US3909385A - Oxygen sensor for automotive use - Google Patents

Oxygen sensor for automotive use Download PDF

Info

Publication number
US3909385A
US3909385A US394431A US39443173A US3909385A US 3909385 A US3909385 A US 3909385A US 394431 A US394431 A US 394431A US 39443173 A US39443173 A US 39443173A US 3909385 A US3909385 A US 3909385A
Authority
US
United States
Prior art keywords
wafer
oxygen sensor
housing portion
accordance
oxygen
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.)
Expired - Lifetime
Application number
US394431A
Other languages
English (en)
Inventor
David H Spielberg
Roy E Svacha
Kenneth R Janowski
George L Hervert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bank of Nova Scotia
Wolverine Tube Inc
Universal Oil Products Co
Original Assignee
Universal Oil Products Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Universal Oil Products Co filed Critical Universal Oil Products Co
Priority to US394431A priority Critical patent/US3909385A/en
Priority to DE2441678A priority patent/DE2441678A1/de
Priority to IT52838/74A priority patent/IT1021620B/it
Priority to FR7429832A priority patent/FR2242564B1/fr
Priority to JP49100594A priority patent/JPS5077090A/ja
Application granted granted Critical
Publication of US3909385A publication Critical patent/US3909385A/en
Assigned to BANK OF NOVA SCOTIA, THE reassignment BANK OF NOVA SCOTIA, THE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: WOLVERINE ACQUISITION CORP. A CORP. OF DE
Assigned to WOLVERINE ACQUISITION CORP., A DE CORP reassignment WOLVERINE ACQUISITION CORP., A DE CORP ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: WOLVERINE TUBE, INC.,
Assigned to WOLVERINE TUBE, INC., A CORP. OF AL reassignment WOLVERINE TUBE, INC., A CORP. OF AL CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: WOLVERINE ACQUISITION CORP.
Assigned to WOLVERINE TUBE, INC., AN AL CORP. reassignment WOLVERINE TUBE, INC., AN AL CORP. RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: BANK OF NOVA SCOTIA, THE
Assigned to SECURITY PACIFIC NATIONAL BANK reassignment SECURITY PACIFIC NATIONAL BANK SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WOLVERINE TUBE, INC.
Anticipated expiration legal-status Critical
Assigned to WOLVERINE TUBE, INC. reassignment WOLVERINE TUBE, INC. RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: BANK OF AMERICA TRUST AND SAVINGS ASSOCIATION, SUCCESSOR BY MERGER TO SECURITY PACIFIC NATIONAL BANK
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • G01N27/4071—Cells and probes with solid electrolytes for investigating or analysing gases using sensor elements of laminated structure
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D41/00—Electrical control of supply of combustible mixture or its constituents
    • F02D41/02—Circuit arrangements for generating control signals
    • F02D41/14—Introducing closed-loop corrections
    • F02D41/1438—Introducing closed-loop corrections using means for determining characteristics of the combustion gases; Sensors therefor
    • F02D41/1444—Introducing closed-loop corrections using means for determining characteristics of the combustion gases; Sensors therefor characterised by the characteristics of the combustion gases
    • F02D41/1454—Introducing closed-loop corrections using means for determining characteristics of the combustion gases; Sensors therefor characterised by the characteristics of the combustion gases the characteristics being an oxygen content or concentration or the air-fuel ratio
    • 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
    • G01N27/4075—Composition or fabrication of the electrodes and coatings thereon, e.g. catalysts
    • G01N27/4076—Reference electrodes or reference mixtures

