CN101482536B - Automatic oxygenation type solid-state reference oxygen sensor - Google Patents
Automatic oxygenation type solid-state reference oxygen sensor Download PDFInfo
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- CN101482536B CN101482536B CN 200910046044 CN200910046044A CN101482536B CN 101482536 B CN101482536 B CN 101482536B CN 200910046044 CN200910046044 CN 200910046044 CN 200910046044 A CN200910046044 A CN 200910046044A CN 101482536 B CN101482536 B CN 101482536B
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Abstract
An automatic oxygenation solid reference oxygen sensor comprises an oxygen measurement unit, a solid reference unit and an oxygenization unit wherein the solid reference oxygen sensor is formed by laminating the oxygen measurement unit, the solid reference unit and the oxygenization unit in turn. A porous platinum measurement electrode, a measurement electrode protection layer are coated and sintered in turn on one surface of a ytrria stable zirconia ceramics and a composite reference electrode, a solid reference layer, an oxygenization electrode 1, an oxygenization electrolyte layer and an oxygenization electrode 2 are coated and sintered in turn on another surface of the ytrria stable zirconia ceramics to form the oxygenation solid reference oxygen sensor. On the basis of the plate type ytrria stable zirconia oxygen-sensing probe, the traditional air reference unit is replaced by the solid reference layer and at the same time the oxygen concentration is stably measured using the oxygen concentration in the direct current field oxygenization unit constant solid reference layer. The oxygen sensor has features of minitype, stability and simple structure.
Description
Technical field
The invention belongs to the gas sensor technical field, the solid reference type membrane type oxygen that is specifically related to automatic oxygenation passes the device technology of preparing.
Background technology
Lambda sensor is a kind of gas sensor that is specifically designed to the acquisition environment oxygen content, and common kind comprises concentration cell type, resistance-type and electrochemical pump formula lambda sensor.Zirconia concentration cell type lambda sensor has the advantages such as measurement range is wide, good stability, and tubular type Zirconium oxide oxygen sensor pottery probe has been widely used in fields such as deciding oxygen in car engine electronic control fuel injection system, Industrial Stoves burning control, the food production at present.
In concentration cell type lambda sensor, its core component is a tubular type yttria-stabilized zirconia pottery probe, and the inside and outside wall of ceramic pipe all applies one deck porous platinum electrode layer.Ceramic pipe places needs testing environment atmosphere, and passes into the reference air in the pipe, produces the oxygen electromotive force because managing inside and outside oxygen concentration difference, and then is used for the detection of environmental oxygen concentration.Along with lambda sensor gradually the applying of automobile, motorcycle fuel oil control system and other industrial circle, the lambda sensor Miniaturization Design has become an important content of new product development.Some small-sized chip oxygen sensor products obtain practical application at auto industry field at present, but because the existence of reference air hose, still there are severely restricts in the miniaturization of chip oxygen sensor.
In order further to dwindle the size of lambda sensor spare, adopt in recent years the lambda sensor development research of solid reference technology to increase gradually.Owing in the solid reference substances such as metal-metallic oxide potpourri, cerium oxide composite oxides, having certain oxygen concentration, therefore utilize the reference air in their replacement lambda sensors, can carry out the detection of ambient oxygen equally.Study at present the more In/In that comprises
2O
3, Sn/SnO
2, Pb/PbO, Pd/PdO
2, CeO
2ZrO
2Solid reference type lambda sensor etc.Yet in the oxygen content detection process, the oxygen in the solid reference substance constantly is consumed, and causes the detection signal of lambda sensor constantly to change in time, finally causes normally oxygen determination.Therefore, if solid reference type lambda sensor is worked all the time, just must take measures to continue to replenish the oxygen that is consumed in the solid reference substance, remain that oxygen concentration is constant, and then reach the purpose of continuous oxygen measuring.
Summary of the invention
But the object of the present invention is to provide a kind of solid reference matrix formula lambda sensor of automatic oxygenation, be stacked successively and form by oxygen determination unit, solid reference cell, oxygenation unit respectively.Wherein the oxygenation unit carries out automatic oxygenation to the solid reference cell and makes it the saturated oxygen concentration that keeps constant, can be worked continually and steadily in the oxygen determination unit.
In the present invention, the core component of oxygen determination unit is the yttria-stabilized zirconia potsherd, and a surface of potsherd applies porous platinum electrode as potential electrode, and its outside applies porous protective layer with the protection electrode.Another surface metallization platinum-bismuth oxide composite oxides of potsherd are as contrast electrode.
