, the processing station 28 includes an electrode 160 supplied by a radio frequency power supply 162 that provides an electric field for generating a plasma in the vessel 80 during processing . In this embodiment, the probe 108 is electrically conductive and grounded to provide a counter electrode within the vessel 80. Also, in certain embodiments, the external electrode 160 may be grounded and the probe 108 may be directly connected to the power supply 162.

IV.A. In the embodiment of FIG. 2, the external electrode 160 may be generally cylindrical, as shown in FIGS. 2 and 8, or it may be of the shape of a cross-section taken along line AA of FIG. 2 Lt; RTI ID = 0.0 > U-shaped < / RTI > long channel as shown in FIG. Each illustrated embodiment has one or more side walls, such as 164 and 166, and optionally, a top 168, all of which are disposed proximate to the vessel 80.

IV.A., IV.B. Figures 12-19 illustrate other variations of the container coating station or device 28 as described above. One or more of these modifications may replace the container coating station or device 28 shown in Figures 1-5.

IV.A. Figure 12 shows another electrode system that can be used at frequencies above 1 GHz (in the same manner as described above using the same vessel supports and gas inlet). At these frequencies, electrical energy from the power supply can be conducted into the interior of the tube through one or more wave guides that are connected to a cavity that absorbs energy or resonates with energy. When energy is resonated, it is coupled with the gas. Because the vessel 80 interacts with the cavity that changes its resonance point to produce a plasma for coating and / or processing, other cavities may be provided for use with vessels such as other frequencies 80 have.

IV.A. 12 may include a microwave power supply 190 that directs microwaves through a waveguide 192 to a microwave cavity 194 that at least partially surrounds the vessel within a vessel 80 in which plasma can be produced . The microwave cavity 194 can be tuned to absorb the microwaves and couple with the plasma-producing gas, in connection with the frequency of the microwaves and the partial pressures and selections of gases. In Figure 13, it is contemplated that not only any of the embodiments shown, but also the container (80) and the cavity (194) (or the electrode, detector or other surrounding structure A small gap 196 may remain. 13, the microwave cavity 194 has a flat end wall 198 such that the gap 196 is not uniform in width, especially on the opposite side of the circular edge of the end wall 198. Optionally, the end 198 may be bent to provide a substantially uniform gap 196.IV.A.2. FIG. 44 is a block diagram of an embodiment of the present invention for use with embodiments of FIGS. 1, 2, 3, 8, 9, 12-16, 18-19, 21-22, 33, 37-43, 46-49, and 52-54 Figure 2 is a view similar to Figure 2 of another possible gas delivery tube / inner electrode. 44, the distal portion 472 of the inner electrode 470 includes an elongated porous sidewall 474 that surrounds the inner passage 476 within the inner electrode. The inner passage 476 is connected to the gas supplier 144 by the proximal portion 478 of the inner electrode 470 extending out of the container 80. In addition, the distal end 480 of the internal electrode 470 may be selectively porous. At least a portion of the reactant gas supplied from the gas supply 144 due to the porosity of the porous sidewall 474 and the porous distal end 480, if present, And supplies the material gas to an adjacent portion of the inner surface 88 of the vessel 80. In this embodiment, the porous portion of the porous sidewall 474 may extend beyond the internal electrode 470 in the vessel 80, even though only a portion of the length of the internal electrode 470 is missing. As shown in FIG. As indicated elsewhere herein, the internal electrode 470 may be longer or shorter than the length shown in Figure 44 for the length of the vessel 80, and the porous portion may be continuous or discontinuous .

IV.A. The outer diameter of the inner electrode 470 may 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 adjacent inner diameter at the side of the vessel. If the inner electrode 470 having a larger diameter is employed in connection with the inner diameter of the container 80, especially if the electrode 470 is concentric with the container 80, The distance between the outer surface of the vessel 80 and the adjacent inner surface 88 of the vessel 80 may be reduced to confine the plasma to a narrower region where the plasma may be more uniform. It should also be noted that employing the internal electrode 470 having a larger diameter may result in an increase in the length of the internal electrode 88 that is very close to the original reaction point, as opposed to flowing from a single point, As fresh gases are introduced into the plasma at closely spaced points, more uniform distribution of the reactant gas and / or carrier gas along the inner surface 80 is achieved.

IV.A. In one contemplated arrangement, shown in solid lines, the power supply 162 has one power connection to the electrode 200, which may be at any point along the electrode 200, Can be grounded. In this configuration, a capacitive load can be used to generate a plasma in the vessel 80. In another contemplated arrangement, shown as an imaginary line (with the connections shown in solid lines removed), the individual leads of the power supply 162 may be referred to herein as " Lt; / RTI > In this configuration, an inductive load can be used to create a plasma in the vessel 80. Also, in other embodiments, a combination of inductive and capacitive loads may be used.

IV.A. Figures 46-48 illustrate an array of two or more gas delivery tubes 510 and 512 (also shown in Figure 2), such as 108, also internal electrodes. The array may be linear or rotational. The rotating array causes the electrodes to be periodically reused.

IV.A. 46-48 illustrate an internal electrode (not shown) for inserting and removing the gas delivery tubes / inner electrodes 108, 510, and 512 from and into one or more of the container supports, such as (50) An extender and a retractor 514, as shown in FIG. These features are an optional means for using gas delivery tubes.

IV.A. In the illustrated embodiment, with reference to Figure 53 as well as Figures 46 through 48, the inner electrodes 108, 510, and 512 are connected by flexible hoses 516, 518, and 520 respectively to isolation valves 522, 524, 526 to a common gas supply 144. [ (The flexible hoses were shortened by omitting the loose portions in Figures 46-48). Referring briefly to FIG. 56, the flexible hoses 516, 518 and 520 may be connected to alternate independent gas sources 144. A mechanism 514 is provided to extend and contract the internal electrode, such as the electrode 108. The internal electrode extender and the retractor are configured to move the internal electrode between a fully advanced position, an intermediate position, and a reduced position with respect to the container support.

IV.A. 46 and 56, the internal electrode 108 extends into the container support 50 and the vessel 80 to an active position, and the isolation valve 522 is open. In addition, the internal electrodes 510 and 512 which are not working in FIG. 46 are reduced and their shutoff valves 524 and 526 are closed. In the illustrated embodiment, one or more of the inactive internal electrodes 510 and 512 are disposed within the electrode cleaning apparatus or station 528. [ One or more of the electrodes may be cleaned and, optionally, the remainder may be replaced within the station 528. The cleaning operations may include, as a non-limiting example, a chemical reaction or solvent treatment to remove deposits, milling to physically remove deposits, or plasma treatment that essentially burns accumulated deposits.

IV.A. In Figure 47, while the operating internal electrode 108 has been reduced out of the vessel 80 such that its distal end remains within the vessel support 50 and the valve 522 is closed, The internal electrodes 510 and 512 are the same as before. In this condition the vessel 80 can be removed and the new vessel can be placed on the vessel support 50 without risk of touching the electrode 108 while the vessels 80 are removed and replaced . After the vessel 80 is removed, the internal electrode 108 may be advanced to the position of FIGS. 46 and 56 and the shutoff valve 522 may be opened again and replaced with a new one using the same internal electrode 108 as before. The coating of the container 80 can be started. Thus, in an arrangement in which a series of vessels 80 are seated on and removed from the vessel support 50, the vessels 80 are installed, or the internal electrodes 108 are in use, As removed from the container support 50, the internal electrode 108 may extend and partially shrink several times.

IV.A. In Figure 48, the container support 50 and its container 80 have been replaced with a new container support 48 and another container 80. Referring to Figure 1, in this type of embodiment, each container 80 remains on its container support, such as (50) or (48), and the internal electrodes, such as 108, Into each container by name.

IV.A. 48, the internal electrodes 108, 510, and 512 are all completely shrunk, and the array of internal electrodes 108, 510, and 512, as compared to their respective positions in FIG. 47, Is moved to the right with respect to the support table 48 and the electrode cleaning station so that the internal electrode 108 is out of position and the internal electrode 510 is moved to the position relative to the container support 48.

IV.A. It should be noted that the movement of the array of internal electrodes may be independent of the movement of the container supports. They can be moved together or independently to switch to a new container support and / or a new internal electrode simultaneously or independently.

IV.A. Also, reference numerals 46 to 48 designate internal electrodes (not shown) for inserting and removing the gas delivery tubes / internal electrodes 108, 510, and 512 from and / or from one or more container supports, such as 50 or 48, An extender and a retractor 514, as shown in FIG. These features are an optional means for using gas delivery tubes.

IV.A. In the illustrated embodiment, with reference to Figure 53 as well as Figures 46 through 48, the inner electrodes 108, 510, and 512 are connected by flexible hoses 516, 518, and 520 respectively to isolation valves 522, 524, 526 to a common gas supply 144. [ (The flexible hoses were shortened by omitting the loose portions in Figures 46-48). A mechanism 514 is provided to extend and contract the internal electrode, such as the electrode 108. The internal electrode extender and the retractor are configured to move the internal electrode between a fully advanced position, an intermediate position, and a reduced position with respect to the container support.

IV.A. 46 and 56, the internal electrode 108 extends into the container support 50 and the vessel 80 to an active position, and the isolation valve 522 is open. Also, in Figures 46 and 56, the non-operating internal electrodes 510 and 512 are shrunk and their isolation valves 524 and 526 are closed. In the illustrated embodiment, the non-operational inner electrodes 510 and 512 are disposed within the electrode cleaner or station 528. Some of the electrodes may be cleaned and, optionally, the remainder may be replaced within the station 528. The cleaning operations may include, as a non-limiting example, a chemical reaction or solvent treatment to remove deposits, milling to physically remove deposits, or plasma treatment that essentially burns accumulated deposits.

IV.A. An array of two or more internal electrodes 108, 510, and 512 is useful because the individual combined gas delivery tubes / internal electrodes 108, 510 and 512 may in some cases be polymerized reactant gases or Because some other types of deposits tend to accumulate as they are used to coat a series of containers, such as 80. The deposits may accumulate to a point that compromises the coating speed or the uniformity caused thereby, which may be undesirable. In order to maintain a uniform process, the internal electrodes may be periodically disabled, replaced or cleaned, and fresh or cleaned electrodes may be used. For example, referring to Figures 46 to 48, the inner electrode 108 may include a new or reoriented internal electrode (not shown) extending easily into the container support 48 and the container 80 to apply the inner coating to the new container. (510).

IV.A. Accordingly, the internal electrode drive 530 moves the first internal electrode 108 from the extended position to the reduced position, replaces the first internal electrode 108 with the second internal electrode 510, And is operatively connected to the inner electrode extender and the retractor 514 (similar to Figs. 46 and 56 except for the replacement of electrodes) to advance the inner electrode 510 to the extended position.

IV.A. The series of gas delivery tubes of Figures 46-48 and internal electrode drive 530, for example, Figures 1, 2, 3, 8, 9, 12-16, 18-19, 21-22, 26-28, 33 -35, 37-45, 49 and 52-54. The mechanism of Figs. 46-48 may be applied to the probes of the container inspection apparatus of Figs. 6 and 7 as well as to the probes of Figs. 2, 3, 8, 9, 12-16, 18-19, 21-22, 26-28, 33-35, 37-45, 49, and 52-54.

The electrode 160 shown in Fig. 2 may be shaped like a "U" channel toward the page in its length, and the puck or container support 50 may be activated Lt; / RTI > electrode). Since external and internal electrodes are used, such a device may use a frequency between 50 Hz and 1 GHz applied from the power supply 162 to the U-channel electrode 160. The probe 108 may be grounded to complete the electrical circuit so that current flows through the low pressure gas (s) within the vessel 80. The current creates a plasma to enable selective treatment and / or coating of the inner surface 88 of the apparatus.

IV. A In addition, the electrode of Fig. 2 may be powered by a pulse power supply. Permits depletion of the reaction gases due to pulsing and then allows removal of byproducts before the activation and (re) depletion of the gases occurs. Pulsed power systems are typically characterized by a duty cycle measuring the amount of time that an electric field (and thus a plasma) is present. The power-on time is relative to the power-off time. For example, a duty cycle of 10% may correspond to a power-on time of 10% of a cycle in which the power is off for 90% of the time. In a particular embodiment, the power may be on for 0.1 seconds and off for 1 second. The pulse power system reduces the active power supply to a given power supply 162 because off-time results in an increase in processing time. When the system is pulsed, the resulting coating can be very pure (no byproducts or contaminants). Another consequence of pulsed systems is the possibility of achieving atomic layer deposition (ALD). In this case, the duty cycle may be adjusted so that the power on time is achieved by a single layer deposition of the desired material. In this manner, a single atomic layer is considered to be deposited in each cycle. This approach can produce a very pure and highly structured coating (even though the temperature is preferably kept low (< 100 [deg.] C) and low temperature coatings may be amorphous at the temperatures required for deposition on the polymer surface have.

IV.A. Another coating station employing a microwave cavity instead of an external electrode is shown in Fig. The applied energy may be, for example, a microwave frequency of 2.45 GHz.

IV.B. Another embodiment is an apparatus for PECVD processing of a vessel employing a gripper as described above. Figures 15 and 16 illustrate a device generally designated 202 during PECVD processing of a first vessel 80 having an open end 82, a closed end 84 and an interior surface defined by the surface 88 / RTI > This embodiment includes a container support 48, at least a first gripper 204 (in this embodiment, for example, a suction cup) A plasma generator represented by electrodes 108 and 160, a container discharge device, which may be an exhaust valve, such as 534, and the same gripper 204 or second gripper (optional) And a second gripper 204).

IV.B. The first gripper 204, as shown in any of the grippers, is configured to selectively support and release the closed end 84 of the vessel 80. The first gripper 204 may transport the container in the vicinity of the container support 48 while holding the closed end 84 of the container. In the illustrated embodiment, the transfer function is facilitated by a serial conveyor 538 to which the grippers 204 are attached in series.

IV.B. The container support 48 has been described above in connection with other embodiments and is configured to seat on the open end 82 of the container 80. The sheet defined by the container port 92 has been described above in connection with other embodiments and the container support is attached to either the container support 48 and the first container, So that a sealed communication is established between the inner space of the inner tube. The reactant feeder 144 is described above in connection with other embodiments and is operatively connected to introduce at least one gaseous reactant within the first vessel 80 via the vessel support 48 have. The plasma generators defined by the electrodes 108 and 160 have been described above in connection with other embodiments and have been described above under the conditions effective to form a reaction product of reactants on the inner surface of the first vessel And is configured to form a plasma in the vessel.

IV.B. Other means, such as introducing an expensive gas, such as a reactant gas, a carrier gas, or compressed nitrogen or air, in the container discharge device 534, or in the seated container 80, Lt; RTI ID = 0.0 > 80 < / RTI >

IV.B. The grippers are configured to axially transfer the first container (80) from the container support (48) and thereafter eject the first container by evacuating suction between the gripper (48) and the container end (84) .

IV.B. Also shown at 15 and 16 are PECVD processing methods for a first vessel that includes some steps. A first container 80 is provided having an open end 82, a closed end 84, and an inner surface 88. At least a first gripper 204 configured to selectively support and release the closed end 84 of the first container 80 is provided. The closed end 84 of the first container 80 is held using the first gripper 204 and is thereby transported near a container support 48 configured to seat at the open end of the first container . In the embodiment of Figure 16, two container supports 48 are provided to allow the containers 80 to be advanced and seated on the container supports 48 two at a time to double the effective production rate . The first gripper 204 then advances the first container 80 axially and seats its open end 82 on the container support 48 so that the container support 48 and the first And is used to establish a sealed communication between the inside of the container. Next, at least one gaseous reactant is optionally introduced into the first vessel through the vessel support, as described for previous embodiments.

IV.B. Continuing, a plasma is formed in the first vessel under conditions effective to form a reaction product of the reactants on the inner surface of the first vessel, optionally as described for previous embodiments. The first container is detached from the container support, as described for previous embodiments. As described for previous embodiments, the first gripper or other gripper is selectively used to axially transfer the first container from the container support. Thereafter, the first container is optionally released from the gripper used to axially transfer from the container support, as described for previous embodiments.

IV.B. Other optional steps that may be performed according to the present method include providing a reaction vessel having an open end and an interior space, the reaction vessel being different from the first vessel, having an open end of the reaction vessel seated in the vessel support object And establishing a sealed communication between the container support and the interior space of the reaction vessel. A PECVD reactant passage may be provided in the interior space. Plasma can be produced in the interior space of the reaction vessel under conditions effective to remove at least a portion of the deposition of the PECVD reaction product from the reactant water bath. These reaction conditions have been described in connection with the embodiments described above. Thereafter, the reaction vessel is detached from the container support, and is transported from the container support.

IV.B. Other optional steps that may be performed according to any embodiment of the method include the following steps:

Providing at least a second gripper;

Operatively coupling at least first and second grippers with a serial conveyor;

Providing a second container having an open end, a closed end, and an inner surface;

Providing a gripper configured to selectively support and release a closed end of the second vessel;

Holding the closed end of the second container using the gripper;

Using the gripper, transferring the second container to a vicinity of a container support configured to seat at an open end of the second container;

Using the gripper to axially advance the second vessel and seat the open end on the vessel support object so as to establish a sealed communication between the interior of the vessel support and the second vessel;

Introducing at least one gas reactive material into the second vessel through the vessel support;

Forming a plasma in the second vessel under conditions effective to form a reaction product of a reactant on the inner surface of the second vessel;

Detaching the second container from the container support; And

Axially transferring the second container from the container support using the second gripper or another gripper; And

Withdrawing the second container from the gripper used to axially transfer from the container support.

IV.B. Figure 16 is an example of using a suction cup type device holding the end of a sample collection tube (in this example) movable through a production line / system. The specific example shown here is one possible step of the coating / processing (of as many of the steps as described above and below). The tube may be moved to a coating step / region and the tube may be lowered to the vessel support and (in this example) cylindrical electrode. The container support, the sample collection tube and the suction cup can then move together to the next step where the electrode is powered and processing / coating takes place. Any one of the above types of electrodes may be used in this example.

IV.B. 15 and 16 employ a vessel transporter generally designated 202 to reciprocate the vessel 80 to the coating station 28 in a coating station 28 similar to that of FIG. The vessel transporter 202 may be provided with a grip 204 that may be a suction cup in the illustrated transporter 202. Also, an adhesive pad, an active vacuum source (using a pump to draw air from the grip, actively creating a vacuum in vacuum) or other means may be employed as the grip. The vessel transporter 202 may be used to lower the vessel 80, for example, to a position seated in a vessel port 92 for positioning the vessel 80 for coating. The vessel transporter 202 may also be used to raise the vessel 80 from the vessel port 92 after processing at the station 28 can be completed. The vessel transporter 202 may also be used to seat the vessel 80 before the vessel 80 and vessel transporter 48 are advanced together to the station. The container transporter can also be used to direct the container 80 against the sheet on the container port 92. It should also be noted that even though Fig. 15 could be pointed at showing the container 80 rising vertically from above, the container conveyor 202 would be underneath the container 80 and would have an inverted orientation Or an orientation that is reversed.

IV.B. Figure 16 shows that vessel conveyors 202 such as suction cups 204 not only (or instead) deliver the vessels 80 horizontally from one station to the next, but also to stations such as 28, And vertically transferring the image data. The containers 80 can be raised and transported in any orientation. Accordingly, 16 illustrates a method of PECVD treatment of a first vessel 80 that includes some steps.

IV.B. In the embodiment of FIG. 13, the outer electrode 160 may be cylindrical in shape with open ends and may be stationary. The container 80 may be advanced through the external electrode 160 until the opening 82 is seated on the container port 96. In this embodiment, the probe 108 is selectively permanently molded or, alternatively, as a wiping seal that allows relative movement between the port 104 and the probe 108, (Not shown).

IV.B. Figure 14 shows another alternative for coupling electrical energy to a plasma of 50 Hz to 1 GHz. This can consist of a coil or a container support that can be raised to position (using the device) which can be lowered to the position. Coiled electrodes are referred to as inductive coupling devices and can impart magnetic components to the interior of the device from which the plasma can be generated.

IV.B. The probe 108 may be used as discussed in Figures 2 and 13. The container supports or other sides of the container supports 48 discussed above can remain in the same state.

IV.B. For example, as shown in FIG. 49, a reaction vessel 532 different from the first vessel 80 is provided, having an open end 540 and an inner space defined by the inner surface 542 . Like the vessels 80, the reaction vessel 532 has its open end 540 on the vessel support 48 and is sealed between the vessel support 48 and the interior space 542 of the reaction vessel. So that the communication can be made.

IV.B. Figure 49 shows the mechanism of delivering the containers 80 to be treated and cleaning reactor 532 to the PECVD coating apparatus of Figure 16 of the container inspection apparatus. In this embodiment, the internal electrode 108 can optionally be cleaned without removing it from the container support 48.

IV.B. Figure 49 is a side view of the reaction vessel 532 in which the reaction vessel is positioned within the interior space 542 of the reaction vessel 532 when it is seated on the vessel support 48 instead of the vessel 80 provided for coating as previously described. The PECVD reactant material channel 108 described above is located. Figure 49 shows the reactant flow channel 108 of this configuration, even though the channel 108 has an inner circle as well as an outer circle. Which is suitable for this purpose and meets this claim if the reactant material channel 108 at least partially extends into the vessel 80 or 532.

IV.B. As shown, the mechanism of 49 is usable with, for example, at least the embodiments of FIGS. 1 and 15-16. The cleaning reactor 532 may also be provided as a simple container that is seated and transported in a container support such as 48 in another embodiment. In this configuration, the cleaning reactor 532 may include at least one of the cleaning reactors 532 of Figures 1 to 3, 8, 9, 12 to 15, 18, 19, 21, 22, 26 to 28, 33 to 35, 37 to 48, and 52 to 54 Device. &Lt; / RTI >

IV.B. The plasma generator defined by the electrodes 108 and 160 is capable of generating plasma within the interior space of the reaction vessel 532 under conditions effective to remove at least a portion of the deposition of the PECVD reaction product from the reactant water channel 108 Or < / RTI > The inner electrode and gas source 108 may be a conductive tube, for example, a metallic tube, and the reaction vessel 532 may include other materials capable of withstanding more heat than a ceramic, quartz, glass, or thermoplastic container It is believed above that the same can be made of any suitable, preferably heat-resistant material. In addition, the material of the reaction vessel 532 may preferably be a plasma that is chemically or otherwise resistant to the conditions used in the reaction vessel to remove deposits of reaction products. Alternatively, the reaction vessel 532 may be made of an electrically conductive material and serves as a special-purpose external electrode for the purpose of removing deposition materials from the reactant material channel 108 by itself. Alternatively, the reaction vessel 532 may comprise a cap that is seated on the external electrode 160, in which case the external electrode 160 preferably is seated on the vessel support 48 Thereby defining a closed cleaning reaction chamber.

IV.B. Reaction conditions effective to remove at least a portion of the deposits of the PECVD reaction product from the reactant material channel 108 include the introduction of a substantial portion of the oxidizing reactant, such as oxygen or ozone (either generated alone or produced by the plasma apparatus) It is believed that it includes higher power levels than those used for deposition, longer cycle times than those used for deposition of coatings, or other means known for removing deposits of undesirable types found on said reaction channels 108 . As another example, mechanical milling can also be used to remove unwanted deposits. Alternatively, solvents or other agents may be forced to remove obstacles through the reactant channel 108. These conditions may be more severe than the containers to be coated 80 can withstand, since the reaction vessel 532 need not be suitable for normal use of the vessel 80. [ Alternatively, however, if the vessel 80 can be used as a reaction vessel and the deposition removal conditions are too harsh, the vessel 80 employed as the reaction vessel may be discarded in another embodiment.

V. PECVD methods for making containers

V.1 Precursors for PECVD Coatings

The PECVD coating precursors of the present invention are broadly defined as organometallic precursors. The organosilicon precursor encompasses compounds of Group III and / or Group IV metal elements of the Periodic Table, which have organic residues such as hydrocarbons, aminocarbon or oxycarbon residues and are used herein for all purposes Is defined. Organometallic compounds, as defined, include any precursors having organic moieties either directly bonded to silicon or other Group III / Group IV metal atoms or alternatively bonded via oxygen or nitrogen atoms. The corresponding elements of group III of the periodic table are boron, aluminum, gallium, indium, thallium, scandium, yttrium and lanthanum, with aluminum and boron being preferred. The corresponding elements of Group IV of the periodic table are silicon, germanium, tin, lead, titanium, zirconium, hafnium and thorium, with silicon and tin being preferred. Other volatile organic compounds may also be considered. However, organosilicon compounds are preferred for carrying out the present invention.

An "organosilicon precursor" is an organosilicon precursor that is broadly defined herein as a compound having at least one of the following connections throughout:

or

The first structure immediately above is a tetravalent silicon atom connected to one oxygen atom and an organic carbon atom (the organic carbon atom is a carbon atom bonded to at least one oxygen atom). The second structure immediately above is a quadrivalent silicon atom connected to one -NH-bond and an organic carbon atom (an organic carbon atom is a carbon atom bonded to at least one oxygen atom). Preferably, the organosilicon precursor is selected from the group consisting of linear siloxanes, monocyclic siloxanes, polycyclic siloxanes, polysilsesquioxanes, linear silazanes, monocyclic silazanes, polycyclic silazanes, And a combination of two or more of these precursors. In addition, alkyltrimethoxysilane is considered as a precursor, although not the two above formulas.

When an oxygen-containing precursor (e.g., siloxane) is used, a typical predicted empirical equation that can be obtained from PECVD under the conditions to form a hydrophobic or lubricous coating is Si _w O _x C _y H _z , where w is 1, x is from about 0.5 to about 1, y is from about 2 to about 3, and z is from 6 to 9, a typical anticipated experimental composition that can be obtained from PECVD under conditions to form a barrier coating is SiO _x , Wherein x is from about 1.5 to about 2.9. When a nitrogen-containing precursor (e.g., silazane) is used, the expected composition is Si _{w *} N _{x *} C _{y *} H _{z *} . That is, for Si _w O _x C _y H _z according to the present invention, oxygen (O) is replaced by nitrogen (N) and exponents are adjusted to a higher mantissa of N relative to oxygen O (3 instead of 2) . The latter will generally follow the proportions of the corresponding indices in w, x, y and z versus aza equivalents in the siloxane. In a particular aspect of the invention, Si _{w *} N _{x *} C _{y *} H _{z *} is defined as w *, y * and z * as in the siloxane counterparts, but with an optional deviation in the number of hydrogens have.

One type of precursor starting material having the empirical formula is a linear siloxane, for example, a material having the following formula:

Each R is independently selected from alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, alkyne and the like and n is 1, 2, 3, Or more, preferably 2 or more. Some examples of linear siloxanes contemplated include

Hexamethyldisiloxane (HMDSO),

Octamethyltrisiloxane,

Decamethyltetrasiloxane,

Dodecamethylpentasiloxane,

Or a combination of two or more thereof. Also similar silazanes in which the -NH- in the above structure is substituted with an oxygen atom are useful for making similar coatings. Some examples of linear silazanes contemplated are octamethyltrisilazane, decamethyltetrasilazane, or combinations of two or more thereof.

V.C. Another type of precursor initiator material is a linear siloxane, e. G., A material having the following structure:

Where R is defined as a linear structure and "a" is from 3 to about 10 or similar monocyclic silazanes. Some examples of hetero-substituted and unsubstituted monocyclic siloxanes and silazanes contemplated include the following

1,3,5-trimethyl-1,3,5-tris (3,3,3-trifluoropropyl) methyl] cyclotrisiloxane

2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane,

Pentamethylcyclopentasiloxane,

Hexamethylcyclotrisiloxane,

Hexaphenylcyclotrisiloxane,

Octamethylcyclotetrasiloxane (OMCTS),

Octaphenylcyclotetrasiloxane,

Decamethylcyclopentasiloxane

Dodecamethylcyclohexasiloxane,

Methyl (3,3,3, -trifluoropropyl) cyclosiloxane,

The following cyclic organosilazanes are also contemplated,

Octamethylcyclotetrasilazane,

1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasilazane hexamethylcyclotrisilazane,

Octamethylcyclotetrasilazane,

Decamethylcyclopentasilazane,

Dodecamethylcyclohexasilazane, or any combination of two or more thereof

Another type of VC precursor starting material is, for example, a polycyclic siloxane that is a material having one of the following structural formulas:

Wherein Y may be oxygen or nitrogen and E is silicon and Z is a hydrogen atom or an alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, Lt; / RTI > When each Y is oxygen, the respective structures going from left to right are silatran, silquasilatran and silpropol. When Y is nitrogen, the respective structures are azacilatran, aza silicate athran and azacyla propionate.

Another type of VC polycyclic siloxane precursor starting material is the empirical formula of RSiO _1.5 and the polysilsesquioxane of the structure:

Each R is a hydrogen atom or an organic substituent which is alkyl such as, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, Two commercially available materials of this type are SST-eM01 poly (methyl silsesquioxane), where each R is methyl, and SST-3MH1.1 poly (methyl - hydridosilsesquioxane). This material can be used, for example, in a 10% solution of tetrahydrofuran. Also, combinations of two or more of these are contemplated. Other examples of contemplated precursors are methyl silatrans, methyl azatilatran, CAS number 2288-13-3 where each Y is oxygen and Z is methyl, SST-eM01 poly ( Methyl silsesquioxane), SST-3MH1.1 poly (methyl-hydridosilsesquioxane) wherein 90% of the R groups are methyl and 10% are hydrogen atoms, or a combination of two or more thereof.

V.C. Also, similar polysilsesquiazanes in which the -NH- in the above structure is substituted with an oxygen atom are useful for making similar coatings. Examples of contemplated polysilsesquiazanes are poly (methylsil sesquiazane), where each R is methyl, and poly (methyl-hydridosiloxazane), where 90% of the R groups are methyl and 10% )to be. Also, combinations of two or more of these are contemplated.

V.C. One precursor specifically contemplated for the lubricous coating according to the present invention is, for example, monocyclic siloxane, which is octamethylcyclotetrasiloxane.

One precursor specifically contemplated for the hydrophobic coating according to the present invention is, for example, monocyclic siloxane, which is octamethylcyclotetrasiloxane.

One precursor specifically contemplated for the barrier coating according to the present invention is, for example, HMDSO, a linear siloxane.

V.C. In any one of the coating methods according to the present invention, the applying step may optionally be performed by evaporating the precursor and providing it near the substrate. For example, OMCTS is mainly evaporated by heating it to about 50 DEG C before applying it to a PECVD apparatus.

V.2 General PECVD method

In the context of the present invention, the following PECVD method comprising the following steps is generally applied:

(a) providing a gas reactant material comprising a precursor, preferably an organosilicon precursor, and optionally O ₂ , as defined herein near the substrate surface; And

(b) generating a plasma from the gas reactive material and forming a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD).

In this method, the coating characteristics are advantageously set by one or more of the following conditions: the plasma properties, the pressure applied to the plasma, the power applied to produce the plasma, the presence and relative amount of O ₂ in the gaseous reactant, Organic Silicon Precursor. Preferably, the coating properties are set by the presence and relative amount of O ₂ in the gaseous reactant and / or the power source applied to produce the plasma.

In all embodiments of the present invention, the plasma is a non-hollow-cathode plasma in the preferred aspect.

In another preferred aspect, the plasma is generated at reduced pressure (relative to ambient or atmospheric pressure). Preferably, the reduced pressure is less than 300 mTorr, more preferably less than 200 mTorr, even more preferably less than 100 mTorr.

Preferably, the PECVD is performed by applying a current to the gaseous reactant comprising the precursor together with the electrodes that are powered at the frequency or radio frequency of the microwave and preferably at the radio frequency. Also, the preferred radio frequency for performing embodiments of the present invention will be referred to as "RF frequency ". A typical radio frequency range for practicing the invention is less than 10 kHz to 300 MHz, more preferably 1 to 50 MHz, even more preferably 10 to 15 MHz. A frequency of 13.56 MHz is most preferred, which is a government approved frequency for performing PECVD operations.

There are several advantages to using RF power for the microwave source: Since the RF operates the lower power source, the heating of the substrate / vessel is lower. Since the center of the present invention is to provide a plasma coating on plastic substrates, lower processing temperatures are desirable to prevent melting / distortion of the substrate. In order to prevent the substrate from overheating when microwave PECVD is used, the picrowave PECVD is applied to short bursts by pulsing the power. Power pulsing increases the cycle time for coating, which is undesirable in the present invention. Also, higher microwave frequencies can cause offgassing of volatile materials such as residual moisture, oligomers, and other materials in the plastic substrate. This degassing can interfere with the PECVD coating. A major concern in using microwaves for PECVD is the removal of coating from the substrate. Peeling occurs because microwaves change the surface of the substrate before depositing the coating layer. To reduce the likelihood of peeling occurring, interfacial coating layers have been developed for microwave PECVD to achieve good bonding between the coating and the substrate. In the case of RF PECVD, an interfacial coating layer free from the risk of peeling is not required. Finally, the lubricous coating and the hydrophobic coating according to the present invention are advantageously applied using lower power. RF power supplies operate at lower power supplies and provide better control over PECVD processes than microwave power supplies. Nevertheless, although not desirable, the microwave power source can be used under appropriate process conditions.

Also, for all of the PECVD methods described herein, there is a specific correlation between the used power source (watts) to generate the plasma and the volume of the lumen in which the plasma is generated. Typically, the lumen is a lumen of a vessel coated in accordance with the present invention. The RF power source should be scaled to the volume of the vessel if the same electrode system is employed. Once the composition of the gaseous reactants, such as the ratio of precursor to O ₂ , and all other parameters of the PECVD coating method, except the power source, are set once, the shape of the vessel is maintained and only its volume changes, It does not change. In this case, the power will be directly proportional to the volume. Thus, starting from the power source to volume ratios provided in this description, a power source that is the same shape but size must be applied in order to achieve the same or similar coating in different vessels can be easily found. The effect of the vessel shape on the applied power source is shown as the results of the embodiments for the tubes as compared to the embodiment for the syringe barrels.

For any coating of the present invention, the plasma is generated using electrodes powered by a power source sufficient to form a coating on the substrate surface. For a lubricous coating or hydrophobic coating in a method according to an embodiment of the present invention, the plasma preferably comprises (i) 0.1 to 25 W, preferably 1 to 22 W, more preferably 3 to 17 W, Preferably between 5 and 14 W, most preferably between 7 and 11 W, for example, 8 W, and / or (ii) a ratio of power to plasma volume of 10 W / ml, preferably Is generated using electrodes having a concentration of 5 W / ml to 0.1 W / ml, more preferably 4 W / ml to 0.1 W / ml, and most preferably 2 W / ml to 0.2 W / ml. For barrier coatings or SiOx coatings, the plasma preferably comprises (i) 8 to 500 W, preferably 20 to 400 W, more preferably 35 to 350 W, even more preferably 44 to 300 W, (Ii) a ratio of power to plasma volume of at least 5 W / ml, preferably between 6 W / ml and 150 W / ml, more preferably between 7 W / ml to 100 W / ml, and most preferably 7 W / ml to 20 W / ml.

In addition, the vessel shape may affect the choice of gas inlet used for the PECVD coating. In certain aspects, the syringe may be coated with an open tube inlet, and the tube may be coated with a gas inlet having small holes extending into the tube.

Also, the power (watts) used for PECVD affects the coating properties. Typically, increasing the power will increase the barrier properties of the coating, and decreasing the power will increase the lubricity and hydrophobicity of the coating. For example, for a coating on the inner wall of a syringe barrel having a volume of about 3 ml, a power of less than 30 W would lead to a coating that was overwhelmingly a barrier coating, while a power source exceeding 30 W was overwhelmingly a lubricant coating Coating (see examples).

Another parameter to determine coating properties is the ratio of O ₂ (or other oxidant) to precursor (e.g., an organosilicon precursor) in the gaseous reactants used to produce the plasma. Typically, increasing the O ₂ content in the gaseous reactant increases the barrier properties of the coating, while decreasing the O ₂ content increases the lubricity and hydrophobicity of the coating. Therefore, the PECVD coating method of the present invention can be used to set the lubrication of the coatings produced by the method, the hydrophobicity of the coatings and the barrier properties of the coatings.

If a lubricous coating is desired, O ₂ is preferably used in a volume to volume ratio of 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 more preferably from 0: 1 to 0.1: 1. Most advantageously, there is essentially no oxygen in the gas reactant. Thus, the gas reactive material comprises less than 1 vol% O ₂ , particularly less than 0.5 vol% O ₂ , most preferably O ₂ . This applies equally to hydrophobic coatings.

Alternatively, if a barrier or SiO _x coating is desired, then O ₂ will preferably have a volume to volume ratio of from 1: 1 to 100: 1, preferably 5: 1 To 30: 1, more preferably from 10: 1 to 20: 1, and even more preferably 15: 1.

A VA specific embodiment is a method of applying a barrier coating of SiO _x (unless otherwise specified in a particular case) as defined herein as a coating comprising silicon, oxygen and optionally other elements, wherein the silicon atoms X is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, or about 2, the ratio of oxygen to oxygen. These different definitions of _x apply to the use of the term SiO _x herein. The barrier coating is applied to the interior of a container, e. G., A sample collection tube, a syringe barrel or other type of container. The method includes some steps.

V.A. For example, a vessel wall is provided as a reaction mixture comprising a plasma-forming gas comprising an organosilicon compound gas, alternatively an oxidizing gas and optionally a hydrocarbon gas.

The VA plasma is formed in the reaction mixture substantially free of cathode hollow plasma. The vessel wall is contacted with the reaction mixture and a coating of SiO _x is deposited on at least a portion of the vessel wall.

VA In certain embodiments, the production of a uniform plasma through the entirety of the portion of the vessel being coated is desirable because it can be seen to produce a SiO _x coating that provides better barrier to oxygen in certain instances. A uniform plasma (which is represented by a higher intensity local region that has a higher emission intensity than a regular plasma and prevents a more uniform intensity of the regular plasma) Means plasma.

V.A. The hollow cathode effect is created by a pair of conductive surfaces facing each other with the same cathode potential for a common cathode. If spacing occurs (depending on the pressure and gas type) and space charge sheaths overlap, as electrons accelerate across the sheath region by a potential gradient, electrons oscillate between the reflective potentials of the opposite wall sheaths Many begin to hit and collide. The electrons are trapped in space charge sheath redundancy leading to very high ionization and high ion density plasma. This phenomenon is described as a hollow cathode effect. Those skilled in the art will be able to vary process conditions such as the power level and the rate or pressure of the gases to form a uniform plasma or a plasma comprising various degrees of hollow cathode plasma throughout.

V.A. For example, in another method, using the apparatus of FIG. 12 described above, microwave energy can be used to generate a plasma in a PECVD process. However, the processing conditions will differ as the microwave energy applied to the thermoplastic vessel excites (vibrates) the water molecules. Because all plastic materials have a small amount of water, microwaves will heat the plastic. As the plastic heats, the large motive force generated by the vacuum inside the device with respect to atmospheric pressure outside the device freely collects or desorbs the materials on the inner surface 88 where they are volatile or readily attached to the surface will be. The easily bonded materials will then form an interface that can prevent subsequent coatings (deposited from the plasma) from adhering to the plastic inner surface 88 of the device.

VA As one way to prevent this coating protection effect from occurring, the coating can be deposited at a very low power source (5 to 20 watts at 2.45 GHz in this example) producing a cap to which subsequent coatings can be adhered. This leads to a two-step coating process (and two coating layers). In this example, the initial gas flows (for the capping layer) can be changed to 2 sccm ("standard square centimeters per minute") HMDSO and 20 sccm oxygen at a process power of 5-20 watts for approximately 2-10 seconds. Thereafter, the gases can be adjusted to the flow rates in the above example and the power level increases, for example, from 35 to 50 W, where x is about 1.5 to about 2.9, or about 1.5 to about 2.6, or about 2 A SiO _x coating can be deposited. And it is noted that in certain embodiments the capping layer may not provide all the functionality or provides little functionality except for the more so as SiO _x coating deposited during the material for high power are not moved to the inside surface 88 vessel do it. Also note that since lower frequencies do not excite (oscillate) molecular species, the transfer of materials that are easily desorbed from the device walls is typically not a problem at lower frequencies.

V.A. As another method for preventing the above-described coating preventing effect, the container 80 may be dried to remove moisture permeated before application of the microwave energy. Dewatering or drying of the vessel 80 can be performed by heating the vessel 80, for example, using an electric heater or forced air heating. Further, dehydration or drying of the container 80 can be performed by exposing gas in contact with the inside of the container 80 or the inside of the container 80 to the desiccant. Other means of drying the vessel, such as vacuum drying, may also be used. Such means may be performed by one or more of the stations or devices shown or by an individual station or device.

V.A. In addition, the above-described coating prevention effect can be solved by selecting or treating the resin in which the containers 80 are molded so as to minimize the moisture content of the resin.

V.B. PECVD coating a limited opening of the vessel (syringe capillary)

V.B. Figures 26 and 27 illustrate a method of coating the inner surface 292 of the limited openings 294 of the generally tubular container 250 to be treated, which is a limited frontal opening 294 of the syringe barrel 250, for example by PECVD And 290, respectively. The process described above is modified by connecting the limited opening 294 to the process vessel 296 and optionally by making certain other changes.

V.B. The generally tubular container 250 being processed is defined by an outer surface 298, an inner or inner surface 254 defining a lumen, a larger opening 302 having an inner diameter, and an inner surface 292 And a limited opening 294 having an inner diameter smaller than the inner diameter of the larger opening 302.

V.B. The processing vessel 296 has a processing vessel opening 306, which is a lumen 304 and optionally a unique opening, although in other embodiments a second opening may be provided that is selectively closed during processing. The processing vessel opening 306 is connected to the processing vessel lumen through the lumen 300 and the limited opening 294 of the vessel 250 to be processed in conjunction with the limited opening 294 of the vessel 250 being processed And communication is established.

V.B. At least partial vacuum within the lumen 300 of the vessel 250 being processed and the lumen 304 of the processing vessel 296. The PECVD reactant is passed through the first opening 302 and then through the lumen 300 of the vessel 250 that is then processed and then through the restricted opening 294 to the gas source 144 To the lumen 304 of the processing vessel 296.

V.B. In another embodiment, adjacent to distal end 314, a plurality of distal openings may be provided and in communication with inner passageway 310, the PECVD reactant may include an inner passageway 310, a proximal end 312, May be introduced through the larger opening 302 of the vessel 250 by providing a generally tubular inner electrode 308 having a distal opening 314 and a distal opening 316. [ The distal end of the electrode 308 may be adjacent to or positioned within the larger opening 302 of the vessel 250 being processed. Reactant gas may be supplied through the distal opening 316 of the electrode 308 into the lumen 300 of the vessel 250 that is silver-treated. The reactant will flow to the subsequent lumen 304 through the limited opening 294 to such an extent that the PECVD reactant is provided at a higher pressure than the vacuum initially made prior to introducing the PECVD reactant.

V.B. Plasma is generated adjacent the confined openings 294 under conditions effective to deposit a coating of the PECVD reaction product on the inner surface of the confined openings 294. In the embodiment shown in FIG. 26, the plasma is generated by providing RF energy to a generally U-shaped outer electrode 160 and grounding the inner electrode 308. In addition, the supply and ground connections to the electrodes may also be varied, although the vessel 250 and hence the inner electrode 308, which is processed due to such a reversal, may also be connected to the U- Even if it is possible to introduce complexity if it moves.

V.B. The plasma 318 generated in the vessel 250 during at least some processing may include the hollow cathode plasma generated within the limited opening 294 and / or the processing vessel lumen 304. The creation of the hollow cathode plasma 318 may contribute to the ability to successfully apply a barrier coating at the limited opening 294, even though the invention is limited by the accuracy or applicability of this theory of operation. Thus, in one contemplated mode of operation, the process may be performed under conditions that produce a uniform plasma through the vessel 250 and throughout the gas inlet and, for example, partially adjacent to the restricted opening 294, Can be performed under conditions that produce a negative electrode plasma.

V.B. The process is preferably operated under conditions that the plasma 318 substantially extends through the syringe lumen 300 and the limited openings 294, as described herein and shown in the Figures. The plasma 318 also extends substantially through the entire lumen 304 of the syringe lumen 300, the limited opening 294 and the processing vessel 296. This assumes that a uniform coating of the interior 254 of the vessel 250 is desired. In other embodiments, non-uniform plasma may be desired.

V.B. The plasma 318 has a substantially uniform hue throughout the syringe lumen 300 and the limited opening 294 during processing and is preferably a substantially uniform color through the syringe lumen 300, the limited opening 294, It is generally desirable to have a substantially uniform idea through the entire lumen 304 of the processing vessel 296. Preferably, the plasma is substantially stable throughout the syringe lumen 300 and the limited openings 294, and preferably throughout the entire lumen 304 of the processing vessel 296.

