CN106706729A - Novel chip-type wide-domain automobile oxygen sensor and preparation method thereof - Google Patents

Novel chip-type wide-domain automobile oxygen sensor and preparation method thereof Download PDF

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Publication number
CN106706729A
CN106706729A CN201611260599.8A CN201611260599A CN106706729A CN 106706729 A CN106706729 A CN 106706729A CN 201611260599 A CN201611260599 A CN 201611260599A CN 106706729 A CN106706729 A CN 106706729A
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electrode
layer
curtain coating
reaction electrode
substrate
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CN106706729B (en
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黄海琴
陈圣龙
韩旭
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Laiding Electronic Material Technology Co ltd
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LAIDING ELECTRONIC MATERIAL TECHNOLOGY Co Ltd
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/10Internal combustion engine [ICE] based vehicles
    • Y02T10/40Engine management systems

Abstract

The invention relates to a novel chip-type wide-domain automobile oxygen sensor. The sensor comprises a protective layer, a signal layer and a heating layer, wherein the protective layer, the signal layer and the heating layer are sequentially superposed and then are sintered. The signal layer comprises five layers of flow-casting substrates superposed in sequence, an inner reaction electrode and a reference reaction electrode are arranged on the lower surface of the third layer of flow-casting substrates in parallel, the inner reaction electrode and the reference reaction electrode are located on the same horizontal plane, and the upper surfaces and the lower surfaces of the inner reaction electrode and the reference reaction electrodes are respectively provided with upper reaction electrode insulation layers and lower reaction electrode insulation layers covering two reaction electrode reaction cavities. The preparation method comprises the steps of preparation of multiple types of flow-casting slurry, flow-casting forming, edge removal and slitting, punching, printing, superimposition, vacuum plastic sealing, warm isostatic pressing, slitting and sintering. The novel chip-type wide-domain automobile oxygen sensor has the advantages that the performance of the oxygen sensor with the structure is more stable by adding the number of the layers of flow-casting substrates in the functional layers and arranging the inner reaction electrode and the reference reaction electrode which are arranged in a superposed mode on the same horizontal plane, and the production consistency is better.

Description

A kind of novel slice type wide area automotive oxygen sensor and preparation method thereof
Technical field
The invention belongs to automotive oxygen sensor technical field, more particularly to a kind of novel slice type wide area automotive oxygen sensor and Its preparation method.
Background technology
Lean Burning Technique can improve the discharge of fuel efficiency reduction exhaust pollutant, but lean burn is easily caused and started Machine stop working, and mix it is unreasonable can produce excessive NOx compounds, cause environmental pollution, broad domain oxygen sensor can be supervised accurately The accurate oxygen content surveyed in gamut vehicle exhaust reacts engine running condition, and then engine computer could be according to it Real time status are adjusted, so as to improve efficiency of combustion, reduce discharge amount of pollution and detection three-element catalytic operation conditions.
The core component of wide area type lambda sensor is its sensitive chip, and it is usually by heating electrode, oxygen pump external electrode, oxygen Inner pump electrode and reference electrode are constituted, and are by five layers of compact zirconia of multilayer printed circuit(ZrO2)Matter substrate overlapping and Into the preparation method of the chip is:Zirconium oxide substrate is made by casting arrangement;Section punching is carried out to substrate;Cutting Good substrate carries out multi-layer silk screen printing, makes each functional layer;Again the overlapping cutting of five layers of substrate, be finally sintered, on The treatment such as glaze.
Chip wide domain type lambda sensor is due to its particularity, each thickness for being cast substrate, the setting of each functional layer and each stream Selection of epitaxial substrate and each functional layer material etc. suffers from important influence to the performance of oxidation sensors;Therefore in known chip The structure of oxidation sensors, curtain coating substrate thickness are optimized on the basis of wide area type sensor construction, to obtain more preferably Performance parameter be current lambda sensor industry research topic.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of novel slice type wide area automotive oxygen sensor, and the oxygen of the structure is passed Sensor is by increasing the number of plies and thickness of curtain coating substrate in each functional layer, changing the interior reaction electrode and reference reaction electricity that are stacked Extremely same level is set, and then causes that the oxygen sensor performance of the structure is more stable, and conformity of production is more preferable;Additionally provide The preparation method of the novel slice type wide area automotive oxygen sensor.
