DE2304464A1 - Exhaust gas oxygen-content measuring probe - for monitoring the performance of an exhaust gas detoxification unit - Google Patents
Exhaust gas oxygen-content measuring probe - for monitoring the performance of an exhaust gas detoxification unitInfo
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- DE2304464A1 DE2304464A1 DE2304464A DE2304464A DE2304464A1 DE 2304464 A1 DE2304464 A1 DE 2304464A1 DE 2304464 A DE2304464 A DE 2304464A DE 2304464 A DE2304464 A DE 2304464A DE 2304464 A1 DE2304464 A1 DE 2304464A1
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- exhaust gas
- electrode
- sensor according
- gas
- measuring
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Links
- 238000012544 monitoring process Methods 0.000 title claims abstract description 5
- 239000000523 sample Substances 0.000 title claims description 4
- 238000001784 detoxification Methods 0.000 title abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 9
- 239000010931 gold Substances 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 239000011241 protective layer Substances 0.000 claims description 7
- -1 platinum metals Chemical class 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 3
- 238000005202 decontamination Methods 0.000 claims description 3
- 230000003588 decontaminative effect Effects 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910000967 As alloy Inorganic materials 0.000 claims description 2
- 229910001260 Pt alloy Inorganic materials 0.000 claims description 2
- PTIQFRFYSQUEOU-UHFFFAOYSA-N [Co]=O.[La] Chemical compound [Co]=O.[La] PTIQFRFYSQUEOU-UHFFFAOYSA-N 0.000 claims description 2
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 abstract 1
- 238000002485 combustion reaction Methods 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- COHCXWLRUISKOO-UHFFFAOYSA-N [AlH3].[Ba] Chemical compound [AlH3].[Ba] COHCXWLRUISKOO-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- SXQXMCWCWVCFPC-UHFFFAOYSA-N aluminum;potassium;dioxido(oxo)silane Chemical compound [Al+3].[K+].[O-][Si]([O-])=O.[O-][Si]([O-])=O SXQXMCWCWVCFPC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011214 refractory ceramic Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000010435 syenite Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 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
- G01N27/4075—Composition or fabrication of the electrodes and coatings thereon, e.g. catalysts
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N11/00—Monitoring or diagnostic devices for exhaust-gas treatment apparatus, e.g. for catalytic activity
- F01N11/007—Monitoring or diagnostic devices for exhaust-gas treatment apparatus, e.g. for catalytic activity the diagnostic devices measuring oxygen or air concentration downstream of the exhaust apparatus
-
- 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
- G01N27/4075—Composition or fabrication of the electrodes and coatings thereon, e.g. catalysts
- G01N27/4076—Reference electrodes or reference mixtures
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2550/00—Monitoring or diagnosing the deterioration of exhaust systems
- F01N2550/02—Catalytic activity of catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/40—Engine management systems
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Combustion & Propulsion (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
Abstract
Description
Meßfühler für die Überwachung der Funktionsfähigkeit von Katalysatoren in Abgasentgiftungsanlagen von Brennkraftmaschinen Die Erfindung bezieht sich auf einen Meßfühler für die über waschung der Funktionsfähigkeit von Katalysatoren in Abgasentgiftungsanlagen von Brennkraftmaschinen unter Verwendung einer Sauerstoff-Konzentrationskette mit ionenleitendem F--:stelektrolyten.Sensor for monitoring the functionality of catalytic converters in exhaust gas decontamination systems of internal combustion engines The invention relates to a sensor for washing over the functionality of catalysts in Exhaust gas decontamination systems for internal combustion engines using an oxygen concentration chain with ion-conducting F -: electrolytes.
Brennkraftmaschinen erzeugen in ihrem Abgas unter anderem Kohlenmonoxid, Stickoxide sowie unverbrannte oder teilverbrannte Kohlenwasserstoffe, die zur Luftverunreinigung beitragen. Um die durch diese Stoffe hervorgerufene Luftverunreinigung auf einen Minimalwert herabzudrwicken, ist es erforderlich, die Abgase von Brennkraftmaschinen möglichst weitgehend von diesen Stoffen zu befreien. Das bedeutet, daß Kohlenmonoxid und Kohlenwasserstoffe möglichst vollständig in ihre höchste Oxidationsstufe, Kohlendioxid - und im Falle der Kohlenwasserstoffe -Wasser, bzw. Stickoxide in elementaren Stickstoff übergeführt werden müssen.Internal combustion engines produce, among other things, carbon monoxide in their exhaust gas, Nitrogen oxides and unburned or partially burned hydrocarbons that pollute the air contribute. In order to reduce the air pollution caused by these substances To reduce the minimum value, it is necessary to reduce the exhaust gases from To rid internal combustion engines as much as possible of these substances. That means, that carbon monoxide and hydrocarbons as completely as possible in their highest oxidation state, Carbon dioxide - and in the case of hydrocarbons - water, or nitrogen oxides in elementary form Nitrogen must be transferred.