When the compound contrast electrode of preparation, at first prepare metal platinum-bismuth oxide composite oxides electrode slurry.The purpose of introducing the bismuth oxide composite oxides in contrast electrode is to reduce the oxygen determination working temperature of lambda sensor.Adopt coprecipitation or sintering process to prepare the bismuth oxide composite oxide powder, its bismuth oxide molar content is that 65-90%, yttria are that 0-35%, baryta are 0-15%, and the powder granule degree is the 0.5-2 micron.Bismuth oxide composite oxide powder and metal platinum powder, high-temperature agglomerant, low temperature bonding agent and solvent are mixed and made into compound reference electrode pastes in proportion, and its quality percentage composition is respectively 10-25%, 5-15%, 10-25%, 2-8%, 40-70%.Wherein the chemical composition of high-temperature agglomerant (quality percentage composition) is respectively the glass dust of sodium oxide molybdena 6-20%, diboron trioxide 20-35%, calcium oxide 5-10%, alundum (Al2O3) 5-10%, silicon dioxide 35-60%; In the optional methylcellulose of low temperature bonding agent, ethyl cellulose, the gum arabic one or more; In the optional water of solvent, ethanol, the terpinol one or more.Prepared electrode slurry can obtain the compound contrast electrode layer that thickness is the 30-100 micron at 750-1000 ℃ of lower sintering 5-60 minute after serigraphy and drying.Adopt the chip oxygen sensor minimum operating temperature of compound contrast electrode can be down to 300-400 ℃.
Adopt the method for serigraphy to apply the surperficial coating solid reference layer of compound contrast electrode at oxygen determination zirconia ceramics sheet, its objective is as the oxygen determination element provides constant reference oxygen concentration.Solid reference layer adopt granularity be the cerium oxide and zirconium oxide solid solution of 0.5-2 micron as solid reference medium, its chemical composition (molar content) is ceria 20-75%, zirconium dioxide 25-80%.With the reference slurry that cerium oxide and zirconium oxide reference medium powder and high-temperature agglomerant, low temperature bonding agent and solvent are mixed with in proportion, its quality percentage composition is respectively 10-25%, 10-25%, 2-8%, 40-70%; Wherein the chemical composition of high-temperature agglomerant (quality percentage composition) is respectively the glass dust of sodium oxide molybdena 6-20%, diboron trioxide 20-35%, calcium oxide 5-10%, alundum (Al2O3) 5-10%, silicon dioxide 35-60%; In the optional methylcellulose of low temperature bonding agent, ethyl cellulose, the gum arabic one or more; In the optional water of solvent, ethanol, the terpinol one or more.Prepared electrode slurry can obtain the solid reference layer that thickness is the 100-500 micron at 750-1000 ℃ of lower sintering 10-60 minute after serigraphy.
In the present invention, the oxygenation unit can be comprised of oxygenation dielectric substrate and oxygenation electrode one, oxygenation electrode two.Apply porous platinum electrode as oxygenation electrode one on solid reference layer surface, adopt again silk screen print method to apply the oxygenation dielectric substrate on the surface of oxygenation electrode one.The oxygenation dielectric substrate adopts and is formed through serigraphy, sintering by the formulated oxygenation electrolyte slurry of stabilized with yttrium oxide cerium oxide and zirconium oxide ceramic powder, high-temperature agglomerant, low temperature bonding agent and solvent, and its quality percentage composition is respectively 20-40%, 5-15%, 2-8%, 40-70%; Wherein the chemical composition of yttria-stabilized zirconia ceramic powder (molar content) is yttria 0-10%, ceria 0-35%, zirconium dioxide 65-95%, and the powder granule degree is the 0.5-2 micron.The chemical composition of high-temperature agglomerant (quality percentage composition) is respectively the glass dust of sodium oxide molybdena 6-20%, diboron trioxide 20-35%, calcium oxide 5-10%, alundum (Al2O3) 5-10%, silicon dioxide 35-60%; In the optional methylcellulose of low temperature bonding agent, ethyl cellulose, the gum arabic one or more; In the optional water of solvent, ethanol, the terpinol one or more.Prepared electrode slurry can obtain the oxygenation dielectric substrate that thickness is the 100-500 micron at 750-1000 ℃ of lower sintering 5-60 minute after serigraphy.Apply porous platinum electrode as oxygenation electrode two on oxygenation dielectric substrate surface, namely consist of the oxygenation unit.