In order to solve the above technical problems, the technical scheme is that:A kind of novel slice type wide area automotive oxygen sensor, its Innovative point is:The sensor includes that protective layer, signals layer and zone of heating are sintered after from top to bottom overlapping successively and forms;
The signals layer includes the ground floor curtain coating substrate, second layer curtain coating substrate, the third layer curtain coating that from top to bottom overlap successively Substrate, the 4th laminar flow epitaxial substrate and layer 5 curtain coating substrate, an outer reaction electricity is set in the upper surface of ground floor curtain coating substrate Pole, it is exhausted with lower outer reaction electrode that upper surface and the lower surface of the outer reaction electrode are respectively provided with outer reaction electrode insulating barrier on Edge layer, and upper outer reaction electrode insulating barrier upper surface on outer reaction electrode also overlaps a protective layer;Base is cast in third layer The lower surface of piece is arranged with parallel in one at reaction electrode and a reference reaction electrode, and interior reaction electrode and reference reaction electrode In in same level, the reaction electricity of covering two is respectively provided with the upper surface of interior reaction electrode and reference reaction electrode and lower surface The upper reaction electrode insulating barrier and lower reaction electrode insulating barrier of pole reaction chamber;In the upper surface of the 4th laminar flow epitaxial substrate, diffusion is set Barrier layer, and diffusion barrier is with leachy alveolate texture;
One end of the reference reaction contact conductor A is connected with reference reaction electrode, and the other end sequentially passes through the 3rd from the bottom to top Reference reaction electrode leadout hole and outer reaction electrode after laminar flow epitaxial substrate, second layer curtain coating substrate and ground floor curtain coating substrate Be connected, form reference electrode extraction electrode pin, one end of interior reaction electrode lead B is connected with interior reaction electrode, the other end by Under it is supreme sequentially pass through third layer curtain coating substrate, the second layer curtain coating substrate and ground floor curtain coating substrate after interior reaction electrode lead Portal and be connected with outer reaction electrode, form interior reaction electrode extraction electrode pin;
The zone of heating includes the layer 6 curtain coating substrate, layer 7 curtain coating substrate and the 8th laminar flow that from top to bottom overlap successively Epitaxial substrate, the lower surface of upper surface and the 8th laminar flow epitaxial substrate of layer 6 curtain coating substrate be respectively arranged with a heating electrode and One heating electrode pin;Upper surface and the lower surface of the heating electrode are respectively provided with two and heat electrode dielectric layer and add with twice Thermode insulating barrier, the heating electrode is connected with heating electrode pin by a lead C, one end and the heating electricity of lead C Extremely it is connected, the other end from top to bottom sequentially passes through layer 6 curtain coating substrate, layer 7 curtain coating substrate and the 8th laminar flow epitaxial substrate On heating electrode leadout hole with heating electrode pin be connected, the 8th laminar flow epitaxial substrate lower surface with heat electrode pin upper table Heating electrode pin insulating barrier is additionally provided between face;
Wherein, ground floor curtain coating substrate to the material of the 8th laminar flow epitaxial substrate is zirconium oxide, and thickness is 115um;Outward Reaction electrode, interior reaction electrode and reference reaction electrode are heated electrode and are added using the strong platinum electrode of porous catalytic capability The aluminum oxide that the material selection of the material selection platinum slurry of thermode pin and corresponding each insulating barrier is matched from different platinum electrodes.
A kind of preparation method of above-mentioned novel slice type wide area automotive oxygen sensor, its innovative point is:The preparation method Comprise the following steps that:
(1)Prepare various casting slurries:
It is main powder with 5mol yttria-stabilized zirconias, solvent, dispersant, binding agent and plasticizer is added, wherein aoxidizing Zirconium powder body, solvent, dispersant, binding agent, the mass ratio of plasticizer are:1000:(300~500):(10~30):(50~80): (20~40), the casting slurry of stable and uniform is made up of ball-milling method;
It is main powder with carbon dust, adds solvent, dispersant, binding agent and plasticizer, wherein carbon dust, solvent, dispersant, bonding Agent, the mass ratio of plasticizer are:500:(300~500):(10~30):(50~80):(30~40), are made up of ball-milling method The casting slurry of stable and uniform;
Be main powder with 5mol yttria-stabilized zirconias, with carbon dust as pore creating material, add solvent, dispersant, binding agent and Plasticizer, wherein Zirconium powder, carbon dust, solvent, dispersant, binding agent, the mass ratio of plasticizer are:1000:(100~ 150):(300~500):(10~30):(50~80):(20~40), the casting slurry of stable and uniform is made up of ball-milling method;
(2)Flow casting molding:
Various casting slurries carry out curtain coating drying and shaping on casting machine, and drying temperature is 40~80 DEG C, and acquisition thickness is 115um Zirconium oxide curtain coating green compact winding;
(3)Trimming is cut:
The zirconium oxide of 115um is cast green compact winding on automatic slitter, the ground floor curtain coating of signals layer on sensor is cut into Substrate, second layer curtain coating substrate, third layer curtain coating substrate, the 4th laminar flow epitaxial substrate and layer 5 curtain coating substrate, the of zone of heating Six laminar flow epitaxial substrates, layer 7 curtain coating substrate and the 8th laminar flow epitaxial substrate;
(4)Punching:
In the ground floor curtain coating substrate, second layer curtain coating substrate, third layer curtain coating substrate, the 4th laminar flow epitaxial substrate and the 5th that cut out Laminar flow epitaxial substrate goes out reference reaction electrode leadout hole and interior reaction electrode leadout hole;Substrate, layer 7 stream are cast in layer 6 Heating electrode leadout hole is gone out on epitaxial substrate and the 8th laminar flow epitaxial substrate;
(5)Silk-screen printing:
In ground floor curtain coating substrate upper surface printing alumina slurry, lower outer reaction electrode insulating barrier is formed, then lower outer anti- Answer electrode dielectric layer upper surface to print Pt electrode slurrys, form outer reaction electrode, then oxidation is printed in outer reaction electrode upper surface Aluminum slurry, outer reaction electrode insulating barrier in formation, finally in upper outer reaction electrode insulating barrier printing external electrode protective layer;
Alumina slurry, reaction electrode insulating barrier in formation, then in upper reaction are printed in the lower surface of third layer curtain coating substrate Electrode dielectric layer lower surface prints Pt electrode slurrys, and interior reaction electrode and reference reaction electrode that formation be arranged in parallel finally exist Interior reaction electrode and reference reaction electrode lower surface printing alumina slurry, form lower reaction electrode insulating barrier;And at the 4th layer It is cast the diffusion barrier of the leachy alveolate texture of upper surface printer belt of substrate;
Alumina slurry twice is printed in layer 6 curtain coating substrate upper surface, twice heating electrode dielectric layers is formed, then under Heating electrode dielectric layer upper surface printing Pt electrode slurrys, form heating electrode, finally printing in heating electrode top twice Alumina slurry, to form and heat electrode dielectric layer on two;
Alumina slurry is printed in the lower surface of the 8th laminar flow epitaxial substrate, heating pin insulating barrier is formed, then insulated in pin Layer lower surface printing heating pin;
Each of which time printing all carries out the record of defective products by pattern detection system;
(6)Lamination:
All printings, the 8th populated laminar flow epitaxial substrate to ground floor curtain coating substrate are overlapped from the bottom to top, is finally folded The protective layer that closes forms lambda sensor green compact;
(7)Vacuum seal is moulded:
Upper steel plate is padded below lambda sensor green compact after overlapping, is then vacuum-packed;
(8)Warm isostatic pressed:
Warm water isostatic pressed compacting is carried out to packaged lambda sensor green compact, all curtain coating substrates is overlapped tight, isostatic pressed temperature It is 80 DEG C to spend, and the time is 30~60min, forms an entirety for stabilization, and the water outside packaging is dried after the completion of isostatic pressed, is taken out Lambda sensor green compact;
(9)Cutting:
Lambda sensor green compact to suppressing carry out heating cutting, carry out the pre-heat treatment to lambda sensor green compact first, make PVB soft Change, be easy to cutting, lambda sensor green compact and blade are heated simultaneously during cutting, cut into regular, accurate sensor base Piece;Wherein, cutting preheating temperature is 50~80 DEG C, and cutting platen temperature is 60~80 DEG C, and the temperature of cutting knife is 80 DEG C;
(10)Sintering:
Sensor substrate is set in high temperature furnace in sequence, is sintered according to sintering procedure, sintering temperature be 1400~ 1500 DEG C, soaking time is 2h.
Further, the step(1)In solvent be absolute ethyl alcohol and dimethylbenzene, dispersant is Modified Fish Oil, bond Agent is polyvinyl butyral resin, and plasticizer is BBP(Butyl Benzyl Phthalate.
The advantage of the invention is that:
(1)Novel slice type wide area automotive oxygen sensor of the invention, changes the interior reaction electrode and reference reaction electrode being stacked For same level is set so that the upper and lower surface of interior reaction electrode and reference reaction electrode can share same anti-respectively Insulating barrier is answered, the setting of reaction electrode insulating barrier is reduced, while also causing that overall structure is compacter, and then curtain coating can be improved The overall intensity of substrate;Upper and lower heating electrode dielectric layer is changed to bilayer by one layer, can be further ensured that heater circuit is wrapped completely It is rolled in heating electrode dielectric layer, completely cuts off with curtain coating substrate;Additionally, diffusion barrier is with leachy alveolate texture, because And it is more beneficial for the flowing of gas;And the structure design is without complicated air duct, by the ECU of car to reference electrode one Specified electric current realizes reference, solves air duct and changes in the presence of a harsh environment, so as to the situation for causing sensor inaccurate, It is applicable the use that vehicle is discharged with state five;This patent is adjusted by these, and the overall performance of oxidation sensors can be made more to stablize, And conformity of production is more preferable;
(2)The preparation method of novel slice type broad domain oxygen sensor of the present invention, using curtain coating green tape membrane operations, after greatly reducing The deformation of continuous printing drying belt, is that the multilayer chromatography of sensor brings very big help, and diaphragm to be difficult to be contaminated, it is easy to Overlapping;And preparation method of the invention, the technological parameter of each preparation process is strictly controlled, and then ensure that final products performance Stability;
(3)The preparation method of novel slice type broad domain oxygen sensor of the present invention, it is dispersant to use Modified Fish Oil, oxygen in Modified Fish Oil Content increases, being capable of more preferable wet granulate surface;It is adhesive to use polyvinyl butyral resin, film forming with height and good Good adhesive property;It is plasticizer to use BBP(Butyl Benzyl Phthalate, good with resin compatible, with good stain resistance, Plasticizing rate is fast.