Definitions

  • ABSTRACT Oxygen sensor for automotive use utilizes a disc shaped wafer of a solid electrolyte, preferably zirconia stabilized with MgO, which is extremely resistant to abrasion and the effects of repeated temperature excursions over long periods of use.
  • the housing comprises a hollow metal tube stepped at one end to support the electrolyte wafer and hermetically sealed to the wafer by a metal oxide frit which is melted in a vauum.
  • the electrodes comprise a thick film Ag Pd alloy which is bonded to the wafer by means of a glass forming binder.
  • One way to accomplish this goal is by running the engine rich and passing the exhaust gases through a first catalyst to reduce the nitrogen oxides and then adding secondary air to the exhaust gases and passing them through an oxidizing catalyst to convert the carbon monoxide and hydrocarbons to carbon dioxide and water.
  • the dual catalyst system is not only relatively costly in the equipment which it requires but is also quite wasteful of fuel. It has been found that a single catalyst is capable of controlling all three exhaust components if the engine can be operated with an air/fuel ratio which is stoichiometric or just on the rich side of stoichiometric. Unfortunately, the carburetors and fuel injection systems which are presently available cannot continually deliver a precise air/fuel ratio to the engine under varying operating conditions.
  • Solid electrolyte oxygen sensing cells which produce a voltage indicative of the difference in oxygen partial pressures between the sampling side of the cell and the reference gas (usually air) side of the cell have been used for many years.
  • various attempts have been made to adapt these units to automotive use since the cells have the property of undergoing a very large change in voltage output when the air/fuel ratio of the exhaust gases they contact moves from one side of stoichiometry to the other.
  • an oxygen sensor in combination with a closed loop control systern it is possible to control the fuel or air input to the engine or to the catalytic converter so that the air/fuel ratio can be precisely controlled.
  • a sensor should be able to withstand continual temperature changes from as low as -50F to l500F with occasional temperature spikes of an even greater temperature.
  • the sensing element and seals should have sufficient thermal shock resistance to withstand heating from -50F to 700F in about 1 second.
  • the sensor should be resistant to poisoning by lead, sulfur and phosphorus, should have a thermal expansion coefficient capable of permitting its seals to withstand continual temperature cycling for 25,000 miles or more of engine operation, and should be impervious to prevent gas leakage from its sampling side to its reference side.
  • it should respond very quickly to produce a voltage output which can be used to produce almost instantaneous corrections in the engine air/fuel ratio.
  • it should be low in cost, compact, vibration resistant, and easy to mount and remove.
  • oxygen sensors which are suitable for the latter use are not suitable for automotive use.
  • Most prior art oxygen sensors utilize heating elements to maintain the solid electrolyte cell at a sufficiently high temperature (over about 750F) for it to produce a voltage.
  • Such sensors are not only bulky but also expensive.
  • a wafer type solid electrolyte oxygen sensing cell is disclosed in East German Pat. No. 21,673, it is quite unlikely that the spring biased seal provided for the wafer to isolate the outer sampling side from the inner reference side would be effective to prevent leakage of gases from the sampling side to the reference side if the sensor were used in an automotive exhaust system.
  • the usual form of the solid electrolyte for automotive type oxygen sensors has been thimble shaped.
  • the material most commonly used for the solid electrolyte is zirconium dioxide mixed with a stabilizing metal oxide such as that of calcium or yttrium to provide a solid solution of ionically conductive oxides, as discussed in copending application Ser. No. 159,936, now U.S. Pat. No. 3,768,259, assigned to a common assignee.
  • U.S. Pat. No. 3,365,317 discloses a stabilized composition of zirconia and magnesium oxide, the composition is not disclosed for use as a solid electrolyte, but, rather, as a material for an extrusion die.
  • U.S. Pat. No. 3,503,809 mentions magnesium oxide as one of several materials which could be used to stabilize a solid electrolyte for use in a fuel cell but seems to rely on calcium oxide as the stabilizing agent.
  • the sensor comprises a housing portion formed of a short length of metal tubing and an externally threaded metal body portion to which the tubing is welded.
  • the tubular housing member is of Series 409 stainless steel or other high temperature, highly corrosion resistant material.
  • the threaded portion may be of the same material or another, such as Series 304 stainless.
  • the inner end of the sensor housing (the sensing end which extends into the exhaust path) is formed with a shelf or shoulder so as to provide a recessed seat for a disc shaped wafer of solid electrolyte.
