WO2002059559A2 - Hydrocarbon sensor - Google Patents
Hydrocarbon sensor Download PDFInfo
- Publication number
- WO2002059559A2 WO2002059559A2 PCT/US2002/001366 US0201366W WO02059559A2 WO 2002059559 A2 WO2002059559 A2 WO 2002059559A2 US 0201366 W US0201366 W US 0201366W WO 02059559 A2 WO02059559 A2 WO 02059559A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrolyte
- metal
- sensor
- oxide electrode
- electrode body
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/4073—Composition or fabrication of the solid electrolyte
- G01N27/4074—Composition or fabrication of the solid electrolyte for detection of gases other than oxygen
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—Specially adapted to detect a particular component
- G01N33/0047—Specially adapted to detect a particular component for organic compounds
Definitions
- the present invention relates generally to hydrocarbon sensors, and, more particularly, to solid state hydrocarbon sensors having metal and metal oxide electrodes.
- the first generation of mixed potential sensors used Gold (Au) and Pt electrodes on a stabilized zirconia electrolyte.
- the Au electrode in these devices was painted onto the electrolyte.
- the morphology of this electrode was not easy to reproduce from sensor to sensor, and also the morphology changes with time as the sensor was being operated at elevated temperatures.
- two other approaches have been tried.
- the Au electrode is replaced with a conductive oxide electrode.
- the refractory nature of the oxide electrode ensures its morphological stability and the sensor is capable of withstanding temperatures as high as 850°C.
- the use of a sintered ceramic pellet (instead of a thin film of oxide) provides excellent control of the electrode area and 3-phase region thus improving the sensor-to-sensor reproducibility.
- the present invention includes a hydrocarbon sensor with an electrolyte body having a first electrolyte surface with a reference electrode depending therefrom and a metal oxide electrode body contained within the electrolyte body and having a first electrode surface coplanar with the first electrolyte surface.
- the sensor is formed by forming a sintered metal-oxide electrode body and placing the metal-oxide electrode body within an electrolyte powder.
- the electrolyte powder with the metal-oxide electrode body is pressed to form a pressed electrolyte body containing the metal-oxide electrode body.
- the electrolyte is removed from an electrolyte surface above the metal-oxide electrode body to expose a metal-oxide electrode surface that is coplanar with the electrolyte surface.
- the electrolyte body and the metal-oxide electrode body are then sintered to form the hydrocarbon sensor.
- FIGURES 1A and 1 B are top and cross-section views, respectively of a sensor according to one embodiment of the present invention.
- FIGURE 4 graphically depicts the response of two different sensors to propylene concentration in 1 % O 2 .
- This invention is a mixed-potential sensor for the detection of non- methane hydrocarbons (NMHCs).
- the sensor utilizes a stabilized-zirconia electrolyte, and platinum (Pt) and perovskite-type oxide electrodes.
- the Pt electrode acts as a pseudo-reference electrode while the oxide electrode gives the mixed potential in the presence of reducing-gases.
- the selectivity of the device is achieved by the proper selection of the oxide electrode, while the stability of the device is achieved by the precise control of the surface area (SA) of the electrode and the 3-phase interface region (3PA) (gas-electrolyte- electrode) of the sensor.
- SA surface area
- 3PA 3-phase interface region
- the oxide electrode is La ⁇ - x A x CrO 3 , where A is Sr, Ca, or Mg, O ⁇ x ⁇ O.5.
- A is Sr, Ca, or Mg, O ⁇ x ⁇ O.5.
- the specific approach involves the following steps: 1 ) Sintering the metal-oxide electrode to form a dense ceramic.
- Lao. ⁇ Sro. 2 CrO 3 powder was obtained from Praixair® and was pressed into a pellet and sintered at 1550-1650°C for 10 hours in order to form a dense ( «60- 70% of theoretical density) ceramic.
- the ceramic pellet was cut into smaller pellets with dimensions 0.2 cm x 0.3 cm x 0.2 cm.
- the pellet was buried in YSZ powder and pressed uniaxially at 1500 lbs in a 3 ⁇ " diameter die for 5 minutes. The excess YSZ was removed from the surface of the oxide electrode pellet using a razor blade. Once a clear electrode/electrolyte interface was exposed, the pellet was sintered at 1000-1100°C for 10-24 hours. The resulting pellet was about 60% of theoretical density.
- a 0.004" diameter Pt wire was fixed onto the surface of the oxide electrode using a small drop of Pt paint.
- the other electrode was a Pt (0.01" diameter) wire buried into the YSZ-electrolyte.
- the sensor was fixed to Pt (0.01" diameter) leads and was heated to 400- 600°C in various gas atmospheres in order to test the sensor response.
- the first sensor was annealed at 800°C for 30 minutes in order to stabilize the Pt electrodes and was then cooled to 500°C, where the sensor was tested.
- the sensor response was very reproducible and was stable with time for at least 10 days (maximum deviation was ⁇ 10%).
- the operating temperature of the sensor was raised to 550°C.
- the response to 500 ppm propylene was about 15 mV with a response time of about 25 sec.
- the sensor response time could be further improved by using a testing system with a lower volume (t ⁇ 10sec) and/or higher space velocities of the test gas.
- the mixed-potential sensor can be used to sense the amount of NMHC in the tailpipe emissions of an automobile. This would help the auto- manufacturers test the efficiency of the catalytic converter.
- the current technology utilizes a two oxygen sensor approach where one oxygen sensor is placed in the exhaust upstream of the catalytic converter and the other downstream. The difference in the signal between the two sensors when the engine is cycled through stoichiometry is a measure of the oxygen capacity in the catalytic converter.
- the above method to determine the health of the converter is indirect (does not measure the actual conversion efficiency) and moreover will work only when the engine is cycled through stoichiometry.