Eine solche Überführung der schädlichen Anteile des Abgases in die unschädlichen Verbindungen Kohlendioxid, Stickstoff und Wasser kann z. B. dadurch geschehen, daß man die Abgase einer Nachverbrennung unterwirft, indem man sie bei Temperaturen oberhalb etwa 6000 C über einen Katalysator leitet. Die Funktionsfähigkeit dieses Katalysators muß jedoch überwacht werden, da nach längerem Gebrauch ein Aktivitätsverlust des Katalysators eintritt.Such a transfer of the harmful components of the exhaust gas in the harmless compounds carbon dioxide, nitrogen and water can, for. B. thereby happen that the exhaust gases are subjected to afterburning by using them at Passes temperatures above about 6000 C over a catalyst. The functionality however, this catalyst must be monitored because of its loss of activity after prolonged use of the catalyst occurs.
Dieser Aktivitätsverlust ist von der Temperatur-Zeit-Beanspruchung, d.h. der Belastung der Brennkraftmaschine abhängig und macht sich normalerweise im Fahrverhalten des Kraftfahrzeuges, in welchem die Brennkraftmaschine eingesetzt ist, nicht bemerkbar.This loss of activity is due to the temperature-time stress, i.e. depending on the load on the internal combustion engine and normally makes itself felt in the driving behavior of the motor vehicle in which the internal combustion engine is used is not noticeable.
Der Erfindung liegt daher die Aufgabe zugrunde, einen Meßfühler anzugeben, der die Überwachung der Funktionsfähigkeit des Katalysators gestattet, so daß er als Geber für eine Einrichtung zur Abgasentgiftung eingesetzt werden kann. Das Signal soll möglichst groß sein, um es ohne großen Aufwand in einem elektronischen Steuergerät weiter verarbeiten zu können. Um eine hohe Lebensdauer zu gewährleisten, soll der Fühler weitgehend unempfindlich sein gegen Katalysatorgifte, vor allem gegen die meistens im Treibstoff vorhandenen Blei-, Schwefel- oder Phosphorverbindungen.The invention is therefore based on the object of specifying a measuring sensor, which allows the monitoring of the functionality of the catalytic converter, so that he can be used as a transmitter for a device for exhaust gas detoxification. The signal should be as large as possible in order to be able to use it in an electronic control unit with little effort to be able to process further. To ensure a long service life, the The sensor is largely insensitive to catalyst poisons, especially to the lead, sulfur or phosphorus compounds usually found in fuel.
Diese Aufgabe wird gemäß der Erfindung dadurch gelöst, daß bei dem Meßfühler die als Meßelektrode dienende, erste Elektrode aus solchen Metallen besteht, die-die Einstellung des thermodynamischen Gasgleichgewichtes nicht zu katalysieren vermögen.This object is achieved according to the invention in that in the The first electrode serving as the measuring electrode consists of such metals, the-not to catalyze the setting of the thermodynamic gas equilibrium capital.
Bei der üblichen Art der Messung eines Sauerstoffpartialdruckes mit Hilfe eines ionenleitenden Festelektrolyten besteht die Meßelektrode, die mit dem zu messenden Gas in Verbindung steht, aus Platin, also einem die Einstellung des thermodynamischen Gasgleichgewichtes katalysierenden Metall.In the usual way of measuring an oxygen partial pressure with The measuring electrode, which is connected to the to be measured gas is connected, made of platinum, so a setting of the thermodynamic gas equilibrium catalyzing metal.
Demgegenüber besteht bei der vorliegenden Erfindung die Meßelektrode aus einem Metall, das die E nstellung des thermodynamischen Gasgleichgewichtes nicht zu katalysieren vermag. Als derartige Metalle kommen vor allem Gold oder Silber in Betracht. Bei dem zu messenden Gas handelt es sich um Abgas von Brennkraftmaschinen, das zum Zwecke der Nachverbrennung durch einen Katalysator hindurchgegangen ist. Das Abgas ist leicht reduzierend eingestellt, die Luftzahl > liegt also bei etwa 0,98 bis 0,99. Bei dieser Abgaszusammensetzung ist noch immer soviel Sauerstoff im Abgas enthalten, daß er sich durch eine Sauerstoff-Konzentrationskette messen läßt.In contrast, in the present invention there is the measuring electrode made of a metal that does not allow the establishment of the thermodynamic gas equilibrium able to catalyze. The main metals of this type are gold or silver into consideration. The gas to be measured is exhaust gas from internal combustion engines, which has passed through a catalytic converter for the purpose of post-combustion. The exhaust gas is set to be slightly reducing, so the air ratio> is around 0.98 to 0.99. With this exhaust gas composition there is still so much oxygen contained in the exhaust gas that it can be measured by an oxygen concentration chain leaves.
