# US 11,077,233 B2 · Pharmaceutical and other packaging with low oxygen transmission rate > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,077,233 B2 - Document ID: US11077233B2 - Status: Granted - Kind: B2 - Application number: 15/753,524 - Filed: 2016-08-18 - Published: 2019-01-17 - Granted: 2021-08-03 - Earliest claimed: 2015-08-18 - Assignees: Sio2 Medical Products, Inc. - Applicants: Sio2 Medical Products, Inc. - Inventors: Matthew Wills; Ahmad Taha; Christopher Weikart - Web page: https://patentgrep.com/patent/US11077233B2 ## CPC - A61L 29/085: {Macromolecular materials} - A61L 27/34: Macromolecular materials - A61L 31/06: obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds {(A61L31/041 takes precedence)} - B05D 1/62: {Plasma-deposition of organic layers (plasma deposition in general C23C14/00, C23C16/00)} - B05D 7/02: to macromolecular substances, e.g. rubber (treatment or coating of shaped articles made of macromolecular substances C08J7/00) - B05D 7/227: {of containers, cans or the like} - C08L 83/04: Polysiloxanes - C23C 16/045: {Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates} - C23C 16/30: Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides - C23C 16/401: {containing silicon} - C23C 16/515: using pulsed discharges - A61L: METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES (preservation of bodies or disinfecting characterised by the agents employed A01N; preserving, e.g. sterilising, food or foodstuffs A23; preparations for medical, dental or toiletry purposes A61K) - B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04) ## Abstract Processing an evacuated blood sample collection tube or other vessel by plasma enhanced chemical vapor deposition to apply a tie coating or layer (289), a barrier coating or layer (288), and optionally one or more additional coatings or layers. The tie coating or layer of SiOxCy is applied under partial vacuum and, while maintaining the partial vacuum unbroken in the lumen, the barrier coating or layer is applied. Then optionally, while maintaining the partial vacuum unbroken in the lumen, a pH protective coating or layer of SiOxCy can be applied. As a result of this processing, a coated vessel is produced having a lower gas permeation rate constant into the lumen than a corresponding vessel made by the same process except breaking the partial vacuum in the lumen between applying the tie coating or layer and applying the barrier coating or layer. Retention features are also described for keeping the vessels stoppered during exposure to reduced ambient pressure. ## Claims ### Claim 1 An evacuated blood collection tube comprising: a thermoplastic vessel wall; and a stopper; the thermoplastic vessel wall having a top defining an opening, an inside surface defining a lumen, the inside surface having one or more coatings applied by PECVD, an outside surface, and a stopper contact area adjacent to the top, the stopper contact area being a portion of the inside surface that contacts the stopper; the stopper being seated in the stopper contact area and sealing the lumen; wherein the stopper contact area is tapered inward between 0 and 1.3 degrees and the entirety of the inside surface below the stopper contact area is tapered inward at least 0.1 degree more than the stopper contact area; and wherein the stopper contact area is continuous with the inside surface below the stopper contact area. ### Claim 2 (depends on 1) The evacuated blood collection tube of claim 1, in which the entirety of the inside surface below the stopper contact area is tapered at least 1.5 degrees. ### Claim 3 (depends on 1) The evacuated blood collection tube of claim 1, the stopper maintaining a vacuum level in the lumen, relative to ambient pressure at sea level, sufficient to draw blood from a patient's vein into the lumen. ### Claim 4 (depends on 3) The evacuated blood collection tube of claim 3, in which the stopper remains seated in the stopper contact area at a vacuum level of 97.5 kPa below ambient pressure. ### Claim 5 (depends on 3) The evacuated blood collection tube of claim 3, having a shelf life of at least 6 months, the shelf life defined by the amount of time after evacuation the tube maintains a draw volume capacity of at least 90% of the draw volume capacity of a newly evacuated vessel of the same kind. ### Claim 6 (depends on 3) The evacuated blood collection tube of claim 3, further comprising a fluid composition in the lumen. ### Claim 7 (depends on 6) The evacuated blood collection tube of claim 6, wherein the fluid composition comprises a blood anticoagulation agent. ### Claim 8 (depends on 7) The evacuated blood collection tube of claim 7, wherein the blood anticoagulation agent is a buffered sodium citrate solution. ### Claim 9 (depends on 3) The evacuated blood collection tube of claim 3, having an oxygen permeation rate constant of from 0.0001 to 0.01 micromol O2/(day×cm2×atm). ### Claim 10 (depends on 3) The evacuated blood collection tube of claim 3, in which the wall has a water vapor transmission rate of less than 2.5 g/m2/day at 50° C. and 90% relative humidity. ### Claim 11 (depends on 1) The evacuated blood collection tube of claim 1, wherein the inside surface comprises: a barrier layer of SiOx applied by a PECVD coating process, wherein x is from 1.5 to 2.9 as determined by XPS, and at least one of: a tie layer of SiOxCy applied by a PECVD coating process, and a pH protective layer of SiOxCy applied by a PECVD coating process. ### Claim 12 (depends on 1) The evacuated blood collection tube of claim 1, wherein the inside surface comprises: a tie layer of SiOxCy applied by a PECVD coating process, a barrier layer of SiOx applied by a PECVD coating process, wherein x is from 1.5 to 2.9 as determined by XPS, between the tie coating or layer and the lumen, and a pH protective layer of SiOxCy applied by a PECVD coating process, wherein x is from about 0.5 to about 2.4 and y is from about 0.6 to about 3, each as determined by XPS, between the barrier layer and the lumen. ### Claim 13 (depends on 1) The evacuated blood collection tube of claim 1, in which the stopper contact area is tapered inward between 0.3 and 1 degree.