  • the shelf can be formed by boring out a short axial portion of the inside of the tubing or by expanding the end of the tubing to a greater diameter than the remainder of the tubing.
  • the threads on the body portion are preferably male pipe threads, similar to those on a spark plug, which are adapted to engage female threads formed in one of the portions of the engine exhaust path.
  • a wafer of stabilized zirconia which performs as a solid electrolyte.
  • Yttria and calcia stabilized zirconia wafers have excellent electrical properties, such as a relatively low resistance, and have been used as solid electrolytes. However, they appear to be vulnerable to wear from particles present in the exhaust stream and to cracking caused by the extreme thermal stresses during the startup of an automotive engine.
  • zirconia stabilized with a small amount of magnesia (about 3%) has been used as an extrusion die material (U.S. Pat. No.
  • a red hot piece can be plunged into ice water without cracking.
  • Wafers of magnesia stabilized zirconia produced by the Zircoa Division of Corhart Refractories Company of Solon, Ohio, as Zircoa Composition No. 1027 have been hermetically sealed to a preoxidized Series 409 stainless steel tubular housing by means of a green, semi-glossy frit material (No. SL- 14230C manufactured by Thomas C. Thompson Company and sold by Chicago Vitreous Corporation of Cicero, Illinois) containing a mixture of CrO TiO and SiO
  • the tube is preferably dipped over its entire length to provide as much protection as possible against corrosion.
  • the tube, with the zirconia wafer in its end recess, is then fired in a vacuum for minutes at I900F to fuse the sealing material to the tube and to the wafer and to degas it.
  • the degassed seal is then subjected to atmospheric pressureat temperature to form a void free seal.
  • Subjection of the aforementioned wafer, tube and sealing material to road testing has indicated that the integrity of the seal can be maintained for more than 15,000 miles when only the wafer end of the tube is coated.
  • the seal life should be substantially higher when the entire length of the tube is coated and protected against corrosion, such as might be caused by road salt entering the reference end of the sensor.
  • the cell EMF is measured between a pair of electrodes attached to its opposite surfaces.
  • a suitable electrode material appears to be a paste comprising an alloy of about 56.4 parts of silver powder and 14.] parts of palladium black in a glass forming binder which is sold by Electro Materials Corporation of America, Mamoroneck, N.Y., as Firon No. 618.
  • the electrode material is first applied to the center of the reference side of the electrolyte wafer and fired for l hour at l700F.
  • a lead wire is then attached to the wafer with additional electrode material and the composite is then fired at I700F for 15 minutes to firmly affix the lead wire.
  • sampling side electrode which is fired at the same time as the reference electrode, is annular in shape and bridges the wafer and the outer end edge of the tubular housing.
  • the frit coating is removed from the end of the housing before the electrode is applied to permit a good electrical Contact with the housing so that the sampling electrode will be electrically connected to the housing, which serves as one of its electrical terminals.
  • FIG. 1 is a side sectional view of the improved oxygen sensor
  • FIG. 2 is an end view of the oxygen sensor of FIG. I.
  • FIG. 3 is a schematic diagram showing two possible arrangements of an oxygen sensor relative to an engine and a catalytic converter.
  • the improved oxygen sensor shown generally at 10, has a tubular metal housing 12 welded to body member 14 by weld bead 16. Pipe threads 18 on the outside of body member 14 permit the sensor to be threaded into the side of a member in the exhaust path of an engine in the same manner as a spark plug.
  • the recess 28 is shown as being formed by an outwardly extending flanged portion 32 of the housing, the recess could also be formed in the end ofa cylindrical tube by decreasing the tube wall thickness by removing a portion of the internal wall.
  • the oxygen sensor 10 Since the oxygen sensor 10 must withstand the rugged, changing environment of an automotive exhaust system, it is essential that the electrolyte wafer 22 be able to remain stable, non-porous and in hermetically sealed contact with the metal housing 12 for long periods of time. We have found that a durable hermetic seal is possible when a particular combination of materials and structural configurations are used in the manufacture of the improved sensor.
  • a housing made of Series 409 stainless steel has been found to provide the degree of oxidation resistance required and to provide a durable hermetic seal with a MgO stabilized zirconia wafer when the housing and wafer are joined to each other by a layer 36 of the previously identified metal oxide frit containing CrO TiO and SiO
  • the frit should have the property of wetting both the surface of the zirconia wafer and the pre-oxidized stainless steel housing. It should also be of a non-electrically conductive material which is non-reactive with the exhaust gases and also non-reactive with the electrodes.