V.B. The order of steps in this method is not considered to be deterministic.

V.B. 26 and 27, the limited opening 294 has a first fitment 332 and the processing vessel opening 306 is seated with the first fitment 332 to define a lumen And a second fitting 334 adapted to communicate between the lumen 300 of the container 250 and the lumen 300 of the container 250 being processed.

V.B. 26 and 27, the limited opening 294 has a first fitment 332 and the processing vessel opening 306 is seated with the first fitment 332 to define a lumen And a second fitting 334 adapted to communicate between the lumen 300 of the container 250 and the lumen 300 of the container 250 being processed. As one of the fittings, in this case the male luer lock fitting 332 includes a locking collar 336 having a generally annular first abutment 338 abutting axially with the threaded inner surface, The other fitting 334 includes a generally annular second abutment 340 that faces axially opposite the first abutment 338 when the fittings 332 and 334 engage.

V.B. In the illustrated embodiment, for example, a seal that is an O-ring 342 may be positioned between the first and second fits 332 and 334. For example, an annular seal may engage between the first and second abutments 338 and 340. The armoring fitting 334 also engages the threaded inner surface of the locking ring 336 to secure the dogs 342 that secure the O-ring 342 between the first and second fittings 332 and 334 Gt; 344 < / RTI > Alternatively, the communication formed between the lumen 300 of the vessel 250 being processed and the processing vessel 304 lumen through the restricted opening 294 is at least substantially leak-free.

V.B. As another option, either or both of the luer lock fits 332 and 334 may be made of an electrically conductive material such as, for example, stainless steel. The structural material forming or adjoining the restricted openings 294 may contribute to the formation of the plasma at the limited openings 294.

V.B. The preferred volume of the lumen 304 of the processing vessel 296 is a small volume that will not divert a significant amount of reactant flow from the desired product surfaces to be coated to a different volume (the pressure difference across the confined openings 294) Off between a large volume to support the total reactant gas flow rate through the limited opening 294 before filling the lumen 304 sufficiently to reduce the flow rate to an undesirable value is considered to be a trade-off. In one embodiment, the considered volume of the lumen 304 is less than three times the volume of the lumen 300 of the vessel 250 being processed or less than three times the volume of the lumen 300 of the vessel 250 being processed Or less than the volume of the lumen 300 of the container 250 being processed or less than 50% of the volume of the lumen 300 of the container 250 being processed, Is less than 25% by volume. Also, other valid relationships of the volumes of each lumen are also contemplated.

V.B. The inventors have found that in certain embodiments the uniformity of the coating can be improved by repositioning the distal end of the electrode 308 relative to the container 250 so that the position of the internal electrode shown in the previous figure Lt; RTI ID = 0.0 > 300, < / RTI > For example, although in certain embodiments the distal opening 316 may be located adjacent the restricted opening 294, the distal opening 316 may, in other embodiments, Less than 7/8 of the distance from the larger opening 302 of the container being treated during the first opening to the limited opening 294, optionally less than 3/4 of the distance, alternatively less than half of the distance. Less than 30%, less than 20%, less than 15% of the distance from the larger opening of the container being treated to the limited opening 294 during processing of the reactant gas , Less than 10%, less than 8%, less than 6%, less than 4%, less than 2%, or less than 1%.

V.B. In addition, the distal end of the electrode 308 communicates with the interior of the vessel 250 and is positioned slightly inside or outside of the larger opening 302 of the vessel 250, Or may be positioned at the same height. The positioning of the distal portion 316 with respect to the container 250 being processed can be optimized for certain dimensions and other conditions of the treatment by testing it at various locations. The particular location of one of the electrodes 308 considered for processing the syringe barrels 250 is about one quarter inch (about 6 mm) penetrating into the container lumen 300 on the larger opening 302 And a position with respect to the distal end 314.

V.B. The present inventors contemplate that at least the distal end 314 of the electrode 308 may be placed in the container 250 to function properly as an electrode, although this is not a requirement. Surprisingly, the plasma 318 produced in the vessel 250 may be more uniform, and the electrode 308 may be less permeable to the lumen 300, as opposed to previously employed, To the processing vessel lumen 304. The processing vessel & Using different arrangements, such as treating a closed vessel, the distal end 314 of the electrode 308 is typically positioned closer to the closed end of the vessel than the inlet.

V.B. 33, the distal end 314 of the electrode 308 may extend beyond the restricted opening 294 or beyond the limited opening 294, for example, to the processing vessel lumen 294, (Not shown). Various means may optionally be provided, such as forming the processing vessel 296 to enhance the gas flow through the limited openings 294.

V.B. 34 and 35, the composite inner electrode and gas supply tube 398 may optionally include distal gas supply openings, such as 400, positioned proximate to a larger opening 302, May have an elongated electrode (402) extending a distal portion of the distal gas supply openings (400), extending to a distal end adjacent the restricted opening (294) and optionally further extending into the processing vessel (324) have. This structure is contemplated to facilitate the formation of the plasma within the inner surface 292 adjacent the limited opening 294. [

V.B. In another contemplated embodiment, the internal electrode 308 may be moved during processing, such as initially in Fig. 26, to extend to the processing vessel lumen 304, and then to the nearer as processing proceeds It can be gradually withdrawn. This means is a particularly contemplated means for the container 250 to be of long length under selected processing conditions and to facilitate a more uniform treatment of the inner surface 254 due to movement of the inner electrode. Using these means, processing conditions such as the gas supply rate, the vacuum discharge rate, the electric energy applied to the external electrode 160, the speed at which the internal electrode 308 is drawn out, or other factors are processed, Lt; / RTI > to other portions of the vessel being processed.

V.B. The larger opening of the generally tubular container 250 to be processed will require a larger opening 302 of the container 250 being processed to be connected to the port (not shown) of the container support 320, as in other processes described herein 322. < / RTI > The inner electrode 308 may then be positioned within the vessel 250 that is seated on the vessel support 320 prior to drawing at least a partial vacuum within the lumen 300 of the vessel 250 being treated. have.

V.B. In another embodiment shown in Fig. 28, as shown in Fig. 26, a first opening 306 fixed to the container 250 to be processed and a second opening 306, which communicates with the vacuum port 330 in the container support 320, A processing vessel 324 in the form of a channel having a second opening 328 may be provided. In this embodiment, the PECVD process gases flow into the vessel 250, then flow into the processing vessel 324 through the limited opening 294, and then return through the vacuum port 330 . Optionally, the vessel 250 may be evacuated through both openings 294 and 302 prior to applying the PECVD reactants.

VB As well, as shown in FIG. 22, a vacuum is formed at the rear end 256 of the barrel 250 to introduce reactants from the source 144 through an opening and to suck through the opening at the tip 260 of the barrel, By using a circle 98 to derive the vacuum, an inner coating of SiO _x where x is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, or about 2, wherein the x is from about 1.5 to about 2.6, A syringe barrel 250 may be provided. For example, the vacuum source 98 may be connected through a second fit 266 seated on the tip 260 of the syringe barrel 250. Using these means, the reactants can flow in one direction (although their directionality is not critical, but upward as shown in FIG. 22), and the reactants can flow from the gas exhausted in the syringe barrel 250 It is not necessary to transfer the reactants through the probe. Also, in other arrangements, the leading and trailing edges 260 and 256 of the syringe barrel 250 may be reversed relative to the coating device. The probe 108 may simply act as an electrode, which in this embodiment may be a tubular or solid rod. As before, the separation between the inner surface 254 and the probe 108 may be uniform over at least the length of the syringe barrel 250.

V.B. FIG. 37 shows another embodiment in which the fitting 266 is independent of the plate electrodes 414 and 416 and is not attached thereto. The fitting 266 may have a luer lock fitting adapted to be fixed to the fit of the syringe barrel 250. This embodiment allows the vacuum channel 418 to move onto the electrode 416 while the container support 420 and the attached vessel 250 are moved between the electrodes 414 and 416 during the coating step Yes.

V.B. FIG. 38 shows another embodiment of the present invention. FIG. 22 illustrates an embodiment in which the distal end 260 of the syringe barrel 250 is open and the syringe barrel 250 is opened by a vacuum chamber 422 seated on the container support 424 Showing another embodiment enclosed. In one embodiment, the pressures P1 in the syringe barrel 250 and the vacuum chamber 422 are approximately the same and the vacuum in the vacuum chamber 422 is selectively applied to the tip 260 of the syringe barrel 250, Lt; / RTI > When the process gases are flowing into the syringe barrel 250 they are in contact with the syringe barrel 250 until the normal composition is provided within the syringe barrel 250 at the time the electrode 160 receives the current to form a coating, (Not shown). Due to the larger volume of the vacuum chamber 422 with respect to the syringe barrel 250 and the location of the counter electrode 426 within the syringe barrel 250, process gases passing through the tip 260, Lt; RTI ID = 0.0 > 422 < / RTI >

V.B. FIG. 39, which is a further embodiment of the present invention, shows a further embodiment in which the rear flange of the syringe barrel 250 includes a container support and a pair of plate electrodes labeled as cylindrical electrodes or 160, Assembly 430. In this embodiment, The volume indicated generally as enclosed 432 outside of the syringe barrel 250 is sufficient to minimize the volume of the syringe barrel 250 operating in this embodiment of the pumping and PECVD process necessary to evacuate the volume 432 It is relatively reduced.

V.B. 40 is a plan view showing another embodiment as an alternative to FIG. 38 where the ratio of the pressure P1 / P2 is provided at a desired level by providing a pressure balance control valve 434, to be. P1 may be a lower vacuum, i.e., a higher pressure, than P 2 during the PECVD process, so that the waste process gases and byproducts will be exhausted through the tip 260 of the syringe barrel 250. In addition, the provision of separate vacuum chamber channels (436) serving as the vacuum chamber (422) makes the vacuum of the larger closed volume (432) faster with the use of an individual vacuum pump.

V.B. 41 is a plan view of the embodiment of Fig. Also, reference numeral 40 denotes the electrode 160 removed from the figure.

V.C. Method of applying a lubricous coating

V.C. Another embodiment is a method of applying a lubricous coating derived from an organosilicon precursor. A "lubricous coating" or similar term is generally defined as a coating that reduces the frictional resistance of a coated surface against an uncoated surface. If the coated object is a syringe (or a syringe part, such as a syringe barrel) or any other item that generally includes a plunger or movable part in sliding contact with the coated surface, - Has breakout force and plunger activity.

The plunger sliding force test is a special test of the sliding friction coefficient of the plunger in a syringe which is characterized by the fact that a normal force associated with the sliding friction coefficient, which is generally measured on a flat surface, The pits between the different vessels are standardized and processed. The parallelism associated with the primarily measured sliding friction coefficient is comparable to the measured plunger sliding force as described herein. The plunger sliding force can be measured, for example, as provided in the ISO 7886-1: 1993 test.

In addition, the plunger sliding force test can be tailored to measure other types of frictional resistance, such as friction, which holds the stopper in the tube, by appropriate variations in apparatus and procedures. In one embodiment, the plunger can be replaced by a closure, and the withdrawing force for removing or inserting the closure can be measured in response to a plunger sliding force.

Also, instead of the plunger sliding force, the breakout force can be measured. The breakout force is the force required to start a stationary plunger moving within the syringe barrel, or the comparable force required to disengage the seized pause closure and initiate its movement. The break-out force is measured by applying a force to the plunger starting at zero or a low value and increasing until the plunger begins to move. The breakout force tends to increase with the storage of the syringe after the pre-filled syringe plunger has pushed out the intervening lubricant or attached to the barrel due to the disintegration of the lubricant between the plunger and the barrel. The breakout force is required to overcome "sticktion" which is the term used in the industry for attachment between the plunger and the barrel needed to get over the plunger and to start moving the plunger. It is power.

V.C. Optionally, some equipment that coats all or part of the container with a lubricous coating, such as on sliding contact surfaces with other components, may cause the insertion or removal of a stopper or a sliding configuration such as a stopper on a piston or sample tube in a syringe Facilitates passage of the element. The container can be made of glass or a polymer such as a polymeric material such as polyester, for example, polyethylene terephthalate (PET), cyclic olefin copolymer (COC), olefins such as polypropylene or other materials. Application of a lubricous coating by PECVD avoids or reduces the need to coat the vessel wall or closure with other lubricants that are typically applied in much greater amounts than those deposited by the organosilicon or PECVD process being sprayed, dipped or applied .

V.C. In any of the above embodiments, a plasma, alternatively a non-hollow-cathode plasma, may optionally be formed in the vicinity of the substrate.

V.C. In any of the embodiments V.C., the precursor may optionally be provided in the substantial absence of oxygen. V.C. In any of the embodiments V.C., the precursor may optionally be provided in the absence of a carrier gas. V.C. In any of the embodiments V.C., the precursor may optionally be provided in the substantial absence of nitrogen. V.C. In any of the embodiments V.C., the precursor may optionally be provided at less than 1 Torr absolute pressure.

V.C. In any of the embodiments V.C., the precursor may optionally be provided in the vicinity of the plasma emission.

V.C. In any of the embodiments V.C, the coating may optionally be applied to the substrate in a thickness of 1 to 5000 nm, or 10 to 1000 nm, or 10 to 200 nm, or 20 to 100 nm thick. The thickness of this and other coatings can be measured, for example, by transmission electron microscopy (TEM).

V.C. The TEM can be performed, for example, as follows. Samples can be fabricated in two ways for focused ion beam (FIB) section cutting. The samples may first be coated with a carbon film (50-100 nm thick) and then coated with a platinum sputtering layer (50-100 nm thick) using a K575X Emitech coating system, or the samples may be coated with a protective sputtered Lt; RTI ID = 0.0 > Pt < / RTI > The coated samples can be placed in an FEI FIB200 FIB system. The platinum addition film can be FIB deposited by injecting an organometallic gas while injecting a 30 kV gallium ion beam onto the region of interest. The region of interest for each sample can be selected at a position below 1/2 the length of the syringe barrel. Thin sections measured at a length of approximately 15 micrometers ("micrometers"), 2 micrometers wide and 15 micrometers deep can be extracted from the die surface using a proprietary in-situ FIB lift-out technique. The sections may be attached to a 200 mesh copper TEM grid using FIB-deposited platinum. One or two windows in each section measured at a width of about 8 占 퐉 may be thinned with electron transparency using the gallium ion beam of the FEI FIB.

Cross-sectional image analysis of the VC manufactured samples can be performed using a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM) or both. All image data can be recorded digitally. For STEM images, a grid with thin foils can be moved to a STEM dedicated to the Hitachi HD2300. Scanned electron images can be obtained by moderately zooming in atomic number mode (ZC) and transferred electron mode (TE). You can use the following tool settings.

For VC TEM analysis, sample grids can be transferred with a Hitachi HF2000 transmission electron microscope. The transmitted electronic images can be obtained by zooming in appropriately. Appropriate tool settings used during image acquisition may be those given below.

V.C. In any one of the embodiments, the substrate is a glass or a polymer, such as a polycarbonate polymer, an olefin polymer, a cyclic olefin copolymer, a polypropylene polymer, a polyester polymer, a polyethylene terephthalate polymer, And may include two or more combinations.

V.C. In any one of the embodiments VC, the PECVD may optionally comprise an RF frequency as defined above, for example between 10 kHz and 300 MHz, more preferably between 1 and 50 MHz, even more preferably between 10 and < RTI ID = Lt; RTI ID = 0.0 > 15 < / RTI > MHz, and most preferably 13.56 MHz, to the gas reactants comprising the precursor.

V.C. In any one of the embodiments V.C, the plasma may be generated by applying power to a gas reactant comprising the precursor using electrodes supplied with sufficient power to form a lubricous coating. Alternatively, the plasma may be applied to the substrate at a temperature of from 0.1 to 25 W, preferably from 1 to 22 W, more preferably from 3 to 17 W, even more preferably from 5 to 14 W, most preferably from 7 to 11 W, Lt; RTI ID = 0.0 > W < / RTI > The ratio of power to plasma volume may be 10 W / ml, preferably 5 W / ml to 0.1 W / ml, more preferably 4 W / ml to 0.1 W / ml, and most preferably 2 W / ml to 0.2 W / ml. These power levels are suitable for applying lubricating coatings to similarly shaped syringes and sample tubes and vessels with a void volume of 1-3 mL where a PECVD plasma is produced. It is believed that the applied power for larger or smaller objects will increase or decrease as the process is scaled relative to the size of the substrate.

V.C. Optionally, one product contemplated as a product may be a syringe having a barrel that is treated by the method of V. C., which is any one or more of the embodiments.

V.D. Liquid-application coatings

Block, or Other examples of different types of VD suitable coatings that can be used in conjunction with the PECVD applied coating or other PECVD process as disclosed herein is directly or Si _w O _x C _y H _z, SiO _x, lubricous coating or both Lubricant, surface energy tailoring, or any other type of coating 90 applied to the inner surface of the vessel, which is manufactured by using one or more intervening PECVD-applied coatings of the present invention.

V.D. Optionally, suitable liquid barrier or other types of coatings 90 may also be used to apply, for example, a liquid monomer or other polymerizable or curable material to the interior surface of the vessel 80, Polymerized or cross-linked to form a solid polymer. In addition, suitable liquid barrier or other types of coatings 90 may be provided by applying a solvent-dispersed polymer to the surface 88 and removing the solvent.

V.D. Any of the methods may include forming a coating 90 on the interior 88 of the vessel 80 through the vessel port 92 at a processing station or apparatus 28. One example of this is the application of a liquid coating of a curable monomer, prepolymer, or polymer dispersion, for example, to the inner surface 88 of the container 80 and curing it to form the contents of the container 80, (88). &Lt; / RTI > The prior art describes polymer coating techniques as being suitable for coating plastic blood collection tubes. For example, the acrylic and polyvinylidene chloride (PVdC) coating materials and coating methods described in U.S. Patent No. 6,165,566, which is incorporated herein by reference, may optionally be used.

V.D. In addition, any of the above methods may comprise forming a coating on the outer wall of the vessel 80. Optionally, the coating may be a barrier coating, optionally an oxygen barrier coating or optionally a moisture barrier coating. An example of a suitable coating is polyvinylidene chloride, which functions as both a moisture barrier and an oxygen barrier. Optionally, the barrier coating may be applied with an aqueous coating. Alternatively, the coating can be applied by dipping the container thereon, spraying it on the container or by other means. Also contemplated is a container having an outer barrier coating as described above.

VI. Container inspection

VI. One station or apparatus shown in Figure 1 may be used to measure the air pressure loss or mass flow rate or volume flow rate through the vessel wall or to inspect the inner surface of the vessel 80 for defects, (Not shown). The device 30 is shown in the illustrated embodiment as a barrier or other type of coating is applied by the station or device 28 prior to reaching the station or device 30, May operate similarly to device 26, except that the container may be required to pass the inspection due to better performance provided (less leaks or infiltration under given process conditions). In one embodiment, inspection of the coated container 80 may be comparable to inspection of the same container 80 at the device or station 26. The less leakage or infiltration at the station or device 30 is to a minimum.

VI. The identity of the container 80 measured at two different stations or by two different devices may be determined by comparing the bar codes, other marks or radio frequency identification (RFID) devices < RTI ID = 0.0 > Or markers, and matching the identities of the containers measured at two or more different points around the endless conveyor shown in FIG. As soon as new containers 80 are seated on the container supports 40 they can be stored in a computer database or other storage of data as the location of the container supports 40 in Figure 1 is reached, Structure and may be removed from the data register at or near the end of the process, for example after they have reached or reached the position of the container support 66 of Figure 1, Is removed by the transfer mechanism (74).

VI. The processing station or device 32 may be configured for inspecting, for example, a barrier or other type of coated coating applied to the vessel to determine whether it is defective. In the illustrated embodiment, the station or device 32 measures the optical source transmission of the coating as a measure of the thickness of the coating. If properly applied, the barrier or other type of coating can make the container 80 more transparent because it provides a more uniform surface, even if additional material is applied.

VI. It is also contemplated that an energy wave bouncing the interior surface 88 of the vessel 80 (which interferes with the atmosphere within the vessel interior 154) bounced into the interior of the coating 90 Other measures for measuring the thickness of the coating are also contemplated, such as using an interference measurement to measure the difference in travel distance between the substrate and the substrate. As is known, the difference in travel distance can be directly measured for the test conditions by measuring the arrival time of each wave with high precision, or indirectly measured by measuring the wavelength of incident energy being compensated or canceled .

VI. Another measurement technique that can be performed to check the integrity of the coating is the ellipsometry on the device. In this case, the polarized laser beam can be projected from the inside or the outside of the vessel 80. In the case of a laser beam projected from the inside, the laser beam can be directed diagonally to the surface and then the transmitted or reflected beam can be measured. A change in beam polarizability can be measured. Since the coating or treatment on the device surface affects (changes) the polarization of the laser beam, a change in polarizability can be a desired result. The polarization change is a direct result of the presence of a coating or treatment on the surface and the amount of change is related to the amount of treatment or coating.

VI. If a polarized beam is projected from the outside of the apparatus, the detector can be located inside to measure the transmitted component of the beam (and the polarization as measured). In addition, the detector can be placed outside the device at a location that may correspond to the reflection point of the beam from the interface between the treatment / coating. Thereafter, the polarization change (s) can be measured as described above.

VI. In addition to measuring optical characteristics and / or leak rate as described above, other probes and / or devices may be inserted into the interior of the device and measurements may be made using the detection device. The device is not limited by measurement techniques or methods. Other test methods employing mechanical, electrical, or magnetic properties or any other physical, optical, or chemical properties may be utilized.

VI. During the plasma processing setup, optionally an optical detection system can be used to record a plasma emission spectrum (wavelength and intensity profile) corresponding to a unique chemical signature of the plasma environment. This characteristic emission spectrum provides confirmation that the coating has been applied and processed. In addition, the system can provide real-time precision measurements and data retention tools for each part being processed.

VI. Either of the methods may include inspecting the interior surface 88 of the vessel 80 to determine whether it is defective at a processing station, such as 24, 26, 30, 32, or 34. A test may be performed by inserting a sensing probe 172 through the reservoir port 92 into the reservoir 80 and inserting a sensing probe 172 into the reservoir inner surface 88 or a barrier or other type of coating 90 A check may be performed at the stations 24, 32 and 34 by detecting the status. Inspection can be performed by copying energy inward through the vessel wall 86 and vessel interior surface 88 and detecting energy in the probe 172, as shown in FIG. Inspection may also be performed by reflecting radiation from the container interior surface 88 and detecting energy using a detector positioned within the vessel 80. Inspection may also be performed by detecting the condition of the vessel interior surface 88 at a number of closely spaced locations on the vessel interior surface.

VI. One of the above methods may be such that when the vessel is initially vacuumed and its wall is exposed to the ambient atmosphere, the barrier or other type of coating (90) % &Lt; / RTI > of the inner surface 88 of the container.

VI. Either of the above methods may be performed for up to 30 seconds per container, or 25 seconds per container, or 20 seconds per container, or 15 seconds per container, or 10 seconds per container, or 5 seconds per container, Performing the inspection step within an elapsed time of not more than 4 seconds per container, not more than 3 seconds per container, not more than 2 seconds per container, or not more than 1 second per container. This may be accomplished, for example, by measuring the effectiveness of a barrier or other type of coated vessel wall, which may include one measurement for the entire vessel 80, as shown in Figure 7, By examining a large number, or even all, of the tested points to be inspected, such as for use with the detectors 172 shown or substituted in FIGS. 6, 10 and 11. The latter step can be used to detect the blocking or other types of coatings at numerous closely spaced locations on the container interior surface 88 over a very short total of time.

VI. In any embodiment of the method, the multi-point container inspection, if necessary, collects data using the charge coupled device 172 while the container 80 is moving downstream, ), And processing the collected data immediately thereafter. The defective vessel 80 may be moved off line at one point in the detection station, such as 34, if the defect in the vessel 80 is later confirmed to be due to data processing (FIG. 10).

VI. In any of the above embodiments, the inspecting step may be performed at any of the initial vacuum levels (i. E., Pressure versus periphery) within the vessel 80 when the vessel is initially evacuated and its wall 86 is exposed to the ambient atmosphere. Optionally 1%, optionally 5%, optionally 2% or more of the ambient atmospheric pressure for at least 12 months or at least 18 months or at least 2 years of life The inspection step may be performed at a sufficient number of locations throughout the entire interior surface 88 of the vessel 80 to determine that it is effective to prevent it from decreasing.

VI. The initial vacuum level may be a low vacuum such as a high vacuum, i.e., a residual pressure of less than 10 Torr, or a positive pressure of less than 20 Torr (i.e., extra pressure to full vacuum), or a positive pressure of less than 50 Torr, , Or less than 150 Torr, or less than 200 Torr, or less than 250 Torr, or less than 300 Torr, or less than 350 Torr, or less than 380 Torr. For example, the initial vacuum level of the vacuum blood collection tubes is determined by the type of test tube used in many cases, and therefore the type and proper amount of reagent added to the tube at the time of manufacture. The initial vacuum level is commonly set to extract the correct blood volume for binding with reagent filling in the tube.

VI. In any of the above embodiments, the blocking or other type of coating 90 inspecting step may be performed by inserting the blocking or other type of coating 90 when the container is initially vacuumed and the wall is exposed to the ambient air, Is effective to prevent the pressure within the vessel from increasing to at least 15% or even 10% of the ambient atmospheric pressure for at least one year of service life. &Lt; RTI ID = 0.0 &Lt; / RTI >

VI.A. Container processing including precoating and postcoat inspection

VI.A. Yet another embodiment is a container treatment method for treating a molded plastic container having a wall defining an opening and an interior surface. Said method comprising the steps of: checking whether the inner surface of said container has been formed or just before coating to see if it is defective; Applying a coating to an inner surface of the container after checking that the container is molded; And inspecting the coating to see if it is defective.

VI.A. Another embodiment is a vessel treatment method in which a barrier coating is applied to the vessel after checking that the vessel has been formed and the inner surface of the vessel is inspected to see if there is a defect after applying the barrier coating .

VI.A. In one embodiment, a station or device 26 (which may function as a station or device 28 applying a coating) may be used as follows to inspect the air pressure vessel. With either or both of the valves 136 and 148 open, the vessel 80 can be vacuumed to a desired degree, preferably very low pressure, such as less than 10 Torr, optionally less than 1 Torr . Any of the valves 136 and 148 which are initially opened is then closed to separate the vacuum interior 154 of the vessel 80 and the pressure gauge 152 from ambient conditions and the vacuum source 98. A change in pressure over the measurement time is then sensed and monitored on the container support 44, whether due to ingress of gas through the container wall or gas removal from the wall material and / or coating on the container wall, 0.0 > 80). &Lt; / RTI > For this purpose, degassing is defined as the selective withdrawal of the adsorbed or occluded gases or water vapor in the at least partial vacuum from the vessel wall.

VI.A. Another alternative variant may be to provide ambient gas at a pressure higher than atmospheric pressure. This may increase the rate of gas delivery through the barrier or other types of layers, providing a measurable difference over a longer period of time than a lower ambient pressure is provided. In addition, the gas may be introduced into the vessel 80 at a higher pressure than atmospheric pressure to further increase the delivery rate through the wall 86.

VI.A. Optionally, inspection of the container at the station or by the device 26 may be altered by providing an inspection gas such as helium on the upstream side with respect to the substrate in or out of the vessel 80 and detecting it on the downstream side . In addition, low molecular weight gases such as hydrogen or low cost available gases such as oxygen or nitrogen can be used as inspection gas.

VI.A. As helium passes through unstable interception or other types of coatings or spill rooms, it can be used as a test gas that can increase leakage or penetration detection rates much faster than normal ambient gases such as nitrogen and oxygen in normal air . Helium is (1) inactive, not adsorbed to a certain extent by the substrate, (2) is not easily ionized, the molecules are very dense due to the high level of attraction between their electrons and nucleus, (3) (Molecular weight 28) and oxygen (molecular weight 32), so that the molecules are more dense and easily pass through the porous substrate or gap, so that a high migration rate through many solid substrates or small gaps . Due to these factors, helium will travel through barriers with a given permeability much faster than many other gases. In addition, since the atmosphere naturally contains a very small amount of helium, the presence of helium is particularly advantageous when helium is introduced into the vessel 80 and is detected outside the vessel 80 to measure leakage and penetration. The detection can be relatively easy. Helium can be detected by upstream of the pressure drop of the substrate or by other means such as spectroscopic analysis of the downstream gas passing through the substrate.

VI.A. An example of atmospheric vessel inspection by measuring oxygen concentration from O ₂ fluorescence detection is as follows.

VI.A. (Ocean Optics USB-LS-450 Pulse Blue LED), Fiber Assembly (Ocean Optics QBIF6000-VIS-NIR), Spectrometer (USB4000-FL Fluorescence Spectrometer), Oxygen Sensing Probe (Ocean Optics FOXY-R) A vacuum supply via a connected adapter (VFT-1000-VIS-275, etc.) is used. Vacuum can be applied to remove ambient air and, if the vessel is at a defined pressure, the amount of oxygen leaked or penetrated to refill the vessel from ambient air can be measured using a detection system. The coated tube replaces the uncoated tube and is capable of O ₂ concentration measurements. The coated tube may have a differential O ₂ surface absorption (SiO _x surface versus uncoated PET or glass surface) on the phase coated tube and / or a different O ₂ diffusion rate from the uncoated sample The oxygen content of the atmosphere will be reproducible. The detection time may be less than one second.

VI.A. These atmospheric pressure methods should not be considered to be limited to the specific gas sensed (helium detection or other gases may be considered) or to a specific device or arrangement.

VI.A. In addition, the processing station or device 34 may be configured to inspect interrupting or other types of coatings to determine whether they are defective. In the embodiment of Figures 1 and 10, at 1 and 10, the processing station or device 34 is now in a closed or other type of coating 90 at a number of closely spaced locations, Or other optical inspection that is intended to scan or separately measure the properties of at least a portion of the coating 90 or substantially the entire barrier or other type of coating 90. [ The number of closely spaced locations may be, in all cases or on average, at least about 1 micron, or about 2 microns, or about 3 microns, or about 4 microns, or about 5 microns, About 6 microns, or about 7 microns, so that some or all small portions of the barrier or other type of coating 90 are measured separately. In one embodiment, separately scanning each small area of the coating finds individual pinholes or other defects, and can be applied to localized areas of pinhole defects from more common defects, such as large areas with too thin or porous coatings It can be useful to distinguish effects.

VI.A. Inspection by the station or device 34 may be accomplished using a radiation or light source 170 or any other suitable radio frequency, microwave, infrared, visible, ultraviolet, x-ray or electron beam source, Into the container 80 and detecting the condition of the interior surface of the container, e.g., the barrier coating 90, and detecting the radiation delivered from the source of radiation using the detector.

VI.A. In addition, the vessel support system may be used to test the apparatus. For example, the probe 108 of FIG. 2, with the gas delivery port 110, may be replaced by a light source 170 (FIG. 10). The light source 170 may illuminate the interior of the tube and then measure transmission or other properties to complete subsequent testing outside the tube. The light source 170 may extend into the interior of the tube in the same manner as the probe 108 is pushed into the puck or container support 62, although vacuum and seals are not necessarily required. The light source 170 may be an optical fiber source, a laser, a point source (such as an LED) or any other source of radiation. The source can copy at one or more frequencies from far ultraviolet (100 nm) to far infrared (100 microns) and at all frequencies there between. There is no limit to the source that can be used.

VI.A. As a specific example, see Fig. In Figure 10, the tube or container 80 is located within the puck or container support 62 and a light source 170 is inserted into the tube in the rear of the probe 108. In this case, the light source 170 may be a blue LED source having sufficient intensity to be received by the detector 172 surrounding the exterior of the vessel 80. The light source 170 may be, for example, a three-dimensional charge-coupled device (CCD) that includes an array of pixels, such as 174, on an inner surface 176 thereof. Such as pixel 174, receive and detect illumination that is copied through blocking or other types of coating 90 and vessel walls 86. [ In this embodiment, the detector 172 has a larger inner diameter relative to the vessel 80 than the separation of the electrode 164 and vessel 80 of FIG. 2, and the cylinder 172 adjacent to the closed end 84 instead of the semi- Shaped upper portion. The outer detector 172 may have a smaller radial gap from the vessel 80 and a more uniform size gap in the upper portion adjacent the closed end 84. [ This can be done, for example, by providing a center of curvature for the closed end 84 and the top of the detector 172 when the container 80 is sealed. This change can provide a more uniform inspection of the curved closed end 84 of the vessel 80, even if any one change is considered appropriate.

VI.A. Prior to lighting the light source, the CCD is measured and the resulting value is stored as a background (which can be subtracted from subsequent measurements). Thereafter, the light source 170 is turned on and measured using a CCD. Thereafter, the resulting measurements were made by measuring the total light transmission (and compared to uncoated tubes to measure average coating thickness) and defect density (taking individual photon counts on each component of the CCD and comparing them to threshold values - If the photoelectron number is lower, then it corresponds to the case where not enough light is transmitted). Low light transmission can be the result of either no coating or too thin coating - which is a defect in coating on the tube. By measuring the number of adjacent components with a low number of photoelectrons, the defect size can be estimated. By combining the sizes and numbers of defects, the quality of the tube can be solved or other properties that can be specific to the frequency of radiation from the light source 170 can be measured.

VI.A. 10, energy may be radiated outward through the interior surface of the vessel, such as through the coating 90 and the vessel wall 86, and may be detected using a detector 172 located outside the vessel . Various types of detectors 172 may be used.

VI.A. Incident radiation coming from a blocking or other type of coating 90 and a light source 170 transmitted through the vessel wall 80 is directed at a lower angle of incidence (compared to a reference line perpendicular to the vessel wall 80 at a given point) Pixels such as 174 on the normals through the vessel wall 86 may be capable of receiving some of the light passing through a given portion of the blocking or other type of coating, , The light that will receive more radiation than adjacent pixels and that passes beyond a given portion of the barrier or other type of coating 90 and vessel wall 80 will be received by a particular pixel such as 174 will be.

VI.A. The resolution of pixels such as 174 to detect radiation penetrating through the blocking or other type of coating 90 and a specific portion of the container wall 86 is increased by placing the CCD so that pixels 174, The array is very close to the container wall 86 and closely conforms to its contours. In addition, the resolution can be increased by selecting a point source that is smaller or essentially as shown schematically in Figure 6 to illuminate the interior of the vessel 80. Also, using smaller pixels will improve the resolution of the array of pixels in the CCD.

VI.A. In Fig. 6, the point source 132 (laser or LED) is located at the end of the rod or probe. (A "clerk" refers to a light source that emits light from a source of small volume resembling a mathematical point, such as can be generated by a small LED or diffusion tip for optical fiber radiation in all directions, The point light source 132 may be stationary or may be stationary while the features of the barrier 90 or other type of coating 90 and container wall 80 are being measured, It can be movable as it is movable on an axis. If it is movable, the point light source 132 can be moved up and down inside the device (tube) 80. In a manner analogous to that described above, the inner surface 88 of the vessel 80 can be scanned and subsequent measurements can be made by the external detector device 134 to measure the integrity of the coating. The advantage of this approach is that a linearly polarized or similar directional focusing light source can be used.

VI.A. The position of the point light source 132 may be exponentially indicated on the pixels, such as 174, so that illumination of the detectors can be measured when the detector is perpendicular to a particular portion of the coating 90 . 10, a cylindrical detector 172 having a curved end that matches the curve (if present) of the closed end 84 of the vessel 80 is used to detect the characteristics of the cylindrical vessel 80 .

VI.A. 10, the inspection station or device 24 or 34 may be altered by reversing the position of the light beam or other radiation source 170 and detector 172 such that the light is directed through the vessel wall 86 to the vessel 80 from the outside to the inside. If this means is chosen, then in one embodiment a uniform source of incident or other radiation may be provided by inserting the container into the opening 182 through the wall 184 of the integrated spherical light source 186. Since the integrated spherical light source will disperse light or radiation from the outside of the container 80 and from the source 170 inside the integrating circle, Will be relatively uniform. This tends to reduce distortion caused by structures on portions of wall 86 having different shapes.

VI.A. In the embodiment of FIG. 11, the detector 172 may appear to conform closely to the barrier or other type of coating (90) or inner surface of the vessel (80). Since the detector 172 may be present on the same side of the vessel wall 86 with a blocking or other type of coating 80, this proximity is, in this embodiment, Or to precisely locate one of the other types of coating 90 so that one of them may rub against each other to damage either the coating or the CCD array, the resolution of pixels such as (174) There is a tendency to increase. In addition, placing the detector 172 immediately adjacent to the coating 90 may result in the formation of a coating or other radiation that occurs after the light or other radiation passes through the blocking or other type of coating 90 in the embodiment of FIG. The effect of refraction by the vessel wall 86 can be reduced so that the detected signal can be differentially refracted according to the local shape of the vessel 80 and the angle of incidence of light or other radiation.

VI.A. Other blocking or other types of coating inspection techniques and devices may also be used. For example, fluorescence measurements can be used to characterize the treatment / coating on the device. Using the same apparatus described in Figures 10 and 6, a light source 132 or 170 (or other photocopy) that can interact with the polymeric material of the wall 86 and / or the polymeric material of the wall 86 Circle) can be selected. When coupled with a detection system, it can be used to characterize various characteristics including defect, thickness and other performance factors.

VI.A. Another test example is to use x-rays to characterize the treatment / coating and / or the polymer itself. 10 or 6, the light source may be replaced by an x-ray source and the external detector may be of a type for measuring x-ray intensity. Elemental analysis of the blocking or other types of coatings may be performed using this technique.

VI.A. After forming the device 80 as in the station 22, there may be some potential problems that can make any subsequent treatment or coating incomplete and useless. If these devices are examined prior to coating for these problems, the devices can be highly optimized to ensure the desired result (or results), and optionally coated with a maximum six-sigma control process.

VI.A. Some potential problems that may interfere with the treatment and coating (depending on the nature of the coated article being produced) include:

VI.A. 1. Large particulate contamination defects (eg, the largest size is greater than 10 micrometers each) or less dense size larger particulate contamination (eg, the largest size is greater than 10 micrometers each).

VI.A. 2. Chemical or other surface contamination (eg silicone mold release or oil).

VI.A. 3. High surface roughness, characterized by large numbers of abrupt peaks and valleys, also can be characterized by quantifying the average roughness (Ra) of less than 100 nm.

VI.A. 4. Any defects in the device, such as holes, that prevent the creation of vacuum.

VI.A. 5. Any defects on the surface of the device that will be used to create the seal (eg, the open end of the sample collection tube).

VI.A. 6. Large wall thickness non-uniformity that can interfere with or alter the power coupling through the thickness during processing or coating.

VI.A. 7. Other defects that will render the barrier or other type of coating useless.

VI.A. In order to ensure that the treatment / coating operation is successful using parameters in the treatment / coating operation, the apparatus may be preliminarily inspected for the presence of one or more of the potential problems or other problems. Previously, an apparatus has been disclosed for supporting a puck (such as a device 38 to 68 or a container support) and moving it through a production process involving various tests and treatment / coating operations. Some tests that may be carried out may be performed so that the device has a suitable surface for treatment / coating. These include:

VI.A. 1. Optical inspection, for example, transmission of radiation through the apparatus, reflection of radiation from the interior or exterior of the apparatus, absorption of radiation by the apparatus, or interference with radiation by the apparatus.

VI.A. 2. Digital inspection - for example, using a digital camera capable of measuring a specific length and shape (eg, how "round" or flattened or accurately shaped the open end of the sample collection tube is relative to the reference).

VI.A. 3. Vacuum leak check or pressure test.

VI.A. 4. Sonic speed (supersonic) test of the device.

VI.A. 5. X-ray analysis.

VI.A. 6. The electrical conductivity of the device (the plastic tube material and SiO _x have different electrical resistances - for example, about 1020 Ohm-cm for quartz and about 1014 Ohm-cm for polyethylene terephthalate, size).

VI.A. 7. The thermal conductivity of the device (for example, the thermal conductivity of quartz as bulk material is about 1.3 W-K / m, whereas the thermal conductivity of polyethylene terephthalate is 0.24 W-K / m).

VI.A. 8. Removal of gas from the vessel walls that can be measured under a post-coating inspection to selectively measure the gas removal baseline, as described below.

VI.A. The test can be performed at the station 24 as shown in the figure. 6. In this figure, the device (e.g., the sample collection tube 80 can be in place and the light source 132 (or other source) can be placed in a suitable detector 134, So that the desired result can be measured.

VI.A. In the case of vacuum leak detection, the container support and the device can be coupled to the vacuum pump and measuring device inserted in the tube. The test can also be performed as described elsewhere herein.

VI.A. The processing station or device 24 may be a visual inspection station and may include one or more of the interior of the vessel wall 86 between the interior surface 88 of the vessel, its exterior surface 118, or surfaces 88 and 118 thereof. May be configured to check for defects. In particular, inspection of the outer surface 118, inner surface 88, or vessel wall 86 may be performed from outside of the vessel 80, if the vessel is transparent or translucent to the type of radiation and wavelength used for inspection . If necessary, inspection of the interior surface 88 may be facilitated by providing an optical fiber probe inserted through the container 80 through the container port 92, Can be obtained from the outside of the container (80). For example, an endoscope or a boscope can be used in such an environment.

VI.A. Another means shown in Fig. 6 is that the light source 132 can be inserted into the container 80. Fig. Light transmitted through the vessel wall 86 and artifacts of the vessel 80 exposed by the light may be detected from outside the vessel 80 using a detector measurement device 134. Such stations or devices 24 may include, for example, unaligned containers 80 that are not properly seated on the vessel port 96 within the wall 86, Can be used to detect and correct or remove defective containers (80). In addition, visual inspection of the container 80 may be performed by an operator observing the container 80, in place of mechanical inspection or mechanical inspection.

VI.A. The processing station or device 26 shown in more detail in FIG. 7 may optionally be configured to inspect the interior surface 88 of the vessel 80 to determine whether it is defective, for example, a barrel or other type May be configured to measure the gas pressure loss through the vessel wall 86 that may be performed before the coating of the vessel wall 86 is provided. This test compresses or vacuums the interior of the vessel 80 and separates the interior 154 of the vessel 80 so that the pressure remains constant around the chamber without leakage or gas penetration through the vessel wall, By measuring the pressure change per hour accumulated from the barrier coating 90 by the pressure difference between the two sides of the barrier coating 90. This measurement allows not only to expose any gas coming through the vessel wall 86 but also to measure the leak chamber between the inlet 82 of the vessel and the O-ring or other chamber 100, Indicating that there is a problem with the alignment of the vessel 80 or the function of the chamber 100. In either case, the tube may not be well seated, or the tube drawn from the processing line may be subjected to an attempt to achieve or maintain an appropriate processing vacuum level and to dilute the process gases by the drawn- Thereby reducing the time for prevention.

VI.A. The systems may be integrated into a fabrication and inspection method comprising a plurality of steps.

VI.A. As previously described, 1 shows a simplified arrangement of steps of one possible method (although the invention is limited to a single concept or approach). First, the container 80 is visually inspected at the station or by the device 24, which may include measuring the size of the container 80. If any defects are found, the device or container 80 is rejected and the puck or container support, such as 38, is inspected, recycled, or removed to check for defects.

VI.A. Next, the leak rate or other characteristics of the assembly of the container support 38 and the seated container 80 are tested at station 26 and stored for comparison after coating. The puck or container support 38 then moves to the coating step 28, for example. The device or vessel 80 is coated with SiO _x or other barrier or other type of coating, for example at a power supply frequency of 13.56 MHz. Once coated, the container support is retested for its leak rate or other characteristics (which can be performed in a second test in a dual or similar station, such as the test station 26 or 30) Can increase system throughput).

VI.A. The coating measurements can be compared to the uncoated measurements. If the ratio of these values exceeds a predetermined required level indicative of acceptable total coating performance, the container supports and the device will continue to move. The optical test station 32 will, for example, go along with the blue light source and the external integrated spherical detector to measure the total light transmitted through the tube. The value may be required to exceed a predetermined limit in which the device is rejected or recycled for further coating. The second optical testing station 34 may then be used (for devices not rejected). In this case, a point light source may be inserted into the tube or vessel 80 and slowly pulled out while measurements are taken with the tubular CCD detector array outside the vessel. The data are then analyzed by a computer to measure the defect density distribution. Based on the measurements, the device is either approved or rejected for final packaging.

VI.A. The data may optionally be recorded (e. G. Electronically) and plotted using statistical process control techniques to ensure maximum 6-sigma quality.

