Oxygen electrode and method for preparation thereof

• US 4,390,405 A
• Filed: 06/23/1981
• Issued: 06/28/1983
• Est. Priority Date: 02/20/1980
• Status: Expired due to Fees

• Current Assignee: Curators of the University of Missouri (University of Missouri)
• Original Assignee: Curators of the University of Missouri (University of Missouri)
• Inventors: Nichols, Michael F., Hahn, Allen W., Sharma, Ashok K., Hellmuth, Eckhard W.
• Primary Examiner(s): Kaplan, G. L.
• Application Number:
  US06/276,713
• Time in Patent Office: 735 Days
• Field of Search: 204/195 P, 204/1 P, 204/38 A, 204/32 R, 427/41, 427/255.6, 128/635
• US Class Current: 204/415
• 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 27/48 using polarography, i.e. measuring changes in current under a slowly-varying voltage

Abstract

An oxygen electrode adapted for use for polarographic, galvanometric or amperometric analyses, that is resistant to poisoning and effective for accurate, reproducible current and voltage measurements. The electrode comprises a conductive sensing member having a working surface which is comprised of a metal that catalyzes the cathodic reduction of oxygen and which is adapted to communicate with an oxygen-containing environment for carrying out such reduction. At the working surface is a layer of an oxide of the aforesaid metal. An insulating jacket covers all of the member except the working surface. There is a thin polymeric coating over said oxide layer and securely adhered to the working surface. The coating comprises a polymer produced by glow discharge polymerization of an aliphatic hydrocarbon and has such properties as to permit the reduction of oxygen at the electrode by electrons supplied at the working surface through the conductive member.

A method for preparing the electrode is also disclosed.

Claims

1. An oxygen electrode, adapted for use in polarography, galvanometry or amperometry, that is resistant to poisoning and effective for accurate, reproducible current and voltage measurements comprising a conductive sensing member having a working surface which is comprised of a metal that catalyzes the cathodic reduction of oxygen and is adapted to communicate with an oxygen-containing environment for such reduction, a layer of an oxide of said metal at said surface, an insulating jacket covering all of said member except said surface, and a thin polymeric coating over said oxide layer and securely adhered to said surface, said coating comprising a polymer produced by glow discharge polymerization of an aliphatic hydrocarbon and having such properties as to permit reduction of oxygen at said electrode by electrons supplied at said surface through said conductive member.

2. An oxygen electrode as set forth in claim 1 wherein said coating has a thickness of between about 500 Angstroms and 0.3 μ

m.

3. An oxygen electrode as set forth in claim 2 wherein said coating has a thickness of between about 0.1 and about 0.15 μ

m.

4. An oxygen electrode as set forth in claim 2 wherein said metal is selected from the group consisting of platinum, gold, palladium, tantalum and iridium.

5. An oxygen electrode as set forth in claim 4 wherein said metal comprises platinum.

6. An oxygen electrode as set forth in claim 5 wherein said oxide layer is predominantly comprised of PtO.

7. An oxygen electrode as set forth in claim 2 wherein said oxide layer is formed by anodization.

8. An oxygen electrode as set forth in claim 2 wherein said polymeric coating is produced by glow discharge polymerization of a monomer selected from the group consisting of ethylene, propylene, butene, methane, ethane, propane and butane.

9. An oxygen electrode as set forth in claim 8 wherein said polymer is cross-linked.

10. An oxygen electrode as set forth in claim 9 wherein said polymer comprises glow discharge polymerized propylene.

11. An oxygen electrode as set forth in claim 10 wherein said polymer contains oxygen.

12. An oxygen electrode as set forth in claim 11 wherein said polymer conforms to the average empirical formula:

space="preserve" listing-type="equation">(C.sub.1 H.sub.x O.sub.y)

where x is at least about 1.0 and y is no greater than about 0.2.

13. An oxygen electrode as set forth in claim 2 wherein said coating is of uniform thickness and conforms to the contours of said oxidized surface.

14. An oxygen electrode as set forth in claim 2 wherein said conductive member comprises a wire having the crossectional face of one end thereof uncovered by said insulating jacket and having said surface on said face.