Der Katalysator soll nun dafür sorgen, daß der Sauerstoff des Abgases möglichst weitgehend umgesetzt wird. Ist der Katalysator dagegen nicht mehr funktionsfähig, so ist der Sauerstoff im Abgas unvollständig umgesetzt und es befinden sich noch unumgesetzte Treibstoffanteile im Abgas, die zur Luftverschmutzung beitragen. Die unvollständige Umsetzung bedeutet, daß der Restsauerstoffgehalt im Abgas wesentlich höher ist als dem thermodynamischen Gleichgewicht entspricht.The catalytic converter should now ensure that the oxygen in the exhaust gas is implemented as widely as possible. If, on the other hand, the catalytic converter is no longer functional, so the oxygen in the exhaust gas is incompletely converted and it is still there unreacted fuel in the exhaust gas that contributes to air pollution. the Incomplete conversion means that the residual oxygen content in the exhaust gas is significant is higher than corresponds to the thermodynamic equilibrium.
Auf einen solchen erhöhten Restsauerstoffgehalt soll der erfindungsgemäße Meßfühler ansprechen. Es muß also dafür gesorgt werden, daß an der Dreiphasengrenze der Meßelektrode des Meßfühlers, die mit dem Abgas in Kontakt steht, in dem Moment ein höheres positives Potential auftritt, in welchem der Sauerstoffgehalt des Abgases höher wird als bei intaktem Katalysator.The invention is intended to target such an increased residual oxygen content Address the sensor. It must therefore be ensured that at the three-phase boundary the measuring electrode of the sensor, which is in contact with the exhaust gas, at the moment a higher positive potential occurs in which the oxygen content of the exhaust gas higher than with an intact catalyst.
Für die als Gegenelektrode oder Bezugselektrode dienende zweite Elektrode gibt es zwei Varianten: Bei der ersten Variante besteht diese aus einem die Einstellung des thermodynamischen Gasgleichgewichtes katalysierenden Material und ist ebenfalls wie die Meßelektrode vom Abgas umspült. In dieser katalytisch aktiven Gegenelektrode ist der Sauerstoffpartialdruck unabhängig vom Zustand des für die Nachverbrennung verwendeten Katalysators immer verschwindend klein; er entspricht dem thermodynamischen Gleichgewichtsdruck, da das Elektrodenmaterial eine vollständige Umsetzung gewährleistet. An der katalytisch inaktiven Meßelektrode dagegen hängt der Sauerstoffpartialdruck von der katalytischen Aktivität des Nachverbrennungskatalysators ab. Ist dieser Katalysator voll wirksam, so ist der Sauerstoffpartialdruck auch an dieser Elektrode verhältnismäßig klein, wohl aber etwas größer als an der'katalytisch aktiven Gegenelektrode. Dies liegt daran, daß der Nachverbrennungskatalysator das thermodynamische Gleichgewicht nicht vollständig einzustellen vermag. Es wird also bei voll wirksamem Katalysator eine Potentialdifferenz von 300 bis 400 Millivolt gemessen. Ist dagegen der Nachverbrennungskatalysator nicht mehr wirksam, so steigt der Sauerstoffpartialdruck im Abgas an. An der Dreiphasengrenze der katalytisch aktiven Gegenelektrode ändert sich nichts, weil das Elektrodenmaterial für eine vollständige Umsetzung sorgt, bevor das Gas an die Dreiphasengrenze gelan;t. An der Dreiphasengrenze der katalytisch inaktiven Meßelektrode dagegen steigt der Sauerstoffpartialdruck an, so daß sich eine um etwa 50 Millivolt höhere Potentialdifferenz als im vorgenannten Falle ergibt. Der Unterschied dieser beiden Potentiale, der sich bei voll wirksamem bzw. bei unwirksamem Nachverbrennungskatalysator ergibt, läßt sich als Warnsignal für eine entsprechende, nicht zu dieser Erfindung gehörende Steuereinrichtung verwenden, um anzuzeigen, daß der Nachverbrennungskatalysator nicht mehr voll wirksam ist.For the second electrode serving as a counter electrode or reference electrode There are two variants: The first variant consists of one setting of the thermodynamic gas equilibrium catalyzing material and is also how the exhaust gas washes around the measuring electrode. In this catalytically active counter electrode the oxygen partial pressure is independent of the state of the afterburning The catalyst used is always vanishingly small; it corresponds to the thermodynamic Equilibrium pressure, as the electrode material ensures complete conversion. On the other hand, the oxygen partial pressure depends on the catalytically inactive measuring electrode on the catalytic activity of the post-combustion catalyst. Is this If the catalyst is fully effective, the oxygen partial pressure is also at this electrode relatively small, but probably somewhat larger than on the catalytically active counter electrode. This is because the post-combustion catalytic converter is in thermodynamic equilibrium unable to fully adjust. So it will be with a fully effective catalyst measured a potential difference of 300 to 400 millivolts. On the other hand, it is the post-combustion catalyst no longer effective, the oxygen partial pressure in the exhaust gas increases. At the three-phase boundary the catalytically active counter electrode does not change anything because the electrode material ensures complete conversion before the gas reaches the three-phase boundary; t. At the three-phase boundary of the catalytically inactive measuring electrode, however, the increases Oxygen partial pressure, so that there is a potential difference that is about 50 millivolts higher than in the aforementioned case. The difference between these two potentials, the results from fully effective or ineffective post-combustion catalytic converters, can be used as a warning signal for a corresponding, not belonging to this invention Use control device to indicate that the afterburning catalytic converter is no longer fully effective.