VI.B. Container Inspection Performed by Detecting the Gas Removal of the Container Wall Through a Shield

VI.B. Another embodiment is a method of inspecting a barrier or other type of layer on a degassing material vapor having several steps. A sample of material is provided which has been degassed and has at least one partial barrier film. Optionally, a pressure differential may be provided across the blocking membrane such that at least a portion of the degassing material is on the high pressure side of the blocking membrane. In another option, the degassed gas may be allowed to diffuse without providing a pressure differential. The degassed gas is measured. If a pressure differential is provided across the blocking membrane, the degassing can be measured on the high or low pressure side of the blocking membrane.

VI.B. In addition, the effectiveness of the inner coating (as applied above) can be determined by measuring the diffusion rate of species or adsorbed materials specific to the walls of the apparatus (prior to coating). When compared to uncoated (untreated) tubes, this type of measurement can provide a direct measure of the barrier or other type of properties of the coating or treatment, or the presence of the coating or treatment. In addition to or in addition to the barrier film, the coating or treatment to be detected may be a lubricity layer, a hydrophobic layer, a decorative coating, or other types of layers that alter or increase the removal of gases from the substrate.

VI.B. 7, the device or container 80 may be inserted into the puck or container support 44 (also referred to as " moving from another operation, such as coating / treatment " The test may be carried out on an enclosed container 80 that is moved in a puck or container support such as in (44). Once the vessel support is moved into the barrier test area, the measurement tube or probe 108 can be inserted internally (in a manner similar to a gas tube for coating, even though the measurement tube does not need to extend to the inside of the tube) have. The valves 136 and 148 can be both open and the interior of the tube can be vacuumed (a vacuum is created).

VI.B. Once the desired measured pressure is reached, the valves 136 and 148 may be closed and the pressure gauge 152 may begin to measure the pressure. Measuring the time at which a specific pressure (higher than the starting pressure) is reached, or measuring the measured pressure measured after a given time, is applied to the tube, the container support, the pump channel and the internal volume, (Or leak-rate) of all the other components separated by the leak rate can be measured. Thereafter, if this value is compared to an uncoated tube, the ratio of the two measurements (dividing the coated tube value by the uncoated tube value) will allow a leak rate measurement through the coated surface of the tube. This measurement technique minimizes the internal volume of all other components that are connected to the vessel support, the pump channel and the internal volume but separated by valves 1 and 2 (except tubes / devices), so that gas infiltration or gas removal To minimize the effect of the < / RTI >

VI.B. In this disclosure, distinctions are made between "penetration "," leakage "and" surface diffusion "

Quot; penetration ", as used herein with reference to the container, refers to the direction in which the material traverses through the wall 346 or other obstruction, from outside the container to the interior, or vice versa, along path 350 of FIG. .

Degassing may be accomplished by removing absorbed or adsorbed material, such as gas molecules 354 or 357 or 359, from the wall 346 of Figure 29 or from within the coating 348 outward, for example, To the container 358 (to the right in Figure 29). In addition, degassing may mean that a material such as 354 or 357 that exits the wall 346 moves to the left as shown in Figure 29 and moves out of the vessel 357 as shown . Degassing may also refer to the removal of adsorbed material from the surface of the item, such as, for example, gas molecules 355 from the exposed surface of the container coating 90.

The leakage means that the material travels around the obstacles presented by the wall 346 and the coating 348, rather than through or through the surface of the obstacle, by passing between the walls of the closed vessel with the closure and the closure.

VI.B. Penetration is indicative of the rate of gas movement through the material that is free of gaps / defects and not associated with leakage or degassing. 29, penetration is shown along path 350 through both layers 346 and coating 348 through the entire surface of substrate 346 and coating 348, showing another substrate 346 with a container wall or barrier coating 348 Is crossing. Penetration is considered to be a relatively slow process thermodynamically.

VI.B. Penetration measurements are very slow because the penetrating gas must pass completely through the unbreakable wall of the plastic item. In the case of vacuum blood collection tubes, the measurement of penetration of gas through the wall is typically used as a direct indication of the tendency of the vessel to lose vacuum over time, but usually to the extremes requiring a test period of 6 days Because it is a slow measurement, it is not fast enough to support the on-line coating test. Such tests are generally used for off-line testing of samples of vessels.

VI.B. Also, penetration testing is not a very sensitive measure of the effectiveness of a thin coating on a thick substrate. Since all gas flow is through both the coating and the substrate, any change in flow through the thick substrate will itself introduce a change, not due to the barrier effectiveness of the coating.

VI.B. The inventors have discovered a much faster and potentially more sensitive method of measuring gas removal of rapidly separated air or other gases or volatile constituents through the coating, which measures the barrier properties of the coating. The gas or volatile components can in fact be any substance that can be depleted or selected from one or more specific substances to be detected. The constituents may include byproducts of the manufacture of coatings such as oxygen, nitrogen, air, carbon dioxide, water vapor, helium, alcohols, ketones, hydrocarbons, coating precursors, substrate components, volatile organosilicon species, , Other components that are accidentally present or are introduced by spiking the substrate, or mixtures or combinations of any of these.

Surface diffusion and degassing are synonymous. Each terminology includes some motifs, such as a wall of the container, such as a vacuum that is initially adsorbed or absorbed into the wall 346 and that pulls out a vacuum (creating the air movement indicated by the arrows in Figure 29) Quot; fluid " refers to a fluid that is forced into adjacent spaces by forces exerted thereon to force fluid out of the walls into the interior of the container. Degassing or diffusion is considered to be a relatively rapid process with motility. Degassing with respect to wall 346 that is substantially resistant to penetration along path 350 results in removal of molecules such as 354 that are closest to interface 356 between said wall 346 and said blocking film 348 It is thought that it drives quickly. This differential degassing is accomplished by a large amount of molecules, such as 354 near interface 356, shown as degassing, and further away from interface 356, such as 358, Of other molecules.

VI.B. Thus, another method is contemplated for inspecting a barrier on a vapor degassing material, including several steps. A sample of material is provided which is gas degassed and has at least one partial barrier film. A pressure differential is provided across the blocking membrane such that at least a portion of the degassing material is initially present on the high pressure side of the blocking membrane. The degassed gas transported to the low pressure side of the barrier during the test is measured to determine whether the barrier is present or how effective it is to the barrier.

VI.B. In this method, the gas deasphalting material may comprise a polymeric compound, a thermoplastic compound or one or more compounds having both properties. The gas degassing material may comprise, for example, a polyester such as polyethylene terephthalate. The gas deasphalting material may comprise polyolefins, for example, polypropylene, cyclic olefins or combinations thereof. The gas deasphalting material is a complex of two different materials, at least one of which can be deaerated. One example is the bilayer structure of polypropylene and polyethylene terephthalate. Another example is the bilayer structure of cyclic olefin copolymer and polyethylene terephthalate. These materials and complexes are illustrative; Any suitable material or combination of materials may be used.

VI.B. Optionally, the gas deasphalting material has an outer surface and an inner surface, said inner surface being provided in the form of a container having a wall surrounding the lumen. In this embodiment, the barrier membrane is optionally provided on the vessel wall, optionally on the inner surface of the vessel wall. Further, the blocking film may be provided on the outer surface of the container wall. Optionally, the material for degassing the gas may be provided in the form of a film.

VI.B. The barrier may be a full or partial coating of any of the presently described barrier films. The barrier may have a thickness of less than 500 nm, or less than 300 nm, or less than 100 nm, or less than 80 nm, or less than 60 nm, or less than 50 nm, or less than 40 nm, Less than 20 nm thick, or less than 10 nm thick, or less than 5 nm thick.

VI.B. In the case of coated walls, the inventors have found that diffusion / removal of gases can be used to measure coating integrity. Optionally, a pressure differential may be provided across the barrier by at least partially evacuating the lumen or interior space of the vessel. This may be done, for example, by connecting the lumen to a vacuum source through a duct and at least partially vacuuming the lumen. For example, the uncoated PET wall 346 of the container exposed to ambient air may be heated to a certain amount of oxygen and other gas molecules, such as 354, from its inner surface for some time after the vacuum is removed Will remove it. If the same PET wall is coated on the inner surface with the barrier coating 348, the barrier coating will stop, retard or reduce this air removal. This example is true for the SiO _x barrier coating 348 to degas less than the plastic surface. By measuring the difference in gas removal between the coated and uncoated PET walls, the blocking effect of the coating 348 on the degassed material can be measured quickly.

VI.B. If the barrier coating 348 is known or is incomplete due to theoretical holes, cracks, gaps or insufficient thicknesses or densities or areas of the composition, then the PET wall is preferentially degassed through this imperfection, Lt; / RTI > The first source of collected gas is not from the outside of the item but from dissolved gas or vaporizable components on the (lower) surface of the plastic item immediately adjacent to the coating. The amount of degassing off the baseline level (e.g., the amount of incomplete or at least incomplete incompleteness or the average and acceptable incompleteness, passed or discharged by the standard coating) Can be measured in various ways.

VI.B. The measurement may be performed, for example, by providing a degassing measurement cell that communicates between the lumen and the vacuum source.

VI.B. The measurement cell may perform one of the different measurement techniques. One example of a suitable measurement technique is the micro-flow technique. For example, the mass flow rate of the degassed material can be measured. The measurement may be performed in a molecular flow operating mode. Exemplary measurements include the measurement of the volume of gas depleted through the barrier per time interval.

VI.B. The gas de-gassed on the low-pressure side of the barrier may be measured under conditions effective to distinguish the presence of the barrier. Optionally, conditions effective to distinguish the presence of the barrier include conditions of less than one minute, or less than 50 seconds or less than 40 seconds, or less than 30 seconds, or less than 20 seconds, or less than 15 seconds, or less than 10 seconds, or less than 8 seconds Or less than 6 seconds, or less than 4 seconds, or less than 3 seconds, or less than 2 seconds, or less than 1 second.

VI.B. Optionally, the measurement of the zone member of the barrier may be ascertained with at least a six sigma level of certainty within any of the identified time intervals.

VI.B. Optionally, the degassed gas on the low pressure side of the barrier is measured under conditions effective to measure the barrier enhancement factor (BIF) of the barrier, as compared to the same material without the barrier. BIF provides, for example, two groups with identical vessels, adding a barrier to one vessel group, and a barrier property (such as the rate of removal of gas per minute or other suitable scale) on vessels with barrier And performing the same test on vessels lacking a barrier, and taking the ratio of the properties of the barrier-barrier material to the barrier barrier-free properties. For example, if the rate of gas removal through the barrier is one-third of the rate of removal of the barrier-free gas, the barrier has a BIF of 3.

VI.B. Alternatively, in the case of one or more types of gases, such as both nitrogen and oxygen, in the case of degassed air, gas removal of a plurality of different gases can be measured. Optionally, gas removal of substantially all or all of the de-gassed gases can be measured. Optionally, gas removal of substantially all or all of the degassed gases can be simultaneously measured using physical measurements such as the combined mass flow rate of all gases.

VI.B. The measurement of the number or partial pressure of individual gas species (such as oxygen or helium) removed from the sample can be performed more quickly than the atmospheric pressure test, but the test rate is such that only a portion of the gas removal is reduced do. For example, if oxygen and nitrogen are removed from the PET wall at a ratio of about 4: 1 in the atmosphere, but only oxygen gas removal is measured, testing to measure all species removed from the vessel wall is equally sensitive (Converted to the number of molecules detected to obtain sufficient statistical query results).

VI.B. For a given sensitivity level, it is believed that the method of occupying the volume of all species removed from the surface will provide the desired confidence level much quicker than a test to determine the removal of specific species such as oxygen atoms. As a result, gas removal data having practical utility for in-line measurement can be generated. Optionally, this in-line measurement can be performed on all vessels produced, reducing the number of specific or separate defects and potentially removing them (at least at the time of measurement).

VI.B. In an actual measurement, the factor that changes the amount of apparent gas removal is the leakage that escapes through an unsafe chamber, such as a thread of a container seated on a vacuum receiver, as the vacuum is removed in the degassing test. Leaks occur between the fluid that bypasses the solid wall of the item, for example, between the blood tube and its closure, between the syringe plunger and the syringe barrel, between the container and its cap, or the container inlet and the container inlet are seated (unstable or misaligned Means the fluid flowing between the chambers. The word "leaking" refers primarily to the movement of gas / gas through openings in plastic items.

VI.B. The leakage and infiltration (in a given situation, if necessary) can be factored into the basic level of gas removal, so that an acceptable test result is obtained when the container is properly seated in the vacuum receiver yarn (the seized surface is not damaged, ), Ensuring that the container wall does not sustain a level that penetration is unacceptable (the container wall is not damaged and is properly formed), and that the coating has sufficient blocking integrity.

VI.B. Gas removal can be measured in a variety of ways by measuring atmospheric pressure (measuring the change in pressure in the vessel at a given time after the initial vacuum is removed) or by measuring the partial pressure or flow rate of the gas removed from the sample. Equipment to measure mass flow rate in the molecular flow operating mode can be used. An example of this type of commercially available equipment employing Micro-Flow Technology is available from ATC of Indianapolis, Indiana. For a further description of these known devices, see U.S. Patent Nos. 5861546, 6308556, 6584828, and EP1356260, which are incorporated herein by reference. It also shows an example of a gas removal measurement that very quickly and reliably distinguishes polyethylene terephthalate (PET) tubes coated with a barrier from uncoated tubes.

VI.B. For vessels made of polyethylene terephthalate (PET), the microflow rate is different for SiO _x coated versus uncoated surfaces. For example, in Working Example 8 in this specification, as shown in FIG. 31, the microflow rate for PET after the test is performed for 30 seconds is 8 or Or more. This rate for uncoated PET was much higher than the measured rate for SiO _x -coated PET, which was less than 6 micrograms after the test was run for 30 seconds, again as shown in Fig.

VI.B. One possible explanation for this difference in flow rate is that uncoated PET contains approximately 0.7 percent equilibrium moisture; This high water content is considered to cause the observed high micro flow rate. Using SiO _x -coated PET plastic, SiO _x coatings can have higher levels of surface moisture than uncoated PET surfaces. However, under the test conditions, the barrier coating prevents further desorption of moisture from the bulk PET plastic and is considered to result in a lower microflow rate. It is expected that the microflow rate of oxygen or nitrogen from the uncoated PET plastic vs. SiO _x coated PET will also be distinguishable.

VI.B. Modification of the above test for PET tubing may be appropriate when using other materials. For example, polyolefin plastics tend to have almost no moisture content. An example of a polyolefin having a low moisture content is a TOPAS cyclic olefin copolymer (COC) having an equilibrium water content (0.01 percent) and a much lower water penetration rate than for PET. In the case of COC, the uncoated COC plastic may have a microflow rate similar to or even lower than the SiO _x coated COC plastic. This is likely due to the higher surface water content of the SiO _x -coating and the lower equilibrium bulk moisture content of the uncoated COC plastic surface and the lower penetration rate. This makes it difficult to distinguish between COC items that are not coated and are coated.

The present invention shows that exposing the surface of COC articles (uncoated and coated) to be tested to moisture results in improved and consistent micro-flow separation between uncoated plastic and SiO _x coated COC plastic. This is shown in Example 19 and Fig. 57 of this specification. The water exposure may be a simple exposure to a relative humidity ranging from 35% to 100%, such as in a controlled relative humidity room or in direct exposure to a mild (humidifier) or cold (vaporizer) moisture source, the latter being preferred.

VI.B. While the effectiveness and scope of the present invention is not limited by the accuracy of this theory, the water doping or spiking of the uncoated COC plastic can be achieved by removing moisture or other gases from the already saturated SiO _x -coated COC surface It seems to increase the possible content. It may also be performed by exposing uncoated tubes coated with other gases including oxygen, nitrogen, or other mixtures such as air, for example.

VI.B. Thus, prior to measuring the degassed gas, the barrier may be contacted with water, for example, water vapor. Water vapor can be provided, for example, by bringing the barrier into contact with air at 35% to 100%, or 40% to 100%, or 40% to 50% relative humidity. Instead of or in addition to water, the barrier membrane can be contacted with oxygen, nitrogen or a mixture of oxygen and nitrogen, e.g., ambient air. The contact time can be from 10 seconds to 1 hour, or from 1 minute to 30 minutes, or from 5 minutes to 25 minutes, or from 10 minutes to 20 minutes.

Further, the gas removing wall 346 may be formed by, for example, introducing the left side of the wall 346 into the wall 346 as shown in Fig. 11, and then, as shown in Fig. 29, May be spiked or supplemented from the side opposite to the barrier layer 348 by exposure to the material that is one to one degassing. Measuring gas removal from the right side (or vice versa) of the spiked material after spiked with a gas inflow and other material, such as the wall or 346 from the left side, The spiked material is distinguished from the penetration measurement because it is present in the wall 346 when gas removal is measured, as opposed to the material moving through the entire path 350. Gas inflow may take place over a long period of time as an embodiment before the coating 348 is applied and as an alternative embodiment after the coating 348 has been applied and before it has been tested for degassing.

VI.B. Another possible way to increase the separation of the microfluidic reaction between uncoated plastic and SiO _x coated plastics is to vary the measured pressure and / or temperature. Increasing the pressure or decreasing the temperature when measuring degassing can cause more relative binding of water molecules in SiO _x coated COC than in uncoated COC. Thus, the degassed gas may be between 0.1 Torr and 100 Torr, or between 0.2 Torr and 50 Torr, or between 0.5 Torr and 40 Torr, or between 1 Torr and 30 Torr, or between 5 Torr and 100 Torr, or between 10 Torr and 80 Torr, Torr to 50 Torr. The degassed gas can be measured at 0 캜 to 50 캜, or 0 캜 to 21 캜, or 5 캜 to 20 캜.

VI.B. In any embodiment of the disclosure, another method contemplated for measuring gas removal is to employ a microcantilever measurement technique. Such a technique is believed to potentially allow the measurement of less mass differences in gas removal to a size of 10 ^-12 g. (Picogram) to 10 ^-15 g. (Femtogram). This less mass detection allows for differences in coated versus uncoated surfaces as well as other coatings in one second, optionally less than 0.1 second, and optionally in microseconds.

VI.B. In some cases, the microcantilever (MCL) sensors may respond to the presence of the provided material by degassing or bending or moving or changing the shape due to absorption of the molecules. In some cases, microcantilever (MCL) sensors may respond due to shifting at the resonant frequency. In other cases, the MCL sensors may change in either of these ways or in other ways. They can be operated in different environments such as in a gas environment, liquid or vacuum. In gas, the microcantilever sensors can be operated as artificial noses, whereby the bending pattern of the micro-fabricated array of eight polymer-coated silicon cantilevers is different from that of solvents, spices, and beverages, with the characteristics of steam. Also, the use of any other type of electronic nose, which is operated by any technique, is also contemplated.

Some MCL electronics designs, including piezoresistance, piezoelectric and capacitive approaches, are applied and are considered to measure movement, shape change or frequency changes of the MCLs upon exposure to chemicals.

VI.B. One specific example of measuring gas removal can be performed as follows. In the presence of the degassed material, there is provided at least one microcantilever having characteristics of movement or variation in different shapes. The microcantilever is exposed to the degassed material under conditions effective to cause the microcantilever to move or change to a different shape. Thereafter, a moving or different shape is detected.

VI.B. For example, it may be desirable to reflect an energy incident beam from a portion of the microcantilever that moves or changes shape before and after exposing the microcantilever to the gas removal, and to deflect the reflected beam at a point spaced from the cantilever It can be measured and moved or a different shape can be detected. Preferably, the shape is measured at a point spaced from the cantilever because the amount of deflection of the beam under given conditions is proportional to the distance of the measurement point from the reflection point of the beam.

VI.B. Some suitable examples of energy incident beams are a photon beam, an electron beam, or a combination of two or more of these. In addition, two or more different beams may be reflected from the MCL along different incident and / or reflected paths to determine movement or shape changes from one or more viewpoints. One particular type of energy incident beam is a beam of coherent photons, such as a laser beam. The "photon" described herein is implicitly defined to include wave energy as well as particle or photon energy by itself.

VI.B. Another example of measurement utilizes the characteristics of specific MCLs of changes in resonant frequency when encountering environmental material in an amount effective to effect a change in the resonant frequency. This type of measurement can be performed as follows. When the degassed material is present, at least one microcantilever resonating at different frequencies is provided. The microcantilever can be exposed to the degassed material under conditions effective to cause the microcantilever to resonate at different frequencies. The different resonant frequencies are then detected by any suitable means.

VI.B. By way of example, different resonance frequencies can be detected by inputting energy to the microcantilever and inducing resonance before and after exposing the microcantilever to gas removal. Differences are measured between the resonant frequencies of the MCL before and after exposure to gas removal. Also, instead of measuring the difference at the resonance frequency, an MCL known to have a specific resonance frequency can be provided if there is sufficient concentration or amount of degassed material present. Equivalent frequencies that signal the presence of different resonance frequencies or the presence of a sufficient amount of degassed material are detected using a harmonic vibration sensor.

As an example of an MCL technique for measuring gas removal, the MCL device can be integrated into a quartz vacuum tube connected to a vessel and a vacuum pump. A harmonic vibration sensor using a commercially available piezoresistive cantilever, a Wheatstone bridge circuit, a positive feedback controller, an excitation piezoelectric element, and a phase locked loop (PLL) demodulator can be constructed. for example,

Hayato Sone, Yoshinori Fujinuma and Sumio Hosaka Picogram Mass Sensor Using Resonance Frequency Shift of Cantilever , Jpn. J. Appl. Phys. 43 (2004) 3648;

Hayato Sone, Ayumi Ikeuchi, Takashi Izumi1, Haruki Okano2 and Sumio Hosaka Femtogram Mass Biosensor Using Self-Sensing Cantilever for Allergy Check, Jpn. 43 (2006) 2301).

To produce the MCL for detection, one side of the microcantilever may be coated with gelatin. See, for example, Hans Peter Lang, Christoph Gerber, STM and AFM Studies on (Bio) molecular Systems: Unraveling the Nanoworld, Topics in Current Chemistry, Volume 285/2008. Water vapor desorbed from the surface of the vacuum coated container is combined with gelatin to cause the cantilever to bend and its resonant frequency to change, as measured by laser deflection from the surface of the cantilever. The change in mass of an uncoated vessel versus a coated vessel can vary within seconds and is considered to be highly reproducible. The items recited above in connection with cantilever technology are incorporated herein by reference to disclose specific MCLs and equipment arrangements that can be used to detect and quantify de-identified species.

Other coatings for moisture detection (phosphoric acid) or for oxygen detection can be applied to MCLs instead of or in addition to the gelatin coating described above.

VI.B. It is also contemplated that any of the gas scrubbing test setups currently under consideration can be combined with a SiO _x coating station. In such an arrangement, measurement cell 362 may be as shown above, using a main vacuum channel for PECVD, such as bypass 386. In one embodiment, the measurement cell, generally designated 362 in Figure 30, is configured such that the bypass channel 386 is comprised of a main vacuum duct 94 and the measurement cell 362 is a side channel 50, Can be integrated into the same container support.

VI.B. This combination of the measurement cell 362 and the vessel support 50 optionally allows the degassing measurement to be performed without breaking the vacuum used in the PECVD. Alternatively, the vacuum pump for PECVD may be operated for a standardized period of time to pump some or all of the remaining reactant gases, preferably short, but remaining after the coating step (pump down to less than 1 Torr, With a small amount of air, nitrogen oxygen, or other gas prior to being pumped out or having other options to dilute the process gases). This will facilitate combined processes of coating the vessel and testing the coating for presence and level of interception.

VI.B. It will also be appreciated that after reviewing the present disclosure, gas removal measurements and all other described barrier measurement techniques can be used for many purposes besides or in addition to measuring the effectiveness of the barrier. As an example, a test may be performed on uncoated or coated containers to determine the extent of degassing of the container walls. This test can be made, for example, when a polymer that is not coated to remove less than a specified amount of gas is needed.

VI.B. As another example, these degas elimination measurements and all other described interception measurement techniques can be used as an in-line test to measure changes in gas removal of film as the stall test or film traverses the measurement cell, Lt; RTI ID = 0.0 > films. &Lt; / RTI > The test can be used to measure the continuity or blocking effectiveness of other types of coatings such as aluminum coatings or EVOH barrier coatings or layers of packaging films.

VI.B. Such gas removal measurements and all other described barrier measurement techniques may be applied to the side of the vessel wall, film, etc., opposite the measurement cell, such as a barrier membrane that is applied to the exterior of the vessel wall and tested for removal of gas into the interior of the vessel wall Can be used to measure the effectiveness of the barrier layer. In this case, it will be a flow differential for penetration through the substrate film or wall after penetration through the barrier coating. Such measurements may be particularly useful when the substrate is film or wall such as a very thin or porous film or wall is permeable.

VI.B. Such degassing measurements and all other described blocking measurement techniques can be used to determine the effectiveness of a barrier, which is an inner layer of a vessel wall, film, etc. In this case, the measurement cell is a layer or layer further away from the measurement cell than the barrier, In addition to removing gas through the barrier of the measuring cell.

VI.B. Such gas removal measurements and all other described barrier measurement techniques are based on the assumption that, as long as the barrier is not present on any portion of the material, the gas removal rate of the partially barrier- Can be used to determine the percentage of coverage of the pattern of blocking material on the material to be removed.

VI.B. One test technique that can be used to increase the test rate for degassing of a vessel, which may be used with any of the degassing test embodiments herein, is to insert a plunger or closure into the vessel to expose a portion of the vessel being tested Reducing the pore volume to reduce the pore volume of the container. Reduce pore volume to allow the vessel to pump down to a given vacuum level more quickly, reducing test intervals.

VI.B. Many other applications of the currently described gas removal measurements and all other described barrier measurement techniques will become apparent after review of this specification by those skilled in the art.

VII. PECVD treated vessels

VII. At least 2 nm, or at least 4 nm, alternatively at least 7 nm, alternatively at least 10 nm, alternatively at least 20 nm, alternatively at least 30 nm, alternatively at least 40 nm, alternatively at least 50 nm, alternatively at least 100 nm, alternatively at least 150 nm, Which may be an SiO _x coating applied to a thickness of at least 200 nm, or at least 300 nm, or at least 400 nm, or at least 500 nm, or at least 600 nm, or at least 700 nm, or at least 800 nm, For example, containers having a barrier coating 90 (shown in FIG. The coating may be at most 1000 nm, or about 900 nm, or about 800 nm, or about 700 nm, or about 600 nm, or about 500 nm, or about 400 nm, or about 300 nm, or about 200 nm, Or about 90 nm or at least about 80 nm or about 70 nm or about 60 nm or about 50 nm or about 40 nm or about 30 nm or about 20 nm or about 10 nm or about 5 nm Or more. In addition to the specific thickness range consisting of any of the minimum thicknesses indicated above, one or more of the maximum thicknesses indicated above is explicitly contemplated. The thickness of the SiO _x or other coating can be measured, for example, by a transmission electron microscope (TEM), and its composition can be measured by X-ray photoelectron spectroscopy (XPS).

VII. It is believed that the choice of material that does not penetrate the coating and the nature of the applied SiO _x coating can affect the barrier efficacy. For example, two of the commonly contemplated substances not to be permeated are oxygen and water / water vapor. In common, materials are better shields for one than the rest. This is believed to be due in part to the fact that oxygen is permeated through the coating by a mechanism other than that through which water is permeated.

VII. Oxygen permeation is affected by physical properties of the coating such as thickness, presence of cracks and other physical details of the coating. On the other hand, it is believed that moisture transmission is typically affected by chemical agents that are above physical factors, such as materials that make up the coating. The present inventors also contemplate that at least one of these chemical factors is a substantial concentration of OH moieties in the coating, which will increase the rate of permeation of water through the barrier. Since SiO _x coatings often contain OH moieties, a physically normal coating that contains a high proportion of OH moieties is better shielded against oxygen than water. Physically normal carbon-based barrier, such as amorphous carbon or diamond-like carbon (DLC) are typically together a better barrier against water than the SiO _x such, which typically is more carbon-based barrier film that the concentration of the OH moiety It is low.

VII. However, other factors lead to preference for SiO _x coatings, such as oxygen barrier efficacy and close chemical similarity to glass and quartz. Glass and quartz are two long-known materials that present a very high barrier to oxygen and water permeation as well as substantial inactivity for many materials commonly contained in containers (when used as the base material of the container). Therefore, it is generally desirable to optimize the aqueous barrier properties, such as the water vapor transmission rate (WVTR) of the SiO _x coating, rather than selecting different or different types of coatings to act as a water permeation barrier.

VII. Some methods to be considered for improving the WVTR of SiO _x coating are as follows.

VII. The concentration ratio of organic moieties (carbon and oxygen compounds) to OH moieties in the deposited coating can be increased. This can be done, for example, by increasing the rate of oxygen in the feed gases (by increasing the oxygen feed rate or by lowering the feed rate of one or more other components). The lower incidence of OH moieties is believed to be due to the increased oxygen supply and hydrogen reactivity at the silicon source, resulting in more volatile water at the PECVD outlet, trapped in the coating, or reduced concentration of integrated OH moieties.

VII. Higher energy may be applied in the PECVD process by increasing the plasma generation power level, applying the power supply for a longer period of time, or both. The increase in applied energy tends to distort the vessel being treated, so when used to coat a plastic tube or other device, the tube must be handled with care to absorb the plasma generating power. This is because the RF power source is preferred in the context of the present application. Cooling the vessels while applying energy, applying the coating in a short period of time (and thus thinning the coating), and applying the coating to the selected base material for coating The distortion of the medical devices can be reduced or eliminated by selecting the frequency of the applied coating that is absorbed to a minimum and / or by applying one or more coatings with the time between each energy application steps. For example, high power pulsing can be used with a duty cycle of operating for one millisecond and stopping for 99 milliseconds while the process gas is continuously supplied. Thereafter, with continued flow between the pulses, the process gas is a refrigerant. Alternatively, a power applicator can be readjusted by adding a magnet to confine the plasma, and an active power application (a power source that, contrary to the hydraulic power that leads to heating or unwanted coatings, . This approach leads to the application of more coating forming energy per watt-hour of total applied energy. See, for example, U.S. Patent No. 5,904,952.

VII. An oxygen post-treatment of the coating can be used to remove the OH moieties from the previously deposited coating. It is also contemplated that this treatment removes residual volatile organosilicon compounds or silicones or oxidizes the coating to form another SiO _x .

VII. The plastic base material tube can be preheated.

VII. Volatile sources of other silicones such as hexamethyldisilazane (HMDZ) can be used as part or all of the silicon supply. Since these compounds do not have oxygen moieties in the feed gas, it is considered that changing the feed gas to the HMDZ will solve the problem. It is contemplated that the source of one of the OH moieties in the HMDSO-source coating is the hydrogenation of at least a portion of the oxygen atoms present in the unreacted HMDSO.

VII. Composite coatings such as carbon-based coatings mixed with SiO _x may be used. This can be done, for example, by changing the reaction conditions or by adding a substituted or unsubstituted hydrocarbon such as an alkane, alkene or alkane, as well as organosilicon compounds to the feed gas. See, for example, U.S. Patent No. 5,904,952, which refers to the relevant section: "For example, if a lower hydrocarbon such as propylene is included, it provides a carbon moiety and most properties of the deposited films (except for light transmission) And bonding analysis shows that the film is silicon dioxide in nature. However, the use of methane, methanol or acetylene produces films that are silicon in nature. Incorporating a small amount of gaseous nitrogen in the gas stream provides nitrogen moieties in the deposited films and increases the deposition rate, improves transmission and reflective optical properties on the glass, and changes the refractive index in response to the change in the amount of N ₂ . Adding nitrogen oxide to the gas stream increases the deposition rate and improves optical properties, but tends to reduce film hardness. "

VII. A diamond-like carbon (DLC) coating may be formed as the first or only deposited coating. This can be done, for example, by changing the reaction conditions or by supplying methane, hydrogen and helium to the PECVD process. Since these reaction feeds do not have oxygen, OH moieties can not be formed. As an example, a SiO _x coating can be applied on the inside of a tube or syringe barrel and an external DLC coating can be applied on the outside surface of a tube or syringe barrel. Alternatively, SiO _x and DLC coatings can be applied as a single layer or multiple layers of either an inner tube or a syringe barrel coating.

VII. Referring to FIG. 2, a barrier or other type of coating 90 reduces the permeation of atmospheric gases into the vessel 80 through the inner surface 88. In addition, a barrier or other type of coating 90 reduces the contact of the contents of the container 80 with the inner surface 88. The barrier or other type of coating may include, for example, SiO _x , amorphous (e.g., diamond-like) carbon or combinations thereof.

VII. Any of the coatings described herein can be used, for example, to coat surfaces that are plastic surfaces. It can also be used, for example, as a barrier to gas or liquid, preferably as a barrier to water vapor, oxygen and / or air. In addition, the coated surface can be used to prevent or reduce the mechanical and / or chemical effects that a compound or composition may have on the surface if the surface is not coated. For example, the precipitation of compounds or compositions such as insulin precipitation or blood clotting or platelet activation can be prevented or reduced.

VII.A. Vacuum collection containers

VII.A.1. Tubes

VII.A.I. Referring to Figure 2, further details of containers such as (80) are shown. The illustrated container 80 may be generally tubular with an opening 82 at one end of the container, as opposed to a closed end 84. The container 80 also has a wall 86 defining an interior surface 88. An example of the container 80 is a medical sample tube, such as a vacuum blood collection tube, as is commonly used by a vascular surgeon to receive a venous puncture sample of a patient ' s blood for use in a medical laboratory.

VII.A.1. The container 80 may be made of, for example, a thermoplastic material. Some examples of suitable thermoplastic materials are polyolefins such as polyethylene terephthalate or polypropylene or cyclic polyolefin polymers.

VII.A.1. The container 80 may be manufactured by any suitable method such as injection molding, blow molding, machining, fabrication from tubing stock, or other suitable means. PECVD may be used to form a coating on the inner surface of SiO _x .

VII.A.1. If it is intended to be used as a vacuum blood collection tube, the container 80 is preferably sufficiently large to withstand substantially the entire internal vacuum without substantial deformation when exposed to external pressures of 760 Torr or atmospheric pressure and other coating process conditions It can be strong. In the thermoplastic container 80, a container 80 made of suitable materials having a suitable size and a glass transition temperature higher than the treatment temperature of the coating process, for example, a cylinder having a sufficient wall thickness for its diameter and material This property can be provided by providing the mold wall 86.

VII.A.1. Medical containers or containers such as sample collection tubes and syringes are injection molded, allowing relatively small and relatively thick walls to be vacuumed without being squeezed by the ambient atmospheric pressure. Thus, they are stronger than carbonated beverage bottles or other large or thin wall plastic containers. Because the sample collection tubes designed for use with vacuum vessels are designed to withstand full vacuum during storage, they can be used as vacuum chambers.

VII.A.1. By aligning the vessel with its own vacuum chambers, it may not be necessary to position the vessels in a vacuum chamber for PECVD processing which is typically performed at very low pressures. Using the vessel as its own vacuum chamber (since loading and unloading of parts from individual vacuum chambers is not required), the processing time is faster and the equipment configuration can be simplified. Also, for certain embodiments, it is also possible to support the device (for alignment with gas tubes and other devices), seal the device (attach the container support to the vacuum pump to create a vacuum) A container support for transferring the device between the treatment steps is contemplated.

VII.A.1. The container 80 used as a vacuum blood collection tube does not leak a significant volume of air or other atmospheric gas into the tube (by bypassing the closure) or penetrate through the wall 86 during its lifetime, While being vacuumed internally with a decompression useful for the intended use, it must be able to withstand external atmospheric pressure. If the molded container 80 can not meet this requirement, it can be treated by coating the inner surface 88 with a barrier or other type of coating 90. It is desirable to treat and / or coat the internal surfaces of such devices (such as sample collection tubes and syringe barrels) to provide various properties that will provide advantages over existing polymer devices and / or to mimic existing glassware . It is also desirable to measure various properties of the devices before and / or after treatment or coating.

VII.A.1.a. Coatings deposited from an organosilicon precursor made by in situ polymerization of an organosilicon precursor

VII.A.1.a. One of the precursors described above is applied on or in the vicinity of a substrate of 1 to 5000 nm, alternatively of 10 to 1000 nm, alternatively of 10 to 200 nm, alternatively of 20 to 100 nm, and is deposited in a PECVD process The process of applying a lubricative coating onto the inside of a substrate, e.g., a barrel of a syringe, comprising cross-linking or polymerizing (or both performing) the coating to provide a lubricating surface is contemplated. Also, the coating applied by this process is considered to be new.

VII.A.1.a. Wherein x is about 0.5 to about 2.4, y is about 0.6 to about 3, z is about 2 to about 9, preferably w is 1, and x is about 0.5 To 1, y is from about 2 to about 3, and z is from 6 to about 9. The coating of Si _w O _x C _y H _z has further utility as a hydrophobic coating. Coatings of this type are considered hydrophobic irrespective of whether they function as lubricous coatings. The coating or treatment is defined as being "hydrophobic" if the wet tension of the surface is lowered compared to the coated or uncoated surface. Thus, hydrophobicity is a function of both uncoated substrate and processing.

The degree of hydrophobicity of the coating may vary by varying its composition, properties, or deposition method. For example, a coating of SiOx with little or no hydrocarbon content is more hydrophilic than a coating of Si _w O _x C _y H _z with substituent values as defined herein. Generally speaking, the higher the CH _x (e.g., CH, CH ₂ or CH ₃ ) moiety content of the coating, by weight, volume or molar ratio relative to the silicon content, the higher the hydrophobicity of the coating.

At least 4 nm, or at least 7 nm, or at least 10 nm, alternatively at least 20 nm, alternatively at least 30 nm, alternatively at least 40 nm, alternatively at least 50 nm, alternatively at least 100 nm, alternatively at least 150 nm, alternatively at least 200 nm, A hydrophobic coating having a thickness of at least 300 nm, or at least 400 nm, or at least 500 nm, or at least 600 nm, or at least 700 nm, or at least 800 nm, or at least 900 nm, may be very thin. The coating may be at most 1000 nm, or about 900 nm, or about 800 nm, or about 700 nm, or about 600 nm, or about 500 nm, or about 400 nm, or about 300 nm, or about 200 nm, Or about 90 nm or at least about 80 nm or about 70 nm or about 60 nm or about 50 nm or about 40 nm or about 30 nm or about 20 nm or about 10 nm or about 5 nm Or more. In addition to the specific thickness range consisting of any of the minimum thicknesses indicated above, one or more of the maximum thicknesses indicated above is explicitly contemplated.

VII.A.1.a. One of the possibilities for such a hydrophobic coating is to separate the thermoplastic tube wall made of, for example, polyethylene terephthalate (PET) from the blood collected in the tube. The hydrophobic coating can be applied to the top of the hydrophilic SiO _x coating on the inner surface of the tube. The SiO _x coating improves the barrier properties of the thermoplastic tube and the hydrophobic coating changes the surface energy of the tube tube and the blood contacting surface. The hydrophobic coating can be made by providing a precursor selected from the precursors identified herein. For example, the hydrophobic coating precursor may comprise hexamethyldisiloxane (HMDSO) or octamethylcyclotetrasiloxane (OMCTS).

VII.A.1.a. Another use for hydrophobic coatings is to manufacture glass cell manufacturing tubes. The tube has a wall defining the lumen, a hydrophobic coating on the inner surface of the glass wall, and a citrate reagent. Hydrophobic coatings can be made by providing precursors selected from precursors identified elsewhere herein. In another example, the hydrophobic coating precursor may comprise hexamethyldisiloxane (HMDSO) or octamethylcyclotetrasiloxane (OMCTS). Other source materials for hydrophobic coatings are those wherein R is a hydrogen atom or an organic substituent such as, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t- butyl, vinyl, alkane,

R-Si (OCH _{3) 3}

Of alkyltrimethoxysilane. Also, combinations of two or more of these are contemplated.

VII.A.1.a. The use of the alkyltrimethoxysilane precursors described above, in combination with acid or base catalysis and heating, allows the precursor to be condensed (by removing ROH by-products) and optionally cross-linked Polymers can be formed. A concrete example is Shimojima et. al. J. Mater. Chem., 2007, 17, 658-663.

VII.A.1.a. The coating of Si _w O _x C _y H _z is particularly advantageous if the surface coating is a liquid organosiloxane compound at the end of the coating process and an SiO _x barrier coating is applied to the inner surface 88 of the vessel 80 to provide a lubricating surface Can be applied as a subsequent coating after application.

VII.A.1.a. Optionally, after the coating of Si _w O _x C _y H _z is applied, it may be post-cured after the PECVD process. Heat as described in the development of novel cycloaliphatic siloxanes for UV-initiated (free radicals or cations), electron-beam (E-beams) and thermal and UV-curable applications (Ruby Chakraborty paper, cans 2008) Radiation curing approaches may be used.

VII.A.1.a. Another approach to providing a lubricous coating is to use a silicone demolding agent when injection molding a lubricated thermoplastic container. For example, it is contemplated that any of the above-described mold release agents and latent monomers that cause in-situ thermal lubricant coating formation during the molding process can be used. Alternatively, the monomers described above can be doped with conventional mold release agents to achieve the same result.

VII.A.1.a. In particular, a lubricative coating is contemplated for the inner surface of the syringe barrel, as described further below. The lubrication inner surface of the syringe barrel may be used to push plunger activity required to advance the plunger in the barrel during operation of the syringe, or lubricant containing the pre-filled syringe plunger, or to dislodge the lubricant between the plunger and the barrel , It is possible to reduce the breakout force required to move the plunger after it is attached to the barrel. As described elsewhere herein, w is 1, where 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, Si _w O _x C _y H _z May also be applied to the inner surface 88 of the vessel 80 to improve adhesion of the subsequent coating of SiO _x .

VII.A.1.a. Thus, the coating 90 is a layer of SiO _x and w is 1, wherein x is about 0.5 to 2.4, y is about 0.6 to about 3, z is about 2 to about 9, 1, and, x is from about 0.5 to 1, y is from about 2 to about 3, z may comprise a layer of 6 to about 9, _{Si w O x C y H z} . A layer of Si _w O _x C _y H _z may be deposited between the layer of SiO _x and the inner surface of the vessel. A layer of SiO _x may also be deposited between the layer of Si _w O _x C _y H _z and the interior surface of the vessel. Also, three or more layers alternating or progressive between the two coating compositions may be used. The layer of SiO _x may be deposited adjacent or at a distance from a layer of Si _w O _x C _y H _z , with at least one intervening layer of another material. A layer of SiO _x may be deposited adjacent the inner surface of the vessel. Also, a layer of Si _w O _x C _y H _z may be deposited adjacent the inner surface of the vessel.

VII.A.1.a. For adjacent layers of SiO _x and Si _w O _x C _y H _z , another means contemplated herein is that w is 1, where x is about 0.5 to 2.4, y is about 0.6 to about 3, and z from 2 to about 9, preferably w is 1, x is from about 0.5 to 1, y is from about 2 to about 3, z is from 6 to about 9, Si _w O _x C _y H _z for SiO _x Of inclined function composite. The gradient functional composite is a separate layer of Si _w O _x C _y H _z and SiO _x with transition or interface of intermediate composition between the separate layers of Si _w O _x C _y H _z and SiO _x , Continuously or stepwise change from a composition of Si _w O _x C _y H _{z to} a composition more similar to SiO _x , while experiencing separate layers of SiwO _x C _y H 2 and SiO _x having an intermediate layer of intermediate composition or coating in a normal direction Lt; / RTI >

VII.A.1.a. The gradient in the gradient complex can go in either direction. For example, the composition Si _w O _x C _y H _z may be applied directly to the substrate and gradually change from the composition to the surface of SiO _x . Alternatively, the composition of SiO _x may be applied directly to the substrate and gradually change to a composition from the surface of Si _w O _x C _y H _z . A coating of one composition is more likely to adhere to the coating than others, and a gradient coating is particularly contemplated if a better-adhering composition is applied, for example, directly to the substrate. The more distant portions of the gradient coating may be less compatible with the substrate than the adjacent portions of the gradient coating because at any point the coating gradually changes in properties such that adjacent points at nearly the same depth of the coating have substantially the same composition It is contemplated that physically wider portions at substantially different depths may have more diverse properties. In addition, a coating portion that forms a better barrier layer against or against material transfer may also be used to prevent further coating portions that form a lower quality barrier layer from being contaminated with materials that are repelled or otherwise obstructed by the barrier layer It is contemplated that it can be directly opposed to the substrate.

VII.A.1.a. Instead of being graded, the coating may optionally have an abrupt transition between one layer and the next, without a substantial draft of the composition. Such coatings can be prepared, for example, by providing gases that produce a layer in a non-plasma state to a steady state flow, and then powering the system with a short plasma discharge to form a coating on the substrate. If a subsequent coating is to be applied, the gases for the previous coating are removed with little or no gradual transition at the interface, and the gases for the next coating activate the plasma and again deposit the other layer on the surface of the substrate or its outermost coating Lt; / RTI > before being formed.

