EP0843813A1 - Detecteur pour determiner la concentration de constituants oxydables d'un melange gazeux - Google Patents
Detecteur pour determiner la concentration de constituants oxydables d'un melange gazeuxInfo
- Publication number
- EP0843813A1 EP0843813A1 EP97923831A EP97923831A EP0843813A1 EP 0843813 A1 EP0843813 A1 EP 0843813A1 EP 97923831 A EP97923831 A EP 97923831A EP 97923831 A EP97923831 A EP 97923831A EP 0843813 A1 EP0843813 A1 EP 0843813A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sensor according
- semiconductor
- measuring
- acceptor
- donor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 150000001875 compounds Chemical class 0.000 title abstract 2
- 239000007789 gas Substances 0.000 claims abstract description 41
- 239000004065 semiconductor Substances 0.000 claims abstract description 16
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 5
- 239000007784 solid electrolyte Substances 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 239000010955 niobium Substances 0.000 claims description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract 1
- 239000000370 acceptor Substances 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000036647 reaction Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- -1 platinum metals Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- 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
-
- 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
- G01N27/4071—Cells and probes with solid electrolytes for investigating or analysing gases using sensor elements of laminated structure
Definitions
- the invention is based on a sensor for determining the concentration of oxidizable constituents in a gas mixture, in particular for determining one or more of the gases NOx, CO, H2 and preferably unsaturated hydrocarbons according to the type of the main claim.
- Exhaust gases from gasoline and diesel engines, internal combustion engines and combustion systems can cause increased concentrations of oxidizable constituents, in particular NOx, CO, H2 and hydrocarbons, for example as a result of a component malfunction, such as an injection valve, or as a result of incomplete combustion. To optimize the combustion reactions, it is therefore necessary to know the concentration of these exhaust gas components.
- JP-OS 60-61654 describes a method for determining oxidizable gases, according to which an ⁇ tochiometric reaction with oxygen takes place on a first measuring electrode made of platinum metals and on one or more further metallic measuring electrodes with reduced catalytic activity for the oxygen equilibrium reaction quasi-equilibrium states can be set. There are the Nernst voltages El and E2 between the measuring electrodes and a reference electrode measured, which is exposed to a reference gas with constant oxygen partial pressure, and from their difference based on calibration curves, the concentration of the gas components is calculated.
- the senor according to the invention with the features of the main claim has improved analytical performance features, in particular a higher sensitivity and selectivity with respect to individual sample gas components to be determined.
- Sensitivity and selectivity of the measuring electrodes are improved by doping the in particular oxidic or mixed-oxide semiconductors with acceptors and / or donors.
- the conductivity of the measuring electrodes is improved by adding donors, especially in higher concentrations compared to the acceptors.
- Particularly powerful electrodes are obtained if the acceptor is selected from the range of transition metals and / or rare earths and / or the donor is one or both of the elements tantalum and niobium.
- An increased miniaturization, a simplification of construction and a less expensive production are achieved by sintering the solid electrolyte porous.
- the thermodynamic equilibrium can advantageously also be set in the solid electrolyte by selecting a catalytically active solid electrolyte material.
- a particular advantage is that the gases that disturb the reference signal can be oxidized in a targeted manner, which simplifies signal evaluation or even makes it possible in the first place.
- the measuring electrodes can also be porous, which further improves the diffusion of the molecules of the measuring gas to the reference electrode. By adding additives to the solid electrolyte in the areas adjacent to the electrodes which correspond to the electrode materials, the electrode adhesion and thus the life of the sensor is improved.
- Figure 1 shows a section through a sensor according to the invention.
- a sensor according to the invention is shown in section in FIG.
- An electrically insulating planar ceramic substrate 6 carries a reference electrode 3 made of, for example, platinum, a solid electrolyte 5, on one large surface in layers one above the other.
- a heater device 7 with a cover ⁇ is applied to the opposite large surface of the substrate.
- the solid electrolyte can be sintered porously, but the person skilled in the art can also choose other solutions known to him, such as via a reference channel or a reference gas atmosphere.
- the sensor generates a cell voltage above the oxygen ion-conducting solid electrolyte by means of a first half-cell reaction set with the aid of the reference electrode and a second half-cell reaction on at least one measuring electrode influenced by the oxidizable gas components to be determined.
