Vessel, coating, inspection and processing apparatus
View Patent ↗Methods for processing a vessel, for example to provide a gas barrier or lubricity, are disclosed. First and second PECVD or other vessel processing stations or devices and a vessel holder comprising a vessel port are provided. An opening of the vessel can be seated on the vessel port. The interior surface of the seated vessel can be processed via the vessel port by the first and second processing stations or devices. Vessel barrier, lubricity and hydrophobic coatings and coated vessels, for example syringes and medical sample collection tubes are disclosed. A vessel processing system and vessel inspection apparatus and methods are also disclosed.
1. A syringe or syringe parts comprising: a barrel and a piston, the barrel having an inner surface and the piston having a side surface engaging the barrel inner surface, wherein at least one of the inner surface and the side surface is a substrate coated with a lubricity layer configured to provide a lower piston sliding force or breakout force than the uncoated substrate
the lubricity layer having one of the following atomic ratios, measured by X-ray photoelectron spectroscopy (XPS), Si w O x C y or Si w N x C y , where w is 1, x in this formula is from about 0.5 to 2.4, and y is from about 0.6 to about 3;
the lubricity layer having a thickness by transmission electron microscopy (TEM) between 10 and 500 nm;
the lubricity layer deposited by plasma enhanced chemical vapor deposition (PECVD) under conditions effective to form a coating from a precursor selected from a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, a linear silazane, a monocyclic silazane, a polycyclic silazane, a polysilsesquiazane, a silatrane, a silquasilatrane, a silproatrane, an azasilatrane, an azasilquasiatrane, an azasilproatrane, or a combination of any two or more of these precursors.
2. The syringe or syringe parts of claim 1 , in which the precursor comprises hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, a poly(methylsilsesquioxane) according to the T8 cube formula:
in which each R is methyl, a poly(Methyl-Hydridosilsesquioxane) according to the T8 cube formula in which 90% of the R groups are methyl and 10% are hydrogen atoms, methyltrimethoxysilane, or a combination of any two or more of these.
3. The syringe or syringe parts of claim 1 , in which the precursor comprises octamethylcyclotetrasiloxane (OMCTS).
4. The syringe or syringe parts of claim 1 , in which the precursor consists essentially of octamethylcyclotetrasiloxane (OMCTS).
5. The syringe or syringe parts of claim 1 , in which the lubricity layer has a thickness of 10-200 nm.
6. The syringe or syringe parts of claim 1 , in which the lubricity layer has a thickness of 20 to 100 nm.
7. The syringe or syringe parts of claim 1 , in which the substrate comprises glass.
8. The syringe or syringe parts of claim 1 , in which the substrate comprises a polymer.
9. The syringe or syringe parts of claim 1 , in which the substrate comprises a polycarbonate polymer.
10. The syringe or syringe parts of claim 1 , in which the substrate comprises an olefin polymer.
11. The syringe or syringe parts of claim 1 , in which the substrate comprises a cyclic olefin copolymer.
12. The syringe or syringe parts of claim 1 , in which the substrate comprises a polypropylene polymer.
13. The syringe or syringe parts of claim 1 , in which the substrate comprises a polyester polymer.
14. The syringe or syringe parts of claim 1 , in which the substrate comprises a polyethylene terephthalate polymer.
15. The syringe or syringe parts of claim 1 , further comprising an outer wall of the syringe barrel and a barrier coating on the outer wall of the syringe barrel.
16. The syringe or syringe parts of claim 15 , in which the barrier coating is an oxygen barrier coating.
17. The syringe or syringe parts of claim 16 , in which the barrier coating is a water barrier coating.
18. The syringe or syringe parts of claim 16 , in which the barrier coating comprises polyvinylidene chloride.
19. The syringe or syringe parts of claim 16 , in which the barrier coating is applied as a water-based coating.
20. The syringe or syringe parts of claim 1 , in which the lubricity layer materials and conditions are effective to reduce the syringe piston sliding force or breakout force moving through the syringe barrel at least 45 percent relative to an uncoated syringe barrel.