In the present invention, the oxygenation unit is responsible for enough oxygen being provided and making it to remain on constant state of saturation to solid reference layer.In the oxygen determination process, take oxygenation electrode one as anode, the oxygenation electrode is negative electrode, the oxygenation dielectric substrate is applied the DC electric field that intensity is 2.5-10 volt/millimeter, this moment DC electric field with the oxygen in the environment by the pumping of oxygenation dielectric substrate to solid reference layer, make solid reference layer remain constant saturated oxygen concentration, and provide stable oxygen concentration reference for the oxygen determination unit.In the oxygenation process, the oxygenation dielectric substrate plays a part evenly, the Stable Oxygen electric current.
In the present invention, can not apply the oxygenation unit on solid reference cell surface yet, only apply oxygenation electrode one on solid reference layer surface, and take compound contrast electrode as anode, oxygenation electrode one is negative electrode, directly solid reference layer is applied the DC electric field that intensity is 2.5-10 volt/millimeter, oxygen in the boot environment directly diffuses into solid reference layer, makes solid reference layer remain constant saturated oxygen concentration, and provides stable oxygen concentration reference for the oxygen determination unit.
Oxygenation type solid-state reference oxygen sensor technology of preparing proposed by the invention can realize the filming design of oxygen sensor ceramic probe, to satisfy the requirement of lambda sensor product miniaturization.
Description of drawings
Fig. 1 is the automatic oxygenation type solid-state reference oxygen sensor STRUCTURE DECOMPOSITION figure of the embodiment of the invention.
Fig. 2 is the automatic oxygenation type solid-state reference oxygen sensor schematic cross section of the embodiment of the invention.
Embodiment
See also Fig. 1; the automatic oxygenation type solid-state reference oxygen sensor of the embodiment of the invention comprises oxygen determination unit 1, solid reference cell 2,3 three parts in oxygenation unit, is comprised of yttria-stabilized zirconia potsherd 4, porous platinum potential electrode 5, potential electrode porous protective layer 6, compound contrast electrode 7, solid reference layer 8, oxygenation electrode 1, oxygenation dielectric substrate 10, oxygenation electrode 2 11.
At first adopt silk screen print method to apply respectively platinum electrode slurry and compound reference electrode pastes on two surfaces of yttria-stabilized zirconia potsherd 4, under 750-1000 ℃ of ventilating air condition, burn till after drying porous platinum potential electrode 5 and compound contrast electrode 7.Then adopt silk screen print method respectively at porous platinum electrode 5 surperficial electrode coated protective seam slurries, at compound contrast electrode 7 surperficial coating solid reference slurries, under 750-1000 ℃ of condition, burn till potential electrode porous protective layer 6 and solid reference layer 8.
Adopt silk screen print method to apply platinum electrode slurry on solid reference layer 8 surface, under 750-1000 ℃ of ventilating air condition, burn till porous platinum oxygenation electrode 1.Apply oxygenation dielectric substrate slurry on oxygenation electrode one 9 surfaces, under 750-1000 ℃ of condition, burn till oxygenation electrode layer 10.Apply platinum electrode slurry on oxygenation electrode layer 10 surfaces, under 750-1000 ℃ of ventilating air condition, burn till porous platinum oxygenation electrode 2 11.
In the oxygen determination process, oxygenation type solid-state reference oxygen sensor is placed ambiance, take oxygenation electrode 1 as anode, oxygenation electrode 2 11 is negative electrode, oxygenation dielectric substrate 10 is applied DC electric field, make solid reference layer 8 remain constant saturated oxygen concentration, and provide stable oxygen concentration reference for oxygen determination unit 1.Also can be in the situation that do not have oxygenation electrode layer 10 and oxygenation electrode 2 11, take compound contrast electrode 4 as anode, oxygenation electrode 1 is as negative electrode, directly solid reference layer 8 is applied DC electric field, make solid reference layer 8 remain constant saturated oxygen concentration, and provide stable oxygen concentration reference for oxygen determination unit 1.
