CN103776872A - Oxygen sensor for car based on oxide protection slurry and manufacturing method thereof - Google Patents
Oxygen sensor for car based on oxide protection slurry and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses an oxygen sensor for a car based on oxide protection slurry. The oxygen sensor comprises a porous protection layer which is made of protection slurry, wherein the protection slurry comprises following substances in parts by weight: 3-5 parts of oxide, 1-3 parts of a pore forming agent, 1-3 parts of an organic carrier and 0.5-1.5 parts of an auxiliary agent. The protection layer of the oxygen sensor for the car is made of an oxide material; the protection layer is in a single-layered structure and has a very strong binding force with an electrode; the electrode can be effectively protected and corrosion to the surface of the electrode, caused by harmful substances including oil and the like, is avoided, so that the service life of the sensor is greatly prolonged; meanwhile, toxic solvents including butanone, xylene and the like are not needed and dangers to a human body, caused by the harmful substances, are avoided.
Description
Technical field
The present invention relates to sensor, relate in particular to a kind of oxygen sensor used in vehicle and manufacture method thereof based on oxide protective paste.
Background technology
In recent years along with the development of automobile market, it has been a kind of trend that automobile enters every household, but vehicle exhaust has become one of main source of atmospheric pollution, especially at the beginning of 2013, the fog thick weather of many days that Beijing area meets with, PM2.5 exceeds standard three times more than, make the people's quality of the life suffer very large threat, fog weather can cause rhinitis, and bronchitis also can be brought out lung cancer in this environment for a long time.On January 1st, 2013, China has started state's four emission standards comprehensively and has controlled the pollution of vehicle exhaust to atmosphere, and oxygen sensor used in vehicle is a unique sensing element that waste gas is detected.The preparation of existing chip oxygen sensor mainly adopts butanone; dimethylbenzene system curtain coating obtains cast sheet; in sensor preparation process, adopt toxic solvent, easily contaminated environment, and health is damaged; the present invention adopts the porous protective layer of strong adhesion; can reduce the corrosion of the objectionable impuritiess such as oil to electrode surface in waste gas, increase sensor serviceable life, simultaneously; adopt nontoxic slurry solvent, environmental protection and easy to operate.
Summary of the invention
The technical problem to be solved in the present invention is; for the deficiencies in the prior art; a kind of oxygen sensor used in vehicle and manufacture method thereof based on oxide protective paste is provided; the protective seam of this oxygen sensor used in vehicle adopts oxide material to make; this protective seam is a kind of single layer structure, has stronger adhesion, effectively guard electrode with matrix material; avoid the corrosion of objectionable impurities to electrode surface such as oil, the serviceable life of greatly improving sensor.
For solving the problems of the technologies described above, the present invention adopts following technical scheme.
A kind of oxygen sensor used in vehicle based on oxide protective paste, it includes the sensitive layer matrix of stacked setting from top to bottom, air duct layer, air duct supporter and zone of heating matrix, the upper surface of described sensitive layer matrix is printed with outer working electrode and porous protective layer successively, the lower surface of this sensitive layer matrix is printed with interior working electrode, on described air duct layer, corresponding described interior working electrode offers air duct, the upper surface of described zone of heating matrix is printed with the first insulation course successively, heating electrode and the second insulation course, the lower surface of described zone of heating matrix is printed with the 3rd insulation course and electric conduction of heating pin successively, described outer working electrode and interior working electrode draw hole by conduction and are electrically connected, described heating electrode and electric conduction of heating pin draw hole by conduction and are electrically connected, wherein, described porous protective layer is made up of protective paste, described protective paste comprises the material of following weight portion: oxide 3-5 part, pore creating material 1-3 part, organic carrier 1-3 part, auxiliary agent 0.5-1.5 part.
Preferably, described protective paste comprises the material of following weight portion: 4 parts of oxides, 2 parts of pore creating materials, 2 parts of organic carriers, 1 part of auxiliary agent, wherein, described oxide comprises one or more mixing of following weight portion material: 20 parts, aluminium oxide, 1 part of zirconia, 1 part, magnesium oxide, 1 part of monox; Described pore creating material is that particle size range is the nano-carbon powder of 0.1um-10um; Described organic carrier comprises the material of following weight portion: 58 parts of terpinols, 25 parts of ethyl celluloses, 2 parts of ethanol; Described auxiliary agent comprises the material of following weight portion: 6 parts of cementing agents, 3 parts of spreading agents, 3 parts, plastifier, 1 part of levelling agent.