Bei der zweiten Variante besteht die Gegen- oder Bezugselektrode aus einem elektronenleitenden Material und steht nicht mit dem Abgas, sondern mit Luft oder mit einem gasdicht abgeschlossenen Bezugssystem aus einem Metall/Metalloxid-Gemisch oder aus einem Gemisch zweier- Oxide eines Metalles in zwei Wertigkeitsstufen in Kontakt. Als derartige Bezugssysteme eignen sich Ni/NiO, Cu/Cu20, Co/CoO, Fe3011/Fe203 oder FeO/Fe.304 wobei die Gemische jeweils im stöchiometrischen Verhältnis 1:1 vorliegen.In the second variant, the counter or reference electrode consists of an electron-conducting material and does not stand with the exhaust gas, but with air or with a gas-tight sealed reference system made of a metal / metal oxide mixture or from a mixture of two oxides of a metal in two valence levels in Contact. Suitable reference systems of this type are Ni / NiO, Cu / Cu20, Co / CoO, Fe3011 / Fe203 or FeO / Fe.304, the mixtures each being present in a stoichiometric ratio of 1: 1.
Weitere Einzelheiten der Erfindung sollen im folgenden anhand der Figuren 1 bis 5 erläutert werden. Es bedeUten: Fig. 1 und 2 Querschnitte durch verschiedene Ausführungsformen des erfindungsgemäßen Meßfühlers, Fig. 3 einen Schnitt und Fig. 4 eine Vorderansicht weiterer Ausführungsarten des erfindungsgemäßen MeßfAhlers, Fig. 5 einen Schnitt durch eine Ausführungsform des erfindungsgemäßen Meßfühlers, bei der die Gegenelektrode mit einem Metall/Metalloxid-Gemisch in Verbindung steht.Further details of the invention are set out below with reference to FIG Figures 1 to 5 are explained. It means: Fig. 1 and 2 cross-sections through different Embodiments of the sensor according to the invention, FIG. 3 shows a section and FIG. 4 shows a front view of further embodiments of the measuring sensor according to the invention, 5 shows a section through an embodiment of the sensor according to the invention, in which the counter electrode is in contact with a metal / metal oxide mixture.
Der Meßfühler gemäß Fig. 1 besteht aus einem rechteckigen Täfelchen aus stabilisiertem, sauerstoffionenleitendem Zirkondioxid 13 als Festelektrolyt, auf den eine katalytisch aktive, cl.h. die Gleichgewichtseinstellung des Abgases katalysierende Gegenelektrode 111 und eine katalytisch inaktive, d.h. die Gleichgewichtseinstellung des Abgases nicht katalysierende Meßelektrode 15 aufgebracht sind.Die katalytisch aktive Gegenelektrode 14 besteht aus Platin, aus einer Platinlegierung mit anderen Platinmetallen als Legierungskomponente oder aus oxidischen Systemen wie Kupfer-Chrom-Oxid, das gegebenenfalls mit Bariumoxid oder Nickeloxid dotiert ist, oder Lanthan-Kobalt-Oxid, das gegebenenfalls mit Strontiumoxid dotiert ist. Die katalytisch inaktive Meßelektrode 15 besteht aus Gold oder Silber. Die Elektroden werden mit Hilfe einer Dünnschicht - oder Dickschichttechnik z. B. durch thermisches Aufdampfen, durch Kathodenzerstäubung, durch Gasphasenabscheidung, durch chemische Reduktion, durch galvanische Abscheidung, durch Einsintern von sieb gedruckten Pasten einzeln oder in Kombination aufgebracht.Wichtig ist, daß die Elektroden für Sauerstoff durchlässig sind. - Es ist vorteilhaft, die von den Elektroden nicht bedeckten Teile des Festelektrolyten mit einer gasdichten Abdeckschicht 16 zu versehen. Diese gasdichte Abdeckschicht besteht aus Kalium-Aluminium-Silikat, Barium-Aluminium- oder Barium-Calcium-Aluminiumsilikaten.The sensor according to FIG. 1 consists of a rectangular tablet made of stabilized, oxygen-ion conductive zirconium dioxide 13 as a solid electrolyte, on the one catalytically active, cl.h. the adjustment of the equilibrium of the exhaust gas catalyzing counter-electrode 111 and a catalytically inactive, i.e. the establishment of equilibrium of the exhaust gas non-catalyzing measuring electrode 15 are applied. The catalytic active counter electrode 14 is made of platinum, a platinum alloy with others Platinum metals as alloy components or from oxidic systems such as copper-chromium-oxide, which is optionally doped with barium oxide or nickel oxide, or lanthanum cobalt oxide, which is optionally doped with strontium oxide. The catalytically inactive measuring electrode 15 is made of gold or silver. The electrodes are made with the help of a thin film - or thick film technology z. B. by thermal vapor deposition, by cathode sputtering, by vapor deposition, by chemical reduction, by galvanic deposition, applied by sintering in screen printed pastes individually or in combination is that the electrodes are permeable to oxygen. - It's beneficial to that Parts of the solid electrolyte not covered by the electrodes with a gas-tight one Cover layer 16 to be provided. This gas-tight cover layer consists of potassium-aluminum-silicate, Barium-aluminum or barium-calcium-aluminum silicates.