Brief description of the drawings
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.
Fig. 1 is the structural representation of novel slice type wide area automotive oxygen sensor of the present invention.
Specific embodiment
The following examples can make professional and technical personnel that the present invention is more fully understood, but therefore not send out this It is bright to be limited among described scope of embodiments.
Embodiment
The present embodiment novel slice type wide area automotive oxygen sensor, as shown in figure 1, the sensor includes protective layer, signals layer And zone of heating from top to bottom overlap successively after sinter and form;
Signals layer includes ground floor curtain coating substrate 1, second layer curtain coating substrate 2, the third layer curtain coating base for from top to bottom overlapping successively Piece 3, the 4th laminar flow epitaxial substrate 4 and layer 5 curtain coating substrate 5, an outer reaction is set in the upper surface of ground floor curtain coating substrate 1 Electrode 22, upper surface and the lower surface of outer reaction electrode 22 are respectively provided with outer reaction electrode insulating barrier 23 and lower outer reaction electricity on one Pole insulating barrier 21, and the upper outer upper surface of reaction electrode insulating barrier 23 on outer reaction electrode also overlaps a protective layer 24; The lower surface of three laminar flow epitaxial substrates 3 is arranged with the reference reaction electrode 9 of reaction electrode 10 and in, and interior reaction electrode 10 in parallel It is in same level with reference reaction electrode 9, in the upper surface and lower surface of interior reaction electrode 10 and reference reaction electrode 9 It is respectively provided with the upper reaction electrode insulating barrier 20 and lower reaction electrode insulating barrier 19 of two reaction electrode reaction chambers of covering;At the 4th layer The upper surface for being cast substrate 4 sets diffusion barrier layer 11, and diffusion barrier 11 is with leachy alveolate texture.
One end of reference reaction contact conductor A is connected with reference reaction electrode 9, and the other end sequentially passes through the 3rd from the bottom to top The laminar flow epitaxial substrate 3, second layer is cast reference reaction electrode leadout hole and outer reaction after substrate 2 and ground floor curtain coating substrate 1 Electrode 22 is connected, and forms reference electrode extraction electrode pin, and one end of interior reaction electrode lead B is connected with interior reaction electrode 10, The other end sequentially passes through interior anti-after third layer curtain coating substrate, second layer curtain coating substrate and ground floor curtain coating substrate from the bottom to top Answer electrode leadout hole to be connected with outer reaction electrode 22, form interior reaction electrode extraction electrode pin.
Zone of heating includes the layer 6 curtain coating substrate 6, layer 7 curtain coating substrate 7 and the 8th layer that from top to bottom overlap successively Curtain coating substrate 8, a heating is respectively arranged with the upper surface of layer 6 curtain coating substrate 6 with the lower surface of the 8th laminar flow epitaxial substrate 8 Electrode 16 and one heats electrode pin 12;The upper surface for heating electrode 16 is disposed with heating electrode dielectric layer from top to bottom 18 and it is upper heating electrode dielectric layer 17, heat electrode 16 lower surface be disposed with from top to bottom it is lower heating electrode dielectric layer 15 With lower heating electrode dielectric layer 14;Heating electrode 16 is connected with heating electrode pin 12 by a lead C, one end of lead C Be connected with heating electrode 16, the other end from top to bottom sequentially passes through layer 6 curtain coating substrate 6, layer 7 and is cast substrate 7 and the 8 heating electrode leadout hole is connected with heating electrode pin 12 on eight laminar flow epitaxial substrates, in the lower surface of the 8th laminar flow epitaxial substrate 8 and Heating electrode pin insulating barrier 13 is additionally provided between heating electrode pin 12 upper surface.