VII.A.1.b. Another embodiment is a cell manufacturing tube containing a water soluble sodium citrate reagent having a wall provided with a hydrophobic coating on the inner surface. In addition, the hydrophobic coating can be applied to the top of the hydrophilic SiO _x coating on the inner surface of the tube. The SiO _x coating improves the barrier properties of the thermoplastic tube and the hydrophobic coating changes the surface energy of the tube tube and the blood contacting surface.

VII.A.1.b. The wall is made of a thermoplastic material having an inner surface defining a lumen.

VII.A.1.b. The blood collecting tube according to example VII.A.1.b is an inner tube of the tube which acts as an oxygen barrier and extends as described herein and which extends the life of a vacuum blood collection tube made of a thermoplastic material And may have a first layer of SiO _{x on} the surface. w is 1, wherein x is about 0.5 to 2.4, y is about 0.6 to about 3, and z is about 2 to about 9, preferably w is 1, x is about 0.5 to 1, y is from about 2 to about 3, z is from 6 to about 9 of the second layer of Si _w O _x C _y H _z may provide a hydrophobic surface film is applied to blocks on the inner surface of the tube. The coating is effective to reduce platelet activation of plasma treated with sodium citrate additive and exposed to the inner surface, compared to uncoated walls of the same type.

VII.A.1.b. PECVD is used to form coatings on internal surfaces with the following structure: Si _w O _x C _y H _z . Unlike conventional citrate blood collection tubes, a blood collection tube having a hydrophobic layer of Si _w O _x C _y H _z can be applied conventionally and baked onto the silicon on the vessel wall, such as making the surface of the tube hydrophobic Lt; / RTI > coating is not required.

VII.A.1.b. For example, both layers can be applied using the same precursor, such as HMDSO or OMCTS, and different PECVD reaction conditions.

VII.A.1.b. A sodium citrate anticoagulation reagent is then provided in the tube, vacuumed and sealed with a closure to create a vacuum blood collection tube. The components and preparation of the reagents are well known to those skilled in the art. The aqueous sodium citrate reagent is provided to the lumen of the tube in an amount effective to inhibit the coagulation of blood introduced into the tube.

VII.A.1.c. Another embodiment is a container having a wall that at least partially surrounds the lumen. The wall has an inner polymer layer surrounded by an outer polymer layer. One of the polymer layers is a layer that is at least 0.1 mm thick of a cyclic olefin copolymer (COC) resin that defines a water vapor barrier. One of the polymer layers is a layer that is at least 0.1 mm thick of the polyester resin.

VII.A.1.c. The wall comprises an oxygen barrier of SiO _x having a thickness of from about 10 to about 500 angstroms.

VII.A.1.c. 36, the container 80 may be a double walled container having an inner wall 408 and an outer wall 410, respectively, made of the same or different materials. One particular embodiment of this type comprises a single wall molded from a cyclic olefin copolymer (COC), such as polyethylene terephthalate (PET), having a SiO _x coating as described above for the inner surface 412 And can be made from other walls molded from polyester. If desired, tie coatings or layers may be inserted between the inner and outer walls to facilitate adhesion therebetween. The advantage of this wall structure is that walls with different properties can combine to form a composite with individual properties of each wall.

VII.A.1.c. As an example, the inner wall 408 may be made of PET coated on the inner surface 412 with a SiO _x barrier, and the outer wall 410 may be made of COC. As shown elsewhere herein, SiO _x coated PET is an excellent oxygen barrier, while COC provides a low water vapor transmission rate (WVTR) as an excellent barrier to water vapor. Such a composite vessel may have excellent barrier properties for both oxygen and water vapor. This structure is contemplated, for example, for a vacuumed medical sample collection tube containing a water-soluble reagent as made and having a substantial lifetime, so that during the life of the tube, And to prevent oxygen or other gases from being transferred to the interior.

VII.A.1.c. In another example, the inner wall 408 may be made of COC coated on the inner surface 412 with an SiO _x barrier, and the outer wall 410 may be made of PET. This structure is contemplated, for example, with pre-filled syringes containing a water-soluble sterile fluid as made. The SiO _x barrier will prevent oxygen from entering the syringe through the wall. The COC inner wall prevents entry or outflow of other materials such as water to prevent water in the aqueous sterile fluid from filtering materials from the wall material into the syringe. The COC inner wall is also contemplated to prevent water drawn from the aqueous sterile fluid from passing out of the syringe (undesirably concentrating the aqueous sterile fluid), and the sterilized water or other fluid outside the syringe Into the syringe and prevent the contents from being sterilized. It is also contemplated that the COC inner wall is useful for reducing the braking force or friction of the plunger against the inner wall of the syringe.

VII.A.1.d. Another embodiment is a method of making a container having a wall having an inner polymer layer surrounded by an outer polymer layer, one layer made of COC and another layer made of polyester. The container is fabricated by a process comprising introducing COC and polyester resin layers into the injection mold through concentric injection nozzles.

VII.A.1.d. Another optional step is to apply an amorphous carbon coating to the vessel by PECVD with an inner coating and an outer coating or an interlayer coating located between the coatings.

VII.A.1.d. An optional additional step is to define the SiO _x as before and to apply the SiO _x barrier to the interior of the vessel wall. Another optional additional step is the step of post-treating the SiO _x film with a process gas essentially consisting of oxygen and essentially free of volatile silicone compounds.

VII.A.1.d. Optionally, the SiO _x coating may be at least partially formed from a silazane feed gas.

VII.A.1.d. The container 80 shown in Fig. 36 may be formed, for example, by injection molding an inner wall in a first molding cavity and then moving a central and molded inner wall from the first molding cavity to a second, By molding the outer wall against the inner wall in the second forming cavity. Alternatively, a tie layer may be provided on the outer surface of the inner wall formed prior to over-molding the outer wall on the tie layer.

VII.A.1.d. The container 80 shown in Fig. 36 can be formed by, for example, inserting a first core into a molding cavity, injection-molding an outer wall in the molding cavity, And after inserting the smaller second center, it can be made inward by in-mold molding of the inner wall against the outer wall still remaining in the molding cavity. Optionally, a tie layer may be provided on the inner surface of the outer wall molded prior to over-molding the inner wall on the tie layer.

VII.A.1.d. The container 80 shown in Fig. 36 can be made of two shot molds. This can be done, for example, by injection molding the material for the inner wall from the inner nozzle and the material for the outer wall from a concentric outer nozzle. Optionally, a tie layer may be provided from a third concentric nozzle disposed between the inner and the lower nozzles. The nozzles may simultaneously supply respective wall materials. One useful means is to begin to supply the outer wall material through the outer nozzle just prior to feeding the inner wall material through the inner nozzle. If there is an intermediate concentric nozzle, the flow sequence can begin with the outer nozzle, continue with the intermediate nozzle, and then start with the inner nozzle. In addition, the supply start order can be worked outward from the inner nozzle, in the reverse order as compared with the preceding description.

VII.A.1.e. Barrier coating made of glass

VII.A.1.e. Another embodiment is a container comprising a container, a barrier coating and a closure. The container is generally tubular and made of a thermoplastic material. The container has a lumen that is at least partially bounded by a wall having an inlet and an interior surface that interfaces with the lumen. There is at least one essentially continuous barrier coating made of glass on the inner surface of the wall. A closure covers the inlet and separates the lumen of the vessel from ambient air.

VII.A.1.e. In addition, the container 80 may be made of any type of glass used in medical or laboratory applications, such as soda lime glass, borosilicate glass or other glass formulations. It is also contemplated that other vessels of any shape or size, made of any material, may be used in the system 20. One function of coating the glass container is to reduce the influx of ions into the glass as a deliberate or impurity such as, for example, sodium, calcium, etc., from the glass into the contents of a container such as a reagent or blood in a vacuum blood collection tube I do not know. Other functions of coating all or part of the glass container, such as on sliding contact surfaces with other parts, may provide lubricity to the coating, such as the insertion or removal of a stopper, or the removal of a sliding component, such as a piston, Facilitates traffic. Another reason for coating the glass container is to prevent the intended sample for the container from sticking to the wall of the container or increasing the rate of solidification of the blood in contact with the wall of the container, such as a reagent or blood.

VII.A.1.e.i. One related embodiment is the container described in the preceding paragraph, wherein said barrier coating is made of soda lime glass or borosilicate glass or other type of glass.

VII.A.2. Stoppers

VII.A.2. 23-25 illustrate a container 268, which may be a vacuum blood collection tube, with a closure 270 separating the lumen 274 from the environment. The closure 270 includes an inner-facing surface 272 exposed to the lumen 274 of the vessel 268 and a wall-contacting surface 276 contacting the inner surface 278 of the vessel wall 280 . In the illustrated embodiment, the closure 270 is an assembly of a stopper 282 and a shield 284.

VII.A.2.a. Another embodiment is a method of applying a coating on an elastic stopper, such as 282. The stopper 282 separated from the vessel 268 is located in a substantially vacuum chamber. A reaction mixture comprising a plasma forming gas, such as an organosilicon compound gas, optionally an oxidizing gas and optionally a hydrocarbon gas, is provided. A plasma is formed in the reaction mixture in contact with the stopper. w is 1, wherein x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, z is from 2 to about 9, preferably w is 1, x is from about 0.5 to 1, y is from about 2 to about 3, z is from about 6 to 9 in the coating of Si _w O _x C _y H _z, is deposited on at least a portion of the stopper.

VII.A.2.a. In the illustrated embodiment, the wall-contacting surface 276 of the closure 270 is coated with a lubricous coating 286.

VII.A.2.a. In some embodiments, the coating of Si _w O _x C _y H _z is effective to reduce the permeation of one or more components of the vessel wall to the vessel lumen, or to the metal ion component of the stopper. Certain elastic compositions of the type useful for making the stopper 282 comprise a trace amount of one or more metal ions. These ions sometimes must not move into the lumen 274 or contact the vessel contents in substantial amounts, especially if the sample vessel 268 is used to collect samples for trace metal analysis. Coatings that contain a relatively insignificant organic content, y and z being low or zero, are considered to be particularly useful herein as metal ion barrier films. Anupama Mallikarjunan, Jasbir Juneja, Guangrong Yang, Shyam P. Murarka, and Toh-Ming Lu, all of which are hereby incorporated by reference in their entirety for silica as a metal ion barrier membrane, The Effect of Interfacial Chemistry on Metal Ion Penetration into Polymeric Films, Mat. Res. Soc. Symp. Proc., Vol. 734, pp. B9.60.1 to B9.60.6 (Materials Research Society, 2003); See U.S. Patent Nos. 5578103 and 6200658 and European Patent Application EP0697378A2. However, it is contemplated that some organic content may be useful in providing a more elastic coating and attaching the coating to the resilient surface of the stopper 282.

VII.A.2.a. In some embodiments, the coating of Si _w O _x C _y H _z is such that the first layer or inner layer 288 interferes with the elastomeric stopper 282, and one or more components of the stopper 282 Lt; RTI ID = 0.0 > and / or < / RTI > The second layer 286 may interfere with the inner wall 280 of the container and may be positioned between the stopper 282 and the container 282 when the stopper 282 is seated on or within the container 268. [ It is effective to reduce the friction between the inner walls 280. Such composites are described elsewhere herein in connection with syringe coatings.

VII.A.2.a. Also, the first and second layers 288 and 286 are defined by a coating of enriched properties, wherein the values of y and z are greater in the first layer than in the second layer.

VII.A.2.a. The coating of Si _w O _x C _y H _z can be applied, for example, substantially by PECVD as described above. The coating of Si _w O _x C _y H _z may for example be a thickness of 0.5 to 5000 nm (5 to 50,000 angstroms), or a thickness of 1 to 5000 nm, or a thickness of 5 to 5000 nm, or 10 to 5000 nm, Or from 50 to 5000 nm thick, or from 100 to 5000 nm thick, or from 200 to 5000 nm thick, or from 500 to 5000 nm thick, or from 1000 to 5000 nm thick, or from 2000 to 5000 nm thick, 5000 nm thick, or 4000 to 10,000 nm thick.

VII.A.2.a. Certain advantages over much thicker (over one micron) conventional spray applied silicone lubricants versus plasma applied lubricous layers are contemplated. Plasma coatings have a lower migration potential in moving into the blood than in sprayed or micron-coated silicones, because the amount of plasma-coated material is much less, which is more closely applied to the coated surface, Because they can be combined well.

VII.A.2.a. As applied by PECVD, nanocoatings are considered to provide a lower resistance to sliding of adjacent surfaces or to the flow of adjacent fluids than to micron coatings because the plasma coating tends to provide a smoother surface.

VII.A.2.a. Another embodiment is a method of applying a coating of Si _w O _x C _y H _z on an elastic stopper. The stopper may, for example, be used to close the container described above. The method includes some steps. The stopper is provided in a substantially vacuum chamber. A reaction mixture comprising a plasma forming gas, such as an organosilicon compound gas, optionally an oxidizing gas and optionally a hydrocarbon gas, is provided. A plasma is formed in the reaction mixture. The stopper is brought into contact with the reaction mixture and deposits a coating of Si _w O _x C _y H _z on at least a portion of the stopper.

VII.A.2.a. In carrying out this method, it is contemplated that to obtain a greater number of y and z, the reaction mixture may comprise hydrocarbon gas, as described above and below. Optionally, if lower values of y and z or higher values of x are considered, the reaction mixture may contain oxygen. Also, in particular, in order to reduce oxidation and increase the values of y and z, the reaction mixture may be essentially free of oxidizing gas.

VII.A.2.a. In implementing the method of coating certain embodiments of the stopper, such as the stopper 282, it is considered unnecessary to project the reaction mixture onto the depressed portions of the stopper. For example, the wall-contacting and inner opposing surfaces 276 and 272 of the stopper 282 can be basically convex to locate a plurality of stoppers, such as 282, in a single substantially vacuum reaction chamber, Lt; / RTI > Also, in some embodiments, the coatings 286 and 288 may be coated on the inner surface 280 of the container 268 with oxygen or water as a barrier coating, since the material of the stopper 282 can perform this function significantly. It is not necessary to suggest that the barrier is strong.

VII.A.2.a. Many variations of the stopper and stopper coating processes are contemplated. The stopper 282 may be in contact with the plasma. In addition, a plasma is formed upstream of the stopper 282 to produce a plasma product, which may contact the stopper 282. The plasma may be formed by exciting the reaction mixture with electromagnetic energy and / or microwave energy.

VII.A.2.a. Changes in the reaction mixture are discussed. The plasma forming gas may comprise an inert gas. The inert gas may be, for example, argon or helium, or other gases described in this disclosure. The organosilicon compound gas can be, or may comprise, any one of HMDSO, OMCTS, other organosilicon compounds mentioned in this disclosure, or a combination of two or more of these. The oxidizing gas may be oxygen or other gases mentioned in this disclosure or a combination of two or more of them. The hydrocarbon gas may be, for example, methane, methanol, ethane, ethylene, ethanol, propane, propylene, propanol, acetylene or a combination of two or more thereof.

VII.A.2.b. Another embodiment is a method of applying a coating of a composition comprising carbon and one or more elements of group III or IV on an elastic stopper. To perform the method, the stopper is located in a vacuum chamber.

VII.A.2.b. A reaction mixture comprising a plasma-forming gas having a gas source of a Group III element, a Group IV element or a combination of at least two of the foregoing is provided in the deposition chamber. Optionally, the reaction mixture comprises an oxidizing gas and optionally a gaseous compound having at least one C-H bond. A plasma is formed in the mixture, and the stopper contacts the reaction mixture. A coating of a Group III element or compound, a Group IV element or compound, or a combination of at least two of the foregoing, is deposited on at least a portion of the stopper.

VII.A.3. Another embodiment is a container comprising a container, a barrier coating and a closure. The container is generally tubular and made of a thermoplastic material. The container has an inlet and a lumen at least partially bounded by the wall. The wall has an inner surface that interfaces with the lumen. At least one essentially continuous barrier coating is applied on the inner surface of the wall. The barrier coating is effective in providing a substantial lifetime. A closure is provided for covering the inlet of the container and separating the lumen of the container from ambient air.

VII.A.3. Referring to Figures 23-25, a container 268, such as a vacuum blood collection tube or other container, is shown.

VII.A.3. In this embodiment, the container is a generally tubular container having at least one essentially continuous barrier coating and a closure. The container has a lumen at least partially bounded by a wall having an inlet and an interior surface that interfaces with the lumen. The barrier coating is deposited on the inner surface of the wall and comprises at least 95%, or at least 90%, of the initial vacuum level of the vessel during a storage life of at least 24 months, alternatively at least 30 months, It is effective to maintain. The closure covers the mouth of the container and separates the lumen of the container from the ambient air.

VII.A.3. Closures, such as closure 270 or other types of closure as shown in the figures, are provided to maintain and / or contain a partial vacuum and to limit or prevent exposure of the sample to oxygen or contaminants. 23-25 are based on the drawings in U.S. Patent No. 6,602,206, but the discovery is not limited to it or any other particular type of closure.

VII.A.3. The closure 270 includes an inner-facing surface 272 exposed to the lumen 274 of the vessel 268 and a wall-contacting surface 276 contacting the inner surface 278 of the vessel wall 280 . In the illustrated embodiment, the closure 270 is an assembly of a stopper 282 and a shield 284.

VII.A.3. In the illustrated embodiment, the stopper 282 defines a wall-contacting surface 276 and an interior surface 278, whereas when the container 268 is open and air comes in and out to equalize pressure differences The shield is generally or wholly outside of the stoppered container 268 and maintains and provides grips against the stopper 282 due to the pressure differentials inside and outside the container 268, So that the removing member is not exposed to any of the contents discharged from the container 268.

VII.A.3. It is also contemplated that the coatings on the container wall 280 and the wall contact surface 276 of the stopper can be adjusted. The stopper may be coated with a lubricous silicone layer, for example a PET or glass container wall 280 may be coated with a harder SiO _x layer or bottommost SiO _x layer and a lubricous overcoat.

VII.B. Syringes

VII.B. The foregoing discussion generally addresses the step of applying a barrier coating to a tube that is permanently closed at one end, such as a blood collection tube or more generally a sample receiving tube 80. The device is not limited to such an apparatus.

VII.B. Another example of a suitable container, shown in FIGS. 20-22, is a syringe barrel 250 for a medical syringe 252. Such syringes 252 are occasionally pre-filled with saline, pharmaceutical preparations, etc. for use in medical technology. Pre-filled syringes 252 may also be positioned on the inner surface (not shown) to prevent the contents of the pre-filled syringe 252 from contacting the plastics of the syringe, e. G., The plastics of the syringe barrel 250 during storage 254) < / RTI _> or other types of coatings. Blocking or other types of coatings can be used to avoid the discolouration components of the plastic from discoloring through the inner surface 254 into the contents of the barrel.

VII.B. The generally shaped syringe barrel 250 includes a trailing end 256 that receives the plunger 258 and a shear that accepts the tubing for the purpose of dispensing the contents of the subcutaneous injection, nozzle or syringe, or receiving the substance into the syringe 252 260, respectively. However, the front end 260 may be selectively capped and the plunger 258 may optionally be in place prior to the use of the pre-filled syringe 252 to close the barrel 250 at both ends have. The cap is removed from the syringe barrel 250 until the cap 262 is removed and (optionally) a hypodermic injection or other delivery channel is placed on the front end 260 to produce the syringe 252 for use, Or to hold an assembled syringe for processing purposes or during storage of a pre-filled syringe 252.

VII.B.1. Assemblies

VII.B.1. 42 can be used, for example, with the embodiments of FIGS. 2, 3, 6-10, 12-22, 26-28, 33-34, and 37-41, And other syringe barrel constructions suitable for use with.

VII.B.1. Figure 50 is an exploded view and Figure 51 is an assembled view of a syringe. The syringe barrel may be treated with the vessel treatment and inspection apparatus of Figs. 1-22, 26-28, 33-35, 37-39, 44, and 53-54.

VII.B.1. The installation of the cap 262 allows the barrel 250 to be a closed vessel in which an SiO _x barrier layer or other type of coating can be provided on the inner surface 254 in the apparatus shown previously, Provides a coating on the interior 264 of the cap and connects the interface between the cap interior 264 and the barrel tip 260. A suitable device adapted for this purpose is, for example, shown in FIG. 21 and is similar to FIG. 2, except that the container 80 in the drawing is replaced by a capped syringe barrel 250. VII.B.

VII.B.1 also. 52 is a view similar to FIG. 42, showing a syringe barrel being processed, without flanges or flanger stops 440. FIG. The syringe barrel may be used with the vessel handling and inspection apparatus of Figs. 1-22, 26-28, 33-35, 37-39, 44, and 53-54.

VII.B.1.a. A syringe having a barrel coated with a lubricous coating coated from an organosilicon precursor

VII.B.1.a. Another embodiment is a vessel having a lubricous coating of Si _w O _x C _y H _z of the type produced by the following process.

VII.B.1.a. A precursor is provided as defined above.

VII.B.1.a. The precursor is applied to the substrate under conditions effective to form the coating. The coating is polymerized, cross-linked, or both to form a lubricating surface with lower plunger force or breakout force than the untreated substrate.

VII.B.1.a. For any one of the embodiments VII or sub-parts of the embodiments, optionally an application step is performed by evaporating the precursor and providing it near the substrate.

VII.B.1.a. Any of the above embodiments VII.A.1.a.i, optionally a plasma, alternatively a non-hollow-cathode plasma, is formed in the vicinity of the substrate. Optionally, the precursor is provided in the substantial absence of oxygen. Optionally, the precursor is provided with carrier gas substantially absent. Optionally, the precursor is provided in the substantial absence of nitrogen. Optionally, the precursor is provided at an absolute pressure of less than 1 Torr. Optionally, the precursor is optionally provided in the vicinity of the plasma emission. Optionally, the reaction product of the precursor is applied to the substrate in a thickness of 1 to 5000 nm, or 10 to 1000 nm, or 10 to 200 nm, or 20 to 100 nm thick. Optionally, the substrate comprises glass. Optionally, the substrate is a polymer, optionally a polycarbonate polymer, optionally an olefin polymer, optionally a cyclic olefin copolymer, optionally a polypropylene polymer, optionally a polyester polymer, optionally a polyethylene terephthalate Polymer.

Alternatively, the plasma may be, for example, an RF frequency as defined above, e.g., 10 kHz to less than 300 MHz, more preferably 1 to 50 MHz, even more preferably 10 to 15 MHz, Is generated by applying power to a gas reactant comprising the precursor using electrodes powered at a frequency of 13.56 MHz.

Alternatively, the plasma may be applied to the substrate at a temperature of from 0.1 to 25 W, preferably from 1 to 22 W, more preferably from 3 to 17 W, even more preferably from 5 to 14 W, most preferably from 7 to 11 W, Lt; RTI ID = 0.0 > W < / RTI > The ratio of power to plasma volume may be 10 W / ml, preferably 5 W / ml to 0.1 W / ml, more preferably 4 W / ml to 0.1 W / ml, and most preferably 2 W / ml to 0.2 W / ml. These power levels are suitable for applying lubricating coatings to similarly shaped syringes and sample tubes and vessels with a void volume of 1-3 mL where a PECVD plasma is produced. It is believed that the applied power for larger or smaller objects will increase or decrease as the process is scaled relative to the size of the substrate.

VII.B.1.a Another embodiment is a lubricous coating on the inner wall of a syringe barrel. The coating is produced from a PECVD process using the following materials and conditions. As defined herein for lubricous coatings, cyclic precursors selected from monocyclic siloxanes, polycyclic siloxanes, or a combination of two or more thereof are preferably employed. An example of a suitable cyclic precursor optionally comprises octamethylcyclotetrasiloxane (OMCTS) mixed in any ratio with other precursor materials. Alternatively, the cyclic precursor is essentially composed of octamethylcyclotetrasiloxane (OMCTS), which is the basic and novel characteristic of the resulting lubricating coating, i.e., the plunging force or breakout force of the coated surface Such as a reduction in the amount of water, can be present in unchanged amounts.

VII.B.1.a At least essentially no oxygen is added to the process. The remaining atmospheric oxygen may be present in the syringe barrel, and may be present in the syringe barrel where the remaining oxygen fed in the previous step and not completely consumed is defined herein as essentially free of oxygen. If no oxygen is added to the process, it is also within the range of "essentially oxygen free ".

VII.B.1.a Sufficient plasma generating power input, for example, any power level successfully used or described herein in one or more working examples of the present disclosure, is provided for inducing coating formation to form a coating .

VII.B.1.a The materials and conditions employed herein include at least about 25%, or at least about 45%, or at least about 60%, or at least about 60% %, Or 60% or more. A plunger force or brake force reduction range of 20 to 95 percent, or 30 to 80 percent, or 40 to 75 percent, or 60 to 70 percent, is contemplated.

VII.B.1.a. Another embodiment is a container having a hydrophobic coating on the inner wall having the following structure: w, x, y and z are defined as Si _w O _x C _y H _z . The coating is prepared as described for a similar composition of lubricant coating, but is produced under conditions effective to form a hydrophobic surface having a higher contact angle than the untreated substrate.

VII.B.1.a. For any of the above embodiments VII.A.1.a.ii, optionally the substrate comprises glass or polymer. Optionally, the glass is a borosilicate glass. The polymer is optionally a polycarbonate polymer, optionally an olefin polymer, alternatively a cyclic olefin copolymer, optionally a polypropylene polymer, optionally a polyester polymer, optionally a polyethylene terephthalate polymer.

VII.B.1.a. Another embodiment is a syringe comprising a plunger, a syringe barrel, and a lubricity layer. The syringe barrel has an inner surface for slidably receiving the plunger. The lubricating layer is provided on the inner surface of the syringe barrel and comprises a coating of a Si _w O _x C _y H _z lubricating layer. The lubricity layer is less than 1000 nm thick and is effective to reduce the breakout force or plunger force required to move the plunger within the barrel. Also, a reduction in plunger force is expressed as a decrease in plunger drag coefficient or a decrease in plunger force within the barrel; These terms are considered to have the same meaning herein.

VII.B.1.a. The syringe 544 of Figures 50-51 includes a plunger 546 and a syringe barrel 548. The syringe barrel 548 has an inner surface 552 that receives the plunger 546 in a slidable manner. The inner surface 552 of the syringe barrel 548 also includes a lubricant coating 554 coating of Si _w O _x C _y H _z . The lubricating layer is less than 1000 nm thick, alternatively less than 500 nm thick, alternatively less than 200 nm thick, alternatively less than 100 nm thick, alternatively less than 50 nm thick, overcoming adhesion of the plunger after storage Or to reduce the plunger force required to move the plunger within the barrel after the plunger is released. The lubricous coating is characterized as having a plunging force or breakout force on the uncoated surface.

VII.B.1.a. Any of the types of precursors may be used alone or in combination of two or more thereof to provide a lubricous coating.

VII.B.1.a. In addition to utilizing vacuum processes, a low temperature atmospheric (non-vacuum) plasma process can also be utilized to induce molecular ionization and deposition through precursor monomer vapor delivery, preferably in a non-oxidizing atmosphere such as helium or argon. Thermal CVD may also be considered to be accomplished through flash pyrolytic deposition.

VII.B.1.a. These approaches are similar to vacuum PECVD in that surface coating and cross-linking mechanisms can occur simultaneously.

VII.B.1.a. Another means contemplated for any of the coatings or coatings described herein is a coating that is not uniformly applied over the entire interior 88 of the container. For example, as compared to the semicircular portion of the interior of the container at the closed end 84, different or different coatings may be selectively applied to the cylindrical portion of the interior of the container, or vice versa. This means is particularly contemplated with respect to the syringe barrel or sample collection tube described below in which a lubricating surface is provided on a plunger piston or a part or all of the cylindrical portion of the barrel to which the closure glides and not provided elsewhere.

VII.B.1.a. Optionally, the precursor may be provided in the presence, substantially or absent of oxygen, in the presence, substantially in the presence or absence of nitrogen, or in the presence, substantially present or absence of a carrier gas. In one embodiment contemplated, the precursor is transferred to the substrate as a hole, and the coating is applied and cured via PECVD.

VII.B.1.a. Optionally, the precursor may be provided at an absolute pressure of less than 1 Torr.

VII.B.1.a. Optionally, the precursor may be provided in the vicinity of the plasma emission.

VII.B.1.a. Optionally, the reaction product of the precursor may be applied to the substrate in a thickness of 1 to 5000 nm, or 10 to 1000 nm, or 10 to 200 nm, or 20 to 100 nm.

VII.B.1.a. In any of the embodiments, the substrate is a glass or polymer, such as a polycarbonate polymer, an olefin polymer (e.g., a cyclic olefin copolymer or a polypropylene polymer), or a polyester polymer (e.g., Polyethylene terephthalate polymers).

VII.B.1.a. In any of the above embodiments, the plasma is generated by applying power to the gas reactant containing the precursor using electrodes powered at the RF frequency, as defined herein.

VII.B.1.a. In any of the above embodiments, the plasma is generated by applying power to the gaseous reactant containing the precursor using electrodes supplied with sufficient power to produce a lubricous coating. Alternatively, the plasma may be applied to the substrate at a temperature of from 0.1 to 25 W, preferably from 1 to 22 W, more preferably from 3 to 17 W, even more preferably from 5 to 14 W, most preferably from 7 to 11 W, Lt; RTI ID = 0.0 > W < / RTI > The ratio of power to plasma volume may be 10 W / ml, preferably 5 W / ml to 0.1 W / ml, more preferably 4 W / ml to 0.1 W / ml, and most preferably 2 W / ml to 0.2 W / ml. These power levels are suitable for applying lubricating coatings to similarly shaped syringes and sample tubes and vessels with a void volume of 1-3 mL where a PECVD plasma is produced. It is believed that the applied power for larger or smaller objects will increase or decrease as the process is scaled relative to the size of the substrate.

VII.B.1.a. The coating may cure by polymerizing, cross-linking, or both performing the coating to form a lubricating surface with lower plunger force or breakout force than the untreated substrate. Curing may occur during the application process, such as PECVD, or may be performed or at least accomplished by other processes.

VII.B.1.a. Other deposition methods can be used so long as the chemical composition of the starting material is maximally preserved during the still desorption of the solid film attached to the base substrate, although plasma deposition is used herein to show coating characteristics.

VII.B.1.a. For example, the coating material can be applied onto the syringe barrel (from the liquid state) by spraying the coating or by immersing the substrate in a coating that is either a pure precursor or a solvent-diluted precursor (enabling mechanical deposition of a thinner coating) . Preferably, the coating can be cross-linked using thermal energy, UV energy, electron beam energy, plasma energy, or any combination thereof.

VII.B.1.a. It is also contemplated to coat the surface of the silicon precursor as described above and then perform a separate curing process. The application and curing conditions may be similar to those used for atmospheric pressure plasma curing of pre-coated polyfluoroalkyl ethers, a process performed under the TriboGlide® brand. More details on this process can be found at http://www.triboglide.com/process.htm.

VII.B.1.a. In such a process, a portion of the part to be coated may optionally be pre-treated with an atmospheric plasma. This preliminary treatment cleans and activates the surface to be accommodated in the lubricant to be sprayed in the next step.

VII.B.1.a. In the case of any of the precursors or polymerized precursors, the lubricating fluid is then sprayed onto the surface to be treated. For example, IVEK precision dispensing technology can be used to accurately spray fluids and create uniform coatings.

VII.B.1.a. The coating is then again bonded or cross-linked to the component using an atmospheric plasma chamber. All of these fix the coating and improve the performance of the lubricant.

VII.B.1.a. Alternatively, the atmospheric plasma may be generated from ambient air in the vessel, in which case gas supply and vacuum evacuation equipment are not required. Preferably, however, the vessel is at least substantially closed during plasma generation to minimize power requirements and prevent contact of the plasma with the surface or material outside the vessel.

VII.B.1.a.i. Lubricous coating: SiO _x Blocking, lubricating layer, surface treatment.

Surface treatment

VII.B.1.a.i. Another embodiment is a syringe with an inner surface that includes a barrel defining a lumen and receives the plunger in a slidable manner, i.e., receives the plunger in sliding contact with the inner surface.

VII.B.1.a.i. The syringe barrel may be made of a thermoplastic material.

VII.B.1.ai Optionally, the inner surface of the barrel is coated with a SiO _x barrier, as described elsewhere herein.

VII.B.1.ai The lubricous coating is applied to the inner surface of the barrel, the plunger, or both, or to the previously applied SiO _x barrier. The lubricity layer may be provided, applied and cured as described in Example VII.B.1.a or elsewhere herein.

VII.B.1.a.i. For example, the lubricous coating may be applied by PECVD in any embodiment. The lubricous coating is deposited from an organosilicon precursor and is less than 1000 nm thick.

VII.B.1.a.i. The surface treatment is performed on the lubricous coating in an amount effective to filter out or reduce the extractability of the lubricous coating, the thermoplastic series material, or both. Thus, the treated surface can act as a solute retainer. Such a surface treatment may be applied to a skin coating, such as at least 1 nm thickness and less than 100 nm, or less than 50 nm thickness, or less than 40 nm thickness, or less than 30 nm thickness, or less than 20 nm thickness, nm, or less than 3 nm thickness, or less than 2 nm thickness, or less than 1 nm thickness, or less than 0.5 nm thickness.

As used herein, "filtration" refers to a substance that is transferred from a substrate, such as a container wall, into the contents of a container such as, for example, a syringe. Typically, the filtration capabilities are measured by storing the container with the intended contents and then analyzing the contents to determine what material is filtered from the container wall into the intended contents. "Extraction" refers to a substance that is removed from a substrate by introducing a solvent or dispersion medium that is not intended contents of the vessel to determine what material can be removed from the substrate to the extraction medium in the test conditions term.

VII.B.1. The surface treatment to be a solute retainer may optionally be SiO _x or Si _w O _x C _y H _z coating, respectively, as defined hereinbefore. In one embodiment, the surface treatment can be applied by PECVD deposition of SiO _x or Si _w O _x C _y H _z . Alternatively, the surface treatment may be applied using either a higher power source or a stronger oxidizing condition, or both, than that used to create the lubricating layer, to provide a harder, thinner, continuous solute retainer 539 can do. The surface treatment may be carried out in a lubricous coating at a depth less than 100 nm, optionally less than 20 nm depth, optionally less than 10 nm depth, optionally less than 5 nm depth, optionally less than 3 nm depth, optionally less than 1 nm depth , Alternatively less than 0.5 nm depth, alternatively between 0.1 and 50 nm depth.

VII.B.1.ai It is contemplated that the solute retainer, including the substrate, provides a base solubility and low solute filtration performance for the other layers as needed. This retainer can be made from a mixture of large solute molecules and oligomers (e.g., HMDSO, OMCTS, fragments thereof, and siloxane monomers such as mobile phase oligomers derived from lubricants, such as, for example, And need not be a gas (O ₂ / N ₂ / CO ₂ / water vapor) barrier film. However, the solute retainer may also be a gas barrier film (e.g., a SiOx coating according to the present invention). Vacuum or atmospheric pressure-series PECVD processes can produce a good filterable retainer without gas barrier performance. The "filterability barrier" is sufficiently thin that the plunger can easily penetrate the "solute retainer " during syringe plunger movement to expose the sliding plunger nipple beneath the lubricating coating to lower plunger activity or break- Thereby forming a lubricating surface having a lubricating surface.

VII.B.1.ai In another embodiment, the surface treatment may be performed by oxidizing the surface of the previously applied lubricity layer by exposing the surface to oxygen in a plasma environment. Plasma environments that form the SiO _x coating described herein can be used. In addition, atmospheric plasma conditions can be employed in an oxygen-rich environment.

VII.B.1.a.i. The lubricating layer and the solute retainer can optionally be cured simultaneously. In another embodiment, the lubricity layer is at least partially cured, optionally fully cured, and after curing a surface treatment may be provided and applied, and the solute retainer may be cured.

VII.B.1.a.i. The lubricating coating and solute retainer are constructed and present in relative amounts effective to provide both a breakout force, a plunger force, or both forces lower than the corresponding force required in the absence of the lubricating coating and surface treatment. That is, the thickness and composition of the solute retainer reduces the filtration of material from the lubricant layer to the contents of the syringe while the underlying lubricant coating lubricates the plunger. It is contemplated that the solute retainer is easily loosened and thin enough to lubricate the plunger as the lubricant layer still functions when the plunger moves.

VII.B.1.ai In one embodiment contemplated, lubricity and surface treatment may be applied on the inner surface of the barrel. In another embodiment contemplated, lubricating and surface treatment may be applied on the plunger. In another embodiment contemplated, lubrication and surface treatment may be applied on the inner surface of the barrel and on the plunger. In any of these embodiments, a selective SiO _x barrier layer may be present or absent on the interior of the syringe barrel.

VII.B.1.ai One embodiment contemplated is a triple layer which is a construction applied to the inner surface of multiple layers, such as syringe barrels. Layer 1 may be an SiO _x gas barrier layer made by HMDSO, OMCTS or both PECVD at an oxidizing atmospheric pressure. Such an atmosphere may be provided, for example, by supplying HMDSO and oxygen gas to the PECVD coating apparatus described herein. Layer 2 may be a lubricating layer using OMCTS applied in a non-oxidizing atmosphere. Such a non-oxidizing atmosphere may be provided, for example, by supplying HMDSO to the PECVD coating apparatus described herein, optionally with substantially or completely free of oxygen. Subsequent solute retainers may be formed as a solute retainer using higher power and oxygen using OMCTS and / or HMDSO, by treatment to form a thin film of SiO _x or Si _w O _x C _y H _z .

VII.B.1.a.i. It is contemplated that certain such multilayer coatings have at least some of the following optional advantages: The solute retainer can define the inner silicon and prevent the contents of the syringe or moving somewhere so that the silicon particles are less likely to be present in the deliverable contents of the syringe and the interaction between the lubricant coating and the contents of the syringe As opportunities are reduced, they can solve the reported difficulties in dealing with silicon. In addition, they can solve the problem of moving the lubricating layer away from the lubrication point, thereby improving the interface between the syringe barrel and the plunger. For example, the brake-free force can be reduced and the pulling on the moving plunger can be reduced or, alternatively, both reduced.

VII.B.1.a.i. If the solute retainer is broken, the solute retainer may be subsequently attached to the lubricous coating and the syringe barrel to inhibit entrainment of the particles into the deliverable contents of the syringe.

VII.B.1.ai In addition, these specific coatings will provide fabrication advantages, especially if the barrier coating, lubricating coating and surface treatment are applied to the same apparatus, for example the PECVD apparatus shown. Alternatively, both the SiO _x barrier coating, the lubricating coating and the surface treatment can be applied in one PECVD apparatus, which can significantly reduce the required throughput.

Other advantages can be obtained by using the same precursors and varying the process to form barrier coatings, lubricating coatings and solute retainers. For example, the SiO _x gas barrier can be applied using the OMCTS precursor under high power / high O ₂ conditions and then applied using the OMCTS precursor while the low power and / or oxygen are substantially or completely absent The lubricant film can be applied and the surface treatment can be completed using the OMCTS precursor under moderate power and oxygen.

VII.B.1.b. Another embodiment shown in FIG. 50 is a syringe 544 that includes a plunger 546, a barrel 548, and inner and outer barrier coatings 554 and 602. The barrel 548 may be made of a thermoplastic material that defines the lumen 604. The barrel 548 may have an inner surface 552 and an outer surface 606 for slidably receiving the plunger. A barrier coating 554 of SiO _x , where x is about 1.5 to about 2.9, may be provided on the inner surface 552 of the barrel 548. A barrier coating 602 of resin may be provided on the outer surface 606 of the barrel 548.

VII.B.1.b. In certain embodiments, the thermoplastic series material is optionally selected from the group consisting of polyolefins, such as polypropylene or cyclic olefin copolymers (e.g., those sold under the trademarks TOPAS®), polyesters such as polyethylene terephthalate Phthalates, polycarbonates, for example, bisphenol A polycarbonate thermoplastics or other materials. Composite syringe barrels having either one of these materials as the outer layer and the same or different one of these materials as the inner layer are contemplated. In addition, any combination of materials of the composite syringe barrels or sample tubes described elsewhere herein can be used.

VII.B.1.b. In certain embodiments, the resin may optionally comprise polyvinylidene chloride in the form of a homopolymer or copolymer. For example, PvDC homopolymers (generic name: Saran) or copolymers described in U.S. Patent No. 6,165,566, which is incorporated herein by reference, may be employed. Optionally, the resin may be applied on the outer surface of the barrel in the form of a latex or other dispersion.

VII.B.1.b. In certain embodiments, the syringe barrel 548 may optionally include a lubricative coating disposed between the plunger and the barrier coating of SiO _x . Suitable lubricating coatings are described herein.

VII.B.1.b. In certain embodiments, the lubricous coating may be selectively applied by PECVD and may optionally include a material having a composition of Si _w O _x C _y H _z .

VII.B.1.b. In certain embodiments, the syringe barrel 548 may include a surface treating the lubricous coating in an amount effective to reduce filtration of the lubricious coating, the components of the thermoplastic series material, or both, into the lumen 604, Processing.

VII.B.1.b SiO _X Method of making a syringe having coated inner and outer barrier coated barrels

VII.B.1.c. Yet another embodiment is a method of making a syringe as described in any of the embodiments of Part VII.B.1.b, including plungers, barrels, and inner and outer barrier coatings. There is provided a barrel having an inner surface and an outer surface for slidably receiving the plunger. A barrier coating of SiO _x is provided on the inner surface of the barrel by PECVD. A barrier coating of the resin is provided on the outer surface of the barrel. The plunger and barrel are assembled to provide a syringe.

VII.B.1.c. It is considered useful to match the surface tension of the latex to the plastic substrate for effective coating (uniform wetting) of the plastic article with water-soluble latex. This may be accomplished, for example, by several approaches that either reduce / reduce the surface tension of the latex (surfactants or solvents) or perform the corona pretreatment of the plastic article and / or the chemical priming of the plastic article independently or in combination Lt; / RTI >

VII.B.1.c. Alternatively, the resin may be provided with plastic-based articles that are dip-coated on the outer surface of the barrel, sprayed on the outer surface of the barrel, or both, to provide enhanced gas and vapor barrier performance can do. Polyvinylidene chloride plastic laminate articles that provide improved gas barrier performance vs. unlaminated plastic articles can be made.

VII.B.1.c. In certain embodiments, the resin may optionally be thermally cured. The resin can optionally be cured by removing water. The resin can be thermally cured, the resin exposed to a partial vacuum or low humidity environment, the resin catalytically cured or the water removed by other means.

VII.B.1.c. It is contemplated that an effective thermal curing schedule will eventually be dried to allow PvDC crystallization to provide blocking performance. The primary curing can, of course, be carried out at a high temperature of, for example, 180 to 310 ° F (82 to 154 ° C), depending on the thermal resistance of the thermoplastic series material. The blocking performance after the primary curing may optionally be about 85% of the final blocking performance that is reached after the final cure.

VII.B.1.c. The final cure is performed at a temperature ranging from ambient temperature such as about 65 to 75 DEG F (18 to 24 DEG C) for a long time (such as 2 weeks) to a high temperature such as 122 DEG F (50 DEG C) for a short time such as 4 hours .

VII.B.1.c. In addition to good barrier performance, it is contemplated that PvDC-plastic laminate articles optionally provide one or more desirable properties such as colorless transparency, good gloss, abrasion resistance, printability and mechanical deformation resistance.

VII.B.2 Plunger

VII.B.2.a Using a piston-coated front face

VII.B.2.a. Another embodiment is a plunger for a syringe comprising a piston and a pushrod. The piston has side and back portions configured to movably seat within a front, generally cylindrical syringe barrel. The front face has a barrier coating. The push rod engages the posterior portion and is configured to advance the piston in a syringe barrel.

VII.B.2.b. Another embodiment is a plunger for a syringe comprising a piston, a lubricous coating and a pushrod. The piston has a front side, a generally cylindrical side and a back side. The side surface is configured to movably seat within the syringe barrel. The lubricant coating is in contact with the side surface. The push rod is configured to engage the anterior portion of the piston and advance the piston in a syringe barrel.

VII.B.3. Two-part syringe and luer fitting

VII.B.3. Another embodiment is a syringe including a plunger, a syringe barrel, and a luer fitting. The syringe includes a barrel having an inner surface for slidably receiving the plunger. The luer fitting includes a luer taper having an inner passageway defined by an inner surface. The luer fitting is formed of a component separated from the syringe barrel and is joined to the syringe barrel by coupling. The internal passage of the luer taper has a barrier coating of SiO _x.