Diese Schichten werden nach den in der Keramik üblichen Verfahren aufgebracht.These layers are made according to the usual methods in ceramics upset.
Fig. 2 zeigt eine Ausführungsform des MeßfUhlers, bei dem die Elektroden gegen mechanischen und chemischen Angriff, z.B gegen Katalysatorgifte geschützt sind, indem die Elektroden 14 und 15 zusätzlich noch eine poröse Schutzschicht 17 erhalten. Diese Schutzschicht besteht aus einem Metall, einer Metallegierung, einem Oxid, einem Mischoxid wie z.B. Magnesium-Spinell, aus dem Gemisch mehrerer Oxide, aus Hartstoffen wie Karbiden, Boriden, Nitriden von Übergangsmetallen, aus silikatischen Materialien wie hochschmelzendem Sinterglas oder aus feuerfesten keramischen Materialien, die auch als Rohstoffe bzw. Rohstoffmischungen wie Kaolin oder Talkum, gegebenenfalls unter Zusatz von Flußmitteln wie Feldspat, Nephelinsyenit oder ollatonit aufgetragen und anschließend eingesintert werden können. Statt einer porösen Schutzschicht über den Elektroden kann der ganze Meßfühler auch von einer porösen Schutzhülse, die aus den gleichen Stoffen, wie sie oben genannt sind, hergestellt ist, umgeben sein. Es ist ferner möglich, eine poröse, elektrisch isolierende Schutzschicht auf den ganzen Meßfühler aufzutrageh, um so die Bildung von Kurzschlußbrücken zwischen den Elektroden zu verhindern und die Meßelektrode gegen katalytisch aktive Niederschläge aus dem Abgas zu schützen.Fig. 2 shows an embodiment of the measuring sensor in which the electrodes protected against mechanical and chemical attack, e.g. against catalyst poisons are in that the electrodes 14 and 15 also have a porous protective layer 17 obtain. This protective layer consists of a metal, a metal alloy, a Oxide, a mixed oxide such as magnesium spinel, made from a mixture of several oxides, from hard materials such as carbides, borides, nitrides of transition metals, from silicate Materials such as high-melting sintered glass or refractory ceramic materials, also as raw materials or raw material mixtures such as kaolin or talc, if appropriate applied with the addition of fluxes such as feldspar, nepheline syenite or ollatonite and can then be sintered in. Instead of a porous protective layer over The entire sensor can also be attached to the electrodes by a porous protective sleeve, which made of the same materials as mentioned above, be surrounded. It is also possible to have a porous, electrically insulating protective layer on the whole measuring sensor to be applied in order to avoid the formation of short-circuit bridges between the To prevent electrodes and the measuring electrode against catalytically active precipitates to protect from the exhaust gas.
Bei Verwendung unterschiedlicher Elektroden 14 und 15 wird der Meßspannung eine Thermospannung Uberlagert. Diese Thermospannung, die zwar nicht groß ist und die nur eine geringe Temperaturabhängigkeit aufweist, kann ausgeschaltet werden, wenn der Festelektrolyt gemäß Fig. 3 auf beiden Elektrodenseiten zunächst mit einer katalytisch inaktiven Elektrodenschicht 15 versehen wird, die dann zusätzlich auf einer Elektrodenseite mit einer katalytisch aktiven Schicht 14 verstärkt wird. Auch hier können die Elektroden mit porösen Schutzschichten 17 abgedeckt sein, wie das in Figur 3 gezeigt ist.When using different electrodes 14 and 15, the measuring voltage a thermal voltage superimposed. This thermal voltage, which although not great and which has only a slight temperature dependency can be switched off, when the solid electrolyte according to FIG. 3 on both electrode sides initially with a catalytically inactive electrode layer 15 is provided, which is then additionally on one electrode side is reinforced with a catalytically active layer 14. Even here the electrodes can be covered with porous protective layers 17, like that is shown in FIG.
