Extended use planar sensors

• US 5,387,329 A
• Filed: 04/09/1993
• Issued: 02/07/1995
• Est. Priority Date: 04/09/1993
• Status: Expired due to Term

• Current Assignee: Siemens Healthcare Diagnostics Incorporated (Siemens AG)
• Original Assignee: CIBA Vision Corporation (Novartis Ag)
• Inventors: Edelman, Peter G., Flaherty, James E., Berger, Joseph, Foos, Joseph S.
• Primary Examiner(s): Niebling, John
• Assistant Examiner(s): Bell, Bruce F.
• Application Number:
  US08/045,847
• Time in Patent Office: 669 Days
• Field of Search: 204/415, 204/426, 204/412, 204/423, 204/421, 204/422, 204/409, 204/403, 204/428
• US Class Current: 204/403.06
• CPC Class Codes: C08F 220/14 Methyl esters , e.g. methyl (meth)acrylate
• CPC Class Codes: G01N 27/404 Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid , e.g. Clark-type oxygen sensors
• CPC Class Codes: G01N 33/4925 measuring blood gas content, e.g. O2, CO2 , HCO3
• CPC Class Codes: Y10T 29/49117 Conductor or circuit manufacturing
• CPC Class Codes: Y10T 29/5313 Means to assemble electrical device
• CPC Class Codes: Y10T 29/5317 Laminated device
• CPC Class Codes: Y10T 29/532 Conductor
• CPC Class Codes: Y10T 29/53204 Electrode

Abstract

A planar, solid-state electrochemical oxygen sensor having a substrate, conductive strips deposited on the substrate, and a dielectric layer insulating portions of the conductive strips except those portions which define a working electrode and at least one second electrode. The working electrode may be defined by an open printed region of the dielectric, or by a needle-punched or laser-burned hole or opening in the dielectric which exposes a small region of one of the conductive strips. A solid electrolyte contacting the electrodes is covered by a semipermeable membrane which may comprise an acrylonitrile butadiene copolymer or an acrylate-based copolymer. A sample chamber is defined by the membrane, a cover member, and a gasket therebetween, and has a volume of from about 1 to about 2 μl. The gasket is formulated from the highly cross-linked polymerization product of epichlorohydrin. All sensor components are selected such that a sensor operable for at least 2 days under normal conditions is produced.

Claims

1. A solid-state planar oxygen sensor comprising:

an electrically nonconductive substrate;

a first electrically conductive material adhered to a first portion of said substrate, at least a portion of said first conductive material being covered with an electrically insulating dielectric coating and at least one portion of said first conductive material remaining uncovered by said electrically insulating dielectric coating, said uncovered portion of said first conductive material defining a working electrode area;

a second electrically conductive material adhered to a portion of the substrate, a portion of said second conductive material being covered with the electrically insulating dielectric coating and at least one portion of said second conductive material remaining uncovered by said electrically insulating dielectric coating, said uncovered portion of said second conductive material defining a counter electrode area;

a hygroscopic solid electrolyte provided on at least the working electrode area and the counter electrode area, said electrolyte having a swell value of less than two times its dry volume when provided with water;

a semipermeable membrane covering said electrolyte having an oxygen permeability of less than 8 Barrers;

a cover member covering said semipermeable membrane and having a recess formed therein, said recess having a perimeter facing the membrane and at least one passageway connected to the recess; and

a gasket contacting the recess perimeter and the membrane to form a seal therebetween, the gasket, cover member, and membrane defining a sample chamber.

2. The solid-state planar oxygen sensor recited in claim 1, wherein said substrate comprises material selected from the group consisting of ceramics, glasses, refractories, polymers and combinations thereof.

3. The solid-state planar oxygen sensor recited in claim 1, wherein said substrate comprises alumina admixed with a glass binder.

4. The solid-state planar oxygen sensor recited in claim 1, wherein said first electrically conductive material comprises a thick-film paste comprising a metal selected from the group consisting of silver, gold, and platinum.

5. The solid-state planar oxygen sensor recited in claim 4, wherein said first electrically conductive material comprises a high-purity thick-film platinum paste.

6. The solid-state planar oxygen sensor recited in claim 1, wherein said first electrically conductive material is deposited so as to have a post-fired thickness of from about 0.002 mm to about 0.04 mm and a width of from about 0.02 to about 0.4 mm in at least one region of the sensor.

7. The solid-state planar oxygen sensor recited in claim 1, wherein said second electrically conductive material comprises a thick-film paste comprising a metal selected from the group consisting of silver, gold, and platinum.

