Gas sensors

• US 5,322,602 A
• Filed: 01/28/1993
• Issued: 06/21/1994
• Est. Priority Date: 01/28/1993
• Status: Expired due to Fees

• Current Assignee: Teledyne Analytical Industries, Inc.
• Original Assignee: Teledyne Industries Incorporated (Teledyne Technologies Incorporated)
• Inventors: Razaq, Mohammed
• Primary Examiner(s): Niebling, John
• Assistant Examiner(s): Bell, Bruce F.
• Application Number:
  US08/010,626
• Time in Patent Office: 509 Days
• Field of Search: 204/153.18, 204/153.22, 204/418, 204/424, 204/421, 204/431, 204/432, 204/412, 204/430, 204/153.1, 204/415, 429/33, 521/27, 521/28, 422/88
• US Class Current: 205/788
• CPC Class Codes: G01N 27/4045 for gases other than oxygen
• CPC Class Codes: G01N 27/423 Coulometry

Abstract

An improved perfluorinated, ion-exchange polymer, either in the form of a membrane or a thin film useful as the electrolyte in chemical sensors. The polymer is treated with an acid, such as boric acid or a mixture of boric acid and phosphoric acid, to maintain the ionic conductivity of the polymer to approximately 180 degrees Centigrade. The improved polymer electrolyte is utilized to sense moisture by a two electrode structure with the electrodes arranged in interdigital fashion and the electrolyte film cast over the electrodes. The electrolyte is included in a 3 electrode sensor for sensing various types of gases.

Claims

1. An electrolyte for use in a sensing cell for sensing the concentrations of an electrochemically active gas in a gas mixture or for electrolytically decomposing a gas, said electrolyte comprising a solid, perfluorinated, ion-exchange polymer material equilibrated with a preselected mixture of phosphoric and boric acid or solely boric acid in an amount fo maintain the ion conductivity of the polymer whereby sensors utilizing said electrolyte material produces sensing cells of improved ionic conductivity that is maintained over extended periods of time and of greater stability, faster response and recovery times.

2. A method of preparing an electrolytic sensor including the steps of providing an insulative, non-moisture absorbing substrate, mounting a plurality of electrodes to said substrate, preparing a mixture of 2.5:

1;

1 of 2.5% of an ion-exchange polymer in alcohol along with 10% phosphoric acid in water and 2.5% boric acid in water, casting a thin film of a set thickness of said thus prepared mixture over the electrodes on said substrate, and heating the substrate assembly to above 100 degrees Centigrade to drive off all the solvents until a solid coating of said ion-exchange polymer is formed over said electrodes whereby the resulting electrolyte is maintained ionic conductive at temperatures of up to approximately 180 degrees Centigrade.

3. A method for electrolytically sensing the moisture content in a gas down to sub-parts per billion levels with fast response and recovery time, including the steps of providing a solid, perfluorinated, ion-exchange polymer electrolyte element that has been pre-equilibrated with boric acid or a preselected mixture of boric acid and phosphoric acid so that the electrolyte element is maintained conductive to temperatures up to approximately 180 degrees Centigrade whereby said electrolyte element is useful in an electrolytic cell for any electrolytic reactions where the reactants or the products thereof do not chemically react with the electrolyte element so that the ionic conductivity of the electrolyte element is lost, and attaching a plurality of electrodes to one or both sides of the electrolyte element, and applying an electric potential between said electrodes of a set value for electrolytically decomposing the moisture from any moisture bearing gas exposed to the electrolyte element whereby the external current flow between the electrodes is a measure of the sensed moisture content of said gas.

4. A method for electrolytically sensing the moisture in a gas as defined in claim 3, including the step of selecting a pure metal or metal alloy from the platinum group of metals for the electrodes thereof and providing a voltage between the electrodes set between 10-70 volts.