Preferably, the thickness of described sensitive layer matrix is: 0.5-0.7mm, and the thickness of described air duct layer is 0.3-0.4mm, and the thickness of described air duct supporter is 0.2-0.3mm, and the thickness of described zone of heating matrix is 0.5-0.7mm.
Preferably; the thickness of described heating electrode is 10-15um; the thickness of described outer working electrode and interior working electrode is 10-15um, and the thickness of described the first insulation course, the second insulation course and the 3rd insulation course is 30-35um, and porous protective layer thickness is 70-80um.
A kind of oxygen sensor used in vehicle manufacture method based on oxide protective paste; it comprises the steps: step S1; prepare protective paste; described protective paste comprises the material of following weight portion: oxide 3-5 part; pore creating material 1-3 part; organic carrier 1-3 part; auxiliary agent 0.5-1.5 part; oxide, pore creating material, organic carrier 1-3 part and auxiliary agent are mixed; and with obtaining protective seam slurry after planetary ball mill ball milling; the viscosity of this protective paste in the time that temperature is 25 ℃ is 300 ± 50Pas, and adhesion is 12N/mm
2; Step S2, utilizes blanking die, and by sensitive layer matrix, air duct layer, air duct supporter and zone of heating matrix, respectively by preset thickness cut-parts, then stamping-out pilot hole and conduction are drawn hole respectively, afterwards to air duct layer stamping-out air duct; Step S3, utilize screen printing apparatus, print successively the first insulation course, heating electrode and the second insulation course at the upper surface of zone of heating matrix, print successively the 3rd insulation course and electric conduction of heating pin at the lower surface of zone of heating matrix, upper surface at sensitive layer matrix prints outer working electrode and protective seam successively, working electrode in the lower surface printing of sensitive layer matrix; Step S4, stacks gradually sensitive layer matrix, air duct layer, air duct supporter and zone of heating matrix, utilize warm isostatic pressing machine under vacuum condition with the pressing of preset pressure lamination, become pre-set dimension with stamping-out grinding tool stamping-out afterwards, obtain sensor green compact; Step S5, covers porous and holds burning pressing plate on sensor green compact, use sintering furnace sintering.
Preferably, described protective paste comprises the material of following weight portion: 4 parts of oxides, 2 parts of pore creating materials, 2 parts of organic carriers, 1 part of auxiliary agent, wherein, described oxide comprises one or more mixing of following weight portion material: 20 parts, aluminium oxide, 1 part of zirconia, 1 part, magnesium oxide, 1 part of monox; Described pore creating material is that particle size range is the nano-carbon powder of 0.1um-10um; Described organic carrier comprises the material of following weight portion: 58 parts of terpinols, 25 parts of ethyl celluloses, 2 parts of ethanol; Described auxiliary agent comprises the material of following weight portion: 6 parts of cementing agents, 3 parts of spreading agents, 3 parts, plastifier, 1 part of levelling agent; In this step; by oxide, organic carrier and dispersant; utilize planetary ball mill take rotating speed as 250r/min ball milling 12 hours; so add successively afterwards cementing agent, plastifier and levelling agent; take rotating speed as 250r/min ball milling 12 hours; the viscosity of this protective paste in the time that temperature is 25 ℃ is 300 ± 50Pas, and adhesion is 12N/mm
2.
Preferably, in described step S2, first utilize vacuum packing machine, upper and lower both sides at each zirconia curtain coating green compact add corrosion resistant plate, recycling pellosil carries out vacuum coater, utilize warm isostatic pressing machine take pressure as 8-15MPa, temperature pressurize 10 minutes under 70 ℃ of conditions, more respectively sensitive layer matrix, air duct layer, air duct supporter and zone of heating matrix are carried out to cut-parts.
Preferably, in described step S2, the thickness of described sensitive layer matrix is: 0.5-0.7mm, and the thickness of described air duct layer is 0.3-0.4mm, and the thickness of described air duct supporter is 0.2-0.3mm, and the thickness of described zone of heating matrix is 0.5-0.7mm.