VII.B.3. 50-51, the syringe 544 optionally includes a luer fitting 556 including a luer taper 558 for receiving a cannula disposed on a secondary luer taper (not shown) . The luer taper 558 has an internal passageway 560 defined by an interior surface 562. The luer fitting 556 is optionally formed from a separate component from the syringe barrel 548 and is joined to the syringe barrel 548 by a coupling 564. 50 and 51, the coupling 564 in this case includes a male part 566 and a female part 568 which are tightly coupled together to secure the luer fitting in an at least substantially leak- ). The inner surface 562 of the luer taper may include a barrier coating 570 of SiO _x . The barrier coating may be less than 100 nm thick and is effective to reduce the inflow of oxygen into the inner passageway of the luer fitting. The barrier coating may be applied before the luer fitting is connected to the syringe barrel. In addition, the syringe of Figures 50-51 has an optional locking ring 572 that is threaded internally to lock the auxiliary luer taper of the capillary on the taper 558.

VII.B.4. Lubricant compositions - lubricated coatings deposited from an organosilicon precursor made by in situ polymerization of an organosilicon precursor

VII.B.4.a. Process products and lubricity

VII.B.4.a. Another embodiment is a lubricous coating. This coating may be of the type produced by the following process.

VII.B.4.a. Any of the precursors mentioned herein may be used alone or in combination. The precursor is applied to the substrate under conditions effective to form the coating. The coating is polymerized, cross-linked, or both to form a lubricating surface with lower plunger force or breakout force than the untreated substrate.

VII.B.4.a. Another embodiment is a method of applying a lubricous coating. The organosilicon precursor is applied to the substrate under conditions effective to form the coating. The coating is polymerized, cross-linked, or both to form a lubricating surface with lower plunger force or breakout force than the untreated substrate.

VII.B.4.b. Process and product characterization

VII.B.4.b. Another aspect of the present invention is to provide a process for the preparation of an organometallic precursor, preferably an organosilicon precursor, preferably a linear siloxane, a linear silazane, a monocyclic siloxane, a monocyclic silazane, a polycyclic siloxane, Or any combination of two or more thereof. The coating is between from 1.25 as measured by X-ray reflectivity ^{(XRR) 1.65 g / cm 3} , optionally from 1.35 1.55 g / cm ^3, alternatively 1.4 from 1.5 g / cm ^3, optionally 1.44 To 1.48 g / cm < ^{3 &} gt ;.

VII.B.4.b. Another aspect of the present invention is to provide a process for the preparation of an organometallic precursor, preferably an organosilicon precursor, preferably a linear siloxane, a linear silazane, a monocyclic siloxane, a monocyclic silazane, a polycyclic siloxane, Or any combination of two or more thereof. The coating has one or more oligomers as repeating (Me) ₂ SiO-moieties as a degassing component, as measured by a gas chromatography / mass spectrometer. Optionally, the coating meets the limitations of any of the embodiments VII.B.4.a or VII.B.4.b. Alternatively, the coating gas removal component measured by a gas chromatography / mass spectrometer is substantially free of trimethylsilanol.

VII.B.4.b. Optionally, the coating gas removal component may comprise at least 10 ng / number of test days of oligomers comprising repeating - (Me) ₂ SiO- moieties, as determined by gas chromatography / mass spectrometry using the following test conditions have:

GC column: 30m X 0.25mm DB-5MS (J & W Scientific),

0.25 μm Film thickness

Flow rate: 1.0 ml / min, uniform flow mode

Detector: mass selective detector (MSD)

Scanning mode: split scan (10: 1 split ratio)

Gas removal conditions: a 1½ "(37 mm) chamber, purge for 3 hours at 85 ° C,

Flow rate 60 ml / min

Oven temperature: 40 ° C (5 minutes) to 300 ° C at a rate of 10 ° C / min;

Keep at 300 ° C for 5 minutes.

VII.B.4.b. Optionally, the degassing component may comprise at least 20 ng / test of oligomers containing repeating - (Me) ₂ SiO- moieties.

VII.B.4.b. Optionally, the feed gas is selected from the group consisting of monocyclic siloxanes, monocyclic silazanes, polycyclic siloxanes, polycyclic silazanes, or any combination of two or more thereof, such as monocyclic siloxanes, Or any combination of two or more thereof.

VII.B.4.b. The lubricous coating of any embodiment has a thickness between 1 and 500 nm, alternatively between 20 and 200 nm, alternatively between 20 and 100 nm, alternatively between 30 and 100 nm, as measured by a transmission electron microscope (TEM) .

VII.B.4.b. Another aspect of the invention is a lubricous coating deposited by PECVD from a feed gas comprising a monocyclic siloxane, a monocyclic silazane, a polycyclic siloxane, a polycyclic silazane, or a combination of any two or more thereof. Wherein the coating is normalized to 100% of carbon, oxygen and silicon as measured by X-ray photoelectron spectroscopy (XPS), and wherein the atomic concentration of carbon, in atomic form relative to the feed gas, . Optionally, the coating meets the limitations of Example VII.B.4.a or VII.B.4.b.

VII.B.4.b. Alternatively, the atomic concentration of carbon may be from 1 to 80 atomic percent, or from 10 to 70 atomic percent, or from 20 to 60 atomic percent, or from 30 to 50 atomic percent (calculated based on the XPS conditions in Example 15) 35 to 45 atomic percent, or 37 to 41 atomic percent.

VII.B.4.b. Another aspect of the invention is a lubricous coating deposited by PECVD from a feed gas comprising a monocyclic siloxane, a monocyclic silazane, a polycyclic siloxane, a polycyclic silazane, or a combination of any two or more thereof. Wherein the coating is normalized to 100% of carbon, oxygen and silicon as measured by X-ray photoelectron spectroscopy (XPS), and wherein the atomic concentration of silicon, less than the atomic concentration of silicon in the atomic form for the feed gas, . Optionally, the coating meets the limitations of Example VII.B.4.a or VII.B.4.b.

VII.B.4.b. Alternatively, the atomic concentration of silicon may be from 1 to 80 atomic percent, or from 10 to 70 atomic percent, or from 20 to 60 atomic percent, or from 30 to 55 atomic percent (calculated based on the XPS conditions in Example 15) 40 to 50 atomic percent, or 42 to 46 atomic percent.

VII.B.4.b. In addition, lubricative coatings having a combination of any two or more of the properties recited in Section VII.B.4 are explicitly contemplated.

VII.C. Container General

VII.C. A coated container or container, prepared according to the methods described herein and described herein, can be used for the reception and / or storage and / or delivery of a compound or composition. The compounds or compositions are sensitive to, for example, air-sensitive, oxygen-sensitive, humidity sensitive and / or mechanical effects. It may be a pharmaceutical, such as a composition comprising a biologically active compound or composition, for example, insulin or insulin. In another aspect, it may be a biological fluid, preferably a body fluid, such as blood or blood fractions. In certain aspects of the invention, the compound or composition may be administered to a subject in need thereof, for example, by administering the product to be injected, such as blood (transfusion from a donor to a blood vessel or reintroduction of blood back to the patient from the patient) And the like.

VII.C. In addition, a coated container or container, as described herein and made in accordance with the methods described herein, protects a compound or composition contained in its internal space from mechanical and / or chemical effects of the surface of the uncoated container material Can be used. Can be used to prevent or reduce precipitation and / or clotting or platelet activation of the compound or components of the composition, such as, for example, insulin precipitation or blood clotting or platelet activation.

VII.C. Also, for example, one or more compounds from the environment surrounding the container can be prevented or reduced from entering the interior space of the container and used to protect the compound or composition contained therein from the environment outside the container. Such environmental compounds may be gases or liquids, e.g., atmospheric gases or liquids comprising oxygen, air and / or water vapor.

VII.C. In addition, the coated container as described herein can be stored in a vacuum and in a vacuum. For example, the coating allows a better vacuum to be maintained compared to the corresponding uncoated vessel. In one aspect of this embodiment, the coated container is a blood collection tube. In addition, the tube may contain agents that prevent blood clotting or platelet activation, such as, for example, EDTA or heparin.

VII.C. Any one of the above embodiments may have a thickness of, for example, from about 1 cm to about 200 cm, alternatively from about 1 cm to about 150 cm, alternatively from about 1 cm to about 120 cm, About 100 cm, alternatively from about 1 cm to about 80 cm, alternatively from about 1 cm to about 60 cm, alternatively from about 1 cm to about 40 cm, alternatively from about 1 cm to about 30 cm And treating it with a probe electrode as described below. It is contemplated that, relative to the longer length in this range, relative motion between the probe and the vessel may be useful during coating formation. This can be done, for example, by moving the container relative to the probe or moving the probe relative to the container.

VII.C. In these embodiments, the coating may be thinner or less perfect than may be preferred for the barrier coating, since in some embodiments the container does not require a high blocking integrity of the vacuum blood collection tube do.

VII.C. An optional feature of any of the preceding embodiments has a central axis.

VII.C. As an optional feature of any of the preceding embodiments, the container wall may extend over a range of radii curved at a central axis of at least substantially 100 times the outer diameter of the container, Lt; RTI ID = 0.0 > C. &Lt; / RTI >

VII.C. As an optional feature of any of the preceding embodiments, the radius of curvature at the central axis is about 90 times, or about 80 times, or about 70 times, or about 60 times, or about 50 times the outer diameter of the container, or About 40 times, or about 30 times, or about 20 times, or about 10 times, or about 9 times, about 8 times, about 7 times, about 6 times, about 5 times, about 4 times, About 3 times, or about twice, or about the outer diameter of the container.

VII.C. As an optional feature of any of the preceding embodiments, the container wall may be a fluid-contacting surface made of a flexible material.

VII.C. As an optional feature of any of the preceding embodiments, the container lumen may be a fluid flow passage of the pump.

VII.C. As an optional feature of any of the preceding embodiments, the container may be a blood bag adapted to maintain a condition of good blood for medical use.

VII.C., VII.D. As an optional feature of any of the preceding embodiments, the polymeric material may be any material suitable for contacting silicone elastomer or thermoplastic polyurethane or blood or insulin as two examples.

VII.C., VII.D. In an alternate embodiment, the container has an inner diameter of at least 2 mm, or at least 4 mm.

VII.C. As an optional feature of any of the preceding embodiments, the container is a tube.

VII.C. As an optional feature of any of the preceding embodiments, the lumen has at least two open ends.

VII.C.1. Another embodiment is a blood containing container. Some non-limiting examples of such containers include a blood transfusion bag, a blood sample collection container in which the sample is collected, a tubing of the heart-lung machine, a flexible wall blood collection bag, or during surgery to collect the patient's blood, Lt; RTI ID = 0.0 > vascular < / RTI > Particularly suitable pumps are centrifugal pumps or peristaltic pumps, if the container comprises pumps for blood pumps. The container having a wall; The wall has an inner surface defining a lumen. The inner surface of the wall is preferably w 1, x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, z is from 2 to about 9, more preferably w is 1, x _Has an at least partial coating of Si _w O _x C _y H _z of from about 0.5 to 1, y is from about 2 to about 3, and z is from 6 to 9. The coating may be as thin as about monomolecular thickness or as thick as about 1000 nm. The container comprises a viable blood capable of returning to the vasculature of the patient placed in the lumen in contact with the Si _w O _x C _y H _z coating.

VII.C.1. One embodiment is a blood containing container having an inner surface that defines a wall and defines a lumen. The inner surface has at least a partial coating of Si _w O _x C _y H _z . In addition, the coating may comprise SiO _x as defined herein, or _x may consist essentially of SiO _x . The thickness of the coating is in the range of monomolecular thickness to about 1000 nm thickness on the inner surface. The container comprises a viable blood capable of returning to the vasculature of the patient placed in the lumen in contact with the Si _w O _x C _y H _z coating.

VII.C.2. Coatings deposited from the organosilicon precursors reduce blood clotting or platelet activation in the vessel

VII.C.2. Another embodiment is a container having a wall. W, x, y and z are as defined above; w is 1; x is from about 0.5 to about 2.4; y is from about 0.6 to about 3; , z is from 2 to about 9, more preferably w is 1, x is from about 0.5 to 1, y is from about 2 to about 3, z is from 6 to about 9, Si _w O _x C _y H _z Lt; / RTI > The thickness of the coating is from monomolecular thickness to about 1000 nm thickness on the inner surface. The coating is effective to reduce coagulation or platelet activation of blood exposed to the inner surface, as compared to walls of the same type not coated with Si _w O _x C _y H _z .

VII.C.2. In comparison with Si _w O _x C _y H _z properties in contact with the polymer or SiO _x surface undeformed because of the mixing of the coatings, it is thought to reduce adhesion formation or coagulation tendency of the blood. This feature reduces the required blood concentration of heparin in patients who experience a type of surgery requiring blood to be removed from the patient and then returned to the patient, if the heart-lung machine is used during heart surgery, Reducing the need to treat with heparin or potentially eliminating this need. It is contemplated that this would reduce the complications of surgery, including the passage of blood through such vessels, by reducing the bleeding complications resulting from the use of heparin.

VII.C.2. Another embodiment is a blood containing container having an inner surface that defines a wall and defines a lumen. Wherein the inner surface has a thickness of the coating ranging from a monomolecular thickness to about 1000 nm thick on said inner surface, said coating comprising at least a portion of Si _w O _x C _y H _z effective to reduce coagulation or platelet activation of blood exposed to the inner surface Lt; / RTI > coating.

VII.C.3. A vessel containing a viable blood and having a coating of Group III or Group IV elements

VII.C.3. Another embodiment is a blood containing container having a wall having an inner surface defining a lumen. The inner surface has at least a partial coating of a composition comprising at least one or more Group III elements, at least one or more Group IV elements, or a combination of two or more thereof. The thickness of the coating is on the inner surface from not less than monomolecular thickness to less than about 1000 nm. The container includes viable blood that can return to the vasculature of the patient disposed within the lumen in contact with the coating.

VII.C.4. Optionally, in the container of the preceding paragraph, the coating of Group III or Group IV elements is effective to reduce coagulation or platelet activation of blood exposed to the inner surface of the container wall.

VII.D. Pharmaceutical delivery containers

VII.D. The coated container or container described herein can be used to prevent or reduce the escape of the compound or composition contained in the container to the environment surrounding the container.

In addition, other uses of the coatings and containers described herein, which are apparent from any of the detailed description and claims, are contemplated.

VII.D.1. Another embodiment is an insulin-containing container comprising a wall having an inner surface defining a lumen. 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, with the proviso that w, x, y and z are as defined above, , and more preferably w is 1, x is from about 0.5 to 1, y is from about 2 to about 3, z is from 6 to have at least a partial coating of about 9, Si _w O _x C _y H _z. The coating may be monomolecular to about 1000 nm thick on the inner surface. Insulin is placed in the lumen in contact with the Si _w O _x C _y H _z coating.

VII.D.1. Yet another embodiment is an insulin-containing container having an inner surface defining a lumen that includes a wall. The inner surface has at least a partial coating of Si _w O _x C _y H _{z with} a thickness of the coating ranging from monomolecular thickness to about 1000 nm thick on the inner surface. An insulin, for example, an FDA-approved pharmaceutical insulin for use in humans, is placed in a lumen in contact with the Si _w O _x C _y H _z coating.

VII.D.1. Compared to the properties in contact with the unmodified polymer surface, it is believed that the mixing of the Si _w O _x C _y H _z coating reduces the tendency of the insulin to stick or coagulate in the delivery tube of the insulin pump . This property is considered to reduce or potentially eliminate the need to filter insulin through the delivery tube to remove solid precipitate.

VII.D.2. Alternatively, as compared in the vessel of the previous paragraph, with the same surface coating of Si _w O _x C _y H _z is not a coating of Si _w O _x C _y H _z, in reducing the precipitation from the insulin in contact with the inside surface effective.

VII.D.2. Yet another embodiment is a container that includes a wall and an interior surface defining a lumen. The inner surface comprises at least a partial coating of Si _w O _x C _y H _z . The thickness of the coating is in the range of monomolecular thickness to about 1000 nm thickness on the inner surface. The coating is effective to reduce precipitation formation from insulin in contact with the inner surface.

VII.D.3. Another embodiment is an insulin-containing container comprising a wall having an inner surface defining a lumen. The inner surface has at least a partial coating of a composition comprising carbon, one or more Group III elements, one or more Group IV elements, or a combination of two or more thereof. The coating may be monomolecular to about 1000 nm thick on the inner surface. Insulin is provided in the lumen in contact with the coating.

VII.D.4. Optionally, in the container of the preceding paragraph, the coating of a composition comprising carbon, one or more Group III elements, one or more Group IV elements, or a combination of two or more thereof, It is effective to reduce the formation of precipitate from the contacting insulin.

Example of work

Example 0: Basic protocols for forming and coating tubes and syringe barrels

The containers tested in the following working examples were formed and coated according to the following exemplary protocols, except as otherwise indicated in the individual examples. The specific parameter values given in the following basic protocols, such as power and process gas flow, are typical values. If the parameter values have changed in comparison to these conventional values, this will be indicated in the subsequent working examples. The same applies to the type and composition of the process gas.

A protocol for forming COC tubes (e.g., used in Examples 1, 19)

Cyclical olefin copolymer (COC) tubes ("COC tubes") of the type and size commonly used as vacuum blood collection tubes are commercially available from Topas, Inc., of Hoechst AG, Frankfurt am Main, Germany, Injection molded from Cyclo® 8007-04 cyclic olefin copolymer (COC) resin: 75 mm long, 13 mm outer diameter and 0.85 mm wall thickness, each having a volume of about 7.25 cm ³ and closed and rounded ends.

Protocols for forming PET tubes (e.g. used in Examples 2, 4, 8, 9, 10)

A polyethylene terephthalate (PET) tube ("PET tube") of the type commonly used as a vacuum blood collection tube is injection molded in the same mold used for the protocol to form the COC tube, having the following dimensions: length 75 mm, outer diameter 13 mm, and 0.85 mm wall thickness, each having a closed volume of about 7.25 cm ³ and rounded ends.

Inside the tube, _x (E.g., used in Examples 1, 2, 4, 8, 9, 10, 18, 19)

As shown in Fig. 2, an apparatus having the sealing mechanism of Fig. 45, which is a specially considered embodiment, was used. The container support 50 may be made from E. I. Wilmington, Delaware, USA. Manufactured from Delrin® acetal resin available from du Pont de Neumours, it has an outer diameter of 1.75 inches (44 mm) and a height of 1.75 inches (44 mm). The container support 50 is housed in a Delrin® structure that allows the device to move in and out of the electrode 160.

The electrode 160 has a Delrin® shield and is made of copper. The Delrin® shield is uniform around the outside of the copper electrode 160. The electrode 160 was measured approximately three inches (76 mm) high (inside) and approximately 0.75 inches (19 mm) wide.

The tube used as the vessel 80 is connected to the container support 50 using Viton® O-rings 490 and 504 (Viton®, trade name of Dupont Performance Elastomers LLC, Wilmington, Delaware, USA) Was inserted into the base seal (Fig. 45). The tube 80 was carefully moved to the sealing position on the elongated (still) 1/8-inch (3-mm.) Diameter brass probe or counter electrode 108 and pushed against the copper plasma screen.

The copper plasma screen 610 is a perforated copper foil material (K & S Engineering, Chicago, Ill., Part # LXMUW5 copper mesh) cut to fit the outer diameter of the tube and has a radially extending Lt; RTI ID = 0.0 > 494 < / RTI > The two pieces of copper mesh fits around the brass probe or counter electrode 108 to ensure good electrical contact.

The brass probe or counter electrode 108 extended approximately 70 mm into the interior of the tube and had an array of # 80 wires (diameter = 0.0135 inches or 0.343 mm). The brass probe or counter electrode 108 extends through the Swagelok® fitting (available from Swagelok, Inc., Solon, OH) at the bottom of the container support 50 and extends through the container support 50 base structure. The brass probe or counter electrode 108 was grounded to the casing of the RF matching network.

The gas delivery port 110 has 12 holes (three in each of the four sides in each of the four sides) at the probe or counter electrode 108 along the length of the tube and an aluminum There are two holes in the cap. The gas delivery port 110 was connected to a stainless steel assembly comprised of Swagelok® fittings incorporating a passive manual ball valve for discharge, a thermocouple pressure gauge and a bypass valve connected to the vacuum pumping line. In addition, process gases, oxygen and hexamethyldisiloxane (HMDSO) were connected to the gas delivery port 110 to allow the process gas (under process pressure) to flow through the gas delivery port 110 into the interior of the tube.

The gas system is an Aalborg® GFC17 mass flow meter (part # EW-32661-34, available from Cole, Inc., Barrington, Ill., USA) to controllably flow oxygen to the process at 90 sccm (or the specific flow reported for a particular example) (OD) 1/16-inch (1.5-mm.), Inner diameter, "ID" 0.004 inch (" PE ") capillary having a length of 49.5 inches (1.26 m) 0.1 mm)). The PEEK capillary end was inserted with liquid hexamethyldisiloxane ("HMDSO", Alfa Aesar® part number L16970, NMR grade, available from Johnson Matthey PLC, London). The liquid HMDSO was sucked through the capillary due to the lower pressure in the tube during the process. Then, the HMDSO was vaporized at the outlet of the capillary as vapor enters the low-pressure region.

To prevent condensation of liquid HMDSO through this point, the gas flow (including oxygen) was switched to a pumping line if it did not flow into the processing tube through a Swagelok 3-way valve. Once the tube is installed, the vacuum pump valve opens into the interior of the tube support 50 and tube.

The Alcatel rotary vacuum pump and blower included a vacuum pump system. Due to the pumping system, the interior of the tube was reduced to a pressure of less than 200 mTorr while the process gases flowed at the indicated rate.

Once the basic vacuum level has been reached, the container support 50 assembly has been moved to the electrode 160 assembly. Gas streams (oxygen and HMDSO vapor) flowed into the brass gas delivery port 110 (by adjusting a three-way valve from the pumping line to the gas delivery port 110). The pressure inside the tube was approximately 300 mTorr as measured by a capacity-based manometer (MKS) installed in the pumping line near the valve to regulate the vacuum. In addition to the tube pressure, the pressure inside the gas delivery port 110 and the gas system was also measured using a thermocouple vacuum gauge connected to the gas system. This pressure was typically less than 8 Torr.

Once the gas had flowed into the tube, the RF power supply operated at a fixed power level. The ENI ACG-6 600 watt RF power supply was used at a fixed power level of approximately 50 watts (at 13.56 MHz). The output power was calibrated in this and all subsequent protocols and embodiments using a Bird Corporation Model 43 RF watt meter connected to the RF output of the power supply while the coating apparatus was booming. The following relationship was found between the dial setting for the power supply and the output power: RF power output = 55 x dial setting. In the priority applications for this application, factor 100 was used, which was inaccurate. The RF power supply was connected to a COMDEL CPMX1000 auto-matching that matched the complex impedance of the plasma (generated in the tube) to the 50 ohm output impedance of the ENI ACG-6 RF power supply. The forward power was 50 watts (or the specific amount reported for a particular embodiment) and the reflected power was 0 watts so that the applied power was delivered to the interior of the tube. The RF power supply was controlled by the power for the laboratory timer and the time set in 5 seconds (or a specific time period reported for a particular embodiment). When the RF power was turned on, a uniform plasma was established inside the tube. The plasma was held for a total of 5 seconds until the RF power was terminated by the timer. The plasma produced a silicon oxide coating on the inner surface of the tube surface, approximately 20 nm thick (or the specific thickness reported in the specific examples).

After coating, the gas flow returned to the vacuum line and the vacuum valve was closed. Then, the exhaust valve was opened to return the inside of the tube to atmospheric pressure (approximately 760 Torr). The tube was then carefully removed from the container support 50 assembly (after moving the container support 50 assembly from the electrode 160 assembly).

A protocol for coating the interior of the tube with a hydrophobic coating (e.g., used in Example 9)

The tube used as the vessel 80 is connected to the outside of the tube using Viton O-rings 490 and 504 (Viton® is a trademark of Dupont Performance Elastomers LLC, Wilmington Del., USA) (Fig. 45). The tube 80 was carefully moved to the sealing position on the elongated (still) 1/8-inch (3-mm.) Diameter brass probe or counter electrode 108 and pushed against the copper plasma screen.

The gas system is an Aalborg® GFC17 mass flow meter (Part # EW-32661-34, Cole, Barrington, Ill., USA) to controllably flow oxygen at a flow rate of 60 sccm (or in certain flows reported for specific examples) (OD) 1/16-inch (1.5-mm.), Inner diameter, "ID" 0.004 inch (" PE ") capillary having a length of 49.5 inches (1.26 m) 0.1 mm)). The PEEK capillary end was inserted with liquid hexamethyldisiloxane ("HMDSO", Alfa Aesar® part number L16970, NMR grade, available from Johnson Matthey PLC, London). The liquid HMDSO was sucked through the capillary due to the lower pressure in the tube during the process. Then, the HMDSO was vaporized at the outlet of the capillary as vapor enters the low-pressure region.

Once the basic vacuum level has been reached, the container support 50 assembly has been moved to the electrode 160 assembly. Gas streams (oxygen and HMDSO vapor) flowed into the brass gas delivery port 110 (by adjusting a three-way valve from the pumping line to the gas delivery port 110). The pressure inside the tube was approximately 270 mTorr, as measured by a capacity-based manometer (MKS) installed in the pumping line near the valve to regulate the vacuum. In addition to the tube pressure, the pressure inside the gas delivery port 110 and the gas system was also measured using a thermocouple vacuum gauge connected to the gas system. This pressure was typically less than 8 Torr.

Once the gas had flowed into the tube, the RF power supply operated at a fixed power level. The ENI ACG-6 600 watt RF power supply was used at a fixed power level of approximately 39 watts (at 13.56 MHz). The RF power supply was connected to a COMDEL CPMX1000 auto-matching that matched the complex impedance of the plasma (generated in the tube) to the 50 ohm output impedance of the ENI ACG-6 RF power supply. The forward power was 39 watts (or the specific amount reported for a particular example) and the reflected power was 0 watts so the applied power was delivered to the inside of the tube. The RF power supply was controlled by the power for the laboratory timer and the time set in 7 seconds (or a specific time period reported for a particular embodiment). When the RF power was turned on, a uniform plasma was established inside the tube. The plasma was held for a total of 7 seconds until the RF power was terminated by the timer. The plasma produced a silicon oxide coating on the inner surface of the tube surface, approximately 20 nm thick (or the specific thickness reported in the specific examples).

Protocols for forming COC syringe barrels (e.g., used in Examples 3, 5, 11 to 18, and 20)

Syringe barrels ("COC syringe barrels"), CV Holdings part 11447, with a nominal 1 mL delivery volume or plunger variation of 2.8 mL total volume (except for luer fitting) and luer adapter type were purchased from Hoechst AG, Frankfurt am Main, Germany (COC) resin, which can be obtained from Topas® 8007-04, which has the following values: total length of about 51 mm, 8.6 mm inner syringe barrel diameter and 1.27 mm wall in the cylindrical region Thickness, integrated 9.5 mm long needle capillary luer adapter molded at one end and two finger flanges molded at the other end.

The inside of the COC syringe barrel was filled with SiO _x (E. G., Used in Examples 3, 5 and 18)

Injection molded COC syringe barrels were coated internally with SiO _x . As shown in FIG. 2, a specially contemplated embodiment was modified to hold a COC syringe barrel having a sealing seal at the bottom of the COC syringe barrel where the apparatus with the sealing mechanism of FIG. 45 was used. Also, a stainless steel luer fitting and a polypropylene cap sealing the end of the COC syringe barrel (shown in Fig. 26) were made to allow the interior of the COC syringe barrel to be evacuated.

The container support (50) Made from Delrin®, it has an outside diameter of 1.75 inches (44 mm) and a height of 1.75 inches (44 mm). The container support 50 is housed in a Delrin® structure that allows the device to move in and out of the electrode 160.

The electrode 160 has a Delrin® shield and is made of copper. The Delrin® shield is uniform around the outside of the copper electrode 160. The electrode 160 was measured approximately three inches (76 mm) high (inside) and approximately 0.75 inches (19 mm) wide. The COC syringe barrel was base sealed with Viton® O-rings and inserted into the container support (50).

The COC syringe barrel was carefully moved to the sealing position on an extended (still) 1/8-inch (3-mm.) Diameter brass probe or counter electrode 108 and pushed against the copper plasma screen. The copper plasma screen is a perforated copper foil material (K & S Engineering, part # LXMUW5 copper mesh) cut to fit the outer diameter of the COC syringe barrel and is held in place by a junction surface 494 serving as a stop for COC syringe barrel insertion Respectively. The two pieces of copper mesh fits around the brass probe or counter electrode 108 to ensure good electrical contact.

The brass probe or counter electrode 108 extends approximately 20 mm into the interior of the COC syringe barrel and is open at its distal end. A brass probe or counter electrode 108 extends through the Swagelok® fitting at the bottom of the container support 50 and extends through the container support 50 basic structure. The brass probe or counter electrode 108 was grounded to the casing of the RF matching network.

The gas delivery port 110 was connected to a stainless steel assembly comprised of Swagelok® fittings incorporating a passive manual ball valve for discharge, a thermocouple pressure gauge and a bypass valve connected to the vacuum pumping line. In addition, process gases, oxygen and hexamethyldisiloxane (HMDSO) were connected to the gas delivery port 110 to allow the process gas (under process pressure) to flow through the gas delivery port 110 into the interior of the COC syringe barrel.

The gas system includes an Aalborg® GFC17 mass flow meter (Cole-Parmer part # EW-32661-34) for flow control of oxygen at 90 sccm (or a specific flow reported for a specific example) (OD 1/16-inch (3-mm.) ID 0.004 inch (0.1 mm)) of PEEK capillary (1.26 m) The PEEK capillary end was inserted with liquid hexamethyldisiloxane (Alfa Aesar (R) part number L16970, NMR grade). Liquid HMDSO was sucked through the capillary during the process due to the lower pressure in the COC syringe barrel. Then, the HMDSO was vaporized at the outlet of the capillary as vapor enters the low-pressure region.

To prevent condensation of liquid HMDSO through this point, the gas flow (including oxygen) was switched to a pumping line if it did not flow into the COC syringe barrel for processing through a Swagelok 3-way valve.

Once the COC syringe barrel is installed, the vacuum pump valve opens into the interior of the container support 50 and the COC syringe barrel. The Alcatel rotary vacuum pump and blower included a vacuum pump system. Due to the pumping system, the interior of the COC syringe barrel was reduced to less than 150 mTorr while the process gases flowed at the indicated rate. Lower pumping pressures can be achieved using COC syringe barrels as opposed to tubes, since COC syringe barrels have much less internal volume.

Once the basic vacuum level has been reached, the container support 50 assembly has been moved to the electrode 160 assembly. Gas streams (oxygen and HMDSO vapor) flowed into the brass gas delivery port 110 (by adjusting a three-way valve from the pumping line to the gas delivery port 110). The pressure inside the COC syringe barrel was approximately 200 mTorr, as measured by a capacity-based manometer (MKS) installed in the pumping line near the valve to regulate the vacuum. In addition to the COC syringe barrel pressure, the pressure inside the gas delivery port 110 and the gas system was also measured using a thermocouple vacuum gauge connected to the gas system. This pressure was typically less than 8 Torr.

Once the gas had flowed into the COC syringe barrel, the RF power supply operated at a fixed power level. The ENI ACG-6 600 watt RF power supply was used at a fixed power level of approximately 39 watts (at 13.56 MHz). The RF power supply was connected to a COMDEL CPMX1000 auto-matching that matched the complex impedance of the plasma (generated within the COC syringe barrel) to the 50 ohm output impedance of the ENI ACG-6 RF power supply. The forward power was 30 watts (or whatever the value was reported in the working example) so that power was transferred into the COC syringe barrel and the reflected power was 0 watts. The RF power supply was controlled by the power for the laboratory timer and the time set in 5 seconds (or a specific time period reported for a particular embodiment).

When the RF power was turned on, a uniform plasma was established inside the COC syringe barrel. The plasma was maintained for a total of 5 seconds (or other coating times as indicated in the specific examples) until the RF power was terminated by the timer. The plasma produced a silicon oxide coating on the inner surface of the COC syringe barrel surface approximately 20 nm thick (or the specific thickness reported in the specific example).

After coating, the gas flow returned to the vacuum line and the vacuum valve was closed. Thereafter, the exhaust valve was opened to return the interior of the COC syringe barrel to atmospheric pressure (approximately 760 Torr). Thereafter, the COC syringe barrel was carefully removed from the container support 50 assembly (after moving the container support 50 assembly from the electrode 160 assembly).

Protocols for coating the interior of a COC syringe barrel with an OMCTS lubricant coating (such as used in Examples 11, 12, 15 to 18, and 20)

The previously identified COC syringe barrels were inside coated with a lubricous coating. As shown in FIG. 2, a specially contemplated embodiment was modified to hold a COC syringe barrel having a sealing seal at the bottom of the COC syringe barrel where the apparatus with the sealing mechanism of FIG. 45 was used. Also, a stainless steel luer fitting and a polypropylene cap sealing the end of the COC syringe barrel (shown in Fig. 26) were made to allow the interior of the COC syringe barrel to be evacuated. Installing the Buna-N O-ring on the luer fitting allows a vacuum tight seal, allowing the interior of the COC syringe barrel to be vacuumed.

The electrode 160 has a Delrin® shield and is made of copper. The Delrin® shield is uniform around the outside of the copper electrode 160. The electrode 160 was measured approximately three inches (76 mm) high (inside) and approximately 0.75 inches (19 mm) wide. The COC syringe barrel was base sealed with the Viton O-rings near the bottom of the finger flanges and the lip of the COC syringe barrel and inserted into the container support 50.

The probe or counter electrode 108 extends approximately 20 mm into the interior of the COC syringe barrel (if not otherwise indicated) and opened at its distal end. A brass probe or counter electrode 108 extends through the Swagelok® fitting at the bottom of the container support 50 and extends through the container support 50 basic structure. The brass probe or counter electrode 108 was grounded to the casing of the RF matching network.

The gas delivery port 110 was connected to a stainless steel assembly comprised of Swagelok® fittings incorporating a passive manual ball valve for discharge, a thermocouple pressure gauge and a bypass valve connected to the vacuum pumping line. In addition, it is also possible to use a process gas (such as octamethylcyclotetrasiloxane (OMCTS) (or a specific process gas reported for a particular embodiment) that is a process gas (under process pressure) to flow through the gas delivery port 110 into the COC syringe barrel A gas system was connected to the delivery port 110.

The gas system consisted of a commercially available Horiba VC1310 / SEF8420 OMCTS 10SC 4CR heated mass flow vaporization system heating the OMCTS to about 100 ° C. The Horiba system was connected to liquid octamethylcyclotetrasiloxane (Alfa Aesar® part number A12540, 98%) via a 1/8-inch (3-mm) outer diameter PFA tube with an inner diameter of 1/16 inch . The OMCTS flow rate was set at 1.25 sccm (or the specific organosilicon precursor flow reported for a particular example). To prevent condensation of the vaporized HMDSO stream past this point, the gas flow was switched to a pumping line if it did not flow into the COC syringe barrel for processing through a Swagelok 3-way valve.

Once the COC syringe barrel is installed, the vacuum pump valve opens into the interior of the container support 50 and the COC syringe barrel. The Alcatel rotary vacuum pump and blower included a vacuum pump system. Due to the pumping system, the interior of the COC syringe barrel was allowed to reduce to less than 100 mTorr while the process gases flowed at the indicated rate. In this case, because the total process gas flow rate was lower, lower pressures could be obtained compared to tubes and previous COC syringe barrel embodiments.

Once the basic vacuum level has been reached, the container support 50 assembly has been moved to the electrode 160 assembly. The gas stream (OMCTS vapor) flowed into the brass gas delivery port 110 (by adjusting a three-way valve from the pumping line to the gas delivery port 110). The pressure inside the COC syringe barrel was approximately 140 mTorr, as measured by a capacity-based manometer (MKS) installed in the pumping line near the valve to regulate the vacuum. In addition to the COC syringe barrel pressure, the pressure inside the gas delivery port 110 and the gas system was also measured using a thermocouple vacuum gauge connected to the gas system. This pressure was typically less than 6 Torr.

Once the gas had flowed into the COC syringe barrel, the RF power supply was turned on at a fixed power level. The ENI ACG-6 600 watt RF power supply was used (at 13.56 MHz) at a fixed power level of approximately 7.5 watts (or another power level indicated in the specific example). The RF power supply was connected to a COMDEL CPMX1000 auto-matching that matched the complex impedance of the plasma (generated within the COC syringe barrel) to the 50 ohm output impedance of the ENI ACG-6 RF power supply. The forward power was 30 watts and the reflected power was 0 watts so that a power of 7.5 watts (or another power level delivered in the given example) was delivered to the interior of the COC syringe barrel. The RF power supply was controlled by power for a time set to the laboratory timer and 10 seconds (or a different time specified in a specific embodiment).

When the RF power was turned on, a uniform plasma was established inside the COC syringe barrel. The plasma was maintained for the entire coating time until the RF power was terminated by the timer. The plasma produced a lubricous coating on the inner surface of the COC syringe barrel surface.

Protocols for coating the interior of a COC syringe barrel with an HMDSO coating (e.g. used in Examples 12, 15, 16 and 17)

In addition, a protocol for coating the interior of the COC syringe barrel with the OMCTS lubricant coating was used to apply the HMDSO coating, except that OMCTS was replaced by HMDSO.

Example 1

V. In the following test, hexamethyldisiloxane (HMDSO) was used as an organosilicon ("O-Si") feed to the PECVD apparatus of FIG. 2 to form cyclic olefin the SiO _x coating on the inner surface of the copolymer (COC) tube was applied. The deposition conditions are summarized in Table 1 and the protocol for coating the inside of the tube with SiO _x . The control group was of the same type as the tubes without the barrier coating. The coated and uncoated tubes were then tested for Oxygen Permeation Rate (OTR) and its water vapor transmission rate (WVTR).

V. Referring to Table 1, the uncoated COC tube had an OTR of 0.215 cc / tube / day. The tubes (A and B) subjected to PECVD for 14 seconds had an average OTR of 0.0235 cc / tube / day. These results show that the SiO _x coating provided oxygen transfer BIF for the uncoated tube of 9.1. That is, the SiO _x barrier coating reduced oxygen transfer through the tube to less than one-ninth of the value in the absence of the coating.

V. The tube (C) subjected to PECVD for 7 seconds had an OTR of 0.026. This result shows that the SiO _x coating provided OTR BIF for an uncoated tube of 8.3. That is, the SiO _x barrier coating applied within 7 seconds reduced oxygen transfer through the tube to less than one-eighth of the value in the absence of the coating.

V. Also, the relative WVTRs of the same barrier coatings on the COC tubes were measured. Uncoated COC tubes had a WVTR of 0.27 mg / tube / day. The tubes (A and B) subjected to PECVD for 14 seconds had an average OTR of 0.10 mg / tube / day. The tube (C) subjected to PECVD for 7 seconds had a WVTR of 0.10 mg / tube / day. This result shows that the SiO _x coating provided a water vapor barrier enhancement factor (WVTR BIF) for an uncoated tube of about 2.7. This was a surprising result because the uncoated COC tube already had a very low WVTR.

Example 2

V. A series of PET tubes, fabricated according to the protocol for forming PET tubes, were coated with SiO _x according to the protocol for coating the interior of the tubes with SiO _x under the conditions reported in Table 2. Controls were made according to the protocol for forming PET tubes, but they remained uncoated. OTR and WVTR samples of the tubes were prepared by epoxy sealing the open end of each tube with an aluminum adapter.

In separate tests using coated PET tubes of the same type, mechanical scratches of varying length were derived using steel needles through an inner coating, and OTR BIF was tested. Controls were coated tubes of the same type without leaving uncoated or induced scratches. OTR BIF was reduced while still improving on uncoated tubes (Table 2A).

V. Tubes were tested for OTR as follows. Each sample / adapter assembly was fitted onto a MOCON® Oxtran 2/21 oxygen permeable device. The samples were allowed to equilibrate to the steady-state permeation rate (1 to 3 days) under the following test conditions:

Test gas: oxygen

Test gas concentration: 100%

Test gas humidity: 0% Relative humidity

Test gas pressure: 760 mmHg

Test temperature: 23.0 캜 (73.4 ℉)

Carrier gas: 98% nitrogen, 2% oxygen

Carrier gas Humidity: 0% Relative humidity

V. OTR is reported as the average of the two measurements in Table 2.

V. Tubes were tested for WVTR as follows. The sample / adapter assembly was fitted onto a MOCON® Permatran-W 3/31 water vapor permeable device. The samples were allowed to equilibrate to the steady-state permeation rate (1 to 3 days) under the following test conditions:

Test gas: water vapor

Test gas concentration: Not applicable

Test gas humidity: 100% relative humidity

Test gas temperature: 37.8 ( ^o C) 100.0 ( ^o F)

Carrier gas: dry nitrogen

Carrier gas Humidity: 0% Relative humidity

The WVTR is reported as the average of the two measurements in Table 2.

Example 3

A series of syringe barrels were made according to the protocol for forming a COC syringe barrel. The syringe barrels were _not shielded membranes coated with SiO _x or under the conditions reported in the protocol for coating the inside of a COC syringe barrel with SiO _x modified as shown in Table 3.

The OTR and WVTR samples of the syringe barrels were prepared by epoxy sealing the open end of each syringe barrel with an aluminum adapter. In addition, the syringe barrel capillary ends were sealed with epoxy. The syringe-adapter assemblies were again tested for OTR or WVTR in the same manner as the PET tube samples, using the MOCON® Oxtran 2/21 Oxygen Permeable Tool and the MOCON® Permatran-W 3/31 Water Permeability Tool. The results are reported in Table 3.

Example 4

Determination of composition of plasma coatings by X-ray photoelectron spectroscopy (XPS) / electron spectroscopy for chemical analysis (ESCA) surface analysis

The PET tubes coated according to the protocol for forming the VA PET tube and coated inside the tube with SiO _x were cut in half to expose the inner tube surface and then to X-ray photoelectron spectroscopy ).

V.A. XPS data were quantified using relative sensitivity factors and a single layered model. The analysis volume is the product of the area of analysis (spot size or aperture size) and the depth of information. Photoelectrons are generated within the X-ray penetration depth (typically a few microns), but only the photoelectrons within the three top electron escape depths are detected. The escape depth is on the order of 15 to 35 Angstroms, which leads to an analytical depth of about 50 to 100 Angstroms. Typically, 95% of the signal is within this depth.

V.A. Table 5 provides the atomic ratios of the detected constituents. The analysis parameters used for XPS are as follows:

Tools: PHI Quantum 2000

X-ray source: monochrome Alka 1486.6eV

Acceptance angle + 23 °

Take-off angle 45 °

Analysis area 600 μm

Charge compensation C1s 284.8 eV

Ion gun conditions Ar +, 1 keV, 2 x 2 mm raster

Sputter speed 15.6 A / min (SiO ₂ equivalent)

V.A. XPS does not detect oxygen or helium. The values given are normalized to Si = 1 for the experimental number (last row) using the detected constituents and to O = 1 for the uncoated polyethylene terephthalate calculation and example. The detection limits are approximately 0.05 to 1.0 electron percent. Also, given values are normalized to 100% Si + O + C atoms.

The VA has an Si / O ratio of 2.4, indicating an SiO _x composition with some residual carbon due to incomplete oxidation of the coating. This analysis shows the composition of the SiO _x barrier film applied to the polyethylene terephthalate tube according to the present invention.

VA Table 4 shows the thickness of SiO _x samples measured using TEM according to the following method. Samples were prepared for a focused ion beam (FIB) by coating the samples with a sputtered layer of platinum (50-100 nm thickness) using a K575X EMITEC coating system. The coated samples were placed in an FEI FIB200 FIB system. The platinum addition film was FIB deposited by injecting an organometallic gas while injecting a 30 kV gallium ion beam onto the region of interest. The area of interest for each sample was chosen to be located at half the tube length. Thin sections measured at a length of approximately 15 micrometers ("micrometers"), 2 micrometers wide and 15 micrometers deep were extracted from the die surface using a proprietary in-situ FIB lift-out technique . The sections were attached to a 200 mesh copper TEM grid using FIB-deposited platinum. One or two windows in each section measured at a width of about 8 microns were thinned with electron transparency using the gallium ion beam of the FEI FIB.

V.C. Cross-sectional image analysis of the prepared samples was performed using a transmission electron microscope (TEM). Imaging data was digitally recorded.

The sample grids were transferred to a Hitachi HF2000 transmission electron microscope. The transmitted electronic images were obtained by zooming in appropriately. Appropriate tool settings used during image acquisition are given below.