8. The solid-state planar oxygen sensor recited in claim 7, wherein said second electrically conductive material comprises a thick-film platinum paste.

9. The solid-state planar oxygen sensor recited in claim 7, wherein said second electrically conductive material comprises a thick-film gold paste.

10. The solid-state planar oxygen sensor recited in claim 1, wherein said second electrically conductive material comprises a silver/silver chloride thick-film paste.

11. The solid-state planar oxygen sensor recited in claim 1, wherein said electrically insulating dielectric coating comprises material selected from the group consisting of ceramics, glasses, polymers and combinations thereof.

12. The solid-state planar oxygen sensor recited in claim 1, wherein said uncovered portion of said first conductive material is defined according to the thick film silk-screening technique.

13. The solid-state planar oxygen sensor recited in claim 1, wherein said uncovered portion of said first conductive material is defined by a laser-burned hole or opening in said electrically insulating dielectric coating.

14. The solid-state planar oxygen sensor recited in claim 11, wherein said uncovered portion of said first conductive material is defined by a needle-punched hole or opening in said electrically insulating dielectric coating.

15. The solid-state planar oxygen sensor recited in claim 1, wherein said hygroscopic solid electrolyte is a cross-linked polymer that has an oxygen permeability of at least 3 Barrers.

16. The solid-state planar oxygen sensor recited in claim 15, wherein said hygroscopic solid electrolyte is a cation or anion exchanger.

17. The solid-state planar oxygen sensor recited in claim 16, wherein said hygroscopic solid electrolyte is an exchanged per fluorocarbon sulfonic acid.

18. The solid-state planar oxygen sensor recited in claim 1, wherein said semipermeable membrane has an oxygen permeability of from about 0.1 Barrers to about 5 Barrers.

19. The solid-state planar oxygen sensor recited in claim 18, wherein said semipermeable membrane has an oxygen permeability of from about 0.2 Barrers to about 3 Barrers.

20. The solid-state planar oxygen sensor recited in claim 1, wherein said semipermeable membrane comprises a polymeric material having a glass transition temperature of from about -40°

C. to about 110°

C. that is not at the operating temperature of said sensor.

21. The solid-state planar oxygen sensor recited in claim 1, wherein said semipermeable membrane comprises a polymeric material having a "Shore A" hardness of at least about 20.

22. The solid-state planar oxygen sensor recited in claim 1, wherein said semipermeable membrane comprises the polymerization product of at least one nitrile monomer and at least one conjugated diene monomer.

23. The solid-state planar oxygen sensor recited in claim 22, wherein said semipermeable membrane comprises the polymerization product of acrylonitrile and butadiene.

24. The solid-state planar oxygen sensor recited in claim 23, wherein said semipermeable membrane further comprises a species selected from the group consisting of the polymerization product of a vinyl halide, the polymerization product of a vinylidene halide, the polymerization product of either a vinyl halide or a vinylidene halide with a nitrile-containing monomer, or a combination thereof.

25. The solid-state planar oxygen sensor recited in claim 24, wherein said polyvinyl halide comprises polyvinylchloride.

26. The solid-state planar oxygen sensor recited in claim 1, wherein said semipermeable membrane comprises the polymerization product of at least one monomer having the formula CH₂ =C(R₁)(COOR₂), where R₁ and R₂ are each selected from the group consisting of hydrogen, hydrocarbon groups, and alcohol groups and R₁ and R₂ can be the same or different.

27. The solid-state planar oxygen sensor recited in claim 26, wherein said semipermeable membrane further comprises the polymerization product of at least one monomer selected from the group consisting of those having the formulas CH₂ =C(R₁)(CONR₂ R₃), CH₂ =C(R₁)(OCOR₂), and nitrile-containing monomers, where R₁, R₂, and R₃ are each selected from the group consisting of hydrogen, hydrocarbon groups, and alcohol groups and R₁, R₂, and R₃ can be the same or different.

28. The solid-state planar oxygen sensor recited in claim 1, wherein said gasket has an oxygen permeability of less than 20 Barrers.

29. The solid-state planar oxygen sensor recited in claim 28, wherein said gasket has an oxygen permeability of less than 5 Barrers.

30. The solid-state planar oxygen sensor recited in claim 29, wherein said gasket is formulated from a material comprising an elastomeric copolymer of an epoxy compound.