Preferably; in described step S3, the thickness of described heating electrode is 10-15um, and the thickness of described outer working electrode and interior working electrode is 10-15um; the thickness of described the first insulation course, the second insulation course and the 3rd insulation course is 30-35um, and porous protective layer is 70-80um.
Preferably, in described step S4, after described sensitive layer matrix, air duct layer, air duct supporter and zone of heating matrix stack gradually, with stainless steel clamping plate, with the precompressed of 0.4-0.6Mpa pressure, recycling pellosil carries out vacuum coater, temperature isostatic pressing machine parameter is set to pressure 8-15Mpa, temperature 70 C, the dwell time is 8-15min, becomes sensor green compact afterwards with blanking die stamping-out, the length of these sensor green compact is 60mm, and width is 5mm; In described step S5, it is that thickness is the Woelm Alumina load bearing board of 0.5-0.8mm that described porous is held burning pressing plate, and described sintering furnace is Si-Mo rod sintering furnace, ℃ sintering 2 hours take temperature as 1450-1550.
In oxygen sensor used in vehicle based on oxide protective paste disclosed by the invention, the 3rd insulation course is made up of protective paste, and protective paste comprises the material of following weight portion: oxide 3-5 part, pore creating material 1-3 part, organic carrier 1-3 part, auxiliary agent 0.5-1.5 part.The protective seam of this oxygen sensor used in vehicle adopts oxide material to make; this protective seam is a kind of single layer structure; there is stronger adhesion with electrode; effectively guard electrode; avoid the corrosion of objectionable impurities to electrode surface such as oil, the serviceable life of greatly improving sensor, simultaneously; without the toxic solvent such as butanone, dimethylbenzene, avoid because of noxious material, human body being worked the mischief.
Accompanying drawing explanation
Fig. 1 is the exploded view of oxygen sensor used in vehicle.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in more detail.
The invention discloses a kind of oxygen sensor used in vehicle based on oxide protective paste, as shown in Figure 1, it includes the sensitive layer matrix 3 of stacked setting from top to bottom, air duct layer 5, air duct supporter 6 and zone of heating matrix 9, the upper surface of sensitive layer matrix 3 is printed with outer working electrode 2 and protective seam 1 successively, the lower surface of this sensitive layer matrix 3 is printed with interior working electrode 4, in corresponding on air duct layer 5, working electrode 4 offers air duct, the upper surface of zone of heating matrix 9 is printed with the first insulation course 12 successively, heating electrode 8 and the second insulation course 7, the lower surface of zone of heating matrix 9 is printed with the 3rd insulation course 10 and electric conduction of heating pin 11 successively, outer working electrode 2 draws hole with interior working electrode 4 by conduction and is electrically connected, heating electrode 8 draws hole with electric conduction of heating pin 11 by conduction and is electrically connected, wherein,
The first insulation course 12, the second insulation course 7 and the 3rd insulation course 10 are made up of insulation paste, and insulation paste comprises the material of following weight portion: inorganic particle 4-6 part, organic carrier 2-4 part, auxiliary agent 1-3 part;
Protective seam 1 is made up of protective paste; protective paste comprises the material of following weight portion: oxide 3-5 part; pore creating material 1-3 part; organic carrier 1-3 part; auxiliary agent 0.5-1.5 part; the protective seam of this oxygen sensor used in vehicle adopts oxide material to make; this protective seam is a kind of single layer structure; there is stronger adhesion with electrode; effectively guard electrode, avoids the corrosion of objectionable impurities to electrode surface such as oil, the serviceable life of greatly improving sensor; meanwhile, also have that shock resistance is good, cost is low, the simple advantage of manufacture craft.
