CN101000320A - Chip oxygen sensor and its preparation method - Google Patents
Chip oxygen sensor and its preparation method Download PDFInfo
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- CN101000320A CN101000320A CN 200610157718 CN200610157718A CN101000320A CN 101000320 A CN101000320 A CN 101000320A CN 200610157718 CN200610157718 CN 200610157718 CN 200610157718 A CN200610157718 A CN 200610157718A CN 101000320 A CN101000320 A CN 101000320A
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Abstract
The invention discloses a sheet type oxygen sensor and its manufacturing method. It includes heater basal body, reference gas channel body, and zirconium oxide sensing basal body. Insulating layer is set between the former two. And its inner is set many heating bodies. The up and down surfaces of the third are respectively set outer and inner electrodes. The reference gas channel is connected with the space and atmosphere where the inner electrode is set. Heater and oxygen sensing probe are burned together high temperature to be a whole to form direct heating structure. The invention has the advantages of simple structure, small size and quality, saving energy, fast response speed, greatly shortening weighting time, and obvious economic and social benefits.
Description
Technical field
The present invention relates to a kind of chip oxygen sensor and preparation method thereof, more particularly, relate to a kind of automobile chip zirconia oxygen and preparation method thereof.
Background technology
Automobile industry development in the recent period is swift and violent, and exhaust emission standard constantly improves, and the requirement of oxygen sensor in use for car is also improved constantly.At present domestic what generally adopt is the tubular type zirconia oxygen, uses tubulose zirconium dioxide sensing probe, the middle aluminium oxide ceramics heating core of introducing, type of heating is an indirect heating, and response speed is slow, and size is big, complex structure is difficult to satisfy the exhaust emissions requirement of present increasingly stringent.
Summary of the invention
The objective of the invention is to overcome above-mentioned defective of the prior art, a kind of chip oxygen sensor and preparation method thereof is provided, and its meaning arrives the stand-by period that lambda sensor heats up and activates after being to shorten engine start, accelerates response speed, energy savings is improved the vehicle exhaust quality.
For achieving the above object; technical scheme provided by the invention is as follows: construct a kind of chip oxygen sensor; comprise well heater and oxygen sensing probe; described well heater comprises the well heater matrix; be located at the insulation course and the some calandrias that are located at described insulation course inside on described well heater matrix top; described oxygen sensing probe comprises the reference gas channel body that is located at described well heater top; be located at the responsive matrix of zirconia on described reference gas channel body top; be located at the external electrode and the interior electrode of the responsive matrix upper and lower surface of described zirconia respectively; the two ends of described each calandria stretch out respectively and converge and finally form two conductive pins at described well heater matrix underpart; be provided with porous protective layer at described external electrode upper surface; described external electrode and interior electrode stretch out respectively and the final electrode pin that forms on described porous protective layer top separately; be provided with reference gas passage in described reference gas channel body, described reference gas passage is communicated with described interior space, electrode place and atmosphere simultaneously.
Described reference gas width of channel and highly be respectively 0.5mm and 0.4mm.
Described chip oxygen sensor is prepared by following method:
A, employing flow casting molding technology and double-pole vocal imitation skill are made the responsive matrix of described well heater matrix, reference gas channel body and zirconia;
B, employing thick film screen printing technique are printed calandria, and are drawn conductive pin at the back side of well heater matrix on described well heater matrix;
C adopts the thick film screen printing technique to print described insulation course on described calandria outside surface;
Electrode and external electrode in D, employing thick film screen printing technique are printed on the responsive matrix of described zirconia;
E, make described porous protective layer at the external electrode outside surface;
F, employing thick film screen printing technique are printed described electrode pin and are made it to be communicated with interior electrode and external electrode respectively on described porous protective layer;
G, described well heater matrix, reference gas channel body and the responsive matrix of zirconia accurately are stacked according to level, form whole slab construction after, sinter molding after insulation a period of time in high temperature furnace.
The responsive matrix of described well heater matrix, reference gas channel body and zirconia is made in conjunction with the double-pole vocal imitation skill by the flow casting molding technology, idiographic flow is: at first add auxiliary material in 5% mole of yttrium partially stabilized Zirconium powder of oxidation, ball milling～hour mix fully is prepared into casting slurry, the viscosity of slurry is controlled to be 30～50Pa.s, pass through double-pole vocal imitation skill flow casting molding on accurate casting machine then, air dry or band auxiliary heating drying.
Described auxiliary material are one or more the potpourri in fish oil, olein, castor oil, PVB, PEG, ethanol and the butanone.
Described calandria, interior electrode, external electrode and electrode pin are to add aluminium oxide and the zirconia micro mist is made pure platinum slurry in platinum powder, adopt the thick film screen printing technique to be printed on separately the matrix then.
In described pure platinum slurry, add one or more the potpourri among fish oil, olein, castor oil, PVB and the PEG.