21. The syringe or syringe parts of claim 1 , in which the lubricity layer materials and conditions are effective to reduce the syringe piston sliding force or breakout force moving through the syringe barrel at least 60 percent relative to an uncoated syringe barrel.
22. The syringe or syringe parts of claim 1 , in which the lubricity layer materials and conditions are effective to reduce the syringe piston sliding force or breakout force moving through the syringe barrel more than 60 percent relative to an uncoated syringe barrel.
23. The syringe or syringe parts of claim 1 , in which the lubricity layer is applied to the barrel inner surface.
24. The syringe or syringe parts of claim 1 , in which the lubricity layer is applied to the piston side surface.
25. The syringe or syringe parts of claim 1 , in which the lubricity layer is applied to the barrel inner surface and the piston side surface.
26. The syringe or syringe parts of claim 1 , further comprising a barrier coating of SiO x , in which x is from about 1.5 to about 2.9, on the interior surface of the barrel.
27. The syringe or syringe parts of claim 26 , in which the lubricity layer is applied to the barrier coating of SiOx.
28. The syringe or syringe parts of claim 1 , in which the lubricity layer interfaces with the side surface of the piston, the piston further comprises a back portion, and the syringe further comprises a push rod engaging the back portion and configured for advancing the piston in a syringe barrel.
29. The syringe or syringe parts of claim 1 , in which the lubricity layer has a density between 1.25 and 1.65 g/cm 3 as determined by X-ray reflectivity (XRR).
30. The syringe or syringe parts of claim 1 , in which the lubricity layer has an outgas component as determined by gas chromatography/mass spectrometry substantially free of trimethylsilanol.
31. The syringe or syringe parts of claim 1 , in which the lubricity layer has an outgas component as determined by gas chromatography/mass spectrometry having at least 10 ng/test of oligomers containing repeating -(Me)2SiO— moieties, as determined by gas chromatography/mass spectrometry using the following test conditions:
GC Column: 30 m×0.25 mm DB-5MS (J&W Scientific),
0.25 μm film thickness
Flow rate: 1.0 ml/min, constant flow mode
Detector: Mass Selective Detector (MSD)
Injection Mode: Split injection (10:1 split ratio)
Outgassing Conditions: 1W (37 mm) Chamber, purge for three hour at 85° C., flow 60 ml/min
Oven temperature: 40° C. (5 min.) to 300° C. @10° C./min.; hold for 5 min, at 300° C.
32. The syringe or syringe parts of claim 1 , in which the lubricity layer has atomic concentrations from 25 to 45% carbon, 25 to 65% silicon, and 10 to 35% oxygen.
33. The syringe or syringe parts of claim 1 , in which the lubricity layer precursor comprises a monocyclic siloxane, a monocyclic silazane, a polycyclic siloxane, a polycyclic silazane, or any combination of two or more of these.
34. The syringe or syringe parts of claim 1 , in which the lubricity layer precursor comprises a monocyclic siloxane, a monocyclic silazane, or any combination of two or more of these.
35. The syringe or syringe parts of claim 1 , in which the lubricity layer precursor comprises a monocyclic siloxane or any combination of two or more of these.
36. The syringe or syringe parts of claim 1 , in which the lubricity layer has an atomic concentration of carbon, normalized to 100% of carbon, oxygen, nitrogen, and silicon, as determined by XPS, greater than the atomic concentration of carbon in the atomic formula for the precursor.
37. The syringe or syringe parts of claim 36 , in which the atomic concentration of carbon increases by from 1 to 80 atomic percent.
38. The syringe or syringe parts of claim 1 , in which the lubricity layer has an atomic concentration of silicon, normalized to 100% of carbon, oxygen, nitrogen, and silicon, as determined by XPS, less than the atomic concentration of silicon in the atomic formula for the precursor.