The mol ratio that at first adopts coprecipitation to prepare yttria, bismuth oxide is that 25: 75, granularity are the bismuth oxide base composite oxide powder of 60-80 nanometer, and being mixed and made in proportion compound reference electrode pastes with metal platinum powder, high-temperature agglomerant, ethyl cellulose and terpinol, its quality percentage composition is respectively 18%, 10%, 18%, 4%, 50%.Wherein the chemical composition of high-temperature agglomerant (quality percentage composition) is respectively the glass dust of sodium oxide molybdena 15%, diboron trioxide 30%, calcium oxide 8%, alundum (Al2O3) 7%, silicon dioxide 40%.Utilizing silk screen print method is that 8: 92, thickness are that 400 microns yttria-stabilized zirconia potsherd 4 two sides apply respectively platinum electrode slurry and compound reference electrode pastes in the mol ratio of yttria, zirconium dioxide, can obtain porous platinum potential electrode 5 and the compound contrast electrode 7 that thickness is the 40-50 micron in 20 minutes at 900 ℃ of lower sintering after drying.
The mol ratio that adopts coprecipitation to prepare ceria, zirconium dioxide is that 25: 75, granularity are the cerium oxide and zirconium oxide solid solution powder of 60-80 nanometer, be mixed with in proportion the reference slurry with high-temperature agglomerant, ethyl cellulose and terpinol, its quality percentage composition is respectively 25%, 18%, 5%, 52%; Wherein the chemical composition of high-temperature agglomerant (quality percentage composition) is respectively the glass dust of sodium oxide molybdena 15%, diboron trioxide 30%, calcium oxide 8%, alundum (Al2O3) 7%, silicon dioxide 40%; Adopt silk screen print method to apply the reference slurry on compound contrast electrode 7 surfaces, can obtain the solid reference layer 8 that thickness is the 180-200 micron in 20 minutes at 900 ℃ of lower sintering after drying.
Adopt silk screen print method to apply platinum electrode slurries on solid reference layer 8 surface, behind drying and the sintering as oxygenation electrode 1.The mol ratio that adopts coprecipitation to prepare yttria, ceria, zirconium dioxide is that 4: 10: 86, granularity are the oxygenation electrolyte powder of 60-80 nanometer, be mixed with in proportion the oxygenation electrolyte slurry with high-temperature agglomerant, ethyl cellulose and terpinol, its quality percentage composition is respectively 25%, 18%, 5%, 52%; Wherein the chemical composition of high-temperature agglomerant (quality percentage composition) is respectively the glass dust of sodium oxide molybdena 15%, diboron trioxide 30%, calcium oxide 8%, alundum (Al2O3) 7%, silicon dioxide 40%; Adopt silk screen print method to apply the oxygenation electrolyte slurry on oxygenation electrode one 9 surfaces, can obtain the oxygenation dielectric substrate 10 that thickness is the 180-200 micron in 20 minutes at 900 ℃ of lower sintering after drying.Adopt silk screen print method to apply platinum electrode slurries on oxygenation dielectric substrate 10 surfaces, behind drying and the sintering as oxygenation electrode 2 11.
In the oxygen determination process, take oxygenation electrode 1 as anode, oxygenation electrode 2 11 is negative electrode, and oxygenation dielectric substrate 10 is applied the DC electric field that intensity is 5 volts/millimeter, plays constant solid reference layer 8 oxygen concentration in the oxygenation process.
The mol ratio that at first adopts sintering process to prepare baryta, bismuth oxide is that 12: 88, granularity are the bismuth oxide base composite oxide powder of 0.5-1.5 micron, and being mixed and made in proportion compound reference electrode pastes with metal platinum powder, high-temperature agglomerant, ethyl cellulose and water, its quality percentage composition is respectively 20%, 15%, 13%, 5%, 47%.Wherein the chemical composition of high-temperature agglomerant (quality percentage composition) is respectively the glass dust of sodium oxide molybdena 8%, diboron trioxide 26%, calcium oxide 8%, alundum (Al2O3) 8%, silicon dioxide 50%.Utilizing silk screen print method is that 8: 92, thickness are that 400 microns yttria-stabilized zirconia potsherd 4 two sides apply respectively platinum electrode slurry and compound reference electrode pastes in the mol ratio of yttria, zirconium dioxide, can obtain porous platinum potential electrode 5 and the compound contrast electrode 7 that thickness is the 50-60 micron in 20 minutes at 950 ℃ of lower sintering after drying.