15. An oxygen electrode as set forth in claim 14 wherein said wire has a diameter of not more than about 500 μ

m.

16. An oxygen electrode as set forth in claim 15 having an overall diameter of not more than about 1.5 mm.

17. An oxygen electrode as set forth in claim 14 wherein said insulating jacket is comprised of glass.

18. An electrode as set forth in claim 2 wherein said coating is produced by deposition at a rate of between about 25 and about 40 Angstroms of thickness per minute.

19. An electrode as set forth in claim 18 wherein said coating is deposited on said surface in a tubular reactor for which electromagnetic power is generated at a rate of between about 0.2 and about 0.9 KWH per gram of monomer continuously fed thereto.

20. An electrode as set forth in claim 18 wherein said coating is deposited on said surface in a Bell jar reactor for which electromagnetic power is generated at a rate of between about 5 and about 15 KWH per gram of monomer continuously fed thereto.

21. A method for producing an oxygen electrode, adapted for use in polarography, galvanometry or amperometry, that is resistant to poisoning and effective for accurate, reproducible current and voltage measurement, the method comprising the steps of:

generating a plasma from a gas in a low pressure chamber containing the working surface of an oxygen electrode, said electrode comprising

a conductive sensing member having a working surface which is comprised of a metal that catalyzes the cathodic reduction of oxygen and is adapted to communicate with an oxygen-containing environment for such reduction, a layer of an oxide of said metal at said surface, and an insulating jacket that covers all of said member except said working surface;

introducing an aliphatic hydrocarbon gas into said low pressure chamber;

polymerizing said hydrocarbon by action of said plasma thereon; and

depositing a thin adherent coating of said polymer over said oxide layer on said working surface.

22. A method as set forth in claim 21 wherein said polymerization reaction is terminated when the thickness of said polymer coating is between about 500 Angstroms and about 0.3 μ

m.

23. A method as set forth in claim 22 wherein said polymerization reaction is terminated when the thickness of said polymer coating is between about 0.1 μ

m and about 0.15 μ

m.

24. A method as set forth in claim 22 wherein said oxide layer is provided by anodizing said surface.

25. A method as set forth in claim 24 wherein said surface is anodized in a strong oxidizing electrolyte that is substantially free of chloride ion.

26. A method as set forth in claim 25 wherein said surface is anodized in sulfuric acid having a normality of between about 0.5 and about 2.0 at a voltage of between about 1 and about 4 volts D.C. for between about 30 sec. and about 5 minutes.

27. A method as set forth in claim 21 wherein said plasma is generated by introduction of electromagnetic energy into said chamber.

28. A method as set forth in claim 27 wherein said coating is deposited at a rate of between about 25 and about 40 Angstroms of thickness per minute.

29. A method as set forth in claim 28 wherein the polymerization is carried out in a tubular reactor and during polymerization electromagnetic power is generated at a rate of between about 0.2 and about 0.9 KWH per gram of monomer continuously fed thereto.

30. A method as set forth in claim 28 wherein the polymerization is carried out in a Bell jar reactor and during polymerization electromagnetic power is generated at a rate of between about 5 and about 15 KWH per gram of monomer continuously fed thereof.

31. A method as set forth in claim 27 wherein said plasma is generated by inductive coupling at a frequency of between about 1 kilohertz and about 40,000 megahertz.

32. A method as set forth in claim 27 wherein the pressure in said chamber is maintained at between about 1 and about 30 pascals absolute during the polymerization of said hydrocarbon.

33. A method as set forth in claim 27 wherein said gas comprises argon.

34. A method as set forth in claim 21 wherein said aliphatic hydrocarbon is selected from the group consisting of ethylene, propylene, butane, methane, ethane, propane and butane.

35. A method as set forth in claim 34 wherein said aliphatic hydrocarbon comprises propylene.

36. A method as set forth in claim 21 wherein said working surface is cleaned and etched by exposure of the working surface to argon plasma prior to deposition of said polymeric coating.

37. A method as set forth in claim 21 wherein said coating is etched to increase its stability and hydrophilicity by exposing it to an oxygen plasma.