Each layer of matrix of above-mentioned oxygen sensor used in vehicle all adopts zirconia material to make, in sintering process, the sinter bonded degree that each base layer has had, especially air duct layer, without fill the organism such as carbon dust, starch in air duct, avoid affecting the sensitivity of sensor because residue is present in air duct.When said structure can guarantee air duct size, reduce the filling to air duct cavity foreign matter in the time of processed sensor green compact, avoid foreign matter after sintering to burn the residual of excess, extend the serviceable life of sensor.The manufacture method of this oxygen sensor used in vehicle comprises the steps:
Step S1, prepare casting slurry, casting slurry comprises the material of following weight portion: Zirconium powder 5-7 part, organic solvent 3-5 part, auxiliary agent 0.5-1.5 part, utilizes planetary ball mill ball milling casting slurry, carries out curtain coating afterwards with casting machine, form zirconia curtain coating green compact, with zirconia curtain coating green compact making sensitive layer matrix 3, air duct layer 5, air duct supporter 6 and zone of heating matrix 9;
Prepare insulation paste, insulation paste comprises the material of following weight portion: inorganic particle 4-6 part, organic carrier 2-4 part, auxiliary agent 1-3 part, inorganic particle, organic carrier and auxiliary agent are mixed, and with obtaining insulation paste after planetary ball mill ball milling, when its physical property is 25 ℃ of temperature, viscosity is 100 ± 20Pas, and adhesion is 12N/mm
2, resistivity is 3.1x10
12Ω cm;
Prepare protective paste; protective paste comprises the material of following weight portion: oxide 3-5 part; pore creating material 1-3 part; organic carrier 1-3 part; auxiliary agent 0.5-1.5 part, mixes oxide, pore creating material, organic carrier 1-3 part and auxiliary agent, and with obtaining protective paste after planetary ball mill ball milling; the viscosity of this protective paste in the time that temperature is 25 ℃ is 300 ± 50Pas, and adhesion is 12N/mm
2;
Step S2, utilizes blanking die, and by sensitive layer matrix 3, air duct layer 5, air duct supporter 6 and zone of heating matrix 9, respectively by preset thickness cut-parts, then stamping-out pilot hole and conduction are drawn hole respectively, afterwards to air duct layer 5 stamping-out air duct;
Step S3, utilize screen printing apparatus, print successively the first insulation course 12, heating electrode 8 and the second insulation course 7 at the upper surface of zone of heating matrix 9, print successively the 3rd insulation course 10 and electric conduction of heating pin 11 at the lower surface of zone of heating matrix 9, print successively outer working electrode 2 and protective seam 1 at the upper surface of sensitive layer matrix 3, working electrode 4 in the lower surface printing of sensitive layer matrix 3;
Step S4, sensitive layer matrix 3, air duct layer 5, air duct supporter 6 and zone of heating matrix 9 are stacked gradually, utilize warm isostatic pressing machine under vacuum condition with the pressing of preset pressure lamination, become pre-set dimension with stamping-out grinding tool stamping-out afterwards, obtain sensor green compact;
Step S5, covers porous and holds burning pressing plate on sensor green compact, use sintering furnace sintering.
For concrete technical scheme of the present invention is described better, the present invention proposes following embodiment about above-mentioned casting slurry, insulation paste and protective paste:
Embodiment 1:
In the present embodiment, casting slurry comprises the material of following weight portion: 6 parts of Zirconium powders, and 4 parts of organic solvents, 1 part of auxiliary agent, the particle diameter < 1um of Zirconium powder, wherein,
Organic solvent comprises the material of following weight portion: analyze pure acetic acid 7 parts, fat and/or acetic acid the third fat, analyze 3 parts of straight alcohol and/or isobutyl alcohols, organic solvent in the present invention, adopt avirulent acetic acid fat and/or acetic acid the third fat and ethanol and/or isobutyl alcohol, it is the middle mode that adopts the toxic solvents such as butanone, dimethylbenzene compared to existing technology, has avoided the pollution to environment and the harm to health;
Auxiliary agent comprises the material of following weight portion: 1 part of spreading agent, 7 parts of cementing agents, 1 part, plastifier.
Wherein, curtain coating auxiliary agent makees cementing agent with imported from America PVB, and its vitrification point is 62-72 ℃; there is very strong cohesiveness; can reduce the superimposed pressure of the static pressure such as green sheet and laminate the time, doing spreading agent with triethanolamine, it is that S2075 reagent makees plastifier that Shou Nuo company of the U.S. provides model.