- the sensor according to the present invention can provide a direct measure of the catalyst efficiency because the sensor can be placed downstream of the converter and the sensor provides a measure of the actual amount of NMHC coming out of the tailpipe. Moreover the sensor works in high oxygen concentrations ( « 1 %) which makes it ideal for operation in the exhaust of a lean-bum engine.
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2002239951A AU2002239951A1 (en) | 2001-01-25 | 2002-01-18 | Hydrocarbon sensor |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US77092801A | 2001-01-25 | 2001-01-25 | |
US09/770,928 | 2001-01-25 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002059559A2 true WO2002059559A2 (en) | 2002-08-01 |
WO2002059559A3 WO2002059559A3 (en) | 2002-10-03 |
Family
ID=25090138
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2002/001366 WO2002059559A2 (en) | 2001-01-25 | 2002-01-18 | Hydrocarbon sensor |
Country Status (2)
Country | Link |
---|---|
AU (1) | AU2002239951A1 (en) |
WO (1) | WO2002059559A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007036454A1 (en) * | 2005-09-30 | 2007-04-05 | Robert Bosch Gmbh | Gas sensor |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3074143A (en) * | 1960-02-01 | 1963-01-22 | Baynard R Smith | Method of making metalized ceramic bodies |
US3723589A (en) * | 1969-08-25 | 1973-03-27 | Bissett Berman Corp | Solid electrolyte electrolytic cell |
US4277323A (en) * | 1979-03-09 | 1981-07-07 | Robert Bosch Gmbh | Electrochemical oxygen sensor, particularly for use in the exhaust system of automotive-type internal combustion engines |
US4304652A (en) * | 1979-06-12 | 1981-12-08 | Nissan Motor Company, Limited | Device for detection of air/fuel ratio from oxygen partial pressure in exhaust gas |
US4478590A (en) * | 1981-12-28 | 1984-10-23 | North American Philips Consumer Electronics Corp. | Depression cathode structure for cathode ray tubes having surface smoothness and method for producing same |
US4502939A (en) * | 1980-05-10 | 1985-03-05 | Robert Bosch Gmbh | Electrochemical oxygen sensor, particularly for analysis of combustion cases from internal combustion engines |
US4614628A (en) * | 1982-05-26 | 1986-09-30 | Massachusetts Institute Of Technology | Solid electrolyte structure and method for forming |
US4735666A (en) * | 1983-08-09 | 1988-04-05 | Ngk Insulators, Ltd. | Method of producing ceramics |
US4820663A (en) * | 1987-09-02 | 1989-04-11 | Kennametal Inc. | Whisker reinforced ceramic and a method of clad/hot isostatic pressing same |
US5215643A (en) * | 1988-02-24 | 1993-06-01 | Matsushita Electric Works, Ltd. | Electrochemical gas sensor |
US6019881A (en) * | 1995-03-10 | 2000-02-01 | Kabushiki Kaisha Riken | NOx sensor |
US6103080A (en) * | 1998-02-11 | 2000-08-15 | The Regents Of The University Of California | Hydrocarbon sensors and materials therefor |
-
2002
- 2002-01-18 AU AU2002239951A patent/AU2002239951A1/en not_active Abandoned
- 2002-01-18 WO PCT/US2002/001366 patent/WO2002059559A2/en not_active Application Discontinuation
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3074143A (en) * | 1960-02-01 | 1963-01-22 | Baynard R Smith | Method of making metalized ceramic bodies |
US3723589A (en) * | 1969-08-25 | 1973-03-27 | Bissett Berman Corp | Solid electrolyte electrolytic cell |
US4277323A (en) * | 1979-03-09 | 1981-07-07 | Robert Bosch Gmbh | Electrochemical oxygen sensor, particularly for use in the exhaust system of automotive-type internal combustion engines |
US4304652A (en) * | 1979-06-12 | 1981-12-08 | Nissan Motor Company, Limited | Device for detection of air/fuel ratio from oxygen partial pressure in exhaust gas |
US4502939A (en) * | 1980-05-10 | 1985-03-05 | Robert Bosch Gmbh | Electrochemical oxygen sensor, particularly for analysis of combustion cases from internal combustion engines |
US4478590A (en) * | 1981-12-28 | 1984-10-23 | North American Philips Consumer Electronics Corp. | Depression cathode structure for cathode ray tubes having surface smoothness and method for producing same |
US4614628A (en) * | 1982-05-26 | 1986-09-30 | Massachusetts Institute Of Technology | Solid electrolyte structure and method for forming |
US4735666A (en) * | 1983-08-09 | 1988-04-05 | Ngk Insulators, Ltd. | Method of producing ceramics |
US4820663A (en) * | 1987-09-02 | 1989-04-11 | Kennametal Inc. | Whisker reinforced ceramic and a method of clad/hot isostatic pressing same |
US5215643A (en) * | 1988-02-24 | 1993-06-01 | Matsushita Electric Works, Ltd. | Electrochemical gas sensor |
US6019881A (en) * | 1995-03-10 | 2000-02-01 | Kabushiki Kaisha Riken | NOx sensor |
US6103080A (en) * | 1998-02-11 | 2000-08-15 | The Regents Of The University Of California | Hydrocarbon sensors and materials therefor |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007036454A1 (en) * | 2005-09-30 | 2007-04-05 | Robert Bosch Gmbh | Gas sensor |
US8133370B2 (en) | 2005-09-30 | 2012-03-13 | Robert Bosch Gmbh | Gas sensor |
Also Published As
Publication number | Publication date |
---|---|
AU2002239951A1 (en) | 2002-08-06 |
WO2002059559A3 (en) | 2002-10-03 |
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