5. A method of preparing an electrolyte element for a sensor for use in an electrolytic sensor including the steps of providing a thin membrane consisting of a solid, perfluorinated, ion-exchange polymer conductive element to function as an electrolyte element for said sensor, treating said electrolyte element with an acid consisting of boric acid or a set mixture of boric acid and phosphoric acid for maintaining the ionic conductivity of the electrolyte element at temperatures up to approximately 180 degrees Centigrade and thereby maintaining improved ionic conductivity that is maintained over extended periods of time.

6. A method of preparing an electrolyte element in the form of a thin film for use in an electrolytic sensor, including the steps of providing a liquid form of a perfluorinated, ion-exchange polymer in alcohol and mixing with 10% phosphoric acid in water and 2.5% boric acid in water.

7. An electrolytic sensing cell for sensing moisture and the like comprising a solid, perfluorinated, ion-exchange polymer electrolyte element, a non-moisture absorbing substrate means for supporting the electrolyte element and permitting a preselected gas to be electrolized to be exposed to the electrolyte element, said polymer electrolyte element further characterized as having been pre-equilibrated with preselected amounts of boric acid and phosphoric acid for maintaining the ionic conductivity of said electrolyte element at temperatures up to approximately 180 degrees Centigrade and maintaining improved ionic conductivity that is maintained over extended periods of time, and a plurality of electrodes constructed of a preselected metal or metal alloys arranged at spaced locations on said substrate and with said electrolyte element overlying said electrodes, the electrodes being adapted to receive a set electrical potential for driving the electrolysis process of the preselected gas exposed to said electrolyte element.

8. An electrolytic sensing cell as defined in claim 7 wherein said electrodes are selected from the platinum group of metals.

9. An electrolytic sensing cell as defined in claims 7 or 8 wherein said substrate means comprises alumina.

10. A moisture sensor comprising an insulative, non-moisture absorbing substrate, a plurality of electrodes deposited on the substrate and a thin, solid film of a perfluorinated, ion-exchange polymer conductive element deposited over the electrodes to function as the electrolyte for the sensor, said film of ion-exchange polymer conductive element having been pre-equilibrated with a boric acid for maintaining the ionic conductivity of said electrolyte up to temperatures of approximately 180 degrees Centigrade and functioning as the electrolyte moisture sensing element for the sensor to absorb moisture upon the application of a set electrolizing potential between said electrodes.

11. A moisture sensor as defined in claim 10 wherein said electrodes are arranged in an interdigitated grid of a pure metal or metal alloy from the platinum group of metals with an interelectrode spacing of a set distance for measuring moisture in a gas down to the low parts per billion level.

12. A moisture sensor as defined in claim 10 or 11 wherein said polymer conductive element is pre-equilibrated with a set combination of boric and phosphoric acids.

13. A moisture sensor as defined in claim 10 or 11 wherein said substrate comprising alumina.

14. A moisture sensor as defined in claim 10 or 11 wherein the set electrolizing potential is set between 10-70 volts in accordance with the desired sensitivity for the moisture sensor.

15. An electrolytic cell comprising an insulative substrate resistant to oxidation and reduction, a plurality of electrodes mounted on said substrate in a set spaced relationship, and a thin film of a perfluorinated, ion-exchange polymer electrolyte element cast over said electrodes, said thin film having been pre-equilibrated with a boric acid or a set mixture of boric acid and phosphoric acid so that the electrolyte element is maintained conductive to temperatures of approximately 180 degrees Centigrade, said electrodes being adapted to have an electrical potential applied thereto for decomposing a gas exposed to said electrolyte element.

16. An electrolytic cell as defined in claim 15 wherein the plurality of electrodes are arranged in an interdigitated grid of a pure metal or metal alloy from the platinum group of metals.

17. An electrolytic cell as defined in claim 16 wherein the plurality of electrodes are working, counter and reference electrodes.