- the calibration values are used to determine the concentrations of the gas components from the voltage values.
- the sensor according to the invention is thus in the simplest case with a reference electrode which
- measuring electrodes as shown in FIG. 1, or also several measuring electrodes, each with different catalytic activity, for setting oxygen Equilibrium states.
- the measuring electrodes then react with different voltages depending on the type of gas, based on the reference electrode.
- the solid electrolyte is formed, e.g. by adding 0.01 to 10% by volume of platinum so that the solid electrolyte converts the gases to be measured catalytically, so that only the gases corresponding to the thermodynamic equilibrium arrive at the reference electrode or that the solid electrolyte only converts the gases which disturb the reference signal.
- one or more measuring electrodes are made porous in addition to the solid electrolyte, thereby facilitating gas diffusion to the reference electrode.
- Semiconductors which have a high specific sensitivity for certain oxidizable gases are used as measuring electrode materials.
- Oxides or mixed oxides, in particular based on rutile or dirutile or mixtures thereof, which can be doped with acceptor and / or donor are particularly suitable. Titanium and / or zirconium dioxide are advantageously used.
- Suitable donors are in particular tantalum and niobium, preferably elements with higher valence than the metals forming the semiconductor; suitable acceptors are transition metals, in particular nickel, copper, cobalt and / or chromium, preferably nickel, copper and / or cobalt, and rare earths.
- the acceptor can be contained in the semiconductor as a solid solution or as a segregated component.
- the concentrations of the acceptors and donors are each in the range from 0.01 to 25%; at lower proportions, there is no improvement in the properties of the measuring electrodes, and at higher proportions grid defects occur.
- the high sensitivity of e.g. Acceptor and donor-doped titanium dioxide for unsaturated hydrocarbons in particular is caused by the adsorptive interaction of the orbitals of the Pi bonds of the unsaturated hydrocarbons with the electrophilic acceptor sites on the semiconductor surface.
- the following example describes a production method for a sensor according to the invention: Rutile doped with 7% niobium and 3% of one of the transition metals nickel, copper or iron is printed as a 30 ⁇ m thick screen printing layer on a substrate which has a reference electrode, for example made of platinum, and above it Solid electrolyte layer carries. A heater device is applied to the opposite side of the substrate. The sensor is sintered at 1200 ° C for 90 minutes with a heating / cooling ramp of 300 ° C / hour.
- the solid electrolyte After sintering, the solid electrolyte has pores in the size range from 10 nm to 100 ⁇ m. With the aid of a platinum conductor track insulated from the solid electrolyte and which only contacts the measuring electrode, the voltage across the cell thus constructed is measured at a resistance of 1 MOhm between the reference and the rutile electrode. The sensor is heated to 600 ° C with its heater.
- Simulated exhaust gas with 10% oxygen, 5% water and 5% carbon dioxide and 30 ppm sulfur dioxide is used as the measurement gas.
- Oxidizable gases are mixed in the amounts given in the table.