Used as embodiment, more specifically implementation method is that ground floor curtain coating substrate to the material of the 8th laminar flow epitaxial substrate is Zirconium oxide, thickness is 115um;Outer reaction electrode 22, interior reaction electrode 10 and reference reaction electrode 9 are catalyzed using porous The strong platinum electrode of ability, the material of the material selection platinum slurry and corresponding each insulating barrier of heating electrode 16 and heating electrode pin 12 Matter is from the aluminum oxide matched from different platinum electrodes.
The preparation method of the present embodiment novel slice type wide area automotive oxygen sensor, it is characterised in that:The preparation method tool Body step is as follows:
(1)Prepare various casting slurries:
It is main powder with 5mol yttria-stabilized zirconias, solvent, dispersant, binding agent and plasticizer is added, wherein aoxidizing Zirconium powder body, solvent, dispersant, binding agent, the mass ratio of plasticizer are:1000:(300~500):(10~30):(50~80): (20~40), the casting slurry of stable and uniform is made up of ball-milling method;
It is main powder with carbon dust, adds solvent, dispersant, binding agent and plasticizer, wherein carbon dust, solvent, dispersant, bonding Agent, the mass ratio of plasticizer are:500:(300~500):(10~30):(50~80):(30~40), are made up of ball-milling method The casting slurry of stable and uniform;
Be main powder with 5mol yttria-stabilized zirconias, with carbon dust as pore creating material, add solvent, dispersant, binding agent and Plasticizer, wherein Zirconium powder, carbon dust, solvent, dispersant, binding agent, the mass ratio of plasticizer are:1000:(100~ 150):(300~500):(10~30):(50~80):(20~40), the casting slurry of stable and uniform is made up of ball-milling method; Wherein, solvent is absolute ethyl alcohol and dimethylbenzene, and dispersant is Modified Fish Oil, and binding agent is polyvinyl butyral resin, and plasticizer is BBP(Butyl Benzyl Phthalate;
(2)Flow casting molding:
Various casting slurries carry out curtain coating drying and shaping on casting machine, and drying temperature is 40~80 DEG C, and acquisition thickness is 115um Zirconium oxide curtain coating green compact winding;
(3)Trimming is cut:
The zirconium oxide of 115um is cast green compact winding on automatic slitter, the ground floor curtain coating of signals layer on sensor is cut into Substrate 1, second layer curtain coating substrate 2, third layer curtain coating substrate 3, the 4th laminar flow epitaxial substrate 4 and layer 5 curtain coating substrate 5, zone of heating Layer 6 curtain coating substrate 6, layer 7 curtain coating the laminar flow epitaxial substrate 8 of substrate 7 and the 8th;
(4)Punching:
In ground floor curtain coating substrate 1, second layer curtain coating substrate 2, the third layer curtain coating substrate 3, the and of the 4th laminar flow epitaxial substrate 4 that cut out Layer 5 curtain coating substrate 5 goes out reference reaction electrode leadout hole and interior reaction electrode leadout hole;Substrate 6, the are cast in layer 6 Heating electrode leadout hole is gone out on seven laminar flow epitaxial substrates 7 and the 8th laminar flow epitaxial substrate 8;
(5)Silk-screen printing:
In ground floor curtain coating substrate 1 upper surface printing alumina slurry, lower outer reaction electrode insulating barrier 21 is formed, then lower outer Pt electrode slurrys are printed in the upper surface of reaction electrode insulating barrier 21, form outer reaction electrode 22, then 22 surfaces on outer reaction electrode Printing alumina slurry, outer reaction electrode insulating barrier 23 in formation, finally in the upper outer printing of reaction electrode insulating barrier 23 external electrode Protective layer 24;
Alumina slurry, reaction electrode insulating barrier 20 in formation, then upper anti-are printed in the lower surface of third layer curtain coating substrate 3 Answer the lower surface of electrode dielectric layer 20 to print Pt electrode slurrys, form the interior reaction electrode 10 and reference reaction electrode 9 be arrangeding in parallel, It is last to print alumina slurry in interior reaction electrode 10 and the lower surface of reference reaction electrode 9, form lower reaction electrode insulating barrier 19; And the diffusion barrier 11 of the leachy alveolate texture of upper surface printer belt in the 4th laminar flow epitaxial substrate;
Alumina slurry twice is printed in layer 6 curtain coating substrate 6 upper surface, twice heating electrode dielectric layers is formed, then under Heating electrode dielectric layer 15 upper surface printing Pt electrode slurrys, form heating electrode 16, finally in heating electrode top printing Alumina slurry, to form and heat electrode dielectric layer on two twice;
Alumina slurry is printed in the lower surface of the 8th laminar flow epitaxial substrate 8, heating pin insulating barrier 13 is formed, it is then exhausted in pin Edge layer lower surface printing heating pin 12;
Each of which time printing all carries out the record of defective products by pattern detection system;
(6)Lamination:
All printings, the 8th populated laminar flow epitaxial substrate to ground floor curtain coating substrate are overlapped from the bottom to top, is finally folded The protective layer that closes forms lambda sensor green compact;
(7)Vacuum seal is moulded:
Upper steel plate is padded below lambda sensor green compact after overlapping, is then vacuum-packed;
(8)Warm isostatic pressed:
Warm water isostatic pressed compacting is carried out to packaged lambda sensor green compact, all curtain coating substrates is overlapped tight, isostatic pressed temperature It is 80 DEG C to spend, and the time is 30~60min, forms an entirety for stabilization, and the water outside packaging is dried after the completion of isostatic pressed, is taken out Lambda sensor green compact;
(9)Cutting:
Lambda sensor green compact to suppressing carry out heating cutting, carry out the pre-heat treatment to lambda sensor green compact first, make PVB soft Change, be easy to cutting, lambda sensor green compact and blade are heated simultaneously during cutting, cut into regular, accurate sensor base Piece;Wherein, cutting preheating temperature is 50~80 DEG C, and cutting platen temperature is 60~80 DEG C, and the temperature of cutting knife is 80 DEG C;
(10)Sintering:
Sensor substrate is set in high temperature furnace in sequence, is sintered according to sintering procedure, sintering temperature be 1400~ 1500 DEG C, soaking time is 2h.