The mol ratio that adopts sintering process to prepare ceria, zirconium dioxide is that 20: 80, granularity are the cerium oxide and zirconium oxide solid solution powder of 0.5-1.5 micron, be mixed with in proportion the reference slurry with high-temperature agglomerant, ethyl cellulose and water, its quality percentage composition is respectively 25%, 15%, 8%, 52%; Wherein the chemical composition of high-temperature agglomerant (quality percentage composition) is respectively the glass dust of sodium oxide molybdena 8%, diboron trioxide 26%, calcium oxide 8%, alundum (Al2O3) 8%, silicon dioxide 50%; Adopt silk screen print method to apply the reference slurry on compound contrast electrode 7 surfaces, can obtain the solid reference layer 8 that thickness is the 200-240 micron in 20 minutes at 950 ℃ of lower sintering after drying.Adopt silk screen print method to apply platinum electrode slurries on solid reference layer 8 surface, behind drying and the sintering as oxygenation electrode 1.
In the oxygen determination process, take compound contrast electrode 7 as anode, oxygenation electrode 1 is as negative electrode, and solid reference layer 8 is applied the DC electric field that intensity is 3 volts/millimeter, plays constant solid reference layer 8 oxygen concentration in the oxygenation process.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (8)
1. a solid-state reference oxygen sensor comprises oxygen determination unit, solid reference cell, it is characterized in that: also comprise the oxygenation unit, this solid-state reference oxygen sensor is stacked successively and is formed by oxygen determination unit, solid reference cell, oxygenation unit; This oxygen determination unit is stacked successively and is formed by yttria-stabilized zirconia potsherd, porous platinum potential electrode, potential electrode porous protective layer; The solid reference cell is stacked successively and is formed by compound contrast electrode, solid reference layer; The oxygenation unit is comprised of oxygenation electrode one.
2. solid-state reference oxygen sensor according to claim 1, it is characterized in that: this oxygenation unit also comprises oxygenation dielectric substrate, oxygenation electrode two, this oxygenation unit is stacked successively and is formed by oxygenation electrode one, oxygenation dielectric substrate, oxygenation electrode two.
3. the method for making of solid-state reference oxygen sensor claimed in claim 2; it is characterized in that: a surface at the yttria-stabilized zirconia potsherd applies and burns till porous platinum potential electrode, potential electrode protective seam successively; and apply successively and burn till compound contrast electrode, solid reference layer, oxygenation electrode one, oxygenation dielectric substrate, oxygenation electrode two on its another surface, consist of automatic oxygenation type solid-state reference oxygen sensor.
4. the method for making of solid-state reference oxygen sensor claimed in claim 2, it is characterized in that: described compound contrast electrode adopts and is formed through serigraphy, sintering by the formulated electrode slurry of bismuth oxide based ceramic powder, metal platinum powder, high-temperature agglomerant, low temperature bonding agent and solvent, and its quality percentage composition is respectively 10-25%, 5-15%, 10-25%, 2-8%, 40-70%; Wherein the chemical composition of bismuth oxide based ceramic powder is yttria 0-35%, baryta 0-15%, bismuth oxide 65-90% in molar content; The chemical composition of high-temperature agglomerant is respectively the glass dust of sodium oxide molybdena 6-20%, diboron trioxide 20-35%, calcium oxide 5-10%, alundum (Al2O3) 5-10%, silicon dioxide 35-60% in the quality percentage composition; The low temperature bonding agent is one or more in methylcellulose, ethyl cellulose, the gum arabic; Solvent is one or more in water, ethanol, the terpinol; Prepared electrode slurry can obtain compound contrast electrode at 750-1000 ℃ of lower sintering 5-60 minute after serigraphy.
5. the method for making of solid-state reference oxygen sensor claimed in claim 2, it is characterized in that: described solid reference layer provides constant reference oxygen concentration for the oxygen determination unit, employing is formed through serigraphy, sintering by the formulated reference slurry of solid solution powder, high-temperature agglomerant, low temperature bonding agent and solvent, and its quality percentage composition is respectively: 10-25%, 10-25%, 2-8%, 40-70%; Wherein the chemical composition of solid solution powder is counted with molar content: ceria 20-75%, zirconium dioxide 25-80%; The chemical composition of high-temperature agglomerant with the score of quality percentage composition is not: the glass dust of sodium oxide molybdena 6-20%, diboron trioxide 20-35%, calcium oxide 5-10%, alundum (Al2O3) 5-10%, silicon dioxide 35-60%; The low temperature bonding agent is one or more in methylcellulose, ethyl cellulose, the gum arabic; Solvent is one or more in water, ethanol, the terpinol; Prepared solid reference slurry can obtain solid reference layer at 750-1000 ℃ of lower sintering 10-60 minute after serigraphy.