  • the melting point of the frit should be below that of the stainless and above that of the engine exhaust gases, e.g., in the range of I700 2200F.
  • the radial space between the wafer and housing is maintained to a close tolerance such as 0.003 inch.
  • the previously identified MgO stabilized zirconia composition No. 1027 has been found to offer superior thermal shock resistance compared to zirconia compositions stabilized with Ygog or CaO, for example.
  • the electrical properties, however, of MgO stabilized zirconia are slightly inferior.
  • the resistance of a Y O stabilized zirconia cell was found to be about an order of magnitude lower than the resistance of the MgO stabilized zirconia cell. Since the resistance of the electrolyte is a function of the degree of stabilization, it is possible other magnesia concentrations might provide more favorable electrical characteristics, possibly to the detriment of the thermal shock behavior.
  • the 1027 composition gives a combination of electrical and thermal shock characteristics which results in a usable material for the electrolyte.
  • the electrode 46 comprises an annular ring of the aforementioned silver-palladium paste which is fired on at a temperature of about l700F. for minutes in air.
  • the reference side electrode 50 is preferably applied and fired as a circular spot in two steps and is preferably of the same silver-palladium alloy as electrode 46.
  • an electrode lead wire 52 is attached to it by the second layer 50b of the electrode.
  • the lead wire 52 is preferably spot welded at 54 to an inner metal tubing ferrule 56.
  • the tubular member 56 comprises a rigid terminal to which electrical connections may readily be made, thus protecting the delicate lead wire 52.
  • the tubular ferrule 56 is electrically insulated from the body member 14 by an alumina insulator sleeve 58.
  • the sleeve 58 is affixed to the body 14 and the ferrule 56 by an electrically insulating ceramic cement 60, such as that sold by Sauereisen Cements Co., Pittsburgh, Pa., under the name of Electrotemp Cement No. 8.
  • the dimensions of the various elements comprising sensor 10 are preferably selected to maximize the ability of the device to instantly respond to changes in the oxygen concentration of exhaust gases being sensed so that the fuel and/or air input 62 to an engine 64 (FIG. 3) can be automatically and continually adjusted by an air/fuel ratio controller 66 connected between the oxygen sensor 10 and the engine input 62.
  • the sensor 10 is shown in its preferred position in full lines downstream of an engine 64 but it could also be positioned immediately downstream of the converter 70 as shown in dotted lines at 10, although such position would cause it to be brought to operating temperature more slowly.
  • An oxygen sensor adapted for use in an automotive exhaust stream wherein it must be repeatedly subjected to rapidly changing temperatures from ambient to as high as 1700F.
  • a corrosion resistant tubular metal housing portion comprising a corrosion resistant tubular metal housing portion; coupling means on a body portion integral with the housing portion for mounting the sensor to complementary coupling means in the engine exhaust path so that the exterior surface of the housing portion can be positioned in the said exhaust path to be contacted by the exhaust stream and the internal surface of the housing portion can be contacted by a reference oxygen source; a wafer of oxygen sensitive solid electrolyte material positioned in a plane at right angles to the axis of the tubular housing portion, said wafer being mounted in a recess in said one end of the housing portion so as to be mechanically restrained against inward axial movement by a ledge portion formed in said housing portion, said wafer closing the end of said tubular housing portion and having opposed outer and inner sampling gas and reference gas contacting surfaces; hermetic fastening and sealing means comprising a metal oxide frit fired
  • each of said pair of electrodes covers only a portion of the surface of the wafer.
  • said means which includes a lead wire portion further includes a hollow metal tube to which said lead wire portion is welded internally of said body member, said hollow metal tube extendingthrough and beyond said insulation member so as to provide a rigid, external electrical connection point.
  • An oxygen sensor in accordance with claim 4 wherein said insulation member is bonded to said body member and to said hollow metal tube by a high temperature electrically insulating cement.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Measuring Oxygen Concentration In Cells (AREA)
US394431A 1973-09-04 1973-09-04 Oxygen sensor for automotive use Expired - Lifetime US3909385A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US394431A US3909385A (en) 1973-09-04 1973-09-04 Oxygen sensor for automotive use
DE2441678A DE2441678A1 (de) 1973-09-04 1974-08-30 Sauerstoffsensor fuer das abgassystem einer brennkraftmaschine
IT52838/74A IT1021620B (it) 1973-09-04 1974-09-02 Dispositivo di verifica continua dei rapporti aria combustibile per motori a scoppio
FR7429832A FR2242564B1 (enrdf_load_stackoverflow) 1973-09-04 1974-09-02
JP49100594A JPS5077090A (enrdf_load_stackoverflow) 1973-09-04 1974-09-03