31. The solid-state planar oxygen sensor recited in claim 1, said sample chamber having a volume of less than 10 μ

l.

32. The solid-state planar oxygen sensor recited in claim 31, said sample chamber having a volume of from about 0.8 μ

l to about 3 μ

l.

33. The solid-state planar oxygen sensor recited in claim 23, wherein said semipermeable membrane further comprises a random copolymer of a polyvinylidene halide and a nitrile-containing monomer.

34. The solid-state planar oxygen sensor recited in claim 33, wherein said polyvinylidene halide comprises polyvinylidene chloride and said nitrile-containing monomer comprises acrylonitrile.

35. The solid-state planar oxygen sensor recited in claim 32, said sample chamber having a volume of from about 1 μ

l to about 2 μ

l.

36. The solid-state planar oxygen sensor recited in claim 1, wherein said sensor further comprises a third electrically conductive material adhered to a third portion of the substrate, a portion of said third conductive material being covered with the electrically insulating dielectric coating and at least one portion of said third conductive material remaining uncovered by said electrically insulating dielectric coating, said uncovered portion of said third conductive material defining a reference electrode area.

37. A solid-state planar oxygen sensor comprising:

an electrically nonconductive substrate;

a first electrically conductive material adhered to a first portion of said substrate, at least one portion of said first conductive material being covered with an electrically insulating dielectric coating and at least one portion of said first conductive material remaining uncovered by said electrically insulating dielectric coating, said uncovered portion of said first conductive material defining a working electrode area;

a second electrically conductive material adhered to at least a second portion of the substrate, a portion of said second conductive material being covered with the electrically insulating dielectric coating and at least one portion of said second conductive material remaining uncovered by said electrically insulating dielectric coating, said uncovered portion of said second conductive material defining a counter electrode area;

an electrolyte provided on at least the working electrode area and the counter electrode area; and

a polymeric semipermeable membrane covering the electrolyte, said membrane comprising the polymerization product of at least one monomer having the formula CH₂ =C(R₁)(COOR₂), where R₁ and R₂ are each selected from the group consisting of hydrogen, hydrocarbon groups, and alcohol groups and R₁ and R₂ can be the same or different.

38. The solid-state planar oxygen sensor recited in claim 37 wherein said substrate comprises material selected from the group consisting of ceramics, glasses, refractories, polymers and combinations thereof.

39. The solid-state planar oxygen sensor recited in claim 37, wherein said first electrically conductive material comprises a high-purity thick-film platinum paste.

40. The solid-state planar oxygen sensor recited in claim 37, wherein said first electrically conductive material is deposited so as to have a post-fired thickness of from about 0.002 mm to about 0.04 mm and a width of from about 0.02 to about 0.4 mm in at least one region of the sensor.

41. The solid-state planar oxygen sensor recited in claim 37, wherein said second electrically conductive material comprises a thick-film platinum paste.

42. The solid-state planar oxygen sensor recited in claim 37, wherein said second electrically conductive material comprises a thick-film gold paste.

43. The solid-state planar oxygen sensor recited in claim 37, wherein said second electrically conductive material comprises a silver/silver chloride thick-film paste.

44. The solid-state planar oxygen sensor recited in claim 37, wherein said electrically insulating dielectric coating comprises material selected from the group consisting of ceramics, glasses, polymers and combinations thereof.

45. The solid-state planar oxygen sensor recited in claim 37, wherein said uncovered portion of said first conductive material is defined according to the thick film silk-screening technique.

46. The solid-state planar oxygen sensor recited in claim 37, wherein said uncovered portion of said first conductive material is defined by a laser-burned hole or opening in said electrically insulating dielectric coating.

47. The solid-state planar oxygen sensor recited in claim 37, wherein said uncovered portion of said first conductive material is defined by a needle-punched hole or opening in said electrically insulating dielectric coating.

48. The solid-state planar oxygen sensor recited in claim 37, wherein said hygroscopic solid electrolyte is a cation or anion exchanger having an oxygen permeability of at least 3 Barrers.

49. The solid-state planar oxygen sensor recited in claim 37, wherein said semipermeable membrane has an oxygen permeability of from about 0.2 Barrers to about 3 Barrers and comprises a polymeric material having a glass transition temperature of from about -40°

C. to about 110°

C. that is not the operating temperature of said sensor, and a Shore A hardness of at least about 20.

50. The solid-state planar oxygen sensor recited in claim 47, wherein said semipermeable membrane further comprises the polymerization product of at least one monomer selected from the group consisting of those having the formulas CH₂ =C(R₁)(CONR₂ R₃), CH₂ =C(R₁)(OCOR₂), and nitrile-containing monomers, where R₁, R₂, and R₃ are each selected from the group consisting of hydrogen, hydrocarbon groups, and alcohol groups and R₁, R₂, and R₃ can be the same or different.