18. An electrolytic cell as defined in claim 15 wherein the plurality of electrodes comprise a sensing and secondary electrode and a reference electrode arranged on said substrate in a set spaced relationship with the sensing and secondary electrodes, and means for applying a set electrical potential between said sensing and reference electrodes, said electrolyte element being cast over said reference electrode along with said plurality of electrodes.

19. An electrolytic cell as defined in claim 18 wherein all said electrodes of said cell are constructed of a pure metal or metal alloy catalyst from the platinum group of metals for sensing oxygen, hydrogen, hydrogen sulfide and carbon monoxide gases.

20. An electrolytic cell as defined in claim 18 wherein said sensing and secondary electrodes are constructed of pure gold or a gold alloy catalyst for sensing sulphur dioxide, nitric oxide and nitrogen dioxide gases.

21. An electrochemical cell for detecting a gas in the presence of air arranged in a polarographic cell type of configuration for detecting gases that may be electrochemically oxidized or reduced;

the cell comprising a solid, perfluorinate, ion-exchange polymer electrolyte element with a sensing gas diffusion electrode, a secondary gas diffusion electrode and a reference gas diffusion electrode attached to said electrolyte element in a preselected geometrical configuration, said solid polymer electrolyte element is further characterized as having been pre-equilibrated with an acid for maintaining the ionic conductivity of said polymer electrolyte element at temperatures up to approximately 180 degrees Centigrade, means for containing and supporting the thus defined polarographic sensing cell elements and for distributing a gas to be detected to the surface of the sensing gas diffusion electrode and adapted for exposing said secondary and reference electrodes to the ambient air to thereby provide an electrical current representative of the quantity of the reactant gas detected by said gas diffusion electrode.

22. An electrochemical cell as defined in claim 21 wherein said acid for pre-equilibrating said polymer comprises phosphoric acid or boric acid--phosphoric acid solution.

23. An electrochemical cell as defined in claim 21 wherein said gas diffusion electrodes are constructed from a pure metal or metal alloy catalyst from the platinum group of metals for sensing oxygen, hydrogen, hydrogen sulfide and carbon monoxide gases.

24. An electrochemical cell as defined in claim 21 wherein said sensing and secondary electrodes are constructed of pure gold or a gold alloy catalyst for sensing sulphur dioxide, nitric oxide and nitrogen dioxide.

25. An electrochemical cell for detecting a gas in the presence of air arranged in a polarographic cell type of configuration for detecting gases that may be electrochemically oxidized or reduced;

the cell comprising a solid, perfluorinate, ion-exchange polymer electrolyte element with a sensing gas diffusion electrode, a secondary gas diffusion electrode and a reference gas diffusion electrode attached to said electrolyte element in a set geometrical spaced configuration;

said solid polymer electrolyte element is further characterized as having been pre-equilibrated with an acid for maintaining the ionic conductivity of said polymer electrolyte element at temperatures up to approximately 180 degrees Centigrade,

means for containing and supporting the thus defined polarographic sensing cell elements and for distributing a gas to be detected to the surface of the sensing gas diffusion electrode and adapted for exposing said secondary and reference electrodes to the ambient air, and

potentiostat circuit means are connectable between said sensing electrode and reference electrode for maintaining a set potential on said sensing electrode relative to said reference electrode for driving the electrochemical reaction in accordance with the gas to be detected.

26. An electrochemical cell as defined in claim 25 including circuit means adapted to be connected between said sensing and secondary electrodes for providing an electrical signal representative of the quantity of the sensed gas.

27. An electrochemical cell as defined in claim 25 for sensing oxygen, hydrogen, hydrogen sulfide and carbon monoxide gases wherein said diffusion electrodes are constructed from a pure metal or metal alloy catalyst selected from the platinum group of metals.

28. An electrochemical cell as defined in claim 25 for sensing sulfur dioxide, nitric oxide and nitrogen dioxide gases wherein said sensing and secondary electrodes are constructed with a pure gold or gold alloy catalyst.