Example 5

Plasma uniformity

The COC syringe barrels manufactured according to the protocol for forming the VA COC syringe barrel are processed using a protocol for coating the interior of the COC syringe barrel with SiO _x , . Three different plasma generation modes have been tested for coating syringe barrels, such as 250, with SiO _x films. In VA mode 1, hollow cathode plasma ignition was generated in the gas inlet 310, the confined area 292 and the processing vessel lumen 304, and the normal or non-hollow-cathode plasma was generated in the rest of the vessel lumen 300 Lt; / RTI >

V.A. In mode 2, hollow cathode plasma ignition has been generated within the confined area 292 and the processing vessel lumen 304 and a conventional or non-hollow-cathode plasma has been generated in the vessel lumen 300 and the remainder of the gas inlet 310 .

V.A. In mode 3, a conventional or non-hollow-cathode plasma was generated in the stagnant vessel lumen 300 and the gas inlet 310. This was done by quenching the hollow cathode ignition with the power up to its maximum. Table 6 shows the conditions used to achieve these modes.

V.A. The syringe barrels 250 were then exposed to the ruthenium oxide staining technique. The dyeing consisted of sodium hypochlorite bleach and Ru (III) chloride hydrate. 0.2 g of Ru (III) chloride hydrate was placed in the vial. 10 ml of bleach was added and mixed thoroughly until the Ru (III) chloride hydrate was dissolved.

V.A. Each syringe barrel was sealed with a plastic Luer seal and 3 drops of dye mixture were added to each syringe barrel. The syringe barrels were then sealed with aluminum tape and left for 30 to 40 minutes. In each set of syringe barrels tested, at least one uncoated syringe barrel was stained. The syringe barrels were stored with the restricted area 292 facing up.

V.A. Based on this staining, the following conclusions were drawn:

V.A. 1. Starting to attack uncoated (or poorly coated) areas with exposure within 0.25 hours due to the staining.

VA 2. The result in the restricted area 292 in the ignition of the SiO _x coating the restricted area 292, it has been made.

V.A. 3. The best syringe barrels were produced by testing without hollow cathode plasma ignition in either the gas inlet 310 or the confined area 292. Perhaps only limited openings 294 were stained due to staining leaks.

V.A. 4. Dyeing is a good qualitative tool to induce uniformity work.

V.A. Based on all of the above, we conclude that:

V.A. 1. Under the test conditions, the hollow cathode plasma in either the gas inlet 310 or the confined area 292 was less uniform in coating.

V.A. 2. Best uniformity was achieved without hollow cathode plasma ignition either in the gas inlet 310 or in the confined area 292.

Example 6

Interference Patterns Obtained from Reflectance Measurements - Prophetic Example

VI.A. (OMEGA optical DH2000-BAL Deuterium tungsten 200-1000 nm), Fiber optic reflection probe (Emitter / Collector Ocean Optics combination QR400-7 SR / BX with an approximate 3 mm probe area), Small detector (Ocean Optics HR4000CG Uncoated PET tube Becton Dickinson (Franklin Lakes, NJ), product number 366703 13x75 mm (without additive), using software that converts the spectrometer signal to a transmittance / wavelength plot on a laptop computer and a UV-NIR spectrometer (Using a probe perpendicular to the coated surface to emit and collect light radially from the centerline of the tube) both in the longitudinal direction around the inner circumference of the tube and along the inner wall of the tube, No interference patterns were observed. Subsequently, Becton Dickinson product number 366703 13x75 mm (without additive) SiO _x plasma-coated BD 366703 tube is coated with a 20 nm thickness SiO ₂ coating as described in the protocol for coating the interior of the tube with SiO _x The tubes are scanned in a manner similar to uncoated tubes. Certain interference patterns are observed for coated tubes, where certain wavelengths are reinforced and others are offset in the periodic pattern, indicating the presence of a coating on the PET tube.

Example 7

Enhanced light transmission from integrative constraint detection

VI.A. The equipment used was a Xenon light source (Ocean Optics HL-2000-HP-FHSA - 20 W output halogen lamp source (185-2000 nm)), an integral constraint detector HR2000 + ES enhanced sensitivity UV with optical ISP-80-8-I) and light transmission source and light receptor fiber optics (QP600-2-UV-VIS - 600um premium optical fiber, UV / VIS, 2m) VIS spectrometer and signal conversion software (SPECTRASUITE - cross-platform spectroscopy operating software). Uncoated PET tubes made according to the protocol for forming the PET tubes were inserted on a TEFZEL tube support (puck) and inserted with an intergrating constraint. Absorbance was set to zero (at 615 nm) using Spectrasuite software in absorbance mode. SiO _x coated tube manufactured in accordance with a protocol for forming the PET tube is coated according to the protocol (except for changes it from the table 16) for coating the inner tube with SiO _x is provided on the subsequent puck (puck), the Inserted with a constraining constraint and absorbance was recorded at a wavelength of 615 nm. The data are recorded in Table 16.

Using the SiO _x coated tubes, an increase in absorbance for the uncoated article was observed; The increase of coating time was indicated by the increase of absorbance. The measurement was less than 1 second.

VI.A. These spectroscopic methods should not be considered to be limited by the acquisition mode (e.g., reflectance vs. transmittance versus absorption), the frequency or type of radiation applied, or other parameters.

Example 8

Measurement of gas removal on PET

VI.B. FIG. 30 from FIG. 15 of US 6,584,828 employs a protocol for forming a PET tube that is seated using seal 360 on the upstream end of a micro-flow technique measurement cell generally designated 362 Up of the test set-up used in the working example of measuring gas removal through the SiO _x barrier coating 348 applied according to the protocol for coating the inside of the tube with SiO _x on the inside wall of the fabricated PET tube 358 Fig.

VI.B. Vacuum pump 364 has flow measurement uncertainty of a second generation IMGS sensor (10 μ / min full range), absolute pressure sensor range: 0-10 Torr, +/- 5% reading in the calibrated range Downstream of a commercially available measurement cell 362 (Intelligent Gas Leakage System with Leakage Test Tool Model ME2) employing a Leak-Tek program for automated data acquisition and a signal / plot of leakage flow versus time Lt; / RTI > This equipment is supplied by ATC and is used to direct gas from the interior of the PET vessel 358 in the direction of the arrow through the measuring cell 362 for measuring the mass flow rate of the vapor removed from the walls into the vessel 358 Consists of.

VI.B. It is understood that the measurement cell 362 shown and described briefly herein operates substantially as follows, although this information may be slightly out of operation with the equipment in actual use. The cell 362 has a conical passage 368 through which the degassed stream is directed. Pressure is supplied to the chambers 374 and 376 formed by the two side holes 370 and 372 spaced longitudinally along the passage 368 and partially formed by the diaphragms 378 and 380 . The pressures accumulated in the respective chambers 374 and 376 deflect the respective diaphragms 378 and 380. This deflection is suitably measured by measuring the change in capacitance between the conductive surfaces of the diaphragms 378 and 380 and the nearby conductive surfaces, such as 382 and 384. Bypass 386 may be optionally provided by bypassing the measurement cell 362 until the desired vacuum level for performing the test is reached to accelerate the initial pump-down.

VI.B. The PET walls 350 of the vessels used in this test were about 1 mm thick and the coating 348 was about 20 nm (nanometers) thick. Thus, the thickness ratio of wall 350 to coating 348 was about 50,000: 1

VI.B. In order to measure the flow rate through the measuring cell 362 including the container chamber 360, fifteen glass containers of substantially the same size and structure as the container 358 were pumped down to an internal pressure of 1 Torr 360, after which the capacitance data was collected using measurement cell 362 and converted to the "degassing" flow rate. The test was performed twice for each container. After the first run, the vacuum was relieved using nitrogen and the vessel allowed to reach equilibrium before proceeding to the second run during the recovery time. This measure is understood to be at least overwhelmingly an indication of the amount of leaking and connection of the container within the measuring cell 362, since the glass container is considered to have little gas removal and infiltration through the wall is impossible, If there is gas removal or penetration, it is hardly reflected. The results are shown in Table 7.

VI.B. The flock of plots 390 of FIG. 31 shows the "degas" flow rate, expressed in micrograms per minute of individual tubes corresponding to the second execution data of Table 7, previously mentioned. Since the flow rate for the plots does not increase substantially over time and is much lower than the other flow rates shown, the flow rate is due to leaks.

VI.B. The groups of plots 392 in Table 8 and Figure 31 show similar data for uncoated tubes made according to the protocol for PET tube formation.

VI.B. This data for uncoated tubes shows much higher flow rates: the increase is due to the gas removal flow of the gases on or within the interior region of the vessel wall. There is some spread between containers that show the sensitivity of the test to small differences between containers and show how containers are seated on the test apparatus.

VI.B. The groups of plots 394 and 396 in Table 9 and Figure 31 are based on a protocol for coating the interior of the PET tube with SiO _x on the inside of the wall 346 of the PET tube made according to the protocol for PET tube formation Similar data is shown for the applied SiO _x barrier coating 348.

VI.B. Because the family of curves 394 for the SiO _x coated, injection molded PET tubes of this example is consistently lower in this test than for PET tubes without flow, the SiO _x The coating acts as a barrier to restrict gas removal from the PET container walls. (The SiO _x coating itself is considered to be the degassing almost should not.) The separation between curves 394 for each of the containers is a test a few different block of SiO _x on said coating have different tube effect Lt; RTI ID = 0.0 > a < / RTI > This spread in the group 394 is largely due to the change in gas tightness between the SiO _x coatings, which results in a change in gas removal or a change in seating integrity between the PET container walls Having a group of confidential curves 392). The two curves for samples 2 and 4 are shown below and the difference from the other data is considered to indicate that the SiO _x coatings of these tubes are defective. This shows that the test can be very clearly separated from the samples that are being treated differently or damaged.

VI.B. Referring to Tables 8 and 9 and 32 mentioned above, the data was statistically analyzed to find the median and numerical values of the above first and third standard deviations and the median (mean) below. These figures are plotted in FIG.

VI.B. First of all, the statistical analysis is that the samples 2 and 4 of Table 9 presenting the coated PET tubes are obvious outliers with a +3 standard deviation or more from the median value. However, these separators are believed to have constant blocking effectiveness because their flow rates are still distinctly (much lower) from the flow rates of uncoated PET tubes.

VI.B. In addition, this statistical analysis can very quickly and accurately analyze the barrier effectiveness of nano-thickness barrier coatings and distinguish coated tubes from uncoated tubes (which are currently regarded as indistinguishable using human senses in coating thickness) Demonstrating the robustness of gas removal measurements. Referring to Figure 32, a coated PET container, shown in the top bar group, exhibiting a gas removal level of at least three standard deviations above an average, is shown in the bottom bar group and has a gas removal level of less than three standard deviations Less gas removal than non-PET containers. This data does not show an overlay for the data with a certain level of confidence outside of 6 sigma (Six Sigma).

VI.B. Based on the success of this test, the zone of SiO _x coating on these PET containers can be detected in a shorter test than this example, especially as statistical data are generated for a larger number of samples . This is evident from the group of clearly apparently separated plots even at times T = 12 seconds for samples of 15 vessels originating at, for example, T = 11 seconds and showing a test duration of about 1 second.

VI.B. It is also contemplated that, based on this data, the barrier effectiveness for SiO _x coated PET containers approaching the blocking effectiveness equivalent to glass or glass can be obtained by optimizing the SiO _x coating.

Example 9

Wet Tension - Plasma Coated PET Tubes Embodiments

VII.A.1.a.ii. The wet tension measurement method is a modification of the method described in ASTM D 2578. Wet tension is a specific measure of the hydrophobicity or hydrophilicity of a surface. This method uses standard wet tension solutions (called dyne solutions) to measure the closest solution to wetting the surface of the plastic film for exactly 2 seconds. This is the wet tension of the film.

VII.A.1.a.ii. The procedure used here is that the substrates are not flat plastic films but are tubes (other than the control) coated according to a protocol for fabricating PET tubes and for coating the interior of the tubes with a hydrophobic coating, It is a modification of ASTM D 2578. A silicone-coated glass syringe (Becton Dickinson Hypak® PRTC glass pre-fillable syringe with Luer-lok® tip) (1 mL) was also tested. The results of this test are listed in Table 10.

Surprisingly, the plasma coating (40 dynes / cm) of the uncoated PET tubes was modified by modifying the plasma process conditions to produce higher (more hydrophilic) or lower (more hydrophobic) hydrophobic polymers using the same hexamethyldisiloxane (HMDSO) Lt; / RTI > energy surfaces. A thin (approximately 20 to 40 nanometer) SiO _x coating (data not shown in the tables) made according to the protocol for coating the interior of the tube with SiO _x provides similar wettability as hydrophobic bulk glass substrates. A thin (about 100 nanometer) hydrophobic coating (data not shown in the tables) made according to the protocol for coating the interior of the tube with a hydrophobic coating provides similar wettability as hydrophobic silicone fluids.

Example 10

Vacuum retention of tubes through accelerated aging

VII.A.3 Accelerated aging will provide a faster assessment of long-life products. Acceleration of aging of blood tubes with or without vacuum is described in US Pat. No. 5,792,940, column 1, lines 11 to 49.

VII.A.3 Three types of polyethylene terephthalate (PET) molded tubes measuring 13 x 75 mm (0.85 mm thick walls) were tested:

Hemogard® system Becton Dickinson product number 366703 13 x 75 mm (without additive) tube sealed with a red stopper and colorless guard [commercial control] (life 545 days or 18 months);

PET tubes made according to the protocol for forming PET tubes sealed with the same type of Hemogard® system red stoppers and colorless guards [internal controls]; And

Molded according to a protocol for forming a PET tube, coated according to a protocol for coating the interior of the tube with SiO _x , and injection molded PET, sealed with the same type of Hemogard® system red stopper and colorless guards [inventive specimen] 13x75 mm tubes.

VII.A.3 BD commercial controls were used as received. The internal control and inventive samples were vacuumed and capped with a stopper system to provide the desired partial pressure (vacuum) inside the tube after sealing. All samples were placed in a 3 gallon (3.8 L) 304 SS wide inlet pressure vessel (Sterlitech No. 740340). The pressure vessel was pressurized to 48 psi (3.3 atm, 2482 mm.Hg). (a) removing 3 to 5 samples at increasing time intervals, (b) allowing water to be drawn into the vacuum tubes from a 1-liter plastic bottle reservoir through a 20-gauge blood collection adapter, and (c) After measuring the change in mass, the measurement of change in water volume inhalation was made.

VII.A.3 The results are shown in Table 11.

VII.A.3 The normalized average decay rate is calculated by dividing the time change in mass by the number of compression days and the initial mass inhale [mass change / (number of days x initial mass)]. Also, the time (in months) accelerated with a 10% loss is calculated. Both data are listed in Table 12.

VII.A.3 This data shows that the commercial control and the uncoated internal control have the same vacuum loss rate and surprisingly improve the vacuum hold time by 2.1 factor due to the incorporation of SiO _x coating on the PET inner walls.

Example 11

Lubricative coating

VII.B.1.a. The following materials were used in this test:

Commercial (BD Hypak® PRTC) glass pre-chargeable syringes (approximately 1 mL) in Luer-lok® tip

COC syringe barrels made according to a protocol for forming COC syringe barrels;

Commercial plastic syringe plungers having elastomer tips taken from Becton Dickinson product number 306507 (obtained as saline pre-filled syringes);

Normal saline solution (taken from Becton Dickinson Part No. 306507 pre-filled syringes);

Dilon test stand with Advanced Force Gauge (Model AFG-50N)

The syringe support and drain jig (made to fit the Dilon test stand above)

VII.B.1.a. The following procedure was used for this test.

VII.B.1.a. The jig was mounted on a Dilon test stand. The platform probe motion was adjusted to 6 inches / minute (2.5 mm / sec) and top and bottom stop positions were set. The stop positions were confirmed using empty syringes and barrels in the contents. Commercial saline-filled syringes were labeled, plungers removed, and saline solution drained through the open ends of the syringe barrels for reuse. Extra plungers were obtained in the same manner for use with COC and glass barrels.

VII.B.1.a. The syringe plungers were inserted into the COC syringe barrels so that the second horizontal forming point of each plunger became parallel to the syringe barrel lip (about 10 mm from the tip end). Using another syringe and needle assembly, the test syringes were filled with 2 to 3 milliliters of saline solution at the top of the capillary through the capillary end. The sides of the syringe were patted to remove large air bubbles at the plunger / fluid interface and along the wall, and any air bubbles were carefully pushed out of the syringe while maintaining the plunger in the vertical direction.

VII.B.1.a. Each filled syringe barrel / plunger assembly was installed with a syringe jig. The test was started by pressing the switch on the test stand and moving the moving metal hammer toward the plunger. If the moving metal hammer is within 5 mm of contact with the top of the plunger, the data button on the Dillon module is repeatedly tapped to allow the plunger to contact the front wall of the syringe barrel prior to the first contact with the syringe plunger, And the force was recorded until it stopped.

VII.B.1.a. All benchmarks and coated syringe barrels were run five times (using a new plunger and barrel for each iteration).

VII.B.1.a. COC syringe barrels made according to the protocol for forming COC syringe barrels are coated with an OMCTS lubricant coating according to a protocol for coating the interior of the COC syringe barrel with an OMCTS lubricant coating, assembled, saline filled, It was tested as described above in the examples. Due to the polypropylene chamber used in accordance with the protocol for coating the inside of the COC syringe barrel with the OMCTS lubricant coating, the OMCTS vapor (and oxygen, if added, see Table 13) flows through the syringe barrel and the syringe capillary into the polypropylene chamber (In which case the lubricous coating may not be needed at the capillary portion of the syringe). Some of the different coating conditions were tested as shown in Table 13 above. All deposits were completed on COC syringe barrels from the same production batch.

The coated samples were then tested using plunger activity according to the protocol of this example and the results are shown in British and Metric power units in Table 13. The data clearly show that in the absence of low power and oxygen, COC and COC provided the lowest plunger activity for coated syringes. Note that when oxygen is added at lower power (6 W) (lower power is a desirable condition), plunger activity increases from 1.09 lb, 0.49 kg (power = 11 W) to 2.27 lb., 1.03 kg . This indicates that the addition of oxygen may not be desirable to achieve the lowest possible plunger force.

VII.B.1.a. In addition, the best plunger force (power = 11 W, plunger force = 1.09 lb, 0.49 kg) avoids glass syringe problems such as breakability and more expensive manufacturing processes, (Active force = 0.58 lb, 0.26 kg). Further optimization is expected to achieve a value above the value of current glass with silicon performance.

VII.B.1.a. COC syringe barrels were coated with COC syringe barrels according to the protocol for coating the interior of the barrel with OMCTS lubricant coatings. Other embodiments of the described herein, for example, to apply the lubricating layer on the other thin film coating such as SiO _x coating according to the protocol for coating the inside COC syringe barrel with SiO _x.

Example 12

Improved syringe barrel lubricated coating

VII.B.1.a. The force required to discharge the 0.9 percent saline load from the syringe through the capillary bore using a plastic plunger was measured against the inner wall-coated syringes.

VII.B.1.a. Three types of COC syringe barrels made according to the protocol for forming a COC syringe barrel were tested: a first type (uncoated control) without internal coating, a protocol for coating the inside of a COC syringe barrel with an HMDSO coating (HMDSO control) with a hexamethyldisiloxane (HMDSO) based plasma-coated inner wall coating according to the protocol for coating the inner part of the COC injector barrel with an OMCTS lubricative coating [OMCTS-concentrate Example 3 A third type with a plasma coated inner wall coating. BD Plastics New plastic plungers with elastomeric tips taken from Becton Dickinson product number 306507 were tested for all embodiments. Also, saline of product number 306507 was used.

VII.B.1.a. Plasma coating methods and apparatus for coating syringe barrel inner walls are described in other experimental sections of this application. Specific coating parameters for the HMDSO-series and OMCTS-series coatings are listed in the protocol for coating the inside of the COC syringe barrel with the HMDSO coating, the protocol for coating the inside of the COC syringe barrel with the OMCTS lubricant coating,

VII.B.1.a. The plunger is inserted about 10 millimeters into the syringe barrel, and a vertical filling of the experimental syringe is achieved using a saline-filled syringe / needle system separated through an open syringe capillary. When the experimental syringe is filled with capillary holes, the syringe is tapped such that air bubbles adhered to the inner walls are discharged and raised through the capillary holes.

VII.B.1.a. The filled test syringe barrel / plunger assembly goes vertically into a household hollow metal jig so that the syringe assembly is supported on the jig in the finger flanges. The jig has a drain tube on the bottom and is mounted on a Dilon test stand using an Advanced Force Gauge (Model AFG-50N). The test stand has a metal hammer that moves vertically downward at a rate of 6 inches per minute (152 millimeters). The metal hammer contacts the elongated plunger that discharges the saline solution through the capillary. Once the plunger contacts the syringe barrel / capillary interface, the experiment is stopped.

VII.B.1.a. During the downward movement of the metal hammer / extended plunger, the resistance imparted on the hammer as measured on the force gauge is recorded on the electronic spreadsheet. From the spreadsheet data, the maximum force for each experiment is ascertained.

VII.B.1.a. Table 14 lists the normalized maximum force measured by dividing the maximum force average and the coated syringe barrel maximum force average from the COC syringe barrels repeatedly coated for each example by the maximum uncoated force average.

VII.B.1.a. This data demonstrates that all OMCTS-family inner wall plasma coated COC syringe barrels (Examples C, E, F, G, and H) are much better than uncoated COC syringe barrels (uncoated Controls A and D) Low plunger activity and surprisingly much less plunger activity than HMDSO-series inner wall plasma coated COC syringe barrels (HMDSO control B). Even more remarkable is that applying an OMCTS series coating on a silicon oxide (SiO _x ) gas barrier coating will keep the plunger sliding force very low (Concentration Example F). The best plunger force was Example C (power = 8, plunger force = 1.1 lb, 0.5 kg). Note that this is very close to the current industry standard of silicon coated glass (active force = 0.58 lb, 0.26 kg), while avoiding glass syringe problems such as cuttability and more expensive manufacturing processes. Further optimization is expected to achieve a value above the value of current glass with silicon performance.

Example 13

Fabrication of COC syringe barrel with external coating - Prophetic example

VII.B.1.c. A COC syringe barrel formed according to the protocol for forming the COC syringe barrel is sealed using disposable closure at both ends. The capped COC syringe barrel was passed through a bath of Daran® 8100 Saran latex (Owensboro specialty plastics). This latex contains 5 percent isopropyl alcohol to reduce the surface tension of the composition to 32 dynes / cm. The latex composition completely wets the outside of the COC syringe barrel. After draining for 30 seconds, the coated COC syringe barrels contained 275 DEG F (135 DEG C) (latex fusion) for 25 seconds and 122 DEG F (50 DEG C) (final cure) for 4 hours in each forced air oven To the heating schedule. The resulting PvDC film is 1/10 mil (2.5 microns) thick. COC syringe barrels and PvDC-COC laminate COC syringe barrels are measured for OTR and WVTR using the MOCON brand Oxtran 2/21 Oxygen Permeable and Permatran- W 3/31 vapor permeable instruments.

VII.B.1.c. Expected OTR and WVTR values are listed in Table 15, which shows the expected barrier enhancement factor (BIF) for the laminate.

Example 15

Atomic compositions of PECVD-applied OMCTS and HMDSO coatings

VII.B.4. (According to the protocol for coating the interior of a COC syringe barrel with an OMCTS lubricant coating) or coated with HMDSO coatings in a COC syringe barrel with an HMDSO coating, according to the protocol for forming a COC syringe barrel Coated COC syringe barrel samples are provided. Atomic compositions of coatings derived from OMCTS or HMDSO have been characterized using X-ray photoelectron spectroscopy (XPS).

VII.B.4. XPS data were quantified using relative sensitivity factors and a single layered model. The analysis volume is the product of the area of analysis (spot size or aperture size) and the depth of information. Photoelectrons are generated within the X-ray penetration depth (typically a few microns), but only the photoelectrons within the three top electron escape depths are detected. The escape depth is on the order of 15 to 35 Angstroms, which leads to an analytical depth of about 50 to 100 Angstroms. Typically, 95% of the signal is within this depth.

VII.B.4. The following analytical parameters were used:

Tools: PHI Quantum 2000

X-ray source: monochrome Alka 1486.6eV

Acceptance angle + 23 °

Take-off angle 45 °

Analysis area 600 ㎛

Charge compensation C1s 284.8 eV

Ion gun conditions Ar +, 1 keV, 2 x 2 mm raster

Sputter rate 15.6 Å / minute (SiO ₂ eq)

VII.B.4. Table 17 provides the atomic concentrations of the detected constituents. XPS does not detect oxygen or helium. The values given are normalized to 100 percent using the detected components. The detection limits are approximately 0.05 to 1.0 electron percent.

VII.B.4.b. From the coating composition results in Table 17 and the calculated starting monomeric precursor element percent, the percentage of carbon atoms of the HMDSO-based coatings is reduced (from 54.1% to 44.4%) compared to the starting HMDSO monomer carbon percentage, surprisingly the OMCTS-series The percentage of coating carbon atoms was increased relative to the percent OMCTS monomer carbon atoms (from 34.8% to 48.4%), which is an increase of 39 atomic% calculated as follows:

100% [(48.4 / 34.8) -1] = 39 atomic%.

In addition, the percentage of silicon atoms in the HMDSO-series coatings is almost unchanged (from 21.8% to 22.2%) compared to the starting HMDSO monomer silicon atoms percent, while surprisingly the percentage of silicon atoms in the OMCTS- (Decreased from 42.0% to 23.6%), which is a decrease of 44 atomic%. Using carbon and silicon changes, the OMCTS monomer-to-coating behavior does not go in the same direction as the behavior observed in normal precursor monomers (e.g., HMDSO). For example, Hans J. Griesser, Ronald C. Chatelier, Chris Martin, Zoran R. Vasic, Thomas R. Gengenbach, George Jessup J. Biomed. Mater. (Appl Biomaster) 53: 235-243, 2000.

Example 16

Volatile components ("degassing") from plasma coatings

VII.B.4. (According to the protocol for coating the interior of the COC syringe barrel with the HMDSO coating) or coated with OMCTS (according to the protocol for coating the inside of the COC syringe barrel with the OMCTS lubricating coating) COC syringe barrel samples coated with HMDSO are provided. Volatile components released from OMCTS or HMDSO coatings were measured using gas removal gas chromatography / mass spectrometry (GC / MS) analysis.

VII.B.4. Syringe barrel samples (four COC syringe barrels cut in half length) were placed in one of the 1½ "(37 mm) diameter chambers of a dynamic headspace sample extraction system (CDS 8400 auto-sampler) Prior to sample analysis, the system blanks were analyzed. The samples were analyzed on an Agilent 7890A gas chromatography / Agilent 5975 mass spectrometer using the following parameters to generate the data set forth in Table 18:

GC column: 30m X 0.25mm DB-5MS (J & W Scientific),

0.25 μm Film thickness

Flow rate: 1.0 ml / min, uniform flow mode

Detector: mass selective detector (MSD)

Scanning mode: split scan (10: 1 split ratio)

Degassing conditions: 1½ "(37 mm) chamber, purged for 3 hours

85 캜, flow rate 60 ml / min

Oven temperature: 40 ° C (5 minutes) to 300 ° C at a rate of 10 ° C / min;

At 300 ° C, hold for 5 minutes.

The gas removal results in Table 18 clearly show the compositional differences between the tested HMDSO-series and OMCTS-series lubricous coatings. The HMDSO-based compositions degassed trimethylsilanol [(Me) ₃ SiOH], but did not degass the measured more oligomers containing repeating - (Me) ₂ SiO- moieties, whereas OMCTS- The measured trimethylsilanol [(Me) ₃ SiOH] was not degassed and more oligomers containing repeating - (Me) ₂ SiO- moieties were degassed. This test is considered to be useful in distinguishing HMDSO-series coatings from OMCTS-series coatings.

Without limiting the present invention to the extent or accuracy of the following theory, the results show that the acyclic structure of HMDSO in which each silicon atom is bonded to three methyl groups versus the methyl groups bonded to each silicon atom It can be explained by considering the cyclic structure of OMCTS having only two. The OMCTS is considered to react by a ring-opening reaction to form a double radical with already-oligomeric repeating - (Me) ₂ SiO- moieties, which can condense to form higher oligomers. On the other hand, HMDSO decomposes at least one O-Si bond to form a single fragment containing a single O-Si bond that reacts with (Me) ₃ SiOH and reacts with [(Me) ₃ Si] ₂ Leaving a different fragment that does not contain an O-Si bond.

The cyclic nature of the OMCTS is considered to lead to the ring opening and condensation of these ring open moieties depleting the higher MW oligomers (26 ng / test). On the other hand, HMDSO-series coatings are considered not to provide relatively low-molecular weight fragments from HMDSO.

Example 17

Density measurements of plasma coatings using X-ray reflectance (XRR)

Sapphire witness samples (0.5 x 0.5 x 0.1 cm) were glued to the inner walls of separate PET tubes made according to the protocol for the formation of PET tubes. The sapphire witness-containing PET tubes (all according to the protocol for coating the interior of the COC syringe barrel with the OMCTS lubricant coating, which is deviated from the double power source), were coated with OMCTS or HMDSO. The coated sapphire samples were then removed and X-ray reflectance (XRR) data was obtained on a PANalytical X'Pert diffractometer equipped with a parabola multilayer incident beam monochromator and an equilibrium plate diffracted beam collimator. The two-layer Si _w O _x C _y H _z model was used to measure the coating density from the critical angle measurement results. This model is considered to provide the best approach to isolate the true Si _w O _x C _y H _z coating. The results are shown in Table 19.

From Table 17, which shows the results of Example 15, the lower oxygen (28%) and higher carbon (48.4%) compositions of OMCTS versus HMDSO exhibit both atomic mass considerations and atomic number (oxygen = 2; By all, OMCTS would mean having a lower density. Surprisingly, XRR density results show that the opposite will be observed, i.e., the OMCTS density is higher than the HMDSO density.

It is contemplated that there is a fundamental difference in the reaction mechanism in the formation of each HMDSO-series and OMCTS-series coatings, without limiting the invention to the extent or accuracy of the following theories. The HMDSO fragments coagulate and react very easily to form nanoparticles, which are then less likely to form dense gaseous nanoparticles while they can be deposited on the surface and react more on the surface. OMCTS reactive species are more likely to condense on the surface in a form similar to the original OMCTS monomer, resulting in a lower density coating overall.

Example 18

Thickness uniformity of PECVD applied coatings

According to the protocol for coating the inside of the SiO _x or COC syringe barrel with the OMCTS lubricative coating according to the protocol for coating the inside of the COC syringe barrel with SiO _x , respectively, according to the protocol for forming the COC syringe barrel. Samples of COC syringe barrels coated with a coating are provided. Moreover, it was provided with a sample of the PET tube is manufactured in accordance with a protocol for forming the PET tube, according to the protocol for coating each of the inner tube to the SiO _x coated with SiO _x is not coated which is subjected to the accelerated aging test. The thickness of the PECVD-applied coatings on the samples was measured using a transmission electron microscope (TEM). The TEM procedure of Example 4 described above was used. The method and apparatus described by the SiOx and lubricous coating protocols used in this example showed a uniform coating as shown in Table 20. < tb >< TABLE >

Example 19

Gas removal measurements on COC

VI.B. The COC tubes were made according to the protocol for forming the COC tubes. Some of the tubes were provided with an inner barrier coating of SiOx according to a protocol for coating the inside of the tubes with SiO _x , and the remaining COC tubes were not coated. Commercial Blood Collection Becton Dickinson 13x75 mm tubes with similar dimensions were also provided as above. The tubes were stored for about 15 minutes in a room containing ambient air at 45% relative humidity and 70 DEG F (21 DEG C), and the following tests were performed at the same ambient relative humidity. The tubes were placed under the following ATC microflow measurement procedure and equipment (second generation IMFS sensor, 10 [mu] / min full range), absolute pressure sensor range: 0-10 Torr, +/- 5% Leak-Tek program for automatic data acquisition (using PC) with flow measurement uncertainty of reading and intelligent gas leak system with leakage test tool model ME2 employing leakage flow versus time signal / plate Was tested. In the present case, each tube undergoes a 22-second bulk water degassing step at a pressure of 1 mm Hg and then compressed using nitrogen gas (to 760 mm Hg) for 2 seconds, And the microflow measurement step was carried out for 1 minute at 1 mm Hg pressure.

VI.B. The result is shown in FIG. 57, which is similar to FIG. 31 produced in Example 8. In Figure 57, the plots for uncoated COC tubes are at 630, the plots for SiOx coated COC tubes are at 632, the plots for glass tubes used as controls are (634) . Also, the degassing measurement started at about 4 seconds, and after a few seconds, plots 630 for uncoated COC tubes and plots 632 for SiOx barrier coated tubes were clearly branched off, It shows that there is a sudden difference between coated and uncoated tubes. A consistent separation of uncoated COC (> 2 micrograms in 60 seconds) vs. SiO _x -coated COC (less than 1.6 micrometers in 60 seconds) was realized.

Example 20

Lubricative coating

VII.B.1.a. COC syringe barrels made according to the protocol for forming COC syringe barrels were coated with a lubricous coating according to the protocol for coating the interior of a COC syringe barrel with an OMCTS lubricant coating. The results are provided in Table 21. The results show that the tendency of the power level to increase from 8 watts to 14 watts in the absence of oxygen improves the lubrication of the coating. Other experiments with power and flow rates can provide different lubricity enhancements.

Example 21

Lubricant Coating - Hypothetical Example

Injection molded cyclic olefin copolymer (COC) plastic syringe barrels are made according to the protocol for forming COC syringe barrels. Some are not coated ("control") and the rest are PECVD lubricated coated ("lubricated syringes") according to a protocol for coating the inside of a COC syringe barrel with an OMCTS lubricant coating. The lubricated syringes and controls measure the force (plunger force) that keeps the plunger moving in the barrel using a force (breakout force) to initiate movement of the plunger in the barrel and a Genesis Packaging Automated Syringe Force Tester, Model AST .

The test is a modified version of the ISO 7886-1: 1993 test. The following procedure is used for each test. New plastic plungers with elastomeric tips taken from Becton Dickinson product number 306507 (obtained as saline pre-filled syringes) are removed from the syringe assembly. The elastomeric tip is dried with clean dry compressed air. The elastomer tip and plastic plunger are then inserted into the COC plastic syringe barrel, which is tested with a plunger positioned flush with the bottom of the syringe barrel. The filled syringes are then adjusted as needed to reach the tested condition. For example, if the test purpose is to determine the effect of the lubricant coating on the breakout forces of the syringes after storing the syringes for three months, the syringes are stored for three months to achieve the desired condition.

The syringe is installed with Genesis Packaging Automated Syringe Force Tester. The tester is calibrated at the start of the test according to the manufacturer's specifications. The tester input variables are speed = 100 mm / min, range = 10,000. Press the start button of the tester. At the completion of the test, the breakout force (to initiate movement of the plunger in the barrel) and the plunger activity force (to maintain movement) are measured and substantially lower for the lubricated syringes than for the control syringes I know.

Figure 59 illustrates a vessel treatment system 20 in accordance with an exemplary embodiment of the present invention. The vessel treatment system 20 in particular includes a first treatment station 5501 and a second treatment station 5502. Embodiments of such processing stations are illustrated, for example, by reference numerals 24, 26, 28, 30, 32 and 34 in FIG.

The first vessel treatment system 5501 includes a vessel support 38 that supports a seated vessel 80. Although FIG. 59 shows a blood tube 80, the container may be a syringe body, vial, conduit, for example, a pipette. The container may be made of, for example, glass or plastic. In the case of a plastic container, the first processing station may include a forming mold for molding the plastic container.

In the first processing station, the first treatment (the treatment may include forming a container, performing a first inspection of the container to see if it is defective, coating the inner surface of the container, and in particular, The container support 38 is transported to the second container processing station 5502 together with the container 82. [ This conveyance is carried out by the conveyor arrangement 70, 72, 74. For example, the gripper or some grippers may be provided to hold the container support 38 and / or the container 80 to move the container / support combination to the next processing station 5502. Also, only the container can be moved without a support. However, it may be advantageous to move the support along with the container when the support is adapted to be transported by the conveyor arrangement.

Figure 60 illustrates a container handling system 20 in accordance with another exemplary embodiment of the present invention. In addition, two vessel treatment stations 5501 and 5502 are provided. Also provided are other vessel processing stations 5503 and 5504 arranged in series and in which the vessel is processed, i.e., inspected and / or coated.

The vessel may be moved from the stock to the left processing station 5504. In addition, the vessel may be molded in a first processing station 5504. In either case, a first vessel treatment such as molding, inspection and / or coating is performed at the treatment station 5504, after which a second inspection may be performed. The vessel is then moved to the next processing station 5501 through the conveyor arrangement 70, 72, 74. Typically, the container is moved with the container support. The second process is performed in the second process station 5501, after which the container and the support are moved to the next process station 5502 where the third process is performed. Thereafter, the vessel (again with the support) is moved to the fourth processing station 5503 for a fourth process, which is then transferred to a conveyor to the reservoir.

Inspection of the entire container, a portion of the container and in particular the inner surface of the container, may be carried out before and after each coating step or molding step or other step of manipulating the container. The results of each test may be communicated to the central processing unit 5505 via the data bus 5507. Each processing station is connected to the data bus 5507. The processor 5505, which may be modified in the form of a central control and control unit, processes the inspection data, analyzes the data, and determines whether the final processing step is successful.

If the final treatment step is determined to be unsuccessful, the container will not enter the next container treatment station, but will be removed from the process (e.g., the conveyor Sections 7001, 7002, 7003, 7004) are moved back to the conveyor for reprocessing.

The processor 5505 is coupled to a user interface 5506 for entering control or adjustment parameters.

61 shows a processing station 5501 of a vessel treatment system according to an exemplary embodiment of the present invention. The station includes a PECVD apparatus 5701 for coating the inner surface of the vessel. In addition, several detectors 5702-5707 are provided for visual inspection. Such detectors may be, for example, electrodes for performing electronic measurements as optical detectors such as CCD cameras, gas detectors or pressure detectors.

Figure 62 shows a container support 38 in accordance with an exemplary embodiment of the present invention, with electrodes with some detectors 5702, 5703, 5704 and gas input ports 108,

The electrode and detector 5702 may be adapted to move into the interior space of the vessel 80 when the vessel is seated on the support 38.

For example, using optical detectors 5703, 5704 arranged outside of the seated container 80, or even using optical detectors 5707 arranged inside the interior space of the container 80, Optical inspection can be performed.

The detectors may include color filters such that other wavelengths may be detected during the coating process. The processing unit 5505 analyzes the optical data and determines whether the coating is successful with a certain coalescence level. If it is determined that the coating is probably not successful, each vessel is separated or reprocessed from the processing system.

While the invention has been illustrated and described in detail in the drawings and foregoing detailed description, such drawings and description are to be considered illustrative or exemplary and not restrictive; The present invention is not limited to the disclosed embodiments. Other modifications to the disclosed embodiments may be understood and effected by those skilled in the art from practicing the claimed invention from a study of the drawings, the disclosure, and the appended claims. In the claims, the word "comprising" does not exclude other elements or steps, and the indefinite article "one" or "one" does not exclude plural. The fact that certain measures are cited in different dependent claims does not indicate that a combination of these measures can not be used to advantage. Any reference signs in the claims should not be construed as limiting the scope.

