Granted Patent B2

US 12,623,813 · App. 18/390,669 · Granted May 12, 2026

Inventors: John T. Felts (Alameda, CA); Thomas E. Fisk (Green Valley, AZ); Robert S. Abrams (Albany, NY); John Ferguson (Auburn, AL); Jonathan R. Freedman (Auburn, AL); Robert J. Pangborn (Harbor Springs, MI); Peter J. Sagona (Pottstown, PA); Christopher Weikart (Auburn, AL)

Assignee: SIO2 MEDICAL PRODUCTS, LLC

B65D25/14A61M5/3129B65D25/04C23C16/045C23C16/30C23C16/36C23C16/401C23C16/507A61J1/05A61M2005/3109A61M2005/3131

Abstract

Claims (152)

1 . An article comprising:

a wall having a surface;

a barrier coating or layer of SiOx, wherein x is from 1.5 to 2.9, from 2 to 1000 nm thick, the barrier coating or layer of SiOx having an outer surface facing the wall surface, the barrier coating or layer being effective to reduce the ingress of atmospheric gas through the wall compared to an uncoated wall; and

a pH protective coating of SiOxCy wherein x is from about 0.5 to about 2.4 and y is from about 0.6 to about 3, on the barrier coating or layer, the pH protective coating being formed by chemical vapor deposition of a precursor selected from a a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, a silatrane, a silquasilatrane, a silproatrane, or a combination of any two or more of these precursors;

in which an FTIR absorbance spectrum of the pH protective coating has a ratio greater than 0.75 between:

the maximum amplitude of the Si—O—Si symmetrical stretch peak between about 1000 and 1040 cm −1 , and

the maximum amplitude of the Si—O—Si asymmetric stretch peak between about 1060 and about 1100 cm −1 ; and

in which the rate of erosion of the pH protective coating, if directly contacted by a fluid composition having a pH of 8, is less than 20% of the rate of erosion of the barrier coating or layer, if directly contacted by the fluid composition under the same conditions.

2 . The article of claim 1 , in which at least a portion of the wall comprises or consists essentially of a polyolefin, a cyclic olefin polymer, a cyclic olefin copolymer, a polyester, and polycarbonate, or polylactic acid.

3 . The article of claim 1 , wherein the barrier coating is from 4 nm to 500 nm thick.

4 . The article of claim 1 , in which the pH protective coating is between 10 and 1000 nm thick.

5 . The article of claim 1 , in which the pH protective coating is coextensive with the barrier coating or layer.

6 . The article of claim 1 , in which the calculated shelf life (total Si/Si dissolution rate) is more than 1 year.

7 . The article of claim 1 , wherein the pH protective coating is applied by PECVD of a precursor feed comprising a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, or any combination of two or more of these precursors.

8 . The article of claim 7 , in which the precursor feed further comprises oxygen.

9 . The article of claim 1 , in which the fluid composition removes the pH protective coating at a rate of 1 nm or less of pH protective coating thickness per 44 hours of contact.

10 . The article of claim 9 , in which the fluid composition removes the pH protective coating at a rate of 1 nm or less of pH protective coating thickness per 88 hours of contact.

11 . The article of claim 1 , wherein the pH protective layer shows an O-Parameter measured with attenuated total reflection (ATR) of less than 0.4, measured as:

O

-

Parameter

=

Intensity

⁢

at

⁢

⁢

1253

⁢

cm

-

1

Maximum

⁢

intensity

⁢

in

⁢

the

⁢

range

⁢

⁢

1000

⁢

to

⁢

1100

⁢

cm

-

1

.

12 . The article of claim 11 , wherein the pH protective layer shows an N-Parameter measured with attenuated total reflection (ATR) of less than 0.7, measured as:

N

-

Parameter

=

Intensity

⁢

at

⁢

840

⁢

cm

-

1

Intensity

⁢

at

⁢

799

⁢

cm

-

1

.

13 . An article comprising:

a wall having a surface;

a barrier coating or layer of SiOx, wherein x is from 1.5 to 2.9, from 2 to 1000 nm thick, the barrier coating or layer of SiOx having an outer surface facing the wall surface, the barrier coating or layer being effective to reduce the ingress of atmospheric gas through the wall compared to an uncoated wall; and

a pH protective coating of SiOxCy wherein x is from about 0.5 to about 2.4 and y is from about 0.6 to about 3, on the barrier coating or layer, the pH protective coating being formed by chemical vapor deposition of a precursor selected from a a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, a silatrane, a silquasilatrane, a silproatrane, or a combination of any two or more of these precursors;

in which the rate of erosion of the passivation layer or pH protective coating, if directly contacted by a fluid composition having a pH at some point between 5 and 9, is less than the rate of erosion of the barrier coating or layer, if directly contacted by the fluid composition; and

in which an FTIR absorbance spectrum of the pH protective coating has a ratio greater than 0.75 between:

the maximum amplitude of the Si—O—Si symmetrical stretch peak between about 1000 and 1040 cm −1 , and

the maximum amplitude of the Si—O—Si asymmetric stretch peak between about 1060 and about 1100 cm −1 .

14 . The article of claim 13 , in which an FTIR absorbance spectrum of the pH protective coating has a ratio of at least 0.9 between:

the maximum amplitude of the Si—O—Si symmetrical stretch peak between about 1000 and 1040 cm −1 , and

the maximum amplitude of the Si—O—Si asymmetric stretch peak between about 1060 and about 1100 cm −1 .

15 . The article of claim 13 , wherein the rate of erosion of the pH protective coating, if directly contacted by the fluid composition having a pH of 8, is less than 20% of the rate of erosion of the barrier coating or layer, if directly contacted by the fluid composition under the same conditions.

16 . The article of claim 13 , in which the pH protective coating is coextensive with the barrier coating or layer.

17 . The article of claim 13 , in which the fluid composition removes the pH protective coating at a rate of 1 nm or less of pH protective coating thickness per 44 hours of contact.

18 . The article of claim 17 , in which the fluid composition removes the pH protective coating at a rate of 1 nm or less of pH protective coating thickness per 88 hours of contact.

19 . The article of claim 13 , wherein the pH protective layer shows an O-Parameter measured with attenuated total reflection (ATR) of less than 0.4, measured as:

O

-

Parameter

=

Intensity

⁢

at

⁢

⁢

1253

⁢

cm

-

1

Maximum

⁢

intensity

⁢

in

⁢

the

⁢

range

⁢

⁢

1000

⁢

to

⁢

1100

⁢

cm

-

1

.

20 . The article of claim 19 , wherein the pH protective layer shows an N-Parameter measured with attenuated total reflection (ATR) of less than 0.7, measured as:

N

-

Parameter

=

Intensity

⁢

at

⁢

840

⁢

cm

-

1

Intensity

⁢

at

⁢

799

⁢

cm

-

1

.

Assignments (1)

Continuity (9)

References Cited (400)