- the last line of the table below shows the voltage values for a mixed potential electrode made of 20% gold and 80% platinum, which represents a measuring electrode according to the prior art.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
L'invention concerne un détecteur pour déterminer la concentration de constituants oxydables d'un mélange gazeux, notamment pour déterminer la présence d'un ou plusieurs des gaz NOx, CO, H2 et de préférence d'hydrocarbures insaturés, par mesure de la tension entre une électrode de mesure (1, 2) et une électrode de référence (3) ou par mesure de la tension entre deux électrodes de mesure [(1) et (2)]. On peut améliorer la sélectivité vis-à-vis des constituants individuels du gaz à mesurer en sélectionnant les matériaux des électrodes de mesure, notamment en utilisant des semi-conducteurs. En utilisant un électrolyte solide poreux, on peut éviter le recours à une atmosphère gazeuse de référence et accroître ainsi la miniaturisation et simplifier la conception.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19623434 | 1996-06-12 | ||
| DE19623434A DE19623434A1 (de) | 1996-06-12 | 1996-06-12 | Sensor zur Bestimmung der Konzentration oxidierbarer Bestandteile in einem Gasgemisch |
| PCT/DE1997/000996 WO1997047963A1 (fr) | 1996-06-12 | 1997-05-16 | Detecteur pour determiner la concentration de constituants oxydables d'un melange gazeux |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0843813A1 true EP0843813A1 (fr) | 1998-05-27 |
Family
ID=7796739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP97923831A Withdrawn EP0843813A1 (fr) | 1996-06-12 | 1997-05-16 | Detecteur pour determiner la concentration de constituants oxydables d'un melange gazeux |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US6022464A (fr) |
| EP (1) | EP0843813A1 (fr) |
| JP (1) | JP4162262B2 (fr) |
| KR (1) | KR19990036337A (fr) |
| CN (1) | CN1195403A (fr) |
| DE (1) | DE19623434A1 (fr) |
| WO (1) | WO1997047963A1 (fr) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19623212A1 (de) * | 1996-06-11 | 1997-12-18 | Bosch Gmbh Robert | Sensor zur Bestimmung der Konzentration oxidierbarer Bestandteile in einem Gasgemisch |
| DE19846487C5 (de) | 1998-10-09 | 2004-12-30 | Basf Ag | Meßsonde für die Detektion der Momentankonzentrationen mehrerer Gasbestandteile eines Gases |
| DE19932048A1 (de) * | 1999-07-09 | 2001-01-11 | Bosch Gmbh Robert | Meßfühler zur Bestimmung einer Konzentration von Gaskomponenten in Gasgemischen |
| DE19944181A1 (de) | 1999-09-15 | 2001-04-12 | Bosch Gmbh Robert | Sensor zur Bestimmung der Konzentration von Gaskomponenten in Gasgemischen |
| US6849239B2 (en) * | 2000-10-16 | 2005-02-01 | E. I. Du Pont De Nemours And Company | Method and apparatus for analyzing mixtures of gases |
| FR2819314B1 (fr) * | 2001-01-08 | 2003-06-13 | Alstom | Procede pour controler de facon non intrusive un taux de melange d'un melange gazeux a au moins deux composants |
| DE10310953B4 (de) * | 2003-03-13 | 2006-03-09 | Robert Bosch Gmbh | Unbeheiztes, planares Sensorelement zur Bestimmung der Konzentration einer Gaskomponente in einem Gasgemisch |
| JP2006126056A (ja) * | 2004-10-29 | 2006-05-18 | Tdk Corp | 二酸化炭素センサ |
| DE102005015569A1 (de) * | 2005-04-05 | 2006-10-12 | Robert Bosch Gmbh | Keramisches Widerstands- oder Sensorelement |
| US20080110769A1 (en) * | 2006-11-09 | 2008-05-15 | Delphi Technologies Inc. | Exhaust gas sensors and methods for measuring concentrations of nox and ammonia and temperatures of the sensors |
| CA2717032A1 (fr) * | 2008-02-28 | 2009-09-03 | Nextech Materials, Ltd. | Cellules electrochimiques amperometriques et capteurs |
| JP4996527B2 (ja) * | 2008-04-14 | 2012-08-08 | 日本特殊陶業株式会社 | 積層型ガスセンサ素子及びガスセンサ |
| US8399883B2 (en) | 2008-09-30 | 2013-03-19 | Iljin Copper Foil Co., Ltd. | Nitrogen-oxide gas sensor with long signal stability |