Coated COC tubes OTR and WVTR measurements Coating ID Power (Watts) O-Si O-Si flow rate
(sccm) O ₂
flow
(sccm) Time (seconds) OTR
(cc /
tube.
Work) WVTR
(mg /
tube.
Work) number
coating 0.215 0. 27 A 50 HMDSO 6 90 14 0.023 0. 07 B 50 HMDSO 6 90 14 0.024 0. 10 C 50 HMDSO 6 90 7 0.026 0. 10

Coated PET tube OTR and WVTR measurements Coating ID Power (Watts) O-Si O-Si flow (sccm) O ₂
Flow (sccm) Time (seconds) OTR
(cc /
tube.
Work) WVTR
(mg /
tube.
Work) Uncoated control group 0.0078 3.65 SiO _x 50 HMDSO 6 90 3 0.0035 1.95

Coated COC COC syringe barrel OTR and WVTR measurement Example syringe
coating O-Si
Composition power
(watt) O-Si
flux
(sccm) O ₂
flux
(sccm) coating
time
(second) OTR
(cc /
Barrel.
Work) WVTR
(mg /
Barrel.
Work) BIF
(OTR) BIF
(WVTR) A Uncoated control group 0.032 0.12 B SiO _x footprint HMDSO 44 6 90 7 0.025 0.11 1.3 1.1 C SiO _x footprint HMDSO 44 6 105 7 0.021 0.11 1.5 1.1 D SiO _x footprint HMDSO 50 6 90 7 0.026 0.10 1.2 1.2 E SiO _x footprint HMDSO 50 6 90 14 0.024 0.07 1.3 1.7 F SiO _x footprint HMDSO 52 6 97.5 7 0.022 0.12 1.5 1.0 G SiO _x footprint HMDSO 61 6 105 7 0.022 0.11 1.4 1.1 H SiO _x footprint HMDSO 61 6 120 7 0.024 0.10 1.3 1.2 I SiO _x footprint HMDZ 44 6 90 7 0.022 0.10 1.5 1.3 J SiO _x footprint HMDZ 61 6 90 7 0.022 0.10 1.5 1.2 K SiO _x footprint HMDZ 61 6 105 7 0.019 0.10 1.7 1.2

SIO detected by TEM _x Coating Thickness (nanometer) sample O-Si Thickness (nm) Power (Watts) HMDSO flow rate (sccm) Oxygen flow rate (sccm) Inventory A HMDSO 25 to 50 39 6 60 Inventory B HMDSO 20 to 35 39 6 90

The atomic ratio of the detected elements (parentheses: percent concentration, normalized to 100% of the detected components) sample Plasma coating Si O C Uncoated PET Tubes - Comparative Example - 0.08 (4.6) 1 (31.5) 2.7 (63.9) Polyethylene terephthalate (calculated) - 1 (28.6) 2.5 (71.4) Coated PET Tubes - Examples SiO _x 1 (39.1) 2.4 (51.7) 0.57 (9.2)

Degree of Hollow Cathode Plasma Ignition sample power time Hollow Cathode Plasma Ignition Dyeing result A 25 watts 7 seconds Is not ignited at the gas inlet 310, and ignites at the limited portion 292 Good B 25 watts 7 seconds At the gas inlet 310 and the restricted portion 292, Bad C 8 watts 9 seconds Is not ignited at the gas inlet 310, and ignites at the limited portion 292 Great D 30 watts 5 seconds Is not ignited at the gas inlet 310 or the restricted portion 292 Very good

Flow rates using glass tubes Glass tube Work # 1 (占 퐂 / min) Work # 2 ([mu] g / min) Mean (/ / min) One 1.391 1.453 1.422 2 1.437 1.243 1.34 3 1.468 1.151 1.3095 4 1.473 1.019 1.246 5 1.408 0.994 1.201 6 1.328 0.981 1.1545 7 Broken Broken Broken 8 1.347 0.909 1.128 9 1.171 0.91 1.0405 10 1.321 0.946 1.1335 11 1.15 0.947 1.0485 12 1.36 1.012 1.186 13 1.379 0.932 1.1555 14 1.311 0.893 1.102 15 1.264 0.928 1.096 Average 1.343 1.023 1.183 maximum 1.473 1.453 1.422 at least 1.15 0.893 1.0405 maximum minimum 0.323 0.56 0.3815 Standard Deviation 0.097781 0.157895 0.1115087

Flow rates using glass tubes Uncoated
PET Work # 1 (占 퐂 / min) Work # 2 ([mu] g / min) Mean (/ / min) One 10.36 10.72 10.54 2 11.28 11.1 11.19 3 11.43 11.22 11.325 4 11.41 11.13 11.27 5 11.45 11.17 11.31 6 11.37 11.26 11.315 7 11.36 11.33 11.345 8 11.23 11.24 11.235 9 11.14 11.23 11.185 10 11.1 11.14 11.12 11 11.16 11.25 11.205 12 11.21 11.31 11.26 13 11.28 11.22 11.25 14 10.99 11.19 11.09 15 11.3 11.24 11.27 Average 11.205 11.183 11.194 maximum 11.45 11.33 11.345 at least 10.36 10.72 10.54 maximum minimum 1.09 0.61 0.805 Standard Deviation 0.267578 0.142862 0.195121

Flow rates for SiOx coated PET tubes Coated
PET Work # 1 (占 퐂 / min) Work # 2 ([mu] g / min) Mean (/ / min) One 6.834 6.655 6.7445 2 9.682 9.513 Separations 3 7.155 7.282 7.2185 4 8.846 8.777 Separations 5 6.985 6.983 6.984 6 7.106 7.296 7.201 7 6.543 6.665 6.604 8 7.715 7.772 7.7435 9 6.848 6.863 6.8555 10 7.205 7.322 7.2635 11 7.61 7.608 7.609 12 7.67 7.527 7.5985 13 7.715 7.673 7.694 14 7.144 7.069 7.1065 15 7.33 7.24 7.285 Average 7.220 7.227 7.224 maximum 7.715 7.772 7.7435 at least 6.543 6.655 6.604 maximum minimum 1.172 1.117 1.1395 Standard Deviation 0.374267 0.366072 0.365902

Measuring wet tension of coated and uncoated tubes Example Tube coating Wet tension
(Dyne / cm) Reference Uncoated glass 72 Honor PET tubes coated with SiO _x according to the SiO _x protocol 60 Comparative Example Uncoated PET 40 Honor Coated PET tube according to the hydrophobic coating protocol 34 Comparative Example Glass (+ silicone fluid) glass syringe, part number 30

Water mass draw (DRAW) (grams) Compression time (days) tube 0 27 46 81 108 125 152 231 BD PET (commercial control) 3.0 1.9 1.0 Uncoated PET (internal control) 4.0 3.1 2.7 SiO _x -coated PET ( _by -product) 4.0 3.6 3.3

Calculated normal average vacuum reduction rate and time to 10% vacuum loss tube Normalized mean reduction rate (delta mL / first mL. Day) 10% loss time (months) - Acceleration BD PET
(Commercial control group) 0.0038 0.9 Uncoated PET
(Internal control group) 0.0038 0.9 SiOx-coated PET (by-product) 0.0018 1.9

Syringe barrel with lubricous coating, unit UK sample Power, (watts) O-Si flow, (sccm) O ₂ Flow, (sccm) Time (seconds) Average power, (lb.) Standard Deviation Glass with silicon No coating No coating No coating No coating 0.58 0.03 Uncoated COC No coating No coating No coating No coating 3.04 0.71 A 11 6 0 7 1.09 0.27 B 17 6 0 14 2.86 0.59 C 33 6 0 14 3.87 0.34 D 6 6 90 30 2.27 0.49 Uncoated COC - - - - 3.9 0.6 SiO _x on COC 4.0 1.2 E 11 1.25 0 5 2.0 0.5 F 11 2.5 0 5 2.1 0.7 G 11 5 0 5 2.6 0.6 H 11 2.5 0 10 1.4 0.1 I 22 5 0 5 3.1 0.7 J 22 2.5 0 10 3.3 1.4 K 22 5 0 5 3.1 0.4

Plunger activity measurements of HMDSO- and OMCTS-series plasma coatings details Monomer Coating time
(Seconds) coating
Si-O flow rate (sccm) coating
power
(watt) maximum
power
(lb, kg.) Normalized
Maximum force Uncoated control group 3.3, 1.5 1.0 HMDSO Coating HMDSO 7 6 8 4.1, 1.9 1.2 OMCTS lubricating coating OMCTS 7 6 8 1.1, 0.5 0.3 Uncoated control group 3.9, 1.8 1.0 OMCTS lubricating coating OMCTS 7 6 11 2.0, 0.9 0.5
Double layer coating
1 COC syringe barrel + SiO _x

2 OMCTS lubricated coating
14

7
6

6
50

8

2.5, 1.1

0.6
OMCTS lubricating coating
OMCTS
5
1.25
11
2, 0.9
0.5
OMCTS lubricating coating
OMCTS
10
1.25
11
1.4, 0.6
0.4

OTR and WVTR measurements (prophetic) sample OTR
(cc / barrel day) WVTR
(Grams / barrels, days) COC syringe - comparison example 4.3 X 3.0 Y PvDC-COC Laminate COC Syringe - Valuation X Y

The optical absorption rate of SiOx coated PET tubes (normalized with uncoated PET tubes) sample Coating time Average absorbance (at 615 nm) copy Standard Deviation Reference (uncoated) - 0.002 to 0.014 4 Invention A 3 seconds 0.021 8 0.001 Invention B 2 x 3 seconds 0.027 10 0.002 Invention C 3 x 3 seconds 0.033 4 0.003

Atomic concentrations (parentheses: percent, normalized to 100% of the detected components) sample Plasma coating Si O C HMDSO-series coated COC COC syringe barrel Si _w O _x C _y 0.76 (22.2) 1 (33.4) 3.7 (44.4) OMCTS-series coated COC syringe barrels Si _w O _x C _y 0.46 (23.6) 1 (28) 4.0 (48.4) HMDSO monomer - calculated Si ₂ OC ₆ 2 (21.8) 1 (24.1) 6 (54.1) OMCTS Monomers - Calculated Si ₄ O ₄ C ₈ 1 (42) 1 (23.2) 2 (34.8)

Volatile components from syringe removal Coating monomer Me ₃ SiOH (ng / test) Highly ordered SiOMe oligomers (ng / test) Uncoated COC Syringe - Comparative Example Uncoated ND ND HMDSO-series coated COC syringe - comparative example HMDSO 58 ND OMCTS-series coated COC syringe barrel - OMCTS ND 26

From the XRR measurement, plasma coating density sample layer Density g / cm ³ HMDSO-Series Coated Sapphire - Comparative Example Si _w O _x C _y H _z 1.21 OMCTS-Series Coated Sapphire - Honeycomb Si _w O _x C _y H _z 1.46

Thickness of PECVD coatings by TEM Sample ID TEM
Thickness I TEM
Thickness II TEM
Thickness III A protocol for forming COC syringe barrels; _{Protocol for Coating the} inside of COC syringe barrel with SiO _x 164 nm 154 nm 167 nm A protocol for forming COC syringe barrels; Protocol for coating COC syringe barrel interior with OMCTS lubricant coating 55 nm 48nm 52 nm A protocol for forming a PET tube; Inside the tube,
Protocol for coating with x 28 nm 26 nm 30 nm A protocol for forming a PET tube; Protocol for coating the inside of a tube with SiOx
PET tube formation (uncoated) - - -

OMCTS Lubricity Coating Performance (UK) sample Average Plug Power (pounds) * Percent force reduction (vs. uncoated) Power (Watts) OMCTS flow (sccm) Comparison (no coating) 3.99 - - - Sample A 1.46 63% 14 0.75 Sample B 1.79 55% 11 1.25 Sample C 2.09 48% 8 1.75 Sample D 2.13 47% 14 1.75 Sample E 2.13 47% 11 1.25 Sample F 2.99 25% 8 0.75 * Average of 4 repetitions

The force measurement is the average of four samples.

For example, in the following list with reference to Figures 59 to 62, exemplary embodiments of the present invention are described. It should be noted that while the use of the terms "claim" or "claims " is used in the following list, the following list refers to exemplary embodiments and not to the claims.

1. In the vessel treatment system (20)

A first processing station (5501, 24, 26, 28, 30) configured to process a vessel having a wall defining an opening and an interior surface;

A second processing station (5502, 24, 26, 28, 30) configured to process a container that is affixed to the first processing station and has a wall defining an opening and an interior surface;

A plurality of container supports (38) each having a container port (92) configured to receive and seat an opening of the container for processing an interior surface of the container seated through the container port at the first processing station Container supports (38); And

A conveyor (70, 72, 72) for transporting a series of vessel supports and seated vessels from the first processing station to a second processing station for processing an interior surface of the vessel seated through the vessel port at the second processing station, 74). &Lt; / RTI >

2. The apparatus of claim 1, further comprising a third processing station (5503) configured to process a vessel spaced from the first and second processing stations and having a wall defining an opening and an interior surface invent.

3. The apparatus of claim 2, wherein the conveyor comprises a series of container supports from the second process station to a third process station for processing the interior surface of the container seated through the container port at the third process station, And transporting the containers.

4. The invention as defined in any one of claims 1 to 3, wherein the at least one container support further comprises a vacuum duct for withdrawing gas from a container seated on the one or more container ports.

5. An invention as claimed in any one of claims 1 to 4, wherein the at least one container support further comprises a vacuum port communicating between the vacuum duct and an external vacuum source.

6. An invention as claimed in any one of claims 1 to 5, wherein the at least one vacuum port has an O-ring for receiving and forming a seal against an external vacuum source.

7. The invention of any one of claims 1 to 6, wherein the at least one container support further comprises a gas inlet port for delivering gas to a container seated on the one or more container ports.

8. The apparatus of any one of claims 1 to 7, wherein the at least one container supports communicate with one or more container ports, each delivering gas to a container that is seated on one or more container ports, Further comprising a composite gas inlet port and a vacuum port for withdrawing the composite gas.

9. An invention as claimed in any one of the preceding claims, characterized in that the one or more container supports are made of a thermoplastic material.

10. The invention as defined in any one of claims 1 to 9, wherein the at least one container ports have a sealing component for receiving and forming a seal with respect to the container opening.

10a. 11. The invention of claim 10, wherein the sealing component is an O-ring.

11. The invention according to any one of claims 1 to 10, characterized in that the processing station is configured to inspect the inner surface of the container to determine whether it is defective.

12. The invention as defined in any one of claims 1 to 11, wherein the processing station is configured to apply a coating to the inner surface of the vessel.

13. The invention as defined in any one of claims 1 to 12, wherein the processing station is configured to inspect the coating to determine whether it is defective.

14. An invention as claimed in any one of claims 176 to 13 wherein the processing station is configured to measure air pressure loss through the vessel wall.

15. A process station according to any one of claims 1 to 14, characterized in that it comprises a bearing surface for supporting one or more container supports at a predetermined position while processing the inner surface of the container seated in the processing station Characterized by.

16. A method according to any one of the preceding claims, wherein another processing station processes a second bearing surface for supporting one or more container supports at a predetermined location while processing an interior surface of the container seated in the other station Wherein the first and second images are recorded on the recording medium.

17. The process of any one of claims 1 to 16, wherein another processing station is configured to support one or more container supports at a predetermined location while processing the interior surface of the container seated through the one or more container ports at the other station And a third bearing surface for the second bearing surface.

18. The invention of any one of claims 1 to 17, further comprising a third processing station spaced from the first and second processing stations, for processing vessels.

19. The invention of claim 18, further comprising a fourth processing station spaced from the first, second and third processing stations, for processing vessels.

20. The invention of claim 19, further comprising a fifth processing station spaced from said first, second, third and fourth processing stations, for processing vessels.

21. The invention of claim 20, further comprising a sixth processing station spaced from the first, second, third, fourth and fifth processing stations, for processing vessels.

22. The apparatus according to any one of claims 1 to 21, further comprising a conveyor for transporting the one or more container supports and the seated containers from the second processing station to the third processing station invent.

23. The invention of claim 22, further comprising a conveyor for transporting the one or more container supports and the seated containers from the third processing station to the fourth processing station.

24. An apparatus according to any one of claims 1 to 23, further comprising a conveyor for transporting the one or more container supports and the seated containers from the fourth processing station to the fifth processing station. .

25. The method of any one of claims 1 to 24 further comprising a conveyor for transporting one or more container supports and the seated containers from the fifth processing station to the sixth processing station. .

26. The invention of any one of claims 1 to 25, further comprising a coater group for forming a coating on the interior of the vessel through one or more vessel ports at the processing station.

27. The invention as claimed in any one of the preceding claims, characterized in that the processing station comprises a PECVD system.

28. The apparatus of claim 27, wherein the PECVD apparatus

An inner electrode positioned to be received in fluid communication with the interior of the container seated in the container support;

An outer electrode having an inner portion positioned to receive a container seated in the container support;

A power supply for supplying an alternating current to the inner and outer electrodes forming a plasma in the container seated on the container support object;

1. A vessel defining a vacuum chamber, comprising: a vacuum source for evacuating the interior of the vessel;

Reactant gas source; And

And a gas supplier for supplying the reactant gas from the reactant gas source to the container placed on the container support object.

29. The invention of claim 28, wherein said internal electrode extends into said container.

30. The invention of claim 28, wherein the internal electrode is located outside the vessel.

31. The invention as claimed in claim 28 or 30, wherein the internal electrode is positioned within the container support.

32. The invention of claim 28, wherein said inner electrode is a probe having a distal portion that is generally coaxially extended to a container resting on said container support.

33. The invention as claimed in claim 28 or 32, wherein the gas supply is at a distal portion of the internal electrode.

34. The method of claim 28, 32 or 33, further comprising a source of reactant gas within the inner electrode and a passageway for transferring the reactant gas from the source of reactant gas to a distal portion of the inner electrode Characterized by.

35. The method of claim 34, wherein the distal portion of the inner electrode comprises an elongated porous sidewall surrounding the passageway for releasing at least a portion of the reactant gas from the passageway into the inner electrode. invent.

36. The invention of claim 35, wherein an outer diameter of the inner electrode is at least about 50% of the inner diameter adjacent the side of the container.

37. The invention of claim 35, wherein the outer diameter of the inner electrode is at least about 60% of the inner diameter adjacent the side of the vessel.

38. The invention of claim 35, wherein the outer diameter of the inner electrode is at least about 70% of the inner diameter adjacent the side of the vessel.

39. The invention of claim 35, wherein the outer diameter of the inner electrode is at least about 80% of the inner diameter adjacent the side of the vessel.

40. The invention of claim 35, wherein the outer diameter of the inner electrode is at least about 90% of the inner diameter adjacent the side of the vessel.

41. The invention of claim 35, wherein the outer diameter of the inner electrode is at least about 95% of the inner diameter adjacent the side of the container.

42. The method according to any one of claims 28 to 34, further comprising a passageway for transferring the carrier gas from the carrier gas source to the reaction gas carrier gas source and to the distal portion of the inner electrode Characterized by.

43. The invention of claims 28 to 42, further comprising an inner electrode extender and a retractor for inserting and removing the inner electrode from the container support.

44. The apparatus of any one of claims 28 to 43, further comprising an array of at least two internal electrodes, wherein the internal electrode extender and retractor are configured to insert and remove the internal electrodes of the array from a container support . &Lt; / RTI >

45. The invention of claim 44, wherein the inner electrode extender and the retractor are configured to move the inner electrode between a fully advanced position, an intermediate position and a reduced position relative to the container support.

46. The method of claim 44 or 45, further comprising: removing the first internal electrode from its extended position to its reduced position, replacing the first internal electrode with a second internal electrode, And an internal electrode driver operable to be connected to the internal electrode extender and the retractor for advancing to an extended position.

47. A method according to any one of claims 28, 32, 33, 34, or 42, wherein said external electrode is substantially cylindrical and positioned generally concentrically around the container resting on said container support .

48. The invention as defined in any one of claims 28 to 47, wherein said external electrode comprises an end cap.

49. The invention of claim 48, wherein the gap defined between the outer electrode and the distal end of the container seated in the container support object is essentially uniform.

50. The invention as defined in any one of claims 28 to 49, wherein the gap defined between the external electrode and the container seated in the container support object is essentially uniform.

51. The apparatus of any one of claims 1 to 50, further comprising a detector configured to be inserted into the vessel through one or more vessel ports at a processing station for detecting the condition of the vessel interior surface invent.

52. The invention of any one of claims 1 to 51, further comprising a detector located at a processing station outside the vessel.

53. The apparatus of any one of claims 1 to 52, further comprising an energy source at a processing station for directing energy inwardly through the vessel wall and vessel interior surface for detection by a detector Invention.

54. A method according to any one of claims 1 to 53, further comprising applying an energy source at a processing station to direct energy towards the vessel wall and to reflect energy from the at least one coating on the wall surface and the wall surface. Wherein the first and second images are recorded on the recording medium.

55. The apparatus of any one of claims 1 to 54, further comprising an energy source at a processing station for directing energy inward through the vessel wall and vessel interior surface for detection by a detector Invention.

56. The invention as defined in any one of claims 1 to 55, comprising an energy source configured to be inserted into a container through a container opening.

57. The invention as defined in any one of claims 51-56, wherein said detector is configured to detect a condition of said container interior surface at a number of closely spaced locations on said container interior surface.

58. The invention as defined in any one of claims 51 to 57, wherein the detector is positioned to receive energy from the energy source.

59. A process according to any one of claims 1 to 58, wherein in the processing station for removing the container from the one or more container supports after processing the inner surface of the seated container at the second processing station, further comprising a picker.

II. Container support

II.A.

60. A portable container support for holding and delivering said container having an opening while the container is being processed,

A container port configured to seat a container opening in a mutually communicating relationship;

A second port configured to receive an external gas supply or exhaust;

A duct for passing one or more gases between the second port and a container opening seated on the container port; And

The container port, the second port and the duct being substantially rigidly attached;

Wherein the portable container support weighs less than 5 pounds.

II.B.

61. A portable container support for holding and delivering said container having an opening while the container is being processed,

A container port configured to receive a container opening in a sealed, communicating relationship;

A vacuum duct for withdrawing gas from the container seated on the container port through the container port;

A vacuum port configured to communicate between the vessel duct and an external vacuum source; And

A transferable housing substantially rigidly attached to the vessel port, the vacuum duct and the vacuum port;

Wherein the portable container support weighs less than 5 pounds.

62. The invention of claim 61, wherein the container port has a sealing component that receives and forms the seal against the container opening.

62a. 62. The invention of claim 61, wherein said sealing component is an O-ring.

63. The invention of any one of claims 61 to 62a, wherein said vacuum port has an O-ring for receiving and forming a seal against an external vacuum source.

64. An invention as claimed in any one of claims 61 to 63, wherein the inlet port has an O-ring for receiving and forming a seal with respect to the gas inlet.

65. The apparatus of any one of claims 61-64, wherein the vessel port is further configured to function as a gas inlet port in communication with the vessel port for delivering gas to a vessel seated on the vessel port Characterized by.

66. The invention as claimed in any one of claims 61 to 65, wherein said housing is made of a thermoplastic material.

67. The apparatus of any one of claims 61 to 66, further comprising a gas inlet port substantially rigidly attached to the deliverable housing and configured to deliver gas to a container seated on the vessel port .

II.C. A container support comprising a sealing arrangement.

68. A container support for receiving an open end of a container having a substantially cylindrical wall adjacent an open end,

A substantially cylindrical inner surface sized to receive the container cylindrical wall;

Characterized in that in a first annular groove coaxial within said substantially cylindrical inner surface said first annular groove has an opening in said substantially cylindrical inner surface and a bottom wall radially spaced from said substantially cylindrical inner surface, A first annular groove; And

In the relationship with the first annular groove, being radially outwardly pressed by a container that extends radially through the opening and is received by the generally cylindrical inner surface, And a first sealing component forming a seal between the bottom walls of the first annular groove.

68a. 69. The container support of claim 68, wherein the sealing component is an O-ring.

69. The container support of claim 68, further comprising a radially extending abutment adjacent the generally cylindrical inner surface on which the open end of the container can be supported.

70. The method of claim 68 or 69, wherein the first upper and lower sidewalls are disposed between the opening and the bottom wall of the first annular groove, Further comprising first sidewalls positioned to support the first O-ring when radially pressed outwardly.

71. A container according to any one of claims 68 to 70, wherein said first O-ring has a cross-sectional diameter greater than the radial depth of said first generally annular groove when not stressed. support fixture.

72. The method according to any one of claims 68 to 71,

A second annular groove coaxially disposed within said substantially cylindrical inner surface and axially spaced from said first annular groove such that a bottom wall radially spaced from said substantially cylindrical inner surface at said substantially cylindrical inner surface, A second annular groove having a second annular groove; And

A first annular groove extending radially through the opening in relation to the second annular groove and radially outwardly pressed by a container received by the generally cylindrical inner surface, Further comprising a second O-ring forming a seal between the bottom wall of the container support.

73. The apparatus of claim 72, wherein the first upper and lower sidewalls are disposed between the opening and the bottom wall of the second annular groove, the second sidewalls defining the second O-ring radially outward And second sidewalls positioned to support the second O-ring when pressed.

74. A container according to any one of claims 72 to 73, wherein said second O-ring has a larger cross-sectional diameter than the radial depth of said first generally annular groove when not stressed. support fixture.

75. The apparatus of any one of claims 69 to 74, further comprising a vacuum source within said junction positioned to draw a vacuum in a container seated within a container support having an opening facing the junction Container support.

76. The apparatus of any of claims 69-75, further comprising a process gas source within said junction positioned to communicate with the interior of a container seated within a container support having an opening opposite said junction. The container support.

III. Container transfer method - Container placed on the container support

III.A. Transporting the vessel support to the processing station

77. A method of treating a container,

Providing a first processing station for processing the vessel;

Providing a second processing station spaced from the first processing station to process the vessels;

Providing a container having a wall defining an opening and an interior surface;

Providing a container support comprising a container port;

Placing an opening of the container on the container port;

Treating the interior surface of the seated vessel through the vessel port at the first processing station;

Transporting the container support and the seated container from the first processing station to the second processing station; And

And processing the interior surface of the seated vessel through the vessel port at the second processing station.

78. The invention of claim 77, wherein said container is generally tubular.

79. The invention as defined in claim 77 or 78, wherein said opening is at one end of said container.

80. The invention as defined in any one of claims 77 to 79, wherein said container is made of a thermoplastic material.

81. The invention as defined in any one of claims 77 to 80, wherein said container is made of polyethylene terephthalate.

82. The invention as defined in any one of claims 77 to 80, wherein said container is made of polyolefin.

83. The invention as defined in any one of claims 77 to 80, wherein said container is made of polypropylene.

84. The invention as defined in any one of claims 77 to 83, wherein said container is made of glass.

85. The invention of claims 77-84, wherein said container is made of borosilicate glass.

86. The invention according to any one of claims 77 to 85, characterized in that the container is made of soda-lime glass.

87. The invention as claimed in any one of claims 77 to 86, wherein said container is made of quartz glass.

88. The invention of claims 77-87 wherein said container is strong enough to withstand substantially total internal vacuum without deformation when exposed to an external pressure of 760 Torr.

89. The invention as defined in any one of claims 77 to 88, wherein said container is provided by injection molding.

90. The invention as defined in any one of claims 77 to 88, wherein the container is provided by blow molding.

91. The invention as defined in any one of claims 77 to 90, wherein the container is provided by closing the end of the tube.

92. The invention of any one of claims 77-91, wherein said container support further comprises a vacuum duct for withdrawing gas from a container seated on said container port.

93. The invention of claim 92, wherein said container support further comprises a vacuum port communicating between said vacuum duct and an external vacuum source.

94. The invention of claim 93, wherein said vacuum port has an O-ring for receiving and forming a seal against an external vacuum source.

95. The invention of claims 77-94, wherein said container support further comprises a gas inlet port for delivering gas to a container seated on said container port.

95. A process according to any one of claims 77 to 95, wherein the container support is in communication with the container port, each of the composite gas for delivering gas to a container seated on the container port and for withdrawing gas from the container, An inlet port and a vacuum port.

97. The invention as claimed in any one of claims 77-96, wherein said container support is made of a thermoplastic material.

98. The invention as defined in any one of claims 77 to 97, wherein said container support comprises an upper portion and a base joined together in a joint.

99. The invention of claim 98, further comprising an O-ring captured between the upper portion and the base at the joint, for sealing the joint.

100. The invention of any one of claims 77-99, wherein the O-ring captured between the upper portion and the base receives the container and forms a seal around the container opening.

101. A container according to any one of claims 77 to 100, wherein the container port comprises O-rings spaced on first and second axes, each container comprising a container And an inner diameter dimensioned to receive an outer diameter of the outer diameter portion.

102. The invention as defined in any one of claims 77 to 101 wherein said container port is in the vicinity of said O-rings and has a radially extending abutment surface surrounding said vacuum duct.

103. The invention as defined in any one of claims 77 to 102, wherein the processing station is configured to inspect the interior surface of the vessel to determine whether it is defective.

104. The invention as defined in any one of claims 77 to 103, wherein the processing station is configured to apply a coating to an interior surface of the vessel.

105. The invention as defined in any one of claims 77 to 104, wherein the processing station is configured to apply a barrier or other type of coating to the interior surface of the vessel.

106. The invention as defined in any one of claims 77 to 105, wherein the processing station is configured to inspect the coating to determine whether it is defective.

107. The invention as defined in any one of claims 77 to 106, wherein the processing station is configured to inspect the barrier coating to determine whether it is defective.

108. The invention as defined in any one of claims 77 to 107, wherein the processing station is configured to measure air pressure loss through the vessel wall.

109. The apparatus according to any one of claims 77 to 108, characterized in that the processing station comprises a bearing surface for supporting the container support at a predetermined position while processing the inner surface of the container seated in the processing station .

110. The invention of claim 109, wherein after the opening of the container is seated on the container port, the container support is moved to engage the bearing surface.

111. The apparatus of any one of claims 77 to 110, wherein the other processing station includes a second bearing surface for supporting the vessel support at a predetermined location while processing an interior surface of the vessel seated in the other station . &Lt; / RTI >

112. The invention of claim 110, wherein after the opening of the container is seated on the container port, the container support is moved to engage the bearing surface.

113. A method according to any one of claims 77 to 112, wherein another processing station is configured to support the container support at a predetermined location while processing the interior surface of the mounted container through the container port at the other station And a third bearing surface.

114. The invention of claim 113, wherein after the opening of the container is seated on the container port, the container support is moved to engage the bearing surface.

115. A method according to any one of claims 77 to 114,

Providing a third processing station spaced from the first and second processing stations for processing vessels;

Transporting the vessel support and the seated vessel from the second processing station to the third processing station; And

Further comprising treating the interior surface of the seated vessel through the vessel port at the third processing station.

116. The invention of any of claims 77 to 115, further comprising the step of seating an opening of the vessel at the processing station on the vessel port.

117. The invention of any of claims 77 to 116, further comprising forming a coating on the interior of the vessel through the vessel port at a processing station.

118. The invention of any of Claims 77 to 117, wherein said processing at the processing station comprises inspecting the interior surface of the vessel to determine whether it is defective.

119. The invention of claim 118, wherein the inspection is performed by inserting a detection probe through the vessel port into the vessel and detecting the condition of the vessel interior surface using the probe.

120. The invention of claim 119, further comprising radiating energy inward through the vessel wall and vessel interior surface and detecting the energy with the probe.

121. The invention as recited in any of claims 119 to 120, further comprising detecting the condition of said container interior surface at a number of closely spaced locations on said container interior surface.

122. The method of any one of claims 118-121, wherein inspecting comprises inserting a source of radiation through the container port into the container and detecting a radiation from the source of radiation using a detector to determine the condition of the interior surface of the container And the detection is performed.

123. The method of any one of claims 118 to 122 further comprising radiating energy outwardly through the surface of the vessel and detecting the energy with a detector located outside the vessel. .

124. The invention of any of claims 120 to 123, further comprising the step of reflecting the radiation from the vessel surface and detecting the energy with a detector located within the vessel.

125. The invention as defined in any one of claims 118 to 124, further comprising detecting a condition of the interior surface of the container at a number of closely spaced locations on the interior surface of the container.

126. The invention as defined in any one of claims 77 to 125, wherein the treatment at the treatment station comprises applying a coating to an interior surface of the container.

127. The invention as defined in any one of claims 77 to 126, wherein the processing at the processing station comprises applying a barrier coating to an interior surface of the vessel.

128. The invention as defined in any one of claims 77 to 127, wherein the treatment at the treatment station comprises applying a liquid barrier coating to an interior surface of the container.

129. The invention as defined in any one of claims 77 to 128, wherein the processing at the processing station includes inspecting the coating on the inner surface of the vessel to determine whether it is defective.

130. The invention as defined in any one of claims 77 to 129, wherein the processing at the processing station comprises inspecting the barrier coating on the inner surface of the vessel to determine whether it is defective.

132. The process of any one of claims 77 to 130, wherein the processing at the processing station comprises the step of inspecting a coating applied as a liquid on the inner surface of the vessel to determine whether it is defective Invention.

132. The method of any one of claims 126 to 131, further comprising the step of inserting a detection probe through the container port into the container and detecting the condition of the coating using the probe. .

133. The invention of any of claims 127 to 132, further comprising radiating energy inward through the vessel wall and detecting the energy with the probe.

134. The invention of any of claims 127 to 133, further comprising detecting a state of the coating at a number of closely spaced locations on the interior surface of the container.

135. A method according to any one of claims 129 to 134, wherein when the vessel is first evacuated and its wall is exposed to the ambient atmosphere, Further comprising the step of performing said inspecting step at a sufficient number of locations throughout said container interior surface to determine that said inspecting step is effective to prevent said container from increasing to more than 20%.

136. The invention of any one of Claims 129 to 135, wherein said inspecting step is performed within an elapsed time of less than 30 seconds per vessel.

137. The invention of any one of Claims 129 to 135 wherein said inspecting step is performed within an elapsed time of less than 25 seconds per vessel.

138. The invention of any one of Claims 129 to 135, wherein said inspecting step is performed within an elapsed time of less than 20 seconds per vessel.

139. The invention of any one of Claims 129 to 135, wherein said inspecting step is performed within an elapsed time of less than 15 seconds per vessel.

140. The invention of any one of claims 129 to 135, wherein said inspecting step is performed within an elapsed time of less than 10 seconds per vessel.

141. The invention of any one of Claims 129 to 135 wherein said coating and testing step is performed within an elapsed time of less than 5 seconds per vessel.

142. The invention of any one of Claims 129 to 135 wherein said coating and inspecting step is performed within an elapsed time of less than 3 seconds per vessel.

143. The invention of any one of Claims 129 to 135 wherein said coating and testing step is performed within an elapsed time of less than 2 seconds per vessel.

144. The invention of any one of Claims 129 to 135, wherein said coating and testing step is performed within an elapsed time of less than 1 second per vessel.

145. The invention of any one of Claims 129 to 135 wherein said coating and inspecting step is performed within an elapsed time of less than 30 seconds per vessel.

146. The invention of any of Claims 129 to 135 wherein said coating and testing step is performed within an elapsed time of less than 25 seconds per vessel.

147. The invention of any of Claims 129 to 135 wherein said coating and testing step is performed within an elapsed time of less than 20 seconds per vessel.

148. The invention of any one of Claims 129 to 135 wherein said coating and testing step is performed within an elapsed time of less than 15 seconds per vessel.

149. The invention of any one of Claims 129 to 135 wherein said coating and testing step is performed within an elapsed time of less than 10 seconds per vessel.

150. The invention of any one of Claims 129 to 135 wherein said coating and inspecting step is performed within an elapsed time of less than 8 seconds per vessel.

151. The invention of any one of Claims 129 to 135 wherein said coating and inspecting step is performed within an elapsed time of less than 7 seconds per vessel.

152. The invention of any one of Claims 129 to 135 wherein said coating and inspecting step is performed within an elapsed time of less than 6 seconds per vessel.

153. The invention of any one of Claims 129 to 135 wherein said coating and testing step is performed within an elapsed time of less than 5 seconds per vessel.

154. The invention of any one of Claims 129 to 135 wherein said coating and inspecting step is performed within an elapsed time of less than 4 seconds per vessel.

155. The invention of any one of Claims 129 to 135 wherein said coating and inspecting step is performed within an elapsed time of less than 3 seconds per vessel.

156. The method of any one of claims 129 to 135, wherein the container is initially evacuated and the wall is exposed to ambient air, the container is increased to at least 20% of ambient atmospheric pressure for a lifetime of at least 18 months Further comprising the step of performing said detecting step at a sufficient number of positions throughout the entire interior surface of said container to determine that it is effective to prevent said < RTI ID = 0.0 >

157. The method of any one of claims 129 to 135, wherein the container is initially evacuated and its wall is exposed to ambient air, the container is increased to at least 20% of ambient atmospheric pressure for at least two years of life Further comprising the step of performing said detecting step at a sufficient number of positions throughout the entire interior surface of said container to determine that it is effective to prevent said < RTI ID = 0.0 >

158. The method of any one of claims 129 to 135, wherein when the vessel is initially evacuated and its wall is exposed to ambient air, the vessel is increased to at least 15% of ambient atmospheric pressure for a lifetime of one year Further comprising the step of performing said detecting step at a sufficient number of positions through the entire inner surface of said container to determine that said container is effective to prevent said container.

159. A method according to any one of claims 129 to 135, wherein when the vessel is first evacuated and its wall is exposed to ambient air, the vessel is increased to at least 10% of ambient atmospheric pressure for a lifetime of one year Further comprising the step of performing said detecting step at a sufficient number of positions through the entire inner surface of said container to determine that said container is effective to prevent said container.

160. The method of any one of claims 129 to 159, wherein the inspection includes inserting a source of radiation through the container port into the container and detecting a radiation from the source of radiation using a detector to detect the condition of the container . &Lt; / RTI >

161. The method of any one of claims 129 to 160, further comprising radiating energy outwardly through the vessel and vessel walls and detecting the energy with a detector located outside the vessel Invention.

162. The method of any one of claims 120-161, further comprising the step of reflecting the radiation from the coating and vessel walls and detecting the energy with a detector located inside the vessel. .

163. The invention of any one of Claims 129 to 162, further comprising detecting the state of the coating at a number of closely spaced locations on the interior surface of the container.

164. The method of any one of claims 129 to 163, wherein the step of inspecting the coating on the inner surface of the vessel to determine whether it is defective is performed by measuring the air pressure cutoff effectiveness of the barrier coated vessel wall Characterized by.

165. The invention as defined in any one of claims 117 to 164, wherein said coating reduces permeation of atmospheric gases to said vessel through its interior surface.

166. The invention of any one of Claims 117 to 165, wherein the coating reduces contact of the contents of the container with the inner surface.

167. A coating according to any one of claims 117 to 166, characterized in that the coating comprises SiOx wherein x is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, or about 2 .

168. The method of any one of claims 77 to 167, further comprising removing the vessel from the vessel support after treating the interior surface of the anchored vessel at the second processing station .

169. The method of claim 168,

Providing a second container having a wall defining an opening and an interior surface after said removing step; And

Further comprising the step of seating an opening of the second container on the container port.

170. The invention of any one of claims 168 to 169, further comprising treating the interior surface of the second container seated in the first processing station through the container port.

171. The invention of any one of Claims 168 to 170, further comprising transporting the container support and the seated container from the first processing station to the second processing station.

172. The invention of any one of Claims 168 to 171, further comprising treating the seated second vessel through the vessel port at the second processing station.

173. The method of any one of claims 77 through 172, further comprising: forming the container in a mold, removing the container from the mold, removing the container from the mold, Further comprising the step of placing said container on said container port.

174. The container according to any one of claims 77 to 173, wherein the container is formed in a mold, the container is removed from the mold, and within 30 seconds after removing the container from the mold, Further comprising the step of placing said container on said container port.

175. A process according to any one of claims 77 to 174, wherein the container is formed in a mold, the container is removed from the mold, and within 25 seconds after removing the container from the mold, Further comprising the step of placing said container on said container port.

176. A container according to any one of claims 77 to 175, wherein the container is formed in a mold, the container is removed from the mold, and within 20 seconds after removing the container from the mold, Further comprising the step of placing said container on said container port.

177. A container according to any one of claims 77 to 176, wherein the container is formed in a mold, the container is removed from the mold, and within 15 seconds after removing the container from the mold, Further comprising the step of placing said container on said container port.

178. A container according to any one of claims 77 to 177, wherein the container is formed in a mold, the container is removed from the mold, and within 10 seconds after removing the container from the mold, Further comprising the step of placing said container on said container port.

179. A container according to any one of claims 77 to 178, wherein the container is formed in a mold, the container is removed from the mold, and within 5 seconds after removing the container from the mold, Further comprising the step of placing said container on said container port.

180. The container according to any one of claims 77 to 179, wherein the container is formed in a mold, the container is removed from the mold, and within 3 seconds after removing the container from the mold, Further comprising the step of placing said container on said container port.

181. A container according to any one of claims 77 to 180, wherein the container is formed in a molding die, the container is removed from the molding die, and within one second after removing the container from the molding die, Further comprising the step of placing said container on said container port.

III.B. Transporting the treatment device to the container support or vice versa.

182. A method of treating a container,

Providing a first processing station for processing vessels;

Providing a second processing station for processing the vessels;

Providing a container support comprising a container port;

Placing an opening of the container on the container port;

&Lt; Desc / Clms Page number 20 > moving the first treatment device in operative engagement with the container support and vice versa;

Treating the interior surface of the seated vessel through the vessel port using the first processing apparatus;

Moving the second treatment device in operative engagement with the container support and vice versa; And

And treating the interior surface of the seated vessel through the vessel port using the second processing apparatus.

183. The method of claim 182,

Providing a third processing apparatus for processing vessels;

Moving the third processing device in operable engagement with the container support and vice versa; And

Further comprising processing the interior surface of the seated vessel through the port using the third processing apparatus.

184. The invention of claim 182 or 183 wherein said container is generally tubular.

185. The invention as defined in any one of claims 182 to 184, wherein the opening is at one end of the container.

186. The invention of any one of claims 182 to 185 wherein said container is made of a thermoplastic material.

187. The invention according to any one of claims 182 to 186, wherein said container is made of polyethylene terephthalate.

188. The invention of any one of claims 182 to 187, wherein said container is made of polyolefin.

189. The invention according to any one of claims 182 to 186, characterized in that said container is made of polypropylene.

190. The invention of any one of claims 182 to 189, wherein said container is sufficiently strong to withstand substantially total internal vacuum without deformation when exposed to an external pressure of 760 Torr.

191. The invention as defined in any one of claims 182 to 190, wherein the container is provided by injection molding.

192. The invention according to any one of claims 182 to 191, wherein the container is provided by blow molding.

193. The invention of any one of claims 182 to 192, wherein said container support further comprises a vacuum duct for withdrawing gas from a container seated on said container port.

194. The invention of claim 193, wherein said container support further comprises a vacuum port communicating between said vacuum duct and an external vacuum source.

195. The invention of claim 194, wherein said vacuum port has an O-ring for receiving and forming a seal against an external vacuum source.

196. The invention of any one of claims 182 to 195, wherein the container support further comprises a gas inlet port for delivering gas to the container seated on the container port.

197. A container according to any one of claims 182 to 196, wherein the container support comprises a composite gas for communicating with the container port and delivering gas to and from a container seated on the container port, respectively, An inlet port and a vacuum port.

198. The invention of any one of claims 182 to 197 wherein said container support is made of a thermoplastic material.

199. The invention as defined in any one of claims 182 to 198, wherein the container port has an O-ring for receiving and forming a seal with respect to the container opening.

200. The invention as defined in any of Claims 182-219, wherein the processing apparatus is configured to inspect the interior surface of the vessel to determine whether it is defective.

201. The invention as defined in any one of claims 182 to 200 wherein the treatment apparatus is configured to apply a coating to an interior surface of the vessel.

202. The invention as defined in any one of claims 182 to 201, wherein the processing apparatus is configured to inspect the coating to determine whether it is defective.

203. The invention as defined in any one of claims 182 to 202 wherein the treatment apparatus is configured to measure air pressure loss through the vessel wall.

204. The apparatus according to any one of claims 182 to 203, wherein the treatment apparatus includes a bearing surface for supporting the container support at a predetermined position while processing the inner surface of the container seated in the treatment apparatus Characterized by.

205. The invention of claim 204, wherein after the opening of the container is seated on the container port, the container support is moved to engage the bearing surface.

206. The apparatus of any one of claims 182 to 205, further comprising a second bearing surface for supporting the container support at a predetermined location while processing the interior surface of the container seated in the processing apparatus Wherein the first and second images are recorded on the recording medium.

207. The invention of claim 206, wherein after the opening of the container is seated on the container port, the container support is moved to engage the bearing surface.

208. The apparatus of any one of claims 182-27, wherein another processing apparatus is configured to support the container support at a predetermined location while processing the interior surface of the container seated therethrough, And a third bearing surface for the second bearing surface.

209. The invention of claim 208, wherein after the opening of the container is seated on the container port, the container support is moved to engage the bearing surface.

210. The method according to any one of claims 182 to 209,

Transporting the container support and the seated container from the second processing device to the third processing device; And

Further comprising treating the interior surface of the seated vessel through the vessel port using the third processing apparatus.

211. The invention of any one of claims 182-210, further comprising seating an opening in the vessel at the processing station on the vessel port.

212. The invention of any one of claims 182-211, further comprising forming a coating on the interior of the vessel through the vessel port in the processing apparatus.

213. The invention as defined in any one of claims 182-212, wherein the processing at the processing station includes inspecting the interior surface of the vessel to determine whether it is defective.

214. The invention of claim 213, wherein inspection is performed by inserting a detection probe through the vessel port into the vessel and detecting the condition of the vessel interior surface using the probe.

215. The invention of claim 214, further comprising radiating energy inward through the vessel wall and vessel interior surface and detecting the energy with the probe.

216. The invention of claim 214 or 215, further comprising detecting a condition of the interior surface of the container at a number of closely spaced locations on the interior surface of the container.

217. A method according to any one of claims 213 to 216, wherein the inspection inserts a source of radiation through the container port into the container and detects a radiation from the source of radiation using a detector to determine the condition of the interior surface of the container And the detection is performed.

218. The method of any one of claims 213 to 217, further comprising radiating energy outwardly through the surface of the vessel and detecting the energy with a detector located outside the vessel. .

219. The invention of any of claims 215 to 216, further comprising the step of reflecting the radiation from the vessel surface and detecting the energy with a detector located within the vessel.

220. The invention of any of claims 213 to 219, further comprising detecting a condition of the interior surface of the container at a number of closely spaced locations on the interior surface of the container.

221. The invention as defined in any one of claims 182-220, wherein the treatment in the treatment apparatus comprises applying a coating to an inner surface of the vessel.

222. The invention as claimed in any one of claims 182-221, wherein the treatment in the treatment apparatus comprises applying a coating of liquid to the inner surface of the vessel.

223. The invention as defined in any one of claims 182-222, wherein the processing at the processing station comprises inspecting the coating on the inner surface of the vessel to see if it is defective.

224. The method of any one of claims 221 to 223, comprising inserting a detection probe through the container port into the container and detecting the condition of the coating using the probe. .

225. The invention of any of claims 221 to 224, further comprising radiating energy inward through the vessel wall and detecting the energy with the probe.

226. The invention of any of claims 221 to 225, further comprising detecting the condition of the coating at a number of closely spaced locations on the interior surface of the container.

227. The method according to any one of claims 223 to 131, wherein when the vessel is first evacuated and its wall is exposed to ambient air, the vessel is increased to at least 20% of the ambient atmospheric pressure for a lifetime of one year Further comprising the step of performing said detecting step at a sufficient number of positions through the entire inner surface of said container to determine that said container is effective to prevent said container.

228. The invention of any one of claims 223 to 227, wherein said inspecting step is performed within an elapsed time of less than 30 seconds per vessel.

229. The invention of any one of claims 223 to 227, wherein said inspecting step is performed within an elapsed time of less than 25 seconds per vessel.

230. The invention of any one of claims 223 to 227, wherein said inspecting step is performed within an elapsed time of less than 20 seconds per vessel.

231. The invention of any one of claims 223 to 227, wherein said inspecting step is performed within an elapsed time of less than 15 seconds per vessel.

232. The invention of any one of claims 223 to 227, wherein said inspecting step is performed within an elapsed time of less than 10 seconds per vessel.

233. The invention of any one of claims 223 to 227, wherein said coating and testing step is performed within an elapsed time of less than 30 seconds per vessel.

234. The invention of any one of claims 223 to 227, wherein said coating and testing step is performed within an elapsed time of less than 25 seconds per vessel.

235. The invention of any one of claims 223 to 227, wherein said coating and inspection step is performed within an elapsed time of less than 20 seconds per vessel.

236. The invention of any one of claims 223 to 227, wherein said coating and testing step is performed within an elapsed time of less than 15 seconds per vessel.

237. The invention of any one of claims 223 to 227, wherein said coating and testing step is performed within an elapsed time of less than 10 seconds per vessel.

238. A method according to any one of claims 223 to 227, wherein when the vessel is first evacuated and its wall is exposed to ambient air, the vessel is increased to at least 20% of ambient atmospheric pressure for a lifetime of at least 18 months Further comprising the step of performing said detecting step at a sufficient number of positions throughout the entire interior surface of said container to determine that it is effective to prevent said < RTI ID = 0.0 >

239. A method according to any one of claims 223 to 227, wherein the barrier coating is initially vacuumed and its wall is exposed to the ambient atmosphere, the barrier coating is at least 20% of the ambient atmospheric pressure for at least two years of life Further comprising the step of performing said detecting step at a sufficient number of positions through the entire interior surface of the container to determine that the cleaning step is effective to prevent the container from being increased.

240. The method of any one of claims 223 to 227, wherein the barrier coating is initially vacuumed and the wall is exposed to the ambient atmosphere, the barrier coating is at least 15% of the ambient atmospheric pressure for a lifetime of one year Further comprising the step of performing said detecting step at a sufficient number of positions through the entire interior surface of the container to determine that the cleaning step is effective to prevent the container from being increased.