Embodiment 2:
In the present embodiment, insulation paste comprises the material of following weight portion: 5 parts of inorganic particles, and 3 parts of organic carriers, 2 parts of auxiliary agents, wherein,
Inorganic particle comprises the material of following weight portion: 20 parts, aluminium oxide, and 1 part of zirconia, wherein aluminium oxide is the potpourri of 14 parts, the aluminium oxide of 6 parts of α phase low-temperature sintered aluminas and γ phase particle diameter < 15nm;
Organic carrier is 80 ℃ of water-bath 8h or magnetic stirring apparatus 3h mixed liquor after treatment, and this organic carrier comprises the material of following weight portion: 25 parts of terpinols, 1 part of ethyl cellulose;
Auxiliary agent comprises the material of following weight portion: 6 parts of spreading agents, 3 parts of cementing agents, 3 parts of levelling agents, 1 part of thixotropic agent.
Embodiment 3:
In the present embodiment, protective paste comprises the material of following weight portion: 4 parts of oxides, and 2 parts of pore creating materials, 2 parts of organic carriers, 1 part of auxiliary agent, wherein,
Oxide comprises one or more mixing of following weight portion material: 20 parts, aluminium oxide, 1 part of zirconia, 1 part, magnesium oxide, 1 part of monox;
Pore creating material is that particle size range is the nano-carbon powder of 0.1um-1um;
Organic carrier comprises the material of following weight portion: 58 parts of terpinols, 25 parts of ethyl celluloses, 2 parts of ethanol;
Auxiliary agent comprises the material of following weight portion: 6 parts of cementing agents, 3 parts of spreading agents, 3 parts, plastifier, 1 part of levelling agent.
About the manufacture method of this oxygen sensor used in vehicle, the present invention proposes following embodiment:
Embodiment 4:
In the present embodiment, in step S1, casting slurry comprises the material of following weight portion: 6 parts of Zirconium powders, and 4 parts of organic solvents, 1 part of auxiliary agent, the particle diameter < 1um of Zirconium powder, wherein,
Organic solvent comprises the material of following weight portion: analyze pure acetic acid 7 parts, fat and/or acetic acid the third fat, analyze 3 parts of straight alcohol and/or isobutyl alcohols;
Auxiliary agent comprises the material of following weight portion: 1 part of spreading agent, 7 parts of cementing agents, 1 part, plastifier;
In this step, first Zirconium powder, organic solvent and spreading agent are mixed by above-mentioned weight portion proportioning, utilize planetary ball mill take rotating speed as 250r/min ball milling 15 hours, add afterwards cementing agent and plastifier, take rotating speed as 250r/min ball milling 12 hours, after ball milling, by casting slurry froth in vacuum, utilize casting machine to carry out curtain coating, obtain zirconia curtain coating green compact.
Embodiment 5:
In the present embodiment, in step S1, insulation paste comprises the material of following weight portion: 5 parts of inorganic particles, and 3 parts of organic carriers, 2 parts of auxiliary agents, wherein,
Inorganic particle comprises the material of following weight portion: 20 parts, aluminium oxide, and 1 part of zirconia, wherein aluminium oxide is the potpourri of 14 parts, the aluminium oxide of 6 parts of α phase low-temperature sintered aluminas and γ phase particle diameter < 15nm;
Organic carrier is 80 ℃ of water-bath 8h or magnetic stirring apparatus 3h mixed liquor after treatment, and this organic carrier comprises the material of following weight portion: 25 parts of terpinols, 1 part of ethyl cellulose;
Auxiliary agent comprises the material of following weight portion: 6 parts of spreading agents, 3 parts of cementing agents, 3 parts of levelling agents, 1 part of thixotropic agent;
In this step, first be 80 ℃ of temperature in water-bath. under time 8h or magnetic agitation time 3h condition, prepare the mixed solution of terpinol and ethyl cellulose, add afterwards inorganic particle and spreading agent, utilize planetary ball mill take rotating speed as 250r/min ball milling 12 hours, add afterwards and add successively cementing agent, levelling agent, thixotropic agent, take rotating speed as 250r/min ball milling 24 hours, obtain insulation paste, when its physical property is 25 ℃ of temperature, viscosity is 100 ± 20Pas, adhesion is 12N/mm2, and resistivity is 3.1x10
12Ω cm.