Each performance parameter detection of this lambda sensor is as follows:
A sensor flatness detections:Sensor is lain on the workbench of high-flatness, with Thickness measuring instrument, in sensor Head, middle part, afterbody take three points respectively and tested, except protective layer region and track region, thickness difference is less than 0.05mm;
B sensor leakages are tested:By leakage tester, the air reference channel to sensor applies the pressure of 380KPa, lets out Leakage quantity is less than 0.1ml/min;
C sensor strength tests:Extracting several lambda sensors carries out destructive strength test, and lambda sensor bending strength is More than 400MPa;
D sensors adding thermal resistance is tested:The normal temperature resistance value of heating electrode, test knot are tested by heating pin with universal meter It is really as shown in the table:
Numbering 1# 2# 3# 4# 5# 6# 7# 8# 9# 10#
Resistance value(Ω) 3.1 2.7 2.9 3.1 2.8 2.9 3.2 3.3 3.5 3.3
Numbering 11# 12# 13# 14# 15# 16# 17# 18# 19# 20#
Resistance value(Ω) 3.0 2.9 3.2 3.4 2.8 3.1 3.5 3.0 2.7 2.6
As seen from the above table, lambda sensor distribution of resistance of the invention is uniform, qualification rate up to more than 95%, adding thermal resistance 3.2 ± 0.5 Ω, domestic many producers can only accomplish ± 1.5 Ω even ± 2 Ω;
E sensors insulating properties are tested:The testing heater insulaion resistance extreme to signal dispatch from foreign news agency is distinguished by the instrument that insulate, is added Insulaion resistance, signal dispatch from foreign news agency extreme insulaion resistance to reference electrode end, test result such as following table of the hot device to reference electrode end It is shown:
Detection project Test voltage(V) Examination criteria Measured value(MΩ)
The heater insulaion resistance extreme to signal dispatch from foreign news agency 800 ﹥ 100M Ω 683
Insulaion resistance of the heater to pump electrode end in signal 800 ﹥ 100M Ω 451
Insulaion resistance of the heater to reference electrode end 800 ﹥ 100M Ω 564
The extreme insulaion resistance to electrode tip in signal of signal dispatch from foreign news agency 800 ﹥ 100M Ω 450
The extreme insulaion resistance to pump electrode end in signal of signal dispatch from foreign news agency 800 ﹥ 100M Ω 350
The extreme insulaion resistance to reference electrode end of signal dispatch from foreign news agency 800 ﹥ 100M Ω 411
As seen from the above table, lambda sensor good insulation preformance of the invention;
After f assembles broad domain oxygen sensor chip, standard atmosphere demarcation is carried out:The sensor that will be assembled is sensed installed in oxygen On device distribution testboard, tested, first according to standard value, carried out the demarcation of build-out resistor, be then reconfigured at different atmosphere Standard Gases compare, show value is very accurate, and deviation is smaller, and it is as shown in the table that different λ values obtain measured data:
Test event Standard value 1# 2# 3# 4# 4# 5# 6#
Light-off time ≤25s 10.2 12.5 11.9 13 12.8 11.9 11.6
λ=0.8 λ=0.8±0.01 0.806 0.804 0.802 0.799 0.803 0.799 0.801
λ=1.0 λ=1.1±0.05 1.102 1.101 1.097 1.096 1.092 1.103 1.104
λ=1.7 λ=1.7±0.05 1.71 1.72 1.69 1.67 1.73 1.74 1.71
As seen from the above table:Lambda sensor prepared by the present invention meets the various use requirements of vehicle exhaust lambda sensor, sensor Flatness is good, and intensity is high, and technical process control is very good, and product percent of pass is high, and properties of product are more stablized, and production is consistent Property is more preferably.