| WO2010038989A2 (fr) * | 2008-09-30 | 2010-04-08 | 일진소재산업(주) | Capteur de gaz d'oxyde d'azote |
| US8974657B2 (en) | 2010-09-03 | 2015-03-10 | Nextech Materials Ltd. | Amperometric electrochemical cells and sensors |
| CH705070B1 (fr) * | 2011-07-15 | 2022-01-14 | Swatch Group Res & Dev Ltd | Capteur d'hydrogène à couche active et procédé de fabrication de capteurs d'hydrogène. |
| KR102168091B1 (ko) | 2012-03-08 | 2020-10-20 | 넥스테크 머티리얼스, 엘티디. | 전류계 전기화학 센서, 센서 시스템 및 검출 방법 |
| CN104374818A (zh) * | 2014-08-08 | 2015-02-25 | 杭州纳瑙新材料科技有限公司 | 一种平面型氧传感器 |
| KR101769303B1 (ko) * | 2016-06-14 | 2017-08-18 | 현대자동차주식회사 | 고체전해질용 co2 센서 및 이의 제조방법 |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2304464C2 (de) * | 1973-01-31 | 1983-03-10 | Robert Bosch Gmbh, 7000 Stuttgart | Meßfühler für die Überwachung der Funktionsfähigkeit von Katalysatoren in Abgas |
| DE3004571A1 (de) * | 1980-02-07 | 1981-08-13 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V., 3400 Göttingen | Feste elektrode in einer elektrolytischen zelle |
| JPS6061654A (ja) * | 1983-09-14 | 1985-04-09 | Ngk Insulators Ltd | 酸素・可燃ガス分圧測定方法及び装置 |
| US5037525A (en) * | 1985-10-29 | 1991-08-06 | Commonwealth Scientific And Industrial Research Organisation | Composite electrodes for use in solid electrolyte devices |
| DE3610364A1 (de) * | 1986-03-27 | 1987-10-01 | Kernforschungsz Karlsruhe | Verfahren zum verringern des no(pfeil abwaerts)x(pfeil abwaerts)-gehaltes in gasen, bei welchem dem gaststrom kontinuierlich nh(pfeil abwaerts)3(pfeil abwaerts) zugesetzt wird |
| US4879016A (en) * | 1986-07-25 | 1989-11-07 | Ceramatec, Inc. | Electrolyte assembly for oxygen generating device and electrodes therefor |
| US4931213A (en) * | 1987-01-23 | 1990-06-05 | Cass Richard B | Electrically-conductive titanium suboxides |
| DE68927087T2 (de) * | 1988-11-01 | 1997-02-06 | Ngk Spark Plug Co | Sauerstoffempfindlicher Sensor und Verfahren zu dessen Herstellung |
| JP2514701B2 (ja) * | 1988-12-02 | 1996-07-10 | 日本特殊陶業株式会社 | 酸素センサ |
| DE4021929C2 (de) * | 1990-07-10 | 1998-04-30 | Abb Patent Gmbh | Sensor |
| US5480535A (en) * | 1992-12-28 | 1996-01-02 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Thin film multilayered air/fuel ratio sensor |
| JPH06235715A (ja) * | 1993-02-10 | 1994-08-23 | Toyota Motor Corp | 酸素濃度センサ |
| DE4311851A1 (de) * | 1993-04-10 | 1994-10-13 | Bosch Gmbh Robert | Sensoranordnung zur Bestimmung von Gaskomponenten und/oder von Gaskonzentrationen von Gasgemischen |
| DE4408504A1 (de) * | 1994-03-14 | 1995-09-21 | Bosch Gmbh Robert | Sensor zur Bestimmung der Konzentration von Gaskomponenten in Gasgemischen |
| DE4408361C2 (de) * | 1994-03-14 | 1996-02-01 | Bosch Gmbh Robert | Elektrochemischer Sensor zur Bestimmung der Sauerstoffkonzentration in Gasgemischen |
-
1996
- 1996-06-12 DE DE19623434A patent/DE19623434A1/de not_active Ceased
-
1997
- 1997-05-16 WO PCT/DE1997/000996 patent/WO1997047963A1/fr not_active Application Discontinuation
- 1997-05-16 US US09/011,577 patent/US6022464A/en not_active Expired - Lifetime
- 1997-05-16 JP JP50103698A patent/JP4162262B2/ja not_active Expired - Fee Related
- 1997-05-16 KR KR1019980701005A patent/KR19990036337A/ko not_active Application Discontinuation
- 1997-05-16 EP EP97923831A patent/EP0843813A1/fr not_active Withdrawn
- 1997-05-16 CN CN97190685A patent/CN1195403A/zh active Pending
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9747963A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11510908A (ja) | 1999-09-21 |
| US6022464A (en) | 2000-02-08 |
| KR19990036337A (ko) | 1999-05-25 |
| WO1997047963A1 (fr) | 1997-12-18 |
| CN1195403A (zh) | 1998-10-07 |
| JP4162262B2 (ja) | 2008-10-08 |
| DE19623434A1 (de) | 1997-12-18 |
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