51. The solid-state planar oxygen sensor recited in claim 37, and further comprising a third electrically conductive material adhered to a third portion of said substrate, a portion of said third electrically conductive material being covered with the electrically insulating dielectric coating and at least one portion of said third conductive material remaining uncovered by said electrically insulating dielectric coating, said uncovered portion of said third conductive material defining a reference electrode area.

52. An electrochemical sensor comprising:

electrochemical means for detecting an analyte in a sample;

a semipermeable membrane covering said electrochemical means, said membrane being permeable to said analyte and to species necessary for the functioning of said electrochemical means;

a cover member covering said semipermeable membrane and having a recess formed therein, said recess having a perimeter facing the membrane and at least one passageway connected to the recess; and

a gasket contacting the recess perimeter and the membrane to form a seal therebetween, the gasket, cover member, and membrane defining a sample chamber.

53. In an electrochemical sensor having electrochemical means including an electrolyte, a cathode contacting said electrolyte, and an anode contacting said electrolyte and having a semipermeable membrane separating said electrochemical means from a sample region, the improvement wherein said semipermeable membrane comprises a first polymerization product of at least one nitrile-containing monomer and at least one conjugated diene monomer.

54. In an electrochemical sensor according to claim 53 the improvement wherein said nitrile-containing monomer comprises acrylonitrile and said conjugated diene monomer comprises butadiene.

55. In an electrochemical sensor according to claim 53, the improvement wherein said semipermeable membrane further comprises the polymerization product of a vinyl halide.

56. In an electrochemical sensor according to claim 55, the improvement wherein said vinyl halide comprises vinyl chloride.

57. In an electrochemical sensor according to claim 53, the improvement wherein said semipermeable membrane further comprises a second polymerization product of a vinylidene halide and a nitrile-containing monomer.

58. In an electrochemical sensor according to claim 57, the improvement wherein said second polymerization product comprises vinylidene chloride copolymerized with acrylonitrile.

59. In an electrochemical sensor according to claim 55, the improvement wherein said nitrile-containing monomer is added in an amount of from about 50% to about 80% by weight based on the weight of the first polymerization product, and said vinyl halide is added in an amount of from about 1% to about 70% by weight, based on the weight of the entire membrane.

60. In an electrochemical sensor according to claim 59, the improvement wherein said nitrile-containing monomer is added in an amount of from about 50% to about 80% by weight based on the weight of the first polymerization product, and said vinyl halide is added in an amount of from about 15% to about 50% by weight, based on the weight of the entire membrane.

61. In an electrochemical sensor according to claim 57, the improvement wherein said nitrile-containing monomer is added in an amount of from about 50% to about 80% by weight based on the weight of the first polymerization product, and said second polymerization product is added in an amount of from about 1% to about 70% by weight, based on the weight of the entire membrane.

62. In an electrochemical sensor according to claim 61, the improvement wherein said nitrile-containing monomer is added in an amount of from about 50% to about 80% by weight based on the weight of the first polymerization product, and said second polymerization product is added in an amount of from about 15% to about 50% by weight, based on the weight of the entire membrane.

63. In an electrochemical sensor according to claim 53, wherein said sensor is an oxygen sensor, the improvement wherein said semipermeable membrane has an oxygen permeability of less than 8 Barrers, has a Shore A hardness of at least about 20, has a water vapor permeability of at least 3 Barrers, is substantially impermeable to liquid water, and is substantially free of cross-linking.

64. In an electrochemical sensor according to claim 63, the improvement wherein said semipermeable membrane has an oxygen permeability of from about 0.1 to about 5 Barrers, and a glass transition temperature of from about -40°

C. to about 110°

C. that is not at the operating temperature of said sensor.

65. In an electrochemical sensor according to claim 64, the improvement wherein said semipermeable membrane has an oxygen permeability of from about 0.2 to about 3 Barrers, and a glass transition temperature of from about -15°

C. to about 85°

C. that is not at the operating temperature of said sensor.

66. In an electrochemical sensor having electrochemical means including an electrolyte, a cathode contacting said electrolyte, and an anode contacting said electrolyte and having a semipermeable membrane separating said electrochemical means from a sample region, the improvement wherein said semipermeable membrane comprises the polymerization product of at least one monomer having the formula CH₂ =C(R₁)(COOR₂), where R₁ and R₂ are each selected from the group consisting of hydrogen, hydrocarbon groups, and alcohol groups and can be the same or different.