241. A method according to any one of claims 223 to 227, wherein the barrier coating is initially vacuumed and the wall is exposed to the ambient atmosphere, the barrier coating is at least 10% of the ambient atmospheric pressure for a lifetime of one year Further comprising the step of performing said detecting step at a sufficient number of positions through the entire interior surface of the container to determine that the cleaning step is effective to prevent the container from being increased.

242. The method of any one of claims 223 to 241, wherein the inspection inserts a source of radiation through the container port into the container and detects a radiation from the source of radiation using a detector to detect the condition of the coating . &Lt; / RTI >

243. The method of any one of claims 223 to 242, further comprising radiating energy outward through the coating and vessel walls and detecting the energy with a detector located outside the vessel. Invention.

244. The method of any one of claims 223 to 243, further comprising the step of reflecting the radiation from the coating and vessel walls and detecting the energy with a detector located inside the vessel. .

245. The invention of any one of claims 223 to 244, further comprising detecting a state of the coating at a number of closely spaced locations on the interior surface of the container.

246. The method of any one of claims 223 to 245, wherein the step of inspecting the coating on the inner surface of the container to determine whether it is defective is performed by measuring the air pressure cutoff effectiveness of the coated container wall .

247. The invention of any one of claims 212-246, wherein the coating reduces permeation of atmospheric gases to the vessel through its interior surface.

248. The invention as defined in any one of claims 212-247, wherein the coating reduces contact of the contents of the container with the interior surface.

249. The coating of any one of claims 212-248, wherein the coating is SiOx, elemental carbon, fluorine, wherein x is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, Wherein x is about 0.5 to about 2.4, y is about 0.6 to about 3, and z is about 2 to about 9, or combinations thereof.

250. The method of any one of claims 182-249 further comprising removing the vessel from the vessel support while processing the interior surface of the seated vessel using the second treatment apparatus .

251. The method of claim 250,

252. The method of any one of claims 250 to 251, further comprising treating the interior surface of the seated second vessel through the vessel port using the first processing apparatus invent.

253. The invention of any one of claims 250 to 252, further comprising transporting the container support and the seated container from the first processing station to the second processing station.

254. The invention of any one of claims 250 to 253, further comprising treating the seated second vessel through the vessel port using the second processing apparatus.

255. The method according to any one of claims 182 to 254, wherein the container is formed in a mold, the container is removed from the mold, and within 60 seconds after removing the container from the mold, Further comprising the step of placing said container on said container port.

256. The method according to any one of claims 182-255, wherein the container is formed in a mold, the container is removed from the mold, and within 30 seconds after removing the container from the mold, Further comprising the step of placing said container on said container port.

257. A method according to any one of claims 182 to 256, wherein the container is formed in a mold, the container is removed from the mold, and within 25 seconds after removing the container from the mold, Further comprising the step of placing said container on said container port.

258. The method according to any one of claims 182 to 257, wherein the container is formed in a mold, the container is removed from the mold, and within 20 seconds after removing the container from the mold, Further comprising the step of placing said container on said container port.

259. The method of any one of claims 182 to 258, wherein the container is formed in a mold, the container is removed from the mold, and within 15 seconds after removing the container from the mold, Further comprising the step of placing said container on said container port.

260. The method according to any one of claims 182 to 259, wherein the container is formed in a mold, the container is removed from the mold, and within 10 seconds after removing the container from the mold, Further comprising the step of placing said container on said container port.

261. The method of any one of claims 182-260, further comprising: forming the container in a mold, removing the container from the mold, removing the container from the mold, Further comprising the step of placing said container on said container port.

262. A container according to any one of claims 182 to 261, wherein the container is formed in a mold, the container is removed from the mold, and within 3 seconds after removing the container from the mold, Further comprising the step of placing said container on said container port.

263. The method of any one of claims 182-262, wherein the container is formed in a mold, the container is removed from the mold, and within one second after removing the container from the mold, Further comprising the step of placing said container on said container port.

III.C. Using a gripper to transport the tube back and forth to the coating station

264. A method for treating a PECVD of a first vessel,

Providing a first container having an open end, a closed end, and an inner surface;

Providing at least a first gripper configured to selectively grasp and unlock the closed end of the first vessel;

Holding the closed end of the first container using the gripper;

Transferring the first container to a vicinity of a container support configured to seat at an open end of the first container using the first gripper;

Using the first gripper to axially advance the first container and seat the open end on the container support so that sealed communication is established between the interior of the container support and the first container;

Introducing at least one gas reactive material into the first vessel through the vessel support;

Forming a plasma in the first vessel under conditions effective to form a reaction product of the reactant on the inner surface of the first vessel;

Detaching the first container from the container support; And

Axially transferring the first container from the container support using the first gripper or another gripper; And

And discharging the first container from the gripper used for axial transfer from the container support.

265. The method of claim 264,

Providing a reaction vessel different from the first vessel, the reaction vessel having an open end and an inner space;

Placing an open end of the reaction vessel on the vessel support object to establish a sealed communication between the vessel support and the inner space of the reaction vessel;

Providing a PECVD reactant material in said inner space;

Forming a plasma within the interior space of the reaction vessel under conditions effective to remove at least a portion of the deposition of the PECVD reaction product from the reactant water stream;

Detaching the first container from the container support; And

Further comprising the step of transporting said reaction vessel from said vessel support.

266. The invention of claim 264 or 265, further comprising.

Providing at least a second gripper;

Operatively coupling at least first and second grippers with a serial conveyor;

Holding the closed end of the second container using the gripper;

Detaching the second container from the container support; And

IV. PECVD apparatus for container manufacturing

IV.A. A PECVD apparatus including a container support, internal electrodes, and a vessel as a reaction chamber

267. In a PECVD apparatus,

A container support having a port for receiving the container in a seated position for treatment;

An inner electrode positioned to be received in a container seated in the container support object;

An outer electrode having a medial portion positioned to receive a container seated on the container support; And

Wherein the power supply includes a power supply for supplying a current to at least one of the inner and outer electrodes to form a plasma in a vessel defining a plasma reaction chamber seated on the vessel support.

268. The invention of claim 267, wherein said internal electrode is a probe having a distal portion that is generally coaxially extending into a container seated in said container support.

268a. 268. The invention of claim 267 or 268, further comprising a gas supplier for supplying a reactant gas source and a reactant gas from the reactant gas source to a container seated in the container support object.

269. The invention of claim 268a wherein said gas supply is at a distal portion of said internal electrode.

270. The invention of claim 268a or 269, further comprising a passageway for transferring the reactant gas from the reactant gas source to the distal portion of the inner electrode in the inner electrode.

271. The gas sensor according to any one of claims 267 to 270, further comprising a carrier gas source in the internal electrode and a passage for transferring the carrier gas from the carrier gas source to a distal portion of the internal electrode invent.

272. The invention as defined in any one of claims 267 to 271, wherein said outer electrode is substantially cylindrical and is positioned generally concentrically around said container mounted on said container support.

273. The invention as defined in any one of claims 267 to 272, wherein said external electrode comprises an end cap.

274. The invention of claim 273 wherein the gap defined between the distal end cap and the distal end of the container resting on the container support object is essentially uniform.

275. The invention as defined in any one of claims 267 to 274, wherein the gap defined between the external electrode and the container seated in the container support object is essentially uniform.

276. The coating of any one of claims 117 to 167 or 212 to 168 wherein w is 1 wherein x is from about 0.5 to about 2.4 and y is from about 0.6 to about 3 And z is about 2 to about 9, a layer of SiOx and a layer of SiwOxCyHz.

278. The invention of claims 276 or 277, wherein said SiwOxCyHz layer is deposited on a layer of SiOx deposited on the inner surface of said vessel.

279. The invention of claim 276 or 277 wherein said layer of SiOx is deposited between said SiwOxCyHz layer and the interior surface of said vessel.

280. The invention as in any of 276 to 279, wherein the layer of SiOx is deposited near the layer of SiwOxCyHz.

281. The invention of claims 276-280, wherein the layer of SiOx is deposited near the inner surface of the vessel.

282. The invention of claims 276-280, wherein the SiwOxCyHz layer is deposited near the inner surface of the vessel.

283. The invention as claimed in any one of claims 280 to 282, wherein the layers of SiOx and SiwOxCyHz are inclined functional composites of SiwOxCyHz to SiOx.

284. The invention of any one of claims 267 to 283, wherein said container further comprises a closure.

285. The invention of claim 284, wherein said closure comprises an interior-facing surface exposed to the lumen of said container.

286. The invention of claim 284 or 285 wherein said closure comprises a wall-contacting surface in contact with an interior surface of said container wall.

287. The invention as defined in any of 284 to 286, wherein the closure comprises a stopper.

288. The invention of claim 287, wherein said closure comprises a shield having a stopper.

289. The invention of claim 287 or 288, wherein said stopper comprises a wall-contacting surface in contact with an interior surface of said container wall.

290. The invention as defined in any of 284 to 289, wherein the stopper includes an interior-facing surface exposed to the lumen of the container.

290a. 290. The invention of any one of claims 267 to 290, further comprising a vacuum source for removing gas from a container that is seated in said container support and defines a vacuum chamber.

291. The invention as claimed in any one of claims 284 to 290a, wherein a portion of the vessel wall in contact with the wall-contacting surface of the closure is coated with a lubricating coating of SiwOxCyHz.

301. The invention as claimed in any one of claims 284 to 300 wherein the coating of SiwOxCyHz is applied by PECVD.

302. The invention as claimed in any one of claims 291 to 301, wherein said SiwOxCyHz coating is between 0.5 and 5000 nm thick.

303. The invention as claimed in any one of claims 291 to 301, wherein said SiwOxCyHz coating is between 100 and 5000 nm thick.

304. The invention as claimed in any one of claims 291 to 301, wherein the coating of SiwOxCyHz is between 200 and 5000 nm thick.

305. The invention as claimed in any one of claims 291 to 301 wherein the coating of SiwOxCyHz is between 500 and 5000 nm thick.

306. The invention as claimed in any one of claims 291 to 301, wherein said SiwOxCyHz coating is between 1000 and 5000 nm thick.

307. The invention as claimed in any one of claims 291 to 301, wherein said SiwOxCyHz coating is between 2000 and 5000 nm thick.

308. The invention as claimed in any one of claims 291 to 301, wherein said SiwOxCyHz coating is between 3000 and 5000 nm thick.

309. The invention as claimed in any one of claims 291 to 301, wherein said SiwOxCyHz coating is between 4000 and 10,000 nm thick.

310. A PECVD apparatus, comprising: a vessel support having a port for receiving the vessel in a seated position for treatment;

An outer electrode having a medial portion positioned to receive a container seated on the container support;

A gas outlet for transferring gas to or from the inner wall of the vessel seated on said port to define a sealed chamber;

Reaction gas source; And

And a gas supplier for supplying a reactant gas from the reactant gas source to a container seated in the container support.

IV.B. PECVD apparatus using a gripper to transport the tube back and forth to the coating station

311. An apparatus for PECVD treatment of a first vessel having an open end, a closed end and an internal space,

A container support configured to rest on an open end of the container;

A first gripper configured to selectively support and release the closed end of the container and configured to transport the container around the container support while holding the closed end of the container;

The container support being configured to establish a sealed communication between the interior space of the container support and the first container;

A reactant supply operatively connected to introduce at least one gas reactant in the first vessel through the vessel support;

A plasma generator configured to form a plasma in the first vessel under conditions effective to form a reaction product of the reactant on the inner surface of the first vessel;

A container emitter for desorbing the first container from the container support; And

Wherein the gripper is a first gripper or other gripper, and the gripper is a first gripper or other gripper configured to axially transfer the first container from the container support and to discharge the first container.

312. The method of claim 311,

A reaction container configured to have an open end and an inner space and to seat the open end of the reaction container on the container support and to establish a sealed communication between the container support and the inner space of the reaction container, Vessel; And

Further comprising a PECVD reaction material located to be positioned within the inner space of the reaction vessel when the reaction vessel is seated on the vessel support object,

Wherein the plasma generator can be configured to form a plasma within the interior space of the reaction vessel under conditions effective to remove at least a portion of the deposition of the PECVD reaction product from the reactant water bath.

313. The method of claim 311 or 312,

A serial conveyor configured to transport grippers; And

Further comprising a second gripper configured to selectively support and release the closed end of the container and configured to transport the container proximate the container support while holding the closed end of the container,

Wherein the first and second grippers are operatively connected to the serial conveyor and successively transport a series of at least two vessels to the vicinity of the vessel support and seat the open ends of the vessels on the vessel support object, And configured to communicate in sealed communication between the interior of the container support and the second container, axially transporting the containers from the container support and releasing the containers from the grippers.

V.B. PECVD coating a limited opening of the vessel (syringe capillary)

316. A method of coating an inner surface of a limited opening of a generally tubular container to be treated by PECVD,

A tubular container comprising a generally tubular container comprising an outer surface, an inner surface defining a lumen, a larger opening having an inner diameter, and a restricted opening defined by the inner surface and having an inner diameter smaller than the larger opening inner diameter, step;

Providing a processing vessel having a lumen and a processing vessel opening;

Coupling the processing vessel opening to a limited opening of the vessel to be treated to allow communication between the processing vessel lumen and the processing vessel lumen through the limited opening;

Drawing at least a partial vacuum within the lumen of the vessel being processed and the vessel lumen being processed;

Flowing a PECVD reactant through the first opening, then through the lumen of the vessel being processed, and then through the restricted opening to the vessel lumen being processed; And

And generating a plasma adjacent the limited opening under conditions effective to deposit a coating of the PECVD reaction product on the inner surface of the restricted opening.

317. The method of claim 316, wherein said treated vessel is a syringe barrel.

318. The method of any one of claims 316 or 317, wherein the limited opening has a first fit and the vessel opening in process is seated in the first fit to provide communication between the vessel lumen being processed and the lumen of the vessel being processed Wherein the first fitting comprises a second fitting adapted to effect the first fitting.

319. The method of claim 318, wherein the first and second fits are Luer lock fits.

320. The method of claim 319, wherein at least one of the first and second fits is made of an electrically conductive material.

321. A method according to any one of claims 299, 319, or 320, wherein at least one of the first and second fits is made of an electrically conductive material.

322. The method according to any one of claims 299, 319, 320, or 299a2, wherein at least one of the first and second fits is made of stainless steel.

323. The method of claim 319, wherein each of the first and second fits is male and female fits.

324. The method of any one of claims 299, 319, or 323, further comprising a seal positioned between the first and second fits.

325. The method of claim 324, wherein the seal is an O-ring.

326. The method of claim 319, 323, 324, or 325 wherein one of said fits has a threaded and locking orientation defining a generally annular first abutment, Wherein the second fitting comprises a ring and the remaining fitting comprises a generally annular second abutment facing axially opposite the first abutment.

327. The method of claim 326, further comprising an annular seal engaged between the first abutment and the second abutment.

328. The method of any one of claims 316 to 318, wherein the lumen of the treated vessel and the communication formed between the vessel lumen in process through the limited opening are at least substantially leak- .

329. A method according to any one of claims 316 to 328,

Wherein the flow of PECVD reactant material through the larger opening of the vessel being treated comprises providing a generally tubular inner electrode having an inner passageway, a proximal end, a distal end and a distal opening proximate the distal end and communicating with the inner passageway ;

Inserting the distal end of the electrode into a larger opening or a larger opening of the container being processed; And

Supplying a reactant gas into the lumen of the vessel being processed through a distal opening of the electrode.

330. The method of claim 329, wherein the distal end of the electrode is located less than one-half the distance from the larger opening of the container being treated to the restricted opening while supplying the reactant gas.

331. The method of claim 329, wherein the distal end of the electrode is positioned less than 40% of the distance from the larger opening to the restricted opening of the vessel being treated while supplying the reactant gas.

332. The method of claim 329, wherein the distal end of the electrode is located less than 30% of the distance from the larger opening of the vessel being treated to the restricted opening while supplying the reactant gas.

333. The method of claim 329, wherein the distal end of the electrode is located less than 20% of the distance from the larger opening of the vessel being treated to the restricted opening while supplying the reactant gas.

334. The method of claim 329, wherein the distal end of the electrode is located at less than 15% of the distance from the larger opening to the restricted opening of the vessel being treated while supplying the reactant gas.

335. The method of claim 329, wherein the distal end of the electrode is located less than 10% of the distance from the larger opening of the vessel being treated to the restricted opening while supplying the reactant gas.

336. The method of claim 329, wherein the distal end of the electrode is located less than 8% of the distance from the larger opening to the restricted opening of the vessel being treated while supplying the reactant gas.

337. The method of claim 329, wherein the distal end of the electrode is located less than 6% of the distance from the larger opening of the vessel being treated to the restricted opening while supplying the reactant gas.

338. The method of claim 329, wherein the distal end of the electrode is located less than 4% of the distance from the larger opening to the restricted opening of the vessel being treated while supplying the reactant gas.

339. The method of claim 329, wherein the distal end of the electrode is located less than 2% of the distance from the larger opening of the vessel being treated to the restricted opening while supplying the reactant gas.

340. The method of claim 329, wherein the distal end of the electrode is located less than 1% of the distance from the larger opening of the vessel being treated to the restricted opening while supplying the reactant gas.

341. The method of claim 329, wherein the distal end of the electrode is positioned within a larger opening of the vessel being treated while supplying the reactant gas.

342. The method of claim 329, wherein the distal end of the electrode is positioned outside the larger opening of the vessel being treated while supplying the reactant gas.

343. The method of any one of claims 329 to 342, wherein the distal end of the electrode is located distal of the restricted opening.

344. The method of any one of claims 329 to 343, wherein the electrode is moved axially during deposition of the PECVD reaction product.

345. The method of any one of claims 316 to 344, wherein the plasma extends substantially through the syringe lumen and the entirety of the limited opening.

346. The method of any one of claims 316 to 345, wherein the plasma extends substantially through the syringe lumen, the limited opening, and the entire vessel lumen being processed.

347. The method of any one of claims 316 to 346, wherein the plasma has a substantially uniform hue throughout the syringe lumen and the limited opening.

348. The method of any one of claims 316 to 347, wherein the plasma has a substantially uniform hue throughout the syringe lumen, the limited opening, and the entire vessel lumen being processed.

349. The method of any one of claims 316 to 348, wherein the plasma is substantially stable throughout the syringe lumen and the limited opening.

350. The method of any one of claims 316 to 349, wherein the plasma is substantially stable through the syringe lumen, the limited opening, and the entire vessel lumen being processed.

351. A method according to any one of claims 316 to 350, wherein the container opening of the vessel under processing is a unique opening.

352. The method according to any one of claims 316 to 351, wherein the volume of the vessel lumen in process is less than three times the volume of the lumen (300) of the vessel (250) being processed.

353. The method of any one of claims 316 to 352, wherein the volume of the vessel lumen in process is less than two times the volume of the lumen of the vessel being processed.

354. The method of any one of claims 316 to 353, wherein the volume of the vessel lumen in process is less than the volume of the lumen of the vessel being processed.

355. The method according to any one of claims 316 to 354, wherein the volume of the container lumen in process is less than 50% of the volume of the lumen (300) of the container (250) being processed.

356. The method according to any one of claims 316 to 355, wherein the volume of the container lumen in process is less than 25% of the volume of the lumen (300) of the container (250) being processed.

357. The method of any one of claims 316 to 356, wherein the generally tubular container being processed in the container support prior to drawing at least a partial vacuum within the lumen (300) of the container (250) &Lt; / RTI > further comprising the step of seating a larger opening of the housing.

358. The method of claim 35, further comprising seating a larger opening of the vessel being treated on the port of the vessel support.

359. The method according to any one of claims 357 and 358, further comprising the step of placing the internal electrode in the container to be treated and seating on the container support object.

360. The method of any one of claims 357, 358, or 359, further comprising: positioning the vessel to be treated with respect to an external electrode having an interior portion positioned to receive the vessel being processed during seating on the vessel support object &Lt; / RTI >

361. A method according to any one of claims 357, 358, 359 or 330, wherein power is applied to a power supply supplying an alternating current to said external power to form a plasma in said vessel to be treated, &Lt; / RTI >

362. The method of claim 361, further comprising grounding the internal electrode.

363. The method of any one of claims 357, 358, 359, 360 or 361, further comprising providing a vacuum source for evacuating the interior of the treated vessel defining a vacuum chamber Lt; / RTI >

364. The method of claim 363, further comprising providing a second vacuum chamber surrounding the vessel to be treated.

365. The method of claim 364, wherein the interior of the vessel is maintained at a lower vacuum level than the second vacuum chamber.

366. The method of claim 363, wherein the vessel under treatment is also a conduit that communicates with a vacuum port in the vessel support.

367. The gas sensor according to any one of claims 357 to 366, further comprising a gas supply for supplying a reactant gas source and a reactant gas from the reactant gas source to a container placed on the container support object invent.

VI. Container inspection

VI.A. Container processing including precoating and postcoat inspection

399. A container treatment method for treating a molded plastic container having an opening and a wall defining an interior surface,

Inspecting the inner surface of the shaped container to determine whether it is defective;

Applying a coating to an inner surface of the container after an inspection step of the molded container; And

And inspecting the coating to see if it is defective.

400. A container processing method for processing a molded plastic container having a wall defining an opening and an interior surface,

Applying a barrier coating to the container after the inspection of the molded container; And

Inspecting the interior surface of the container to determine whether it is defective after the step of applying the barrier coating.

401. The invention of claim 400, wherein the inner surface of the shaped container is inspected at a number of closely spaced locations on the inner surface of the container.

402. The invention of claims 400 or 401, wherein after the step of applying the barrier coating, the inner surface of the container is inspected at a number of closely spaced locations on the inner surface of the container.

403. The method of claim 400, 401 or 402, wherein a number of closely spaced locations on the container interior surface are inspected for location and location on the molded container, after coating with the barrier coating Is re-inspected.

V.I.B. Container Inspection Performed by Detecting the Gas Removal of the Container Wall Through a Shield

404. A method for inspecting a barrier film on a material that removes steam,

Removing the gas and providing a sample of material having at least one partial barrier film; And

And measuring the degassed gas. &Lt; Desc / Clms Page number 21 >

405. The method of claim 404, wherein the gas-removing material is a polymeric compound.

406. The method of claim 404 or 405, wherein the gas removing material comprises a thermoplastic compound.

407. A method as claimed in any one of claims 404 to 406, wherein the gas-removing material comprises polyester.

408. The method of any one of claims 404 to 407, wherein the gas-removing material comprises polyethylene terephthalate.

409. A method according to any one of claims 404 to 408, wherein the gas-removing material comprises a polyolefin.

410. A method as claimed in any one of claims 404 to 409, wherein the gas removing material comprises polypropylene.

411. The method of any one of claims 404 to 410, wherein the gas-removing material comprises a cyclic olefin copolymer.

411a. 41. The method of any one of claims 404 to 419, further comprising contacting the barrier film with water prior to measuring the degassed gas.

411b. 41. The method of any one of claims 404 to 419, further comprising contacting the barrier film with water prior to measuring the degassed gas.

411c. A method according to any one of claims 404 to < RTI ID = 0.0 > 41, < / RTI > further comprising the step of contacting the barrier film with air at a relative humidity of 35% to 100% Way.

411d. A method as claimed in any one of claims 404 to < RTI ID = 0.0 > 411, < / RTI > further comprising the step of contacting the barrier film with air at a relative humidity between 40% and 100% Way.

411e. A method according to any one of claims 404 to 411, further comprising contacting the barrier film with air at a relative humidity of 40% to 50% prior to measuring the degassed gas Way.

411f. 41. The method of any one of claims 404 to 419, further comprising contacting the barrier film with oxygen prior to measuring the degassed gas.

411g. 44. The method of any one of claims 404 to < RTI ID = 0.0 > 411, < / RTI > further comprising contacting the barrier film with nitrogen prior to measuring the degassed gas.

411h. The method according to any one of claims 411 to 411g, wherein the contact time is from 10 seconds to 1 hour.

411i. The method according to any one of claims 411 to 411g, wherein the contact time is from 1 minute to 30 minutes.

411j. The method according to any one of claims 411 to 411g, wherein the contact time is from 5 minutes to 25 minutes.

411k. The method according to any one of claims 411 to 411g, wherein the contact time is from 10 minutes to 20 minutes.

411.1. The method of any one of claims 404 to 411, wherein the degassed gas is measured at a pressure of 0.1 Torr to 100 Torr.

411m. The method of any one of claims 404 to 411, wherein the degassed gas is measured at a pressure of 0.2 Torr to 50 Torr.

411n. The method of any one of claims 404 to 411, wherein the degassed gas is measured at a pressure of 0.5 Torr to 40 Torr.

411o. The method of any one of claims 404 to 411, wherein the degassed gas is measured at a pressure of 1 Torr to 30 Torr.

411p. The method of any one of claims 404 to 411, wherein the degassed gas is measured at a pressure of 5 Torr to 100 Torr.

411q. The method of any one of claims 404 to 411, wherein the degassed gas is measured at a pressure of 10 Torr to 80 Torr.

411r. The method of any one of claims 404 to 411, wherein the degassed gas is measured at a pressure of 15 Torr to 50 Torr.

411s. The method of any one of claims 404 to < RTI ID = 0.0 > 411, < / RTI >

411t. The method of any one of claims 404 to < RTI ID = 0.0 > 411, < / RTI >

411u. 41. The method of any one of claims 404 to < RTI ID = 0.0 > 41, < / RTI >

412. The method of any one of claims 404 through 411, wherein the gaseous material removed is provided in the form of a container having a wall having an outer surface and an inner surface surrounding the lumen.

413. The method of claim 412, wherein the barrier film is provided on the inner surface of the vessel wall.

414. The method of claim 412 or 413, wherein a pressure differential is provided across the barrier membrane by at least partially vacuuming the lumen.

415. The method of any one of claims 412 to 414, further comprising coupling the lumen through a duct to a vacuum source that at least partially vacuums the lumen.

416. The method of claim 41, further comprising providing a degassing measurement cell in communication with the lumen and the vacuum source.

417. The method of any one of claims 404 to 416, wherein the measurement is performed by measuring the volume of material de-gassed through the barrier membrane per time interval.

418. The method of any one of claims 404 to 417, wherein the measurement is performed using a micro-flow technique.

419. The method of any one of claims 404 to 418, wherein the measurement is performed by measuring a mass flow rate of the degassed material.

420. The method of any one of claims 404 to 419, wherein the measurement is performed in a molecular flow mode of operation.

420a. The method of any one of claims 404 to 420,

Providing at least one microcantilever having characteristics that move or change to a different shape when the degassed material is present;

Exposing the microcantilever to the degassed material under conditions effective to cause the microcantilever to move or change to a different shape; And

Moving or detecting a different shape. &Lt; Desc / Clms Page number 19 >

420b. Wherein the different shape reflects an energy incident beam from a portion of the microcantilever that changes shape before and after exposing the microcantilever to the degassing and reflects the reflected energy at a point spaced from the cantilever, And measuring the deflection of the beam.

420c. 420. The method of claim 420, wherein the energy incident beam is selected from a photon beam, an electron beam, and a combination of at least two of the foregoing.

420d. 420. The method of claim 420, wherein the energy incident beam is a photon beam.

420e. 420. The method of claim 420, wherein the energy incident beam is a laser beam.

420f. The method of any one of claims 404 to 420,

Providing at least one microcantilever resonating at a different frequency when the degassed material is present;

Exposing the microcantilever to the degassed material under conditions effective to cause the microcantilever to resonate at different frequencies; And

And detecting the different resonance frequencies.

420g. 420. The method of claim 420, wherein the different resonance frequencies are generated by introducing energy into the microcantilever to induce resonance before and after exposing the microcantilever to gas removal, and before and after exposing the microcantilever to gas removal, Gt; is detected by measuring the difference in the < RTI ID = 0.0 >

420h. 42. The method of claim 420, wherein said different resonance frequencies are detected using a harmonic vibration sensor.

421. The method of claim 404, wherein the gas degassed material is provided in the form of a film.

422. The method of any one of claims 404 to 421, wherein the barrier film is all or part of a coating on a surface of the degassing material.

425. The method of any one of claims 404 to 424, wherein the barrier film comprises SiOx wherein x is from about 1.5 to about 2.9.

426. The method of any one of claims 404 to 425, wherein the barrier film essentially consists of SiOx with x between about 1.5 and about 2.9.

427. The method of any one of claims 404 to 426, wherein the barrier film is less than 500 nm thick.

428. The method of any one of claims 404 to 427, wherein the barrier film is less than 300 nm thick.

429. The method of any one of claims 404 to 428, wherein the barrier film is less than 100 nm thick.

430. The method of any one of claims 404 to 429, wherein the barrier film is less than 80 nm thick.

431. A method according to any one of claims 404 to 430, wherein the barrier film is less than 60 nm thick.

432. The method of any one of claims 404 to 431, wherein the barrier film is less than 50 nm thick.

433. The method of any one of claims 404 to 432, wherein the barrier film is less than 40 nm thick.

434. The method of any one of claims 404 to 433, wherein the barrier film is less than 30 nm thick.

435. The method of any one of claims 404 to 434, wherein the barrier film is less than 20 nm thick.

435. The method of any one of claims 404 to 435, wherein the barrier film is less than 10 nm thick.

437. The method of any one of claims 404 to 436, wherein said barrier film is less than 5 nm thick.

438. A method according to any one of claims 404 to 437, wherein the measurement of the degassed gas is performed under conditions effective to distinguish the presence of the barrier film.

439. The method of claim 438, wherein the effective condition for distinguishing the presence of the barrier film comprises a test duration of less than one minute.

440. The method of claim 438, wherein the effective condition for distinguishing the presence of the barrier film comprises a test duration of less than 50 seconds.

441. The method of claim 438, wherein the effective condition for distinguishing the presence of the barrier film comprises a test duration of less than 40 seconds.

442. The method of claim 438, wherein the effective condition for distinguishing the presence of the barrier film comprises a test duration of less than 30 seconds.

443. The method of claim 438, wherein the effective conditions for distinguishing the presence of the barrier film include a test duration of less than 20 seconds.

444. The method of claim 438, wherein the effective condition for distinguishing the presence of the barrier film comprises a test duration of less than 15 seconds.

445. The method of claim 438, wherein the effective conditions for distinguishing the presence of the barrier film include a test duration of less than 10 seconds.

446. The method of claim 438, wherein the effective condition for distinguishing the presence of the barrier film comprises a test duration of less than 8 seconds.

447. The method of claim 438, wherein the effective condition for distinguishing the presence of the barrier film comprises a test duration of less than 6 seconds.

448. The method of claim 438, wherein the effective condition for distinguishing the presence of the barrier film comprises a test duration of less than 4 seconds.

449. The method of claim 438, wherein the effective condition for distinguishing the presence of the barrier film comprises a test duration of less than 3 seconds.

450. The method of claim 438, wherein the effective condition for distinguishing the presence of the barrier film comprises a test duration of less than 2 seconds.

451. The method of claim 438, wherein the effective condition for distinguishing the presence of the barrier film comprises a test duration of less than one second.

452. A method according to any one of claims 438 to 451, wherein the measurement of the zone member of the barrier is identified with at least a 6 sigma level of confidence.

453. The method of any one of claims 438 to 452, wherein the measurement is identified with at least a 6-sigma level of confidence.

454. The method of any one of claims 404 to 453, wherein the degassed gas measurement on the low pressure side of the blocking membrane is effective to measure the barrier enhancement factor of the barrier membrane as compared to the same material without a blocking membrane &Lt; / RTI >

455. The method of any one of claims 404 to 454, wherein gas removal of a plurality of different gases is measured.

456. The method of any one of claims 404 to 455, wherein gas removal of substantially all of said de-gassed gases is measured.

457. The method of any one of claims 404 to 456, wherein gas removal of substantially all of said degassed gases is measured simultaneously.

458. The method of any one of claims 404 to 457, wherein gas removal of substantially all of said de-gassed gases is measured simultaneously.

20 Container processing system
22 Injection molding machine
24 Visual inspection station
26 Inspection station (pre-coated)
28 Coating station
30 Inspection station (post-coating)
32 Light source transmission station (thickness)
34 Light source transmission station (defect)
36 Output
38 container support
40 container support
42 container support
44 Container support
46 Container support
48 container support
50 container support
52 Container support
54 Container support
56 Container Support
58 Container support
60 container support
62 Container support
64 container support
66 Container support
68 Container support
70 conveyor
72 Delivery mechanism (operational)
74 Delivery mechanism (outage)
80 containers
82 opening
84 occlusion block
86 wall
88 internal surface
90 barrier coating
92 vessel port
94 Vacuum duct
96 Vacuum port
98 vacuum source
100 O-rings (of 92)
102 O-rings (of 96)
104 Gas input port
106 O-ring (of 100)
108 probe (counter electrode)
110 gas delivery port (of 108)
112 container support (Figure 3)
114 housing (50 or 112)
116 collar
118 outer surface (of 80)
120 Container support (array)
122 "vessel port (Figures 4 and 58)
130 frames (Fig. 5)
132 light source
134 Side Channel
136 Isolation valve
138 Probe port
140 Vacuum port
142 PECVD gas input port
144 PECVD gas source
146 vacuum line (up to 98)
148 Isolation valve
150 flexible lines (of 134)
152 Pressure gauge
154 Inside the Container 80
160 electrodes
162 power supply
164 side walls 160,
166 side walls (of 160)
168 occlusion (160)
170 light source (Fig. 10)
172 detector
174 pixels (172)
176 inner surface (of 172)
182 Apoche (186)
184 walls (of 186)
186 integrator
190 microwave power supply
192 waveguide
194 Microwave cavity
196 Gap
198 Top (194)
200 Electrodes
202 Tube transportation
204 suction cup
208 Mold center
210 mold cavity
212 Mold cavity liner
220 bearing surface (Figure 2)
222 Bearing surface (Figure 2)
224 Bearing surface (Figure 2)
226 Bearing surface (Figure 2)
228 Bearing surface (Figure 2)
230 bearing surface (Figure 2)
232 bearing surface (Figure 2)
234 Bearing Surface (Figure 2)
236 Bearing surface (Figure 2)
238 Bearing surface (Figure 2)
240 bearing surface (Figure 2)
250 syringes barrels
252 syringe
254 inner surface (250)
256 rear end (250)
258 Plunger (252)
260 Shear (250)
262 Caps
264 inner surface 262)
266 Fitting
268 containers
270 Closures
272 Inner facing surface
274 lumens
276 Wall-contact surface
278 inner surface (of 280)
280 Container wall
282 Stopper
284 Shield
286 Lubricating Coating
288 barrier coating
290 coating apparatus, for example, 250
292 inner surface (294)
294 limiting opening (250)
296 Processing vessel
298 outer surface (250)
300 lumens (250)
302 large opening (250)
304 Processing vessel lumen
306 Processing vessel opening
308 internal electrode
310 internal passageway (308)
312 proximal end (308)
314 won (308)
316 distal opening (of 308)
318 Plasma
320 Container support
322 port (320)
324 Processing vessel (water supply type)
326 container opening (of 324)
328 second opening 324,
330 Vacuum port (328 receptacles)
332 1st fitting (male thread taper)
334 2nd fitting (female taper)
336 Locking ring (of 332)
338 first connection portion (of 332)
340 of the second joint portion 332,
342 O-ring
344 Cock (Dog)
346 Walls
348 coating (346 phase)
350 penetration route
352 Vacuum
354 gas molecule
355 gas molecule
356 interface (Between 346 and 348)
357 Gas molecule
358 PET containers
359 Gas molecule
360 sealing
362 Measurement cell
364 Vacuum pump
366 Arrows
368 conical passage
370 perforator
372 Perforators
374 chamber
376 chamber
378 diaphragm
380 diaphragm
382 Conductive surface
384 Conductive surface
386 Bypass
390 plot (glass tube)
392 plots (PET uncoated)
Plot 394 shares (the SiO ₂ coating)
396 separated waters (as SiO ₂ coated)
398 Internal electrode and gas supply tube
400 distal opening
402 extension counter electrode
404 outlet (Figure 7)
406 valve
408 inner wall (FIG. 36)
410 outer wall (Figure 36)
412 inner surface (Figure 36)
414 plate electrode (Figure 37)
416 plate electrode (Figure 37)
418 Vacuum water supply
420 container support
422 Vacuum chamber
424 container support
426 counter electrode
428 Vessel support (Figure 39)
430 electrode assembly
432 A volume surrounded by 430
434 Pressure balance control valve
436 Vacuum chamber number
438 syringe barrel (Figure 42)
440 Flange (438)
442 Posterior opening (of 438)
444 Barrel Wall (438)
450 container support (Figure 42)
452 Phantom lip
454 approximately cylindrical side wall 438,
456 approximately cylindrical inner surface (450)
458 connection
460 pockets
462 O-ring
464 outer wall (of 460)
466 Floor Walls (460's)
468 upper wall (460)
470 internal electrodes (Figure 44)
472 distal site (of 470)
474 porous sidewalls 472,
476 Internal passage (472)
478 proximal region (470)
480 won (470)
482 Casing Support Body
484 upper part (482)
486 basal area (482)
488 Joints (Between 484 and 486)
490 O-ring
492 Phantom pocket
494 A radially extending abutment surface
496 Radially extending wall
498 Screw
500 Screw
502 container port
504 second O-ring
506 inner diameter (490)
508 Vacuum Duct (of 482)
510 internal electrode
512 internal electrode
514 Insertion and removal mechanism
516 Flexible Hose
518 Flexible Hose
520 Flexible Hose
522 valve
524 valve
526 valve
528 Electrode Cleaning Station
530 Internal electrode drive
532 Cleaning Reactor
534 outlet valve
536 2nd gripper
538 Conveyor
539 Solute retainer
540 open end (532)
542 inner space (532)
544 syringe
546 plunger
548 body
550 barrels
552 inner surface (of 550)
554 Coating
556 Luer fitting
558 Lure Taper
560 Internal passage (558)
562 internal surface
564 Coupling
566 male parts (564)
568 Arm part (564)
570 barrier coating
572 Locking ring
574 main vacuum valve
576 Vacuum line
578 Manual bypass valve
580 Bypass Line
582 outlet valve
584 Primary reactant gas valve
586 Primary reactant supply line
588 Organic silicone liquid reservoir
590 Organic Silicon Supply Line (capillary)
592 Organic Silicon Shutoff Valve
594 oxygen tank
596 oxygen supply line
598 Flow controller
600 oxygen shutoff valve
602 Outer barrier coating of syringe
604 lumens
606 Outer surface of barrel
610 Plasma Screen
612 Plasma Screen Cavity
614 space portion
616 Pressure source
618 pressure line
620 Capillary connection
630 Plots for uncoated COC
632 Plots for SiOx uncoated COC
Plots for 634 glass
5501 First processing station
5502 Second processing station
5503 Third processing station
5504 Fourth processing station
5505 processor
5506 User Interface
5507 bus
5701 PECVD equipment
5702 first detector
5703 second detector
5704 detector
5705 detector
5706 detector
5707 detector
7001 Conveyor outlet branch
7002 Conveyor outlet branch
7003 Conveyor outlet branch
7004 Conveyor outlet branch

Claims

A method for setting the lubrication of a coating on a surface of a substrate,
(a) providing a gaseous reactant material comprising an organosilicon precursor and optionally oxygen (O ₂ ) that is octamethylcyclotetrasiloxane (OMCTS) near the substrate surface; And
(b) generating a plasma from the gas reactive material and forming a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD)
Lt; / RTI >
(c) said coating has an atomic ratio of Si _w O _x C _y (where w is 1, x is 0.5 to 2.4 and y is 0.6 to 3) as measured by X-ray photoelectron spectroscopy (XPS)
That the lubricating properties of the coating setting the oxygen (O ₂₎ and the ratio of the organosilicon precursor in the gas reactant and / or by setting the lubricity of the coating to the substrate surface will be set by setting the power used for generating the plasma Way.

A method of making a hydrophobic coating on a substrate,
(a) providing a gaseous reactant material comprising an organosilicon precursor and optionally oxygen (O ₂ ) that is octamethylcyclotetrasiloxane (OMCTS) near the substrate surface; And
(b) generating a plasma from the gas reactive material and forming a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD)
Lt; / RTI >
(c) said coating has an atomic ratio of Si _w O _x C _y (where w is 1, x is 0.5 to 2.4 and y is 0.6 to 3) as measured by X-ray photoelectron spectroscopy (XPS)
Wherein the hydrophobic property of the coating is set by setting the ratio of oxygen (O < ₂ >) to the organosilicon precursor in the gas reactant and / or by setting the power used to generate the plasma .

3. A coating according to claim 1 or 2, characterized in that the coating is characterized in that the atomic ratio of C: O is increased and / or the atomic ratio of Si: O is reduced compared to the chemical formula of said organosilicon precursor / RTI >

According to claim 1 or 2, wherein O ₂ is the volume of gas to the reactant-volume ratio of 0: The method of the present in a 1: 1 to 5.

According to claim 1 or 2, wherein said gas reactant comprises O ₂ of less than 1% by volume.

3. The method of claim 1 or 2, wherein the plasma is a non-ball-borne cathode plasma.

3. The method according to claim 1 or 2,
(i) the plasma is generated and / or produced using electrodes supplied with sufficient power to form a coating on the substrate surface; (ii) the ratio of the power of the electrode to the plasma volume is less than 10 W / ml.

delete

A method for producing a SiO _x barrier coating on a substrate,
(a) providing a gas reactive material comprising an organosilicon precursor and O ₂ near the substrate surface; And
(b) generating a non-pore-anodic plasma from the gas reactant under reduced pressure to form a SiO _x barrier coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD)
Lt; / RTI >
Wherein the barrier properties of the coating are set by setting the ratio of O ₂ to the organosilicon precursor in the gas reactant and / or by setting the power used to generate the plasma.

10. The method of claim 9,
(i) the plasma is generated and / or produced using electrodes supplied with sufficient power to form a coating on the substrate surface;
(ii) the ratio of the power of the electrode to the plasma volume is at least 5 W / ml.

Ninth according to any one of claims 10 or 11, in relation to the silicon containing precursor the O ₂ gas is the volume of the reactants: the method is present in 1: a volume ratio of 1: 1 to 100.

delete

11. The method of claim 9 or 10, wherein the substrate is a polymer selected from the group consisting of polycarbonate, olefin polymers, cyclic olefin copolymers and polyesters.

11. The method of claim 9 or 10, wherein the plasma is generated using electrodes powered at a radio frequency.

A coating obtainable according to claim 1 or 2.

18. The coating of claim 17, wherein the coating is a lubricating and / or hydrophobic coating.

19. The coating of claim 18 wherein the atomic ratio of carbon to oxygen is increased relative to the organosilicon precursor and / or the atomic ratio of oxygen to silicon is reduced relative to the organosilicon precursor.

19. The coating of claim 18 having a lower frictional resistance than the uncoated surface.

19. The method of claim 18, further comprising: (i) having a lower wet tension than the uncoated surface; (ii) is more hydrophobic than an uncoated surface.

17. A container coated on at least a portion of an interior surface thereof with a coating according to claim 17,
(i) a sample collection tube; or
(ii) a vial; or
(iii) a syringe or syringe portion; or
(iv) a pipe; or
(v) A container that is cubic.

23. The method of claim 22, wherein the SiO _x (where, x is from 1.5 to 2.9 being) comprising at least one layer of a further,
(i) the coating is positioned between the SiO _x layer and the substrate surface or vice versa, or
(ii) the coating is located between two SiO _x layers or vice versa, or
(iii) the SiO _x layers and said coating are a stepped composite from Si _w O _x C _y H _z to SiO _x or vice versa.

23. The coated container of claim 22, wherein the lumen contains a compound or composition.

23. The method of claim 22,
(a) providing a gas reactive material comprising an organosilicon precursor that is octamethylcyclotetrasiloxane (OMCTS) near the substrate surface and substantially free of oxygen (O ₂ ) gas; And
(b) generating a plasma from the gas reactive material and forming a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD);
A syringe barrel made by a method comprising:
(c) said coating has an atomic ratio of Si _w O _x C _y (where w is 1, x is 0.5 to 2.4 and y is 0.6 to 3) as measured by X-ray photoelectron spectroscopy (XPS)
The lubrication characteristic of the coating is set by setting the power used to generate the plasma,
Wherein the force to move the plunger through the coated barrel is reduced by at least 25% relative to the uncoated syringe barrel.

(i) a lubricous coating having a lower frictional resistance than an uncoated surface; And / or
(ii) a hydrophobic coating that is more hydrophobic than the uncoated surface
Si _w O _x C _y H _z wherein w is 1, x is 0.5 to 2.4, y is 0.6 to 3, and z is 2 to 9.

23. The coated container of claim 22, wherein the coated or enclosed compound or composition in the coated container is protected from mechanical and / or chemical influences of the uncoated container material surface.

28. The composition of claim 27, wherein the compound or composition comprises
(i) a biologically active compound or composition; or
(ii) a compound or composition that is a biological fluid.