General principle of the invention and principal character and advantages of the present invention has been shown and described above.The skill of the industry Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the simply explanation described in above-described embodiment and specification Principle of the invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appending claims and Its equivalent thereof.

Claims (3)

1. a kind of novel slice type wide area automotive oxygen sensor, it is characterised in that:The sensor include protective layer, signals layer and Zone of heating is sintered after from top to bottom overlapping successively and formed;
The signals layer includes the ground floor curtain coating substrate, second layer curtain coating substrate, the third layer curtain coating that from top to bottom overlap successively Substrate, the 4th laminar flow epitaxial substrate and layer 5 curtain coating substrate, an outer reaction electricity is set in the upper surface of ground floor curtain coating substrate Pole, it is exhausted with lower outer reaction electrode that upper surface and the lower surface of the outer reaction electrode are respectively provided with outer reaction electrode insulating barrier on Edge layer, and upper outer reaction electrode insulating barrier upper surface on outer reaction electrode also overlaps a protective layer;Base is cast in third layer The lower surface of piece is arranged with parallel in one at reaction electrode and a reference reaction electrode, and interior reaction electrode and reference reaction electrode In in same level, the reaction electricity of covering two is respectively provided with the upper surface of interior reaction electrode and reference reaction electrode and lower surface The upper reaction electrode insulating barrier and lower reaction electrode insulating barrier of pole reaction chamber;In the upper surface of the 4th laminar flow epitaxial substrate, diffusion is set Barrier layer, and diffusion barrier is with leachy alveolate texture;
One end of the reference reaction contact conductor A is connected with reference reaction electrode, and the other end sequentially passes through the 3rd from the bottom to top Reference reaction electrode leadout hole and outer reaction electrode after laminar flow epitaxial substrate, second layer curtain coating substrate and ground floor curtain coating substrate Be connected, form reference electrode extraction electrode pin, one end of interior reaction electrode lead B is connected with interior reaction electrode, the other end by Under it is supreme sequentially pass through third layer curtain coating substrate, the second layer curtain coating substrate and ground floor curtain coating substrate after interior reaction electrode lead Portal and be connected with outer reaction electrode, form interior reaction electrode extraction electrode pin;
The zone of heating includes the layer 6 curtain coating substrate, layer 7 curtain coating substrate and the 8th laminar flow that from top to bottom overlap successively Epitaxial substrate, the lower surface of upper surface and the 8th laminar flow epitaxial substrate of layer 6 curtain coating substrate be respectively arranged with a heating electrode and One heating electrode pin;Upper surface and the lower surface of the heating electrode are respectively provided with two and heat electrode dielectric layer and add with twice Thermode insulating barrier, the heating electrode is connected with heating electrode pin by a lead C, one end and the heating electricity of lead C Extremely it is connected, the other end from top to bottom sequentially passes through layer 6 curtain coating substrate, layer 7 curtain coating substrate and the 8th laminar flow epitaxial substrate On heating electrode leadout hole with heating electrode pin be connected, the 8th laminar flow epitaxial substrate lower surface with heat electrode pin upper table Heating electrode pin insulating barrier is additionally provided between face;
Wherein, ground floor curtain coating substrate to the material of the 8th laminar flow epitaxial substrate is zirconium oxide, and thickness is 115um;Outward Reaction electrode, interior reaction electrode and reference reaction electrode are heated electrode and are added using the strong platinum electrode of porous catalytic capability The aluminum oxide that the material selection of the material selection platinum slurry of thermode pin and corresponding each insulating barrier is matched from different platinum electrodes.