39. The syringe or syringe parts of claim 38 , in which the atomic concentration of silicon decreases by from 1 to 80 atomic percent.
40. The syringe or syringe parts of claim 1 , in which the lubricity layer is characterized by a sum formula wherein the atomic ratio C:O is increased and/or the atomic ratio Si:O is decreased in comparison to the sum formula of the organosilicon precursor.
41. The syringe or syringe parts of claim 1 , wherein the substrate is the inside wall of the syringe barrel defining a lumen, the lumen having a void volume of from 0.5 to 50 mL.
42. The syringe or syringe parts of claim 1 , wherein the lubricity layer has a lower wetting tension than the uncoated surface.
43. The syringe or syringe parts of claim 1 , additionally comprising at least one barrier layer of SiOx, wherein x is from 1.5 to 2.9, wherein the SiOx layer is situated between the substrate surface and the lubricity layer.
44. The syringe or syringe parts of claim 43 , wherein the layer of SiOx and the lubricity layer are a graded composite of SiOx to the lubricity layer.
45. The syringe or syringe parts of claim 1 , comprising at least one further barrier layer of plastic or SiOx, wherein x is from 1.5 to 2.9, formed over the lubricity layer.
46. The syringe or syringe parts of claim 1 , which contains a compound or composition in a lumen of the barrel which is a biologically active compound or composition, a biological fluid, a citrate or a citrate containing composition, a medicament, blood or blood cells.
47. A syringe having a barrel and a plunger, the barrel having an inner surface and the plunger having a side surface engaging the barrel inner surface, wherein at least one of the inner surface and the side surface is a substrate treated by applying a lubricity layer having one of the following atomic ratios, measured by X-ray photoelectron spectroscopy (XPS), Si w O x C y or Si w N x C y , where w is 1, x in this formula is from about 0.5 to 2.4, and y is from about 0.6 to about 3, wherein the lubricity layer is configured to provide a lower piston sliding force or breakout force than the uncoated substrate and is applied by the following process:
providing a precursor selected from a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, a linear silazane, a monocyclic silazane, a polycyclic silazane, a polysilsesquiazane, a silatrane, a silquasilatrane, a silproatrane, an azasilatrane, an azasilquasiatrane, an azasilproatrane, or a combination of any two or more of these precursors; and
applying the precursor as a coating to a substrate and polymerizing or crosslinking the coating, or both, by plasma enhanced chemical vapor deposition (PECVD).
48. The syringe of claim 47 , in which the applying step is carried out by vaporizing the precursor and providing it in the vicinity of the substrate.
49. The syringe of claim 47 , in which during polymerizing or crosslinking a plasma is formed in the vicinity of the substrate.
50. The syringe of claim 47 , in which during polymerizing or crosslinking a non-hollow-cathode plasma is formed in the vicinity of the substrate.
51. The syringe of claim 47 , in which during polymerizing or crosslinking the precursor is provided in the substantial absence of oxygen.
52. The syringe of claim 47 , in which during polymerizing or crosslinking the precursor is provided in the substantial absence of a carrier gas.
53. The syringe of claim 47 , in which during polymerizing or crosslinking the precursor is provided in the substantial absence of nitrogen.
54. The syringe of claim 47 , in which during polymerizing or crosslinking the precursor is provided at less than 1 Torr absolute pressure.
55. The syringe of claim 47 , in which during polymerizing or crosslinking the precursor is provided to the vicinity of a plasma emission.
56. The syringe of claim 47 , in which the lubricity layer has a thickness of 10 to 5000 nm.
57. The syringe of claim 47 , in which the lubricity layer has a thickness of 10 to 1000 nm.
58. The syringe of claim 47 , in which during polymerizing or crosslinking the precursor is contacted with a plasma made by energizing the vicinity of the precursor with electrodes powered at a frequency of 10 kHz to 2.45 GHz.