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US394431A US3909385A (en) 1973-09-04 1973-09-04 Oxygen sensor for automotive use

Publications (1)

Publication Number Publication Date
US3909385A true US3909385A (en) 1975-09-30

Family

ID=23558925

Family Applications (1)

Application Number Title Priority Date Filing Date
US394431A Expired - Lifetime US3909385A (en) 1973-09-04 1973-09-04 Oxygen sensor for automotive use

Country Status (5)

Country Link
US (1) US3909385A (enrdf_load_stackoverflow)
JP (1) JPS5077090A (enrdf_load_stackoverflow)
DE (1) DE2441678A1 (enrdf_load_stackoverflow)
FR (1) FR2242564B1 (enrdf_load_stackoverflow)
IT (1) IT1021620B (enrdf_load_stackoverflow)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4040930A (en) * 1976-02-05 1977-08-09 Uop Inc. Oxygen sensor
US4061117A (en) * 1975-03-31 1977-12-06 Nissan Motor Co., Ltd. Method of controlling air-fuel mixture in internal combustion engine and a system therefor
US4127463A (en) * 1976-07-17 1978-11-28 Brown, Boveri & Cie Ag Probe for an electrochemical oxygen measurement pickup
US4157948A (en) * 1977-03-09 1979-06-12 Robert Bosch Gmbh Oxygen sensor to determine the oxygen content in gases
US4208266A (en) * 1978-10-27 1980-06-17 General Motors Corporation Exhaust gas oxygen sensor
US4214967A (en) * 1977-11-08 1980-07-29 Westinghouse Electric Corp. Technique for reducing solid electrolyte cell drift
WO1980001840A1 (en) * 1979-03-03 1980-09-04 Jenaer Glaswerk Schott & Gen Probe for measuring the partial pressure of oxygen in gases
US4247380A (en) * 1975-09-25 1981-01-27 Westinghouse Electric Corp. Technique for in situ calibration of a gas detector
US4310402A (en) * 1979-11-13 1982-01-12 Westinghouse Electric Corp. Gas tight sealant for zirconia sensors
EP0330775A1 (en) * 1988-03-03 1989-09-06 The Carborundum Company Oxygen-sensing element
US4956072A (en) * 1987-11-26 1990-09-11 Ngk Spark Plug Co., Ltd. Oxygen sensor
WO1993021519A1 (de) * 1992-04-22 1993-10-28 Leszlauer Zoltan Verfahren zur herstellung von elektrochemischen fühlern, sowie elektrochemischer fühler
EP0624791A1 (en) * 1993-05-11 1994-11-17 General Motors Corporation Exhaust sensor with tubular shell
US5472580A (en) * 1994-06-09 1995-12-05 General Motors Corporation Catalytic converter diagnostic sensor
US5490412A (en) * 1993-05-11 1996-02-13 General Motors Corporation Exhaust sensor with removable electrical connector
US6592731B1 (en) 1999-09-23 2003-07-15 Ceramphysics, Inc. Amperometric oxygen sensor
US6824661B2 (en) 1999-09-23 2004-11-30 Ceramphysics, Inc. Combined oxygen and NOx sensor
US10330635B2 (en) * 2014-06-30 2019-06-25 Denso Corporation Gas sensor including sensor element, housing and element cover

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1491429A (en) * 1975-03-27 1977-11-09 Leeds & Northrup Co Galvanic cell
IT1173894B (it) * 1984-03-20 1987-06-24 Alfa Romeo Auto Spa Impianto di scarico per un motore a c.i. dotato di una sonda per il rilievo dell'ossigeno nei gas di scarico
DE3544161A1 (de) * 1985-12-13 1987-06-19 Interatom Sonde mit auswechselbarem messeinsatz