2. the preparation method of novel slice type wide area automotive oxygen sensor described in a kind of claim 1, it is characterised in that:The preparation Method is comprised the following steps that:
(1)Prepare various casting slurries:
It is main powder with 5mol yttria-stabilized zirconias, solvent, dispersant, binding agent and plasticizer is added, wherein aoxidizing Zirconium powder body, solvent, dispersant, binding agent, the mass ratio of plasticizer are:1000:(300~500):(10~30):(50~80): (20~40), the casting slurry of stable and uniform is made up of ball-milling method;
It is main powder with carbon dust, adds solvent, dispersant, binding agent and plasticizer, wherein carbon dust, solvent, dispersant, bonding Agent, the mass ratio of plasticizer are:500:(300~500):(10~30):(50~80):(30~40), are made up of ball-milling method The casting slurry of stable and uniform;
Be main powder with 5mol yttria-stabilized zirconias, with carbon dust as pore creating material, add solvent, dispersant, binding agent and Plasticizer, wherein Zirconium powder, carbon dust, solvent, dispersant, binding agent, the mass ratio of plasticizer are:1000:(100~ 150):(300~500):(10~30):(50~80):(20~40), the casting slurry of stable and uniform is made up of ball-milling method;
(2)Flow casting molding:
Various casting slurries carry out curtain coating drying and shaping on casting machine, and drying temperature is 40~80 DEG C, and acquisition thickness is 115um Zirconium oxide curtain coating green compact winding;
(3)Trimming is cut:
The zirconium oxide of 115um is cast green compact winding on automatic slitter, the ground floor curtain coating of signals layer on sensor is cut into Substrate, second layer curtain coating substrate, third layer curtain coating substrate, the 4th laminar flow epitaxial substrate and layer 5 curtain coating substrate, the of zone of heating Six laminar flow epitaxial substrates, layer 7 curtain coating substrate and the 8th laminar flow epitaxial substrate;
(4)Punching:
In the ground floor curtain coating substrate, second layer curtain coating substrate, third layer curtain coating substrate, the 4th laminar flow epitaxial substrate and the 5th that cut out Laminar flow epitaxial substrate goes out reference reaction electrode leadout hole and interior reaction electrode leadout hole;Substrate, layer 7 stream are cast in layer 6 Heating electrode leadout hole is gone out on epitaxial substrate and the 8th laminar flow epitaxial substrate;
(5)Silk-screen printing:
In ground floor curtain coating substrate upper surface printing alumina slurry, lower outer reaction electrode insulating barrier is formed, then lower outer anti- Answer electrode dielectric layer upper surface to print Pt electrode slurrys, form outer reaction electrode, then oxidation is printed in outer reaction electrode upper surface Aluminum slurry, outer reaction electrode insulating barrier in formation, finally in upper outer reaction electrode insulating barrier printing external electrode protective layer;
Alumina slurry, reaction electrode insulating barrier in formation, then in upper reaction are printed in the lower surface of third layer curtain coating substrate Electrode dielectric layer lower surface prints Pt electrode slurrys, and interior reaction electrode and reference reaction electrode that formation be arranged in parallel finally exist Interior reaction electrode and reference reaction electrode lower surface printing alumina slurry, form lower reaction electrode insulating barrier;And at the 4th layer It is cast the diffusion barrier of the leachy alveolate texture of upper surface printer belt of substrate;
Alumina slurry twice is printed in layer 6 curtain coating substrate upper surface, twice heating electrode dielectric layers is formed, then under Heating electrode dielectric layer upper surface printing Pt electrode slurrys, form heating electrode, finally printing in heating electrode top twice Alumina slurry, to form and heat electrode dielectric layer on two;
Alumina slurry is printed in the lower surface of the 8th laminar flow epitaxial substrate, heating pin insulating barrier is formed, then insulated in pin Layer lower surface printing heating pin;
Each of which time printing all carries out the record of defective products by pattern detection system;
(6)Lamination:
All printings, the 8th populated laminar flow epitaxial substrate to ground floor curtain coating substrate are overlapped from the bottom to top, is finally folded The protective layer that closes forms lambda sensor green compact;
(7)Vacuum seal is moulded:
Upper steel plate is padded below lambda sensor green compact after overlapping, is then vacuum-packed;
(8)Warm isostatic pressed:
Warm water isostatic pressed compacting is carried out to packaged lambda sensor green compact, all curtain coating substrates is overlapped tight, isostatic pressed temperature It is 80 DEG C to spend, and the time is 30~60min, forms an entirety for stabilization, and the water outside packaging is dried after the completion of isostatic pressed, is taken out Lambda sensor green compact;
(9)Cutting:
Lambda sensor green compact to suppressing carry out heating cutting, carry out the pre-heat treatment to lambda sensor green compact first, make PVB soft Change, be easy to cutting, lambda sensor green compact and blade are heated simultaneously during cutting, cut into regular, accurate sensor base Piece;Wherein, cutting preheating temperature is 50~80 DEG C, and cutting platen temperature is 60~80 DEG C, and the temperature of cutting knife is 80 DEG C;
(10)Sintering:
Sensor substrate is set in high temperature furnace in sequence, is sintered according to sintering procedure, sintering temperature be 1400~ 1500 DEG C, soaking time is 2h.
3. the preparation method of chip type wide-area automobile oxygen sensor according to claim 2, it is characterised in that:The step(1) In solvent be absolute ethyl alcohol and dimethylbenzene, dispersant is Modified Fish Oil, and binding agent is polyvinyl butyral resin, and plasticizer is neighbour Phthalic acid butyl benzyl.
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