Sensors for hydrogen, ammonia

• US 8,646,311 B1
• Filed: 10/31/2008
• Issued: 02/11/2014
• Est. Priority Date: 11/09/2007
• Status: Active Grant

• Current Assignee: Atmospheric Sensors Ltd.
• Original Assignee: Atmospheric Sensors Ltd.
• Inventors: Moseley, Patrick T.
• Primary Examiner(s): Bullock, In Suk
• Assistant Examiner(s): EOM, ROBERT J
• Application Number:
  US12/290,478
• Time in Patent Office: 1,929 Days
• Field of Search: 73/290.1, 7333502-33505, 422/83, 422/90, 422/94
• US Class Current: 73/31.06
• CPC Class Codes: G01N 27/12 of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid , for detecting components in the fluid
• CPC Class Codes: G01N 27/125 Composition of the body, e.g. the composition of its sensitive layer
• CPC Class Codes: G01N 33/005 for H2
• CPC Class Codes: G01N 33/0054 for ammonia
• CPC Class Codes: Y02A 50/20 Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

A sensor for detecting hydrogen or ammonia gas uses a gas sensitive material based on Cr₂O₃ with a small percentage of the chromium replaced by transition metal ions having a valency greater than four, but still having a corundum crystal structure. Electrodes in contact with the gas sensitive material are connected by conductors to electrical measuring means for measuring the resistance, conductance, capacitance, or impedance of the gas sensitive material. A temperature sensing means and heating means allow the temperature of the gas sensitive material to be regulated. The gas sensitive material is formed on an insulator substrate over one or both electrodes. One electrode can be on the non-substrate side of the gas sensitive material. The gas sensitive material can be formed by deposition from a suspension or colloidal dispersion and firing. The gas sensitive material is contacted with gas and changes in electrical properties of the material are observed.

Claims

1. A sensor apparatus for sensing hydrogen or ammonia in air, comprising

a hydrogen and ammonia gas sensitive material based on Cr₂O₃, wherein a small percentage of chromium cation sites in the Cr₂O₃ are replaced and occupied by transition metal ions having a valency greater than four, but still having a corundum crystal structure,

first and second electrodes in contact with the gas sensitive material, and wherein

the transition metal ions having a valency greater than four are selected from the group consisting of tungsten ions and molybdenum ions.

2. The sensor apparatus of claim 1, further comprising an electrical measuring means for measuring resistance, conductance, capacitance, or impedance, and conductors connecting the electrodes to the electrical measuring means.

3. The sensor apparatus of claim 1, further comprising a temperature sensing means and a heating means connected to the gas sensitive material for heating the sensor.

4. The sensor apparatus of claim 1, wherein the transition metal ions having a valency greater than four make up 0.1% to 5% of the gas sensing material by mass.

5. The sensor apparatus of claim 1, further comprising an insulating substrate carrying the gas sensitive material.

6. The sensor apparatus of claim 5, wherein part of the first electrode is between the substrate and the gas sensitive material and the second electrode is on the opposite side of the gas sensitive material from the first electrode.

7. The sensor apparatus of claim 5, wherein part of the first electrode and part of the second electrode are between the substrate and the gas sensitive material and do not overlap, and wherein the portions of the first and second electrodes between the substrate and the gas sensitive material are interdigitated.

8. A method for producing a sensor apparatus for sensing hydrogen or ammonia in air, comprising

providing an insulating substrate,

applying a first electrode to the insulating substrate,

forming a layer of gas sensitive material over a portion of the first electrode and insulating substrate, and

applying a second electrode,

wherein the gas sensitive material is based on Cr₂O₃, wherein a small percentage of chromium cation sites in the Cr₂O₃ are replaced and occupied by transition metal ions having a valency greater than four, but still having a corundum crystal structure, and wherein

the transition metal ions having a valency greater than four are selected from the group consisting of tungsten ions and molybdenum ions.

9. The method for producing a sensor apparatus of claim 8, further comprising providing an electrical measuring means for measuring resistance, conductance, capacitance, or impedance, and

providing conductors connecting the first and second electrodes to the electrical measuring means.

10. The method for producing a sensor apparatus of claim 8, wherein the applying a second electrode comprises applying part of the second electrode on the layer of gas sensitive material.

11. The method for producing a sensor apparatus of claim 8, wherein the applying a second electrode comprises applying the second electrode on the substrate before the layer of gas sensitive material is formed.

12. The method of producing a sensor apparatus of claim 11, wherein the applying a second electrode comprises interdigitating the first and second electrodes.

13. The method for producing a sensor apparatus of claim 8, wherein forming a layer of gas sensitive material comprises forming the layer of gas sensitive material by deposition from a suspension or colloidal dispersion and firing.

14. The method for producing a sensor apparatus of claim 13, wherein the firing is done at a temperature in the range of 450-900°

C.

15. The method for producing a sensor apparatus of claim 13, wherein the firing is done at a temperature in the range of 450-700°

C.

16. The method for producing a sensor apparatus of claim 13, wherein the deposition comprises screen printing or doctor blading.

17. The method for producing a sensor apparatus of claim 8, wherein applying the first or second electrode comprises screen printing or sputtering.

18. A hydrogen or ammonia gas sensing method, comprising

providing a hydrogen or ammonia gas sensor comprising a gas sensitive material based on Cr₂O₃, wherein a small percentage of chromium cation sites in the Cr₂O₃ are replaced and occupied by transition metal ions having a valency greater than four, but still having a corundum crystal structure, and first and second electrodes connected by conductors to an electrical measuring means for measuring resistance, conductance, capacitance, or impedance,

contacting the hydrogen or ammonia gas sensor with a gas or gaseous mixture, and

measuring the resistance, conductance, capacitance, or impedance of the gas sensitive material with the electrical measuring means, and wherein

the transition metal ions having a valency greater than four are selected from the group consisting of tungsten ions and molybdenum ions.

19. A sensor apparatus for sensing hydrogen or ammonia in air, comprising

an insulating substrate,

a first electrode to the insulating substrate,

a layer of gas sensitive material over a portion of the first electrode and insulating substrate, and

a second electrode in contact with the gas sensitive material,

wherein the gas sensitive material is based on Cr₂O₃, wherein a small percentage of chromium cation sites in the Cr₂O₃ are replaced and occupied by transition metal ions having a valency greater than four, but still having a corundum crystal structure, and wherein

the transition metal ions having a valency greater than four are selected from the group consisting of tungsten ions and molybdenum ions.