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3400054A (en) * 1966-03-15 1968-09-03 Westinghouse Electric Corp Electrochemical method for separating o2 from a gas; generating electricity; measuring o2 partial pressure; and fuel cell
US3454486A (en) * 1966-04-12 1969-07-08 Gkn Group Services Ltd Apparatus for measurement of oxygen potential of gases at high temperatures
US3738341A (en) * 1969-03-22 1973-06-12 Philips Corp Device for controlling the air-fuel ratio {80 {11 in a combustion engine
US3768259A (en) * 1971-07-06 1973-10-30 Universal Oil Prod Co Control for an engine system
US3791954A (en) * 1970-08-06 1974-02-12 Ngk Insulators Ltd Device for measuring oxygen concentration of molten metal
US3819500A (en) * 1972-02-21 1974-06-25 Philips Corp Measuring cell for determining oxygen concentrations in a gas mixture
US3841987A (en) * 1972-03-10 1974-10-15 Bosch Gmbh Robert Electro-chemical oxygen sensor,particularly for use in the exhaust system of internal combustion engines

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3628859A (en) * 1969-12-22 1971-12-21 Xerox Corp Imaging machine improvement

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3400054A (en) * 1966-03-15 1968-09-03 Westinghouse Electric Corp Electrochemical method for separating o2 from a gas; generating electricity; measuring o2 partial pressure; and fuel cell
US3454486A (en) * 1966-04-12 1969-07-08 Gkn Group Services Ltd Apparatus for measurement of oxygen potential of gases at high temperatures
US3738341A (en) * 1969-03-22 1973-06-12 Philips Corp Device for controlling the air-fuel ratio {80 {11 in a combustion engine
US3791954A (en) * 1970-08-06 1974-02-12 Ngk Insulators Ltd Device for measuring oxygen concentration of molten metal
US3768259A (en) * 1971-07-06 1973-10-30 Universal Oil Prod Co Control for an engine system
US3819500A (en) * 1972-02-21 1974-06-25 Philips Corp Measuring cell for determining oxygen concentrations in a gas mixture
US3841987A (en) * 1972-03-10 1974-10-15 Bosch Gmbh Robert Electro-chemical oxygen sensor,particularly for use in the exhaust system of internal combustion engines

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4061117A (en) * 1975-03-31 1977-12-06 Nissan Motor Co., Ltd. Method of controlling air-fuel mixture in internal combustion engine and a system therefor
US4247380A (en) * 1975-09-25 1981-01-27 Westinghouse Electric Corp. Technique for in situ calibration of a gas detector
US4040930A (en) * 1976-02-05 1977-08-09 Uop Inc. Oxygen sensor
US4127463A (en) * 1976-07-17 1978-11-28 Brown, Boveri & Cie Ag Probe for an electrochemical oxygen measurement pickup
US4157948A (en) * 1977-03-09 1979-06-12 Robert Bosch Gmbh Oxygen sensor to determine the oxygen content in gases
US4214967A (en) * 1977-11-08 1980-07-29 Westinghouse Electric Corp. Technique for reducing solid electrolyte cell drift
US4208266A (en) * 1978-10-27 1980-06-17 General Motors Corporation Exhaust gas oxygen sensor
FR2451030A1 (fr) * 1979-03-03 1980-10-03 Jenaer Glaswerk Schott & Gen Palpeur pour determiner la pression partielle de l'oxygene dans des gaz
WO1980001840A1 (en) * 1979-03-03 1980-09-04 Jenaer Glaswerk Schott & Gen Probe for measuring the partial pressure of oxygen in gases
US4310402A (en) * 1979-11-13 1982-01-12 Westinghouse Electric Corp. Gas tight sealant for zirconia sensors
US4956072A (en) * 1987-11-26 1990-09-11 Ngk Spark Plug Co., Ltd. Oxygen sensor
EP0330775A1 (en) * 1988-03-03 1989-09-06 The Carborundum Company Oxygen-sensing element
WO1993021519A1 (de) * 1992-04-22 1993-10-28 Leszlauer Zoltan Verfahren zur herstellung von elektrochemischen fühlern, sowie elektrochemischer fühler
EP0624791A1 (en) * 1993-05-11 1994-11-17 General Motors Corporation Exhaust sensor with tubular shell
US5490412A (en) * 1993-05-11 1996-02-13 General Motors Corporation Exhaust sensor with removable electrical connector
US5472580A (en) * 1994-06-09 1995-12-05 General Motors Corporation Catalytic converter diagnostic sensor
US6592731B1 (en) 1999-09-23 2003-07-15 Ceramphysics, Inc. Amperometric oxygen sensor
US6824661B2 (en) 1999-09-23 2004-11-30 Ceramphysics, Inc. Combined oxygen and NOx sensor
US10330635B2 (en) * 2014-06-30 2019-06-25 Denso Corporation Gas sensor including sensor element, housing and element cover