67. In an electrochemical sensor according to claim 66, the improvement wherein said semipermeable membrane further comprises the polymerization product of at least one monomer selected from the group consisting of those having the formulas CH₂ =C(R₁)(CONR₂ R₃), CH₂ =C(R₁)(OCOR₂), and nitrile-containing monomers, where R₁, R₂, and R₃ are each selected from the group consisting of hydrogen, hydrocarbon groups, and alcohol groups and R₁, R₂, and R₃ can be the same or different.

68. In an electrochemical sensor according to claim 66, the improvement wherein said semipermeable membrane further comprises at least one nitrile-containing monomer.

69. In an electrochemical sensor according to claim 66, the improvement wherein said semipermeable membrane further comprises the polymerization product of at least one monomer having the formula CH₂ =C(R₁)(CONR₂ R₃), where R₁, R₂, and R₃ are each selected from the group consisting of hydrogen, hydrocarbon groups, and alcohol groups and R₁, R₂, and R₃ can be the same or different.

70. In an electrochemical sensor according to claim 66, the improvement wherein said semipermeable membrane further comprises the polymerization product of at least one monomer having the formula CH₂ =C(R₁)(OCOR₂), where R₁ and R₂ are each selected from the group consisting of hydrogen, hydrocarbon groups, and alcohol groups and R₁ and R₂ can be the same or different.

71. In an electrochemical sensor according to claim 66, the improvement wherein said semipermeable membrane comprises:

the polymerization product of at least one monomer having the formula CH₂ =C(R₁)(COOR₂), where R₁ is selected from the group consisting of hydrogen and lower alkyl groups, R₂ is selected from the group consisting of linear, branched and cyclic hydrocarbons and alcohols of from 1 to 20 carbon atoms, R₁ and R₂ being the same or different, said monomer being present in an amount of from about 20% to about 80% by weight based on the weight of the membrane;

the polymerization product of at least one nitrile-containing monomer, said nitrile-containing monomer being present in an amount of from about 15% to about 80% by weight; and

the polymerization product of at least one monomer selected from the group consisting of those having the formula CH₂ =C(R₁)(OCOR₂) where R₁ and R₂ are each selected from the group consisting of hydrogen, lower alkyl groups and lower alcohols and can be the same or different, those having the formula CH₂ =C(R₁)(CONR₂ R₃) where R₁, R₂, and R₃ are each selected from the group consisting of hydrogen and lower alkyl groups and R₁, R₂, and R₃ can be the same or different, and a combination of the two.

72. In an electrochemical sensor according to claim 71, the improvement wherein said semipermeable membrane comprises:

the polymerization product of at least one monomer having the formula CH₂ =C(R₁)(COOR₂), where R₁ is selected from the group consisting of hydrogen and lower alkyl groups, R₂ is selected from the group consisting of linear, branched and cyclic hydrocarbons and alcohols of from 1 to 20 carbon atoms, R₁ and R₂ being the same or different, said monomer being present in an amount of from about 40% to about 60% by weight based on the weight of the membrane;

the polymerization product of at least one nitrile-containing monomer, said nitrile-containing monomer being present in an amount of from about 20% to about 30% by weight; and

the polymerization product of at least one monomer having the formula CH₂ =C(R₁)(OCOR₂), where R₁ and R₂ are each selected from the group consisting of hydrogen, lower alkyl groups and lower alcohols and R₁ and R₂ can be the same or different, said monomer being present in an amount of from about 15% to about 30% by weight.

73. In an electrochemical sensor according to claim 66, wherein said sensor is an oxygen sensor, the improvement wherein said semipermeable membrane has an oxygen permeability of less than 8 Barrers, has a Shore A hardness of at least about 20, has a water vapor permeability of at least 3 Barrers, is substantially impermeable to liquid water, and is substantially free of cross-linking.