Ein höheres Meßsignal ist dadurch erzielbar, daß mindestens zwei Elektrodenpaare aus je einer katalytisch aktiven Gegenelektrode und einer katalytisch inaktiven Meßelektrode in Reihe geschaltet werden. Dies kann entweder dadurch geschehen, daß mindestens zwei Meßfühler in Reihe geschaltet werden. Einfacher ist es jedoch, wenn gemäß Fig. 4 mehrere Elektrodenpaare auf einem einzigen Festelektrolytkörper untergebracht werden, so daß auch hier eine Reihenschaltung mehrerer Zellen entsteht.A higher measurement signal can be achieved by using at least two pairs of electrodes from one catalytically active counter electrode and one catalytically inactive one Measuring electrode are connected in series. This can be done either by at least two sensors are connected in series. However, it is easier when 4 accommodated several pairs of electrodes on a single solid electrolyte body so that a series connection of several cells is created here as well.
Gemäß Fig. 4 ergibt sich dabei auf dem Festelektrolyt-Körper 13 der folgende Aufbau: Es werden zunächst drei Streifen 20, 21 und 22 aus Gold auf den Festelektrolyten aufgebracht. Zwischen diesen Streifen 20, 21 und 22 befinden sich unbedeckte Streifen von Festelektrolyt 13. Auf die untere Hälfte der Goldstreifen 21 und 22 wird in der halben Breite des Goldstreifens auf diesen je ein Streifen aus Platin 23 bzw.According to FIG. 4, this results on the solid electrolyte body 13 of the following structure: There are first three strips 20, 21 and 22 made of gold on the Solid electrolyte applied. Between these strips 20, 21 and 22 are located uncovered strips of solid electrolyte 13. On the lower half of the gold strips 21 and 22 are half the width of the gold stripe on each of these stripes made of platinum 23 resp.
24 aufgebracht. Ein weiterer Platinstreifen 25 befindet sich in entsprechendem Abstand von dem Goldstreifen 22 im oberen Teil des Meßfühlers. Auf diese Weise erreicht man eine Hintereinanderschaltung dreier Meßfühler und somit eine Verdreifachung des Meßsignals. Die drei hintereinandergeschalteten Einzelspannungen Ul - U3 entstehen zwischen den folgenden Punkten: U1 zwischen 20 und 23, U2 zwischen 21 und 24, U3 zwischen 22 und 25. Auch hier können die von den Elektroden nicht bedeckten Teile des Festelektrolyten 13 mit hier nicht dargestellten, -gasdichten Abdeckschichten bedeckt sein, wie das in den Figuren 1 und 2 als Ziffer 16 gezeigt ist.24 applied. Another platinum strip 25 is located in the corresponding Distance from the gold strip 22 in the upper part of the probe. Achieved this way a series connection of three sensors and thus a tripling of the measurement signal. The three individual voltages Ul - U3 connected in series arise between the following points: U1 between 20 and 23, U2 between 21 and 24, U3 between 22 and 25. Again, the electrodes cannot covered parts of the solid electrolyte 13 with gas tightness, not shown here Cover layers be covered, as shown in Figures 1 and 2 as numeral 16 is.
In Fig. 5 ist eine Ausführungsform des erfindungsgemäßen Meßfühlers dargestellt, bei dem die Gegenelektrode nicht mit dem Abgas in Kontakt ist. Der Meßfühler besteht aus einem einseitig geschlossenen Rohr 26 aus ionenleitendem Zirkondioxid als Festelektrolyt, dessen äußere, dem Abgas ausgesetzte Fläche eine als Meßelektrode dienende Schicht 27 aus katalytisch inaktivem Gold oder Silber trägt. Auf der inneren Oberfläche des einseitig geschlossenen Rohres 26 befindet sich eine schmale Leiterbahn 28 aus Gold oder Silber zur Kontaktierung des aus einem stöchiometrischen Ni/NiO-Gemisch bestehenden Bezugssystems 29, das für einen konstanten Sauerstoffpartialdruck sorgt. Das Bezugssystem 29 ist mit einem Deckel 30, der aus gas dicht abgedeckter Keramik oder aus einer gasdichten Glasur bzw. Glaseinschmelzung besteht, verschlossen. Das Potential wird zwischen den Punkten 31 und 32 abgenommen. An die Stelle des Bezugssystems 29 kann auch Luft treten, wenn dafür gesorgt wird, daß in das Innere des Rohres 26 kein Abgas gelangt, z. B. durch gasdichten Einbau des Meßfühlers in eine Halterung.In Fig. 5 is an embodiment of the sensor according to the invention shown in which the counter electrode is not in contact with the exhaust gas. Of the The sensor consists of a tube 26, closed on one side, made of ion-conducting zirconium dioxide as a solid electrolyte, the outer surface of which is exposed to the exhaust gas as a measuring electrode serving layer 27 made of catalytically inactive gold or silver carries. On the inner On the surface of the tube 26, which is closed on one side, there is a narrow conductor track 28 made of gold or silver for contacting the one made of a stoichiometric Ni / NiO mixture existing reference system 29, which ensures a constant oxygen partial pressure. The reference system 29 is provided with a cover 30 made of gas-tight ceramic or consists of a gas-tight glaze or glass seal, closed. That Potential is tapped between points 31 and 32. In place of the reference system 29 air can also enter if care is taken to get inside the tube 26 no exhaust gas enters, z. B. by gas-tight installation of the sensor in a holder.