Also Published As

Publication number Publication date
IT1021620B (it) 1978-02-20
JPS5077090A (enrdf_load_stackoverflow) 1975-06-24
FR2242564B1 (enrdf_load_stackoverflow) 1977-10-28
DE2441678A1 (de) 1975-03-06
FR2242564A1 (enrdf_load_stackoverflow) 1975-03-28

Similar Documents

Publication Publication Date Title
US3909385A (en) Oxygen sensor for automotive use
JP2708915B2 (ja) ガス検出センサ
US4559126A (en) Electrochemical device
US7156967B2 (en) Gas sensor element containing a getter
US4121988A (en) Oxygen sensor
JP5638984B2 (ja) ガスセンサ
US5670032A (en) Electro-chemical measuring sensor with a potential-free sensor element and method for producing it
JPS58166252A (ja) セラミツクヒ−タ付酸素センサ素子及びその製造方法
US4212720A (en) Electrically heated electrochemical sensor construction, particularly to determine oxygen concentration in exhaust gases from combustion engines
JPS5924382B2 (ja) 主として内燃機関の廃ガス中の酸素濃度を測定するセンサの製造法
US4121989A (en) Method of making oxygen sensor
GB2031156A (en) Solid electrolyte sensors for determining the oxygen content of gases
US3940327A (en) Oxygen sensing device
US4123344A (en) Two fire ceramic sealed oxygen sensing device and method of forming same
US4049524A (en) Oxygen sensor with noncatalytic electrode
US4152232A (en) Oxygen concentration detector
US4327054A (en) Gas sensor assembly
US4223293A (en) Terminal pin arrangement for an exhaust gas sensor
US5435901A (en) Electrochemical measuring sensor
KR100327079B1 (ko) 무전위방식으로센서소자가부착된전기화학센서
US5662786A (en) Electrochemical sensor
US10345257B2 (en) Gas sensor
JPS637342B2 (enrdf_load_stackoverflow)
CN111521661A (zh) 一种参考泵电流式氧传感器
JPH0679007B2 (ja) 固体基準物質を備えたセンサプローブ

Legal Events

Date Code Title Description
AS Assignment

Owner name: BANK OF NOVA SCOTIA, THE, 44 KING STREET, WEST, TO

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:WOLVERINE ACQUISITION CORP. A CORP. OF DE;REEL/FRAME:004696/0897

Effective date: 19870313

AS Assignment

Owner name: WOLVERINE ACQUISITION CORP., CORPORATION TRUST CEN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:WOLVERINE TUBE, INC.,;REEL/FRAME:004728/0083

Effective date: 19870318

Owner name: WOLVERINE ACQUISITION CORP., A DE CORP,DELAWARE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:WOLVERINE TUBE, INC.,;REEL/FRAME:004728/0083

Effective date: 19870318

AS Assignment

Owner name: WOLVERINE TUBE, INC., A CORP. OF AL

Free format text: CHANGE OF NAME;ASSIGNOR:WOLVERINE ACQUISITION CORP.;REEL/FRAME:004827/0237

Effective date: 19870626

Owner name: WOLVERINE TUBE, INC., A CORP. OF AL,ALABAMA

Free format text: CHANGE OF NAME;ASSIGNOR:WOLVERINE ACQUISITION CORP.;REEL/FRAME:004827/0237

Effective date: 19870626

AS Assignment

Owner name: WOLVERINE TUBE, INC., 2100 MARKET STREET, N.E., P.

Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:BANK OF NOVA SCOTIA, THE;REEL/FRAME:005639/0755

Effective date: 19910123

AS Assignment

Owner name: SECURITY PACIFIC NATIONAL BANK

Free format text: SECURITY INTEREST;ASSIGNOR:WOLVERINE TUBE, INC.;REEL/FRAME:005648/0195

Effective date: 19910124

AS Assignment

Owner name: WOLVERINE TUBE, INC., ALABAMA

Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:BANK OF AMERICA TRUST AND SAVINGS ASSOCIATION, SUCCESSOR BY MERGER TO SECURITY PACIFIC NATIONAL BANK;REEL/FRAME:006401/0575

Effective date: 19930108