Embodiment 6
In the present embodiment, in step S1, protective paste comprises the material of following weight portion: 4 parts of oxides, and 2 parts of pore creating materials, 2 parts of organic carriers, 1 part of auxiliary agent, wherein,
Oxide comprises one or more mixing of following weight portion material: 20 parts, aluminium oxide, 1 part of zirconia, 1 part, magnesium oxide, 1 part of monox;
Pore creating material is that particle size range is the nano-carbon powder of 0.1um-1um;
Organic carrier comprises the material of following weight portion: 58 parts of terpinols, 25 parts of ethyl celluloses, 2 parts of ethanol;
Auxiliary agent comprises the material of following weight portion: 6 parts of cementing agents, 3 parts of spreading agents, 3 parts, plastifier, 1 part of levelling agent;
In this step; by oxide, organic carrier and dispersant; utilize planetary ball mill take rotating speed as 250r/min ball milling 12 hours; then add afterwards cementing agent, plastifier and levelling agent; take rotating speed as 250r/min ball milling 12 hours; obtain protective paste, the viscosity of this protective paste in the time that temperature is 25 ℃ is 300 ± 50Pas, and adhesion is 12N/mm
2.In the present embodiment; porous protective layer 1 hole aperture reaches 0.5-10um; factor of porosity reaches 5-50%; be a kind of single layer structure, have stronger adhesion with electrode, its advantage is can effectively protect the corrosion on electrode surface of objectionable impurities in gasoline and affect its catalytic action; and shock resistance is good; life-span is long, and cost supports, and manufacture craft is simple.
Embodiment 7:
In the present embodiment, in step S2, first utilize vacuum packing machine, upper at each zirconia curtain coating green compact, lower both sides add corrosion resistant plate, recycling pellosil carries out vacuum coater, utilize warm isostatic pressing machine take pressure as 8-15MPa, temperature is pressurize 10 minutes under 70 ℃ of conditions, again respectively to sensitive layer matrix 3, air duct layer 5, air duct supporter 6 and zone of heating matrix 9 carry out cut-parts, the thickness of sensitive layer matrix 3 is: 0.5-0.7mm, the thickness of air duct layer 5 is 0.3-0.4mm, the thickness of air duct supporter 6 is 0.2-0.3mm, the thickness of zone of heating matrix 9 is 0.5-0.7mm.
Embodiment 8:
In the present embodiment, in step S3, the thickness of heating electrode 8 is 10-15um, the thickness of outer working electrode 2 and interior working electrode 4 is 10-15m, the thickness of the first insulation course 12, the second insulation course 7 and the 3rd insulation course 10 is 30-35um, and porous protective layer thickness is 70-80um, and it is complete that printing electrode wherein will guarantee to connect, without open circuit, short circuit, the halo-free phenomenon of dying of slurry printing, keeps any surface finish smooth when printing printing insulation course, protective seam, electrode layer, flawless, granule foreign;
In step S4, after sensitive layer matrix 3, air duct layer 5, air duct supporter 6 and zone of heating matrix 9 stack gradually, with stainless steel clamping plate with the precompressed of 0.4-0.6Mpa pressure, recycling pellosil carries out vacuum coater, and warm isostatic pressing machine parameter is set to pressure 8-15Mpa, temperature 70 C, dwell time is 8-15min, become sensor green compact with blanking die stamping-out afterwards, the length of these sensor green compact is 60mm, and width is 5mm; In the present embodiment, in the time of packing, use corrosion resistant plate to add pellosil and support up and down orbicula, can effectively guarantee that air duct size is complete, and without filling the foreign matters such as carbon dust, starch.
In step S5, it is that thickness is the Woelm Alumina load bearing board of 0.5-0.8mm that porous is held burning pressing plate, and sintering furnace is Si-Mo rod sintering furnace, ℃ sintering 2 hours take temperature as 1450-1550.
In oxygen sensor used in vehicle disclosed by the invention, sensitive layer matrix 3, air duct layer 5, air duct supporter 6 and zone of heating matrix 9 are made up of casting slurry, casting slurry comprises the material of following weight portion: Zirconium powder 5-7 part, organic solvent 3-5 part, auxiliary agent 0.5-1.5 part; The first insulation course 12, the second insulation course 7 and the 3rd insulation course 10 are made up of insulation paste, and insulation paste comprises the material of following weight portion: inorganic particle 4-6 part, organic carrier 2-4 part, auxiliary agent 1-3 part; Porous protective layer 1 is made up of protective paste, and protective paste comprises the material of following weight portion: oxide 3-5 part, pore creating material 1-3 part, organic carrier 1-3 part, auxiliary agent 0.5-1.5 part.Each layer of matrix of this oxygen sensor used in vehicle all adopts zirconia material to make, in sintering process, the sinter bonded degree that each base layer has had, especially air duct layer, without fill the organism such as carbon dust, starch in air duct, avoid affecting the sensitivity of sensor because residue is present in air duct.Simultaneously, curtain coating organic solvent in the present invention, adopted avirulent acetic acid fat and/or acetic acid the third fat and ethanol and/or isobutyl alcohol, it is the middle mode that adopts the toxic solvents such as butanone, dimethylbenzene compared to existing technology, has avoided the pollution to environment and the harm to health.