74. In an electrochemical oxygen sensor according to claim 73, the improvement wherein said semipermeable membrane has an oxygen permeability of from about 0.1 to about 5 Barrers, and a glass transition temperature of from about -40°

C. to about 110°

C. that is not at the operating temperature of said sensor.

75. In an electrochemical oxygen sensor according to claim 74, the improvement wherein said semipermeable membrane has an oxygen permeability of from about 0.2 to about 3 Barrers, and a glass transition temperature of from about -15°

C. to about 85°

C. that is not at the operating temperature of said sensor.

76. In an electrochemical oxygen sensor having a semipermeable membrane, electrochemical means on a first side of said membrane for detecting an analyte in a sample, and a sample chamber on a second side of said membrane for receiving said sample, said chamber defined in part by said second side of said membrane and a cover member having a recess formed therein, said recess having a perimeter facing said second side of said membrane, the improvement comprising:

a gasket for forming a liquid and gas impermeable seal between said second side of said semipermeable membrane and said cover member recess perimeter, said gasket having a Shore A hardness of from about 10 to about 100, an oxygen permeability of less than 20 Barrers, being liquid impermeable and formulated to be substantially free of mobile extractable materials which, when the gasket is used with an adjacent semipermeable membrane, would leach into said membrane affecting physical or permeability characteristics therein, formulated to be substantially free of mobile sulfides and battery metals, and being effective in forming and maintaining said seal for at least 2 days under normal sensor operation.

77. In an electrochemical sensor according to claim 76, the improvement wherein said gasket comprises a copolymer of an epoxy compound and a second monomer which provides sites of unsaturation in said copolymer, said second monomer added in an amount to give said gasket crosslinking of from about 0.1% to about 20% upon cure.

78. In an electrochemical sensor according to claim 77, the improvement wherein said gasket copolymer further comprises a hydrophilic monomer which imparts a desired swell value to said gasket.

79. In an electrochemical sensor according to claim 77, the improvement wherein said epoxy compound comprises epichlorohydrin, said hydrophilic monomer is selected from the group consisting of allyl alcohol, crotyl alcohol, methylvinyl carbinol, cinnamyl alcohol, ethylene glycol, propylene glycol, 1,3-propanediol, glycerol, pentaerythritol, and the like, and said monomer providing sites of unsaturation comprises allyl glycidyl ether.

80. In an electrochemical sensor according to claim 79, the improvement wherein said hydrophilic monomer comprises ethylene glycol.

81. In an electrochemical sensor according to claim 76, the improvement wherein said epoxy compound comprises epichlorohydrin and said hydrophilic monomer is selected from the group consisting of allyl alcohol, crotyl alcohol, methylvinyl carbinol, cinnamyl alcohol, ethylene glycol, propylene glycol, 1,3-propanediol, glycerol, pentaerythritol, and the like.

82. In an electrochemical sensor according to claim 81, the improvement wherein said hydrophilic monomer comprises ethylene glycol.

83. In an electrochemical sensor according to claim 76, the improvement wherein said gasket has an oxygen permeability of less than 5 Barrers, and a Shore A hardness of from about 40 to about 70.

84. In an electrochemical oxygen sensor according to claim 83, the improvement wherein said gasket has an oxygen permeability of less than 0.5 Barrers, and a Shore A hardness of from about 45 to about 55.

85. In an electrochemical sensor according to claim 77, the improvement wherein said gasket further comprises one or more additives selected from the group consisting of antioxidants, processing aids, and curing aids.

86. In an electrochemical sensor having a semipermeable membrane, electrochemical means on a first side of said membrane for detecting an analyte in a sample, and a sample chamber on a second side of said membrane for receiving said sample, said chamber defined in part by said second side of said membrane and a cover member having a recess formed therein, said recess having a perimeter facing said second side of said membrane, the improvement comprising:

a gasket for forming a liquid and gas impermeable seal between said second side of said semipermeable membrane and said cover member recess perimeter, said gasket comprising a copolymer of an epoxy compound.

87. In an electrochemical sensor according to claim 86, the improvement wherein said gasket further comprises at least one second monomer which provides sites of unsaturation in said copolymer.

88. In an electrochemical sensor according to claim 87, the improvement wherein said second monomer is added in an amount to give said gasket crosslinking of from about 0.1% to about 20% upon cure.

89. In an electrochemical sensor according to claim 86, the improvement wherein said gasket has a Shore A hardness of from about 10 to about 100, an oxygen permeability of less than 20 Barrers, is liquid impermeable and formulated to be substantially free of mobile extractable materials which, when the gasket is used with an adjacent semipermeable membrane, would leach into said membrane affecting physical or permeability characteristics therein, is formulated to be substantially free of mobile sulfides and battery metals, and is effective in forming and maintaining said seal for at least 2 days under normal sensor operation.