6. the method for making of solid-state reference oxygen sensor claimed in claim 2 is characterized in that: the oxygenation electrode one in the described oxygenation unit, oxygenation electrode two are porous platinum electrode; The oxygenation dielectric substrate adopts and is formed through serigraphy, sintering by the formulated oxygenation electrolyte slurry of stabilized with yttrium oxide cerium oxide and zirconium oxide ceramic powder, high-temperature agglomerant, low temperature bonding agent and solvent, and its quality percentage composition is respectively 20-40%, 5-15%, 2-8%, 40-70%; Wherein the chemical composition of yttria-stabilized zirconia ceramic powder is in molar content, for yttria is that 0-10%, ceria 0-35%, zirconium dioxide are 65-95%; The chemical composition of high-temperature agglomerant with the score of quality percentage composition is not: the glass dust of sodium oxide molybdena 6-20%, diboron trioxide 20-35%, calcium oxide 5-10%, alundum (Al2O3) 5-10%, silicon dioxide 35-60%; The low temperature bonding agent is one or more in methylcellulose, ethyl cellulose, the gum arabic; In the optional water of solvent, ethanol, the terpinol one or more; Prepared electrode slurry can obtain the oxygenation dielectric substrate at 750-1000 ℃ of lower sintering 5-60 minute after serigraphy.
7. the using method of solid-state reference oxygen sensor claimed in claim 2, it is characterized in that: take oxygenation electrode one as anode, oxygenation electrode two is negative electrode, the oxygenation dielectric substrate is applied the DC electric field that intensity is 2.5-10 volt/millimeter, oxygen in the boot environment successively diffuses into oxygenation dielectric substrate and solid reference layer, makes solid reference layer remain constant saturated oxygen concentration.
8. the using method of solid-state reference oxygen sensor claimed in claim 1, it is characterized in that: described oxygenation unit take compound contrast electrode as anode, oxygenation electrode one is negative electrode, directly solid reference layer is applied the DC electric field that intensity is 2.5-10 volt/millimeter, oxygen in the boot environment diffuses into solid reference layer, makes solid reference layer remain constant saturated oxygen concentration.
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CN101949882B (en) * | 2010-08-31 | 2014-11-26 | 佛山市科傲电子科技有限公司 | Flat plate type oxygen sensor chip structure and manufacturing method thereof |
CN104374818A (en) * | 2014-08-08 | 2015-02-25 | 杭州纳瑙新材料科技有限公司 | Planar oxygen sensor |
CN107880594B (en) * | 2017-10-31 | 2020-04-07 | 湖南镭目科技有限公司 | Coating for auxiliary electrode of top-blown converter phosphorus determination sensor and top-blown converter phosphorus determination sensor |
CN118604096A (en) * | 2024-08-09 | 2024-09-06 | 中国第一汽车股份有限公司 | Method and device for testing oxygen supplementing capacity of reference airway of high-temperature ceramic sensor |
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US5277781A (en) * | 1990-06-25 | 1994-01-11 | Nisshin Steel Company Ltd. | Zirconia oxygen sensor |
CN1300940A (en) * | 1999-12-21 | 2001-06-27 | 冯永生 | Servoreference-type micro oxygen analyzer |
EP1555525A1 (en) * | 2004-01-19 | 2005-07-20 | Hitachi Ltd. | Oxygen sensor and method of producing same |
CN101251509A (en) * | 2008-04-16 | 2008-08-27 | 湖南大学 | Zirconium oxide oxygen sensor for automobile |
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Publication number | Priority date | Publication date | Assignee | Title |
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US5277781A (en) * | 1990-06-25 | 1994-01-11 | Nisshin Steel Company Ltd. | Zirconia oxygen sensor |
CN1300940A (en) * | 1999-12-21 | 2001-06-27 | 冯永生 | Servoreference-type micro oxygen analyzer |
EP1555525A1 (en) * | 2004-01-19 | 2005-07-20 | Hitachi Ltd. | Oxygen sensor and method of producing same |
CN101251509A (en) * | 2008-04-16 | 2008-08-27 | 湖南大学 | Zirconium oxide oxygen sensor for automobile |
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