More than preferred embodiment of the present invention just, is not limited to the present invention, all modifications of making in technical scope of the present invention, is equal to and replaces or improvement etc., all should be included in the scope that the present invention protects.
Claims (10)
1. the oxygen sensor used in vehicle based on oxide protective paste, it is characterized in that, include the sensitive layer matrix of stacked setting from top to bottom, air duct layer, air duct supporter and zone of heating matrix, the upper surface of described sensitive layer matrix is printed with outer working electrode and porous protective layer successively, the lower surface of this sensitive layer matrix is printed with interior working electrode, on described air duct layer, corresponding described interior working electrode offers air duct, the upper surface of described zone of heating matrix is printed with the first insulation course successively, heating electrode and the second insulation course, the lower surface of described zone of heating matrix is printed with the 3rd insulation course and electric conduction of heating pin successively, described outer working electrode and interior working electrode draw hole by conduction and are electrically connected, described heating electrode and electric conduction of heating pin draw hole by conduction and are electrically connected, wherein,
Described porous protective layer is made up of protective paste, and described protective paste comprises the material of following weight portion: oxide 3-5 part, pore creating material 1-3 part, organic carrier 1-3 part, auxiliary agent 0.5-1.5 part.
2. the oxygen sensor used in vehicle based on oxide protective paste as claimed in claim 1, is characterized in that, described protective paste comprises the material of following weight portion: 4 parts of oxides, and 2 parts of pore creating materials, 2 parts of organic carriers, 1 part of auxiliary agent, wherein,
Described oxide comprises one or more mixing of following weight portion material: 20 parts, aluminium oxide, 1 part of zirconia, 1 part, magnesium oxide, 1 part of monox;
Described pore creating material is that particle size range is the nano-carbon powder of 0.1um-1um;
Described organic carrier comprises the material of following weight portion: 58 parts of terpinols, 25 parts of ethyl celluloses, 2 parts of ethanol;
Described auxiliary agent comprises the material of following weight portion: 6 parts of cementing agents, 3 parts of spreading agents, 3 parts, plastifier, 1 part of levelling agent.
3. the oxygen sensor used in vehicle based on oxide protective paste as claimed in claim 1; it is characterized in that; the thickness of described sensitive layer matrix is: 0.5-0.7mm; the thickness of described air duct layer is 0.3-0.4mm; the thickness of described air duct supporter is 0.2-0.3mm, and the thickness of described zone of heating matrix is 0.5-0.7mm.
4. the oxygen sensor used in vehicle based on oxide protective paste as claimed in claim 1; it is characterized in that; the thickness of described heating electrode is 10-15um; the thickness of described outer working electrode and interior working electrode is 10-15um; the thickness of described the first insulation course, the second insulation course and three-layer insulated layer is 30-35um, and protective layer thickness is 70-80um.
5. the oxygen sensor used in vehicle manufacture method based on oxide protective paste, is characterized in that, comprises the steps:
Step S1, prepare protective paste, described protective paste comprises the material of following weight portion: oxide 3-5 part, pore creating material 1-3 part, organic carrier 1-3 part, auxiliary agent 0.5-1.5 part, oxide, pore creating material, organic carrier and auxiliary agent are mixed, and with obtaining protective paste after planetary ball mill ball milling, the viscosity of this protective paste in the time that temperature is 25 ℃ is 300 ± 50Pas, and adhesion is 12N/mm2;
Step S2, utilizes blanking die, and by sensitive layer matrix, air duct layer, air duct supporter and zone of heating matrix, respectively by preset thickness cut-parts, then stamping-out pilot hole and conduction are drawn hole respectively, afterwards to air duct layer stamping-out air duct;
Step S3, utilize screen printing apparatus, print successively the first insulation course, heating electrode and the second insulation course at the upper surface of zone of heating matrix, print successively the 3rd insulation course and electric conduction of heating pin at the lower surface of zone of heating matrix, upper surface at sensitive layer matrix prints outer working electrode and porous protective layer successively, working electrode in the lower surface printing of sensitive layer matrix;
Step S4, stacks gradually sensitive layer matrix, air duct layer, air duct supporter and zone of heating matrix, utilize warm isostatic pressing machine under vacuum condition with the pressing of preset pressure lamination, become pre-set dimension with stamping-out grinding tool stamping-out afterwards, obtain sensor green compact;
Step S5, covers porous and holds burning pressing plate on sensor green compact, use sintering furnace sintering.