Der erfindungsgemäße Meßfühler gestattet in einfacher Weise die Kontrolle der Funktionsfähigkeit eines Nachverbrennungskatalysators für die Abgase von Brennkraftmaschinen. Die Tatsache, daß bei Meßfühlern nach den Ausführungsformen der Figuren 1 - 4 ein Bezugsgas für die Messung nicht notwendig ist, führt zu einem einfachen Aufbau des Meßfühlers. Charakteristisch für diese Meßfühler ist der Umstand, daß das Meßsignal bei einem funktionsfähigen Nachverbrennungskatalysator kleiner ist als bei einem nicht mehr funktionsfähigen Nachverbrennungskatalysator. Die Vergrößerung des Meßsignals kann daher direkt für eine Warneinrichtung verwendet werden. Eine weitere Vergrößerung des Signals kann durch elektrische Hintereinanderschaltung mehrerer Zellen erreicht werden.The sensor according to the invention allows control in a simple manner the functionality of an afterburning catalytic converter for the exhaust gases from internal combustion engines. The fact that in the case of sensors according to the embodiments of FIGS Reference gas is not necessary for the measurement, leads to a simple structure of the Probe. A characteristic of these sensors is the fact that the Measurement signal is smaller in the case of a functional afterburning catalytic converter than in the case of one post-combustion catalytic converter that is no longer functional. The enlargement of the measurement signal can therefore be used directly for a warning device. Another enlargement the signal can be achieved by electrically connecting several cells in series will.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2304464A DE2304464C2 (en) | 1973-01-31 | 1973-01-31 | Sensor for monitoring the functionality of catalytic converters in exhaust gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2304464A DE2304464C2 (en) | 1973-01-31 | 1973-01-31 | Sensor for monitoring the functionality of catalytic converters in exhaust gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE2304464A1 true DE2304464A1 (en) | 1974-08-08 |
| DE2304464C2 DE2304464C2 (en) | 1983-03-10 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2304464A Expired DE2304464C2 (en) | 1973-01-31 | 1973-01-31 | Sensor for monitoring the functionality of catalytic converters in exhaust gas |
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| Country | Link |
|---|---|
| DE (1) | DE2304464C2 (en) |
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| US4096048A (en) * | 1976-10-26 | 1978-06-20 | Toyota Jidosha Kogyo Kabushiki Kaisha | Oxygen sensor and manufacturing method thereof |
| US4126532A (en) * | 1976-09-22 | 1978-11-21 | Nissan Motor Company, Limited | Oxygen sensor |
| FR2402870A1 (en) * | 1977-09-09 | 1979-04-06 | Bendix Autolite Corp | GALVANIC CELL TYPE OXYGEN SENSOR |
| US4157282A (en) * | 1974-11-18 | 1979-06-05 | General Motors Corporation | Method for maintaining stoichiometric air/fuel mixtures |
| US4177125A (en) * | 1977-05-25 | 1979-12-04 | Regie Nationale Des Usines Renault | Electrochemical detector of the oxygen content of the exhaust gases of combustion engines |
| DE2831478A1 (en) * | 1978-07-18 | 1980-01-31 | Bosch Gmbh Robert | ELECTROCHEMICAL PROBE AND METHOD FOR PRODUCING THE SAME |
| US4189355A (en) * | 1976-12-02 | 1980-02-19 | Nissan Motor Company, Limited | Method for detection of fluctuation in air/fuel ratio of air-fuel mixture fed to internal combustion engine |
| US4212720A (en) * | 1977-07-20 | 1980-07-15 | Robert Bosch Gmbh | Electrically heated electrochemical sensor construction, particularly to determine oxygen concentration in exhaust gases from combustion engines |
| US4226692A (en) * | 1978-05-22 | 1980-10-07 | Isenberg Arnold O | Solid state combustion sensor |
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| US4248941A (en) * | 1979-12-26 | 1981-02-03 | United Tecnologies Corporation | Solid electrolyte electrochemical cell |
| FR2461948A1 (en) * | 1979-07-16 | 1981-02-06 | Nissan Motor | PROCESS FOR PRODUCING FLAT LAYER OF SOLID ELECTROLYTE FOR OXYGEN SENSOR OF FLAT FILM TYPE |