59. The syringe of claim 47 , in which during polymerizing or crosslinking the precursor is contacted with a plasma made by energizing the vicinity of the precursor with electrodes supplied with electric power at from 1 to 22 Watts.
60. The syringe of claim 47 , in which during polymerizing or crosslinking the precursor is contacted with a plasma made by energizing the vicinity of the precursor with electrodes supplied with electric power at less than 10 Watts per ml, of plasma volume.
61. The syringe of claim 47 , in which during polymerizing or crosslinking the precursor is contacted with a plasma made by energizing the vicinity of the precursor with electrodes supplied with electric power from 0.1 to 5 Watts per ml, of plasma volume.
62. The syringe of claim 47 , the lubricity layer having a thickness by transmission electron microscopy (TEM) between 10 and 500 nm.
63. The syringe of claim 47 , wherein during polymerizing or crosslinking a gaseous reactant comprising the precursor and O 2 is present, and the O 2 is present in a volume-volume ratio to the gaseous reactant of from 0:1 to 0.5:1.
64. The syringe of claim 63 , wherein the gaseous reactant comprises less than 1 vol % O 2 .
65. The syringe of claim 47 , wherein the substrate is the inside wall of the syringe barrel defining a lumen, the lumen having a void volume of from 0.5 to 50 mL.
66. The syringe of claim 47 , wherein the polymerizing or crosslinking step is carried out by generating plasma with electrodes powered with sufficient power to form a coating on the substrate surface.
67. The syringe of claim 66 , wherein the electrodes are supplied with an electric power of from 0.1 to 25 W.
68. The syringe of claim 66 , wherein the ratio of the electrode power to the plasma volume is less than 10 W/ml.
69. The syringe of claim 47 , wherein the plasma enhanced chemical vapor deposition (PECVD) is performed at a flow of the organosilicon precursor of not more than 6 sccm.
70. The syringe of claim 47 , wherein:
the polymerizing or crosslinking step comprises plasma enhanced chemical vapor deposition (PECVD),
the substrate surface is part or all of the inner surface of the syringe barrel,
the syringe barrel has at least one opening and an inner surface, and
the gaseous reactant fills an interior lumen of the barrel and the plasma is generated in part or all of the interior lumen of the barrel.
71. The syringe of claim 47 , wherein the polymerizing or crosslinking step comprises plasma enhanced chemical vapor deposition (PECVD), wherein the plasma is generated with electrodes powered at a frequency of from 10 kHz to less than 300 MHz.
72. The syringe of claim 47 , wherein the polymerizing or crosslinking step comprises plasma enhanced chemical vapor deposition (PECVD), wherein the plasma is generated at less than 300 mTorr.
73. The syringe of claim 47 , wherein the polymerizing or crosslinking step comprises plasma enhanced chemical vapor deposition (PECVD), wherein the PECVD deposition time is from 1 to 30 sec.
74. The syringe of claim 47 , wherein the lubricity layer has a thickness of in the range of from 1 to 100 nm.
75. The syringe of claim 47 , wherein the polymerizing or crosslinking step comprises plasma enhanced chemical vapor deposition (PECVD), wherein the atomic ratio of carbon to oxygen is increased in comparison to the organosilicon precursor, or wherein the atomic ratio of oxygen to silicon is decreased in comparison to the organosilicon precursor, or both.
76. The syringe of claim 47 , wherein the polymerizing or crosslinking step comprises plasma enhanced chemical vapor deposition (PECVD), wherein the precursor is octamethylcyclotetrasiloxane and wherein the coating has a density higher than the density of a coating made from HMDSO under the same plasma enhanced chemical vapor deposition (PECVD) reaction conditions.
77. The syringe of claim 47 , wherein the polymerizing or crosslinking step comprises plasma enhanced chemical vapor deposition (PECVD), wherein the coating has a lower frictional resistance than the uncoated surface.