6. the oxygen sensor used in vehicle manufacture method based on oxide protective paste as claimed in claim 5, is characterized in that, in described step S1; described protective paste comprises the material of following weight portion: 4 parts of oxides, 2 parts of pore creating materials, 2 parts of organic carriers; 1 part of auxiliary agent, wherein
Described oxide comprises one or more mixing of following weight portion material: 20 parts, aluminium oxide, 1 part of zirconia, 1 part, magnesium oxide, 1 part of monox;
Described pore creating material is that particle size range is the nano-carbon powder of 0.1um-1um;
Described organic carrier comprises the material of following weight portion: 58 parts of terpinols, 25 parts of ethyl celluloses, 2 parts of ethanol;
Described auxiliary agent comprises the material of following weight portion: 6 parts of cementing agents, 3 parts of spreading agents, 3 parts, plastifier, 1 part of levelling agent;
In this step; by oxide, organic carrier and dispersant; utilize planetary ball mill take rotating speed as 250r/min ball milling 12 hours; add successively afterwards cementing agent, plastifier and levelling agent; take rotating speed as 250r/min ball milling 12 hours; obtain protective paste, the viscosity of this protective paste in the time that temperature is 25 ℃ is 300 ± 50Pas, and adhesion is 12N/mm
2.
7. the oxygen sensor used in vehicle manufacture method based on oxide protective paste as claimed in claim 5; it is characterized in that; in described step S2; first utilize vacuum packing machine; upper and lower both sides at each zirconia curtain coating green compact add corrosion resistant plate; recycling pellosil carries out vacuum coater, utilize warm isostatic pressing machine take pressure as 8-15MPa, temperature pressurize 10 minutes under 70 ℃ of conditions, more respectively sensitive layer matrix, air duct layer, air duct supporter and zone of heating matrix are carried out to cut-parts.
8. the oxygen sensor used in vehicle manufacture method based on oxide protective paste as claimed in claim 5; it is characterized in that; in described step S2; the thickness of described sensitive layer matrix is: 0.5-0.7mm; the thickness of described air duct layer is 0.3-0.4mm; the thickness of described air duct supporter is 0.2-0.3mm, and the thickness of described zone of heating matrix is 0.5-0.7mm.
9. the oxygen sensor used in vehicle manufacture method based on oxide protective paste as claimed in claim 5; it is characterized in that; in described step S3; the thickness of described heating electrode is 10-15um; the thickness of described outer working electrode and interior working electrode is 10-15um, and the thickness of described the first insulation course, the second insulation course and the 3rd insulation course is 30-35um, porous protective layer thickness is 70-80um.
10. the oxygen sensor used in vehicle manufacture method based on oxide protective paste as claimed in claim 5, it is characterized in that, in described step S4, after described sensitive layer matrix, air duct layer, air duct supporter and zone of heating matrix stack gradually, with stainless steel clamping plate with the precompressed of 0.4-0.6Mpa pressure, recycling pellosil carries out vacuum coater, temperature isostatic pressing machine parameter is set to pressure 8-15Mpa, temperature 70 C, dwell time is 8-15min, become sensor green compact with blanking die stamping-out afterwards, the length of these sensor green compact is 60mm, and width is 5mm;
In described step S5, it is that thickness is the Woelm Alumina load bearing board of 0.5-0.8mm that described porous is held burning pressing plate, and described sintering furnace is Si-Mo rod sintering furnace, ℃ sintering 2 hours take temperature as 1450-1550.
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