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| FR2465224A1 (en) * | 1979-09-13 | 1981-03-20 | Bosch Gmbh Robert | ELECTROCHEMICAL MEASURING DEVICE FOR DETERMINING THE OXYGEN CONTENT IN GASES, ESPECIALLY IN THE EXHAUST GASES OF INTERNAL COMBUSTION ENGINES |
| FR2470383A1 (en) * | 1979-11-23 | 1981-05-29 | Renault | Probe for detecting oxygen in engine exhaust gas - has gold conductor connecting two electrolytic circuits in series |
| FR2472187A1 (en) * | 1979-12-18 | 1981-06-26 | Nissan Motor | ELEMENT DETECTING SOLID ELECTROLYTE OXYGEM IN LAMINATED STRUCTURE AND DEVICE USING THE SAME |
| 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 |
| US4283261A (en) * | 1978-12-20 | 1981-08-11 | Robert Bosch Gmbh | Electrochemical sensor structure to determine oxygen content in combustion exhaust gases |
| FR2488408A1 (en) * | 1980-08-08 | 1982-02-12 | Carbonisation Entr Ceram | Oxygen determn. appts. esp. for exhaust gas from motor vehicles - using thin solid electrolyte coated on each side with thin metal film electrode to make probe which can be rapidly heated |
| EP0058897A1 (en) * | 1981-02-20 | 1982-09-01 | Nissan Motor Co., Ltd. | Oxygen sensing element having barrier layer between ceramic substrate and solid electrolyte layer |
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| US4157282A (en) * | 1974-11-18 | 1979-06-05 | General Motors Corporation | Method for maintaining stoichiometric air/fuel mixtures |
| DE2720474A1 (en) * | 1976-05-07 | 1977-11-24 | Thomson Csf | SENSOR FOR SENSING THE CONCENTRATION OF A SPECIES IN A FLUID |
| US4126532A (en) * | 1976-09-22 | 1978-11-21 | Nissan Motor Company, Limited | Oxygen sensor |
| US4096048A (en) * | 1976-10-26 | 1978-06-20 | Toyota Jidosha Kogyo Kabushiki Kaisha | Oxygen sensor and manufacturing method thereof |
| US4189355A (en) * | 1976-12-02 | 1980-02-19 | Nissan Motor Company, Limited | Method for detection of fluctuation in air/fuel ratio of air-fuel mixture fed to internal combustion engine |
| US4177125A (en) * | 1977-05-25 | 1979-12-04 | Regie Nationale Des Usines Renault | Electrochemical detector of the oxygen content of the exhaust gases of combustion engines |
| US4212720A (en) * | 1977-07-20 | 1980-07-15 | Robert Bosch Gmbh | Electrically heated electrochemical sensor construction, particularly to determine oxygen concentration in exhaust gases from combustion engines |
| FR2402870A1 (en) * | 1977-09-09 | 1979-04-06 | Bendix Autolite Corp | GALVANIC CELL TYPE OXYGEN SENSOR |
| US4226692A (en) * | 1978-05-22 | 1980-10-07 | Isenberg Arnold O | Solid state combustion sensor |
| DE2831478A1 (en) * | 1978-07-18 | 1980-01-31 | Bosch Gmbh Robert | ELECTROCHEMICAL PROBE AND METHOD FOR PRODUCING THE SAME |
| US4283261A (en) * | 1978-12-20 | 1981-08-11 | Robert Bosch Gmbh | Electrochemical sensor structure to determine oxygen content in combustion exhaust gases |
| 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 |
| FR2451580A1 (en) * | 1979-03-10 | 1980-10-10 | Bosch Gmbh Robert | ELECTRONIC MEASURING PROBE FOR DETERMINING THE OXYGEN CONTENT IN GASES, ESPECIALLY IN EXHAUST GASES |
| US4282080A (en) * | 1979-03-10 | 1981-08-04 | Robert Bosch Gmbh | Electrochemical sensor, particularly for oxygen determination in combustion gases |
| FR2461946A1 (en) * | 1979-07-14 | 1981-02-06 | Bosch Gmbh Robert | ELECTROCHEMICAL DETECTORS FOR DETERMINING THE OXYGEN CONTENT IN GASES, ESPECIALLY IN EXHAUST GASES OF INTERNAL COMBUSTION ENGINES, AND PROCESS FOR THE PRODUCTION OF THESE DETECTORS |
| FR2461948A1 (en) * | 1979-07-16 | 1981-02-06 | Nissan Motor | PROCESS FOR PRODUCING FLAT LAYER OF SOLID ELECTROLYTE FOR OXYGEN SENSOR OF FLAT FILM TYPE |
| FR2465224A1 (en) * | 1979-09-13 | 1981-03-20 | Bosch Gmbh Robert | ELECTROCHEMICAL MEASURING DEVICE FOR DETERMINING THE OXYGEN CONTENT IN GASES, ESPECIALLY IN THE EXHAUST GASES OF INTERNAL COMBUSTION ENGINES |
| FR2470383A1 (en) * | 1979-11-23 | 1981-05-29 | Renault | Probe for detecting oxygen in engine exhaust gas - has gold conductor connecting two electrolytic circuits in series |
| FR2472187A1 (en) * | 1979-12-18 | 1981-06-26 | Nissan Motor | ELEMENT DETECTING SOLID ELECTROLYTE OXYGEM IN LAMINATED STRUCTURE AND DEVICE USING THE SAME |
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