Described insulation course is to be that starting material adopt the thick film screen printing technique to be molded over the calandria outside surface with the aluminium oxide.
After the responsive matrix of described well heater matrix, reference gas channel body and zirconia accurately is stacked according to level, at 50-100 ℃, the pressure of 25～50MPa is incubated 1～3 hour sinter molding after forming whole slab construction down in 1400～1500 ℃ high temperature furnace.
Described porous protective layer is to be raw material with the aluminate micro mist, and the method by high temperature sintering or plasma sputtering electrode top outside forms.
The beneficial effect of a kind of chip oxygen sensor provided by the invention and preparation method thereof is:
1, adaptability is strong, is base material owing to adopted 5% mole of yttrium partially stabilized zirconia of oxidation, has promptly taken into account the intensity and the thermal stability of material, also takes into account the high-temperature electric conduction of material simultaneously, so the present invention can satisfy bad working environment in the engine.
3, response speed is fast, owing in the preparation raw material platinum powder of pure platinum slurry, added aluminium oxide and the side's of the adjusting resistance of zirconic micro mist, adhesion and formation microcellular structure, guaranteed penetrating smoothly of oxonium ion under the high temperature, shortened and arrived the stand-by period that lambda sensor heats up and activates after the engine start, accelerated response speed.
4, energy consumption is low, and the present invention adopts slice structure, and well heater and oxygen sensing probe are formed an integral body by high temperature co-firing, becomes real direct heating arrangement, and the power of calandria is 6～9 watts under direct current 12V voltage.This is about half of conventional tubular lambda sensor heating power.
5, good looking appearance, accurately control thickness owing to adopt advanced at present flow casting molding technology and double-pole vocal imitation skill, adopt the way of mechanical punching to reserve linked hole, the present invention simultaneously adopts the mode of high temperature co-firing, sintering was carried out in insulation in 1-3 hour in 1400-1500 ℃ high temperature furnace, special temperature control program is used for the preceding organic discharge of green compact of each functional layer densified sintering product in the sintering process, controls the distortion of product effectively.
6, long service life; with high-temperature behavior and the good magnesium aluminate spinel micro mist of structure; method by high temperature sintering or plasma sputtering forms porous protective layer on external electrode, alleviated the poison deactivation phenomenon of platinum electrode effectively, has prolonged product serviceable life.
Description of drawings
Fig. 1 is the vertical view of chip oxygen sensor;
Fig. 2 is the upward view of chip oxygen sensor;
Fig. 3 is the cut-open view of chip oxygen sensor.
Annotate: description of reference numerals
Well heater matrix (1); Insulation course (2); Calandria (3); Reference gas channel body (4); Reference gas passage (5); The responsive matrix (6) of zirconia; Interior electrode (7); External electrode (8); Well heater (9); Porous protective layer (10); Electrode pin (11); Conductive pin (12); Oxygen sensing probe (13).
Embodiment
With reference to Fig. 1; a kind of chip oxygen sensor and preparation method thereof is provided; chip oxygen sensor comprises well heater (9) and oxygen sensing probe (13); well heater (9) comprises well heater matrix (1); be located at the insulation course (2) on well heater matrix (1) top and be located at the inner some calandrias (3) of insulation course (2); oxygen sensing probe (13) comprises the reference gas channel body (4) that is located at well heater (9) top; be located at the responsive matrix (6) of zirconia on reference gas channel body (4) top; be located at the external electrode (8) and the interior electrode (7) of responsive matrix (6) upper and lower surface of zirconia respectively; the two ends of each calandria (3) stretch out respectively and converge and finally form in well heater matrix (1) bottom two conductive pins (12); be provided with porous protective layer (10) at external electrode (8) upper surface; external electrode (8) and interior electrode (7) stretch out respectively and finally form separately electrode pin (11) on porous protective layer (10) top; be provided with reference gas passage (5) in reference gas channel body (4), reference gas passage (5) is communicated with interior electrode (7) space, place and atmosphere simultaneously.
When the present invention specifically implements, with reference to Fig. 1 and 2, the responsive matrix of described well heater matrix (1), reference gas channel body (4), insulation course (2) and zirconia (6) accurately is stacked according to level, at 50-100 ℃, the pressure of 25～50MPa is incubated 1～3 hour sinter molding after forming whole slab construction down in 1400～1500 ℃ high temperature furnace.
The responsive matrix of well heater matrix (1), reference gas channel body (4) and zirconia (6) is to be that starting material are made by 5% mole of yttrium partially stabilized zirconia of oxidation, has taken into account the intensity and the thermal stability of material, also takes into account the high-temperature electric conduction of material simultaneously.Because the requirement of schistose texture and engine condition is abominable, the high strength of material is necessary, and 8% mole of yttria-stabilized zirconia of tradition during as flat substrates intensity can not reach requirement.
Reference gas passage (5) is a long and narrow end via, the width in hole and highly be 0.5*0.4mm, openend UNICOM atmosphere.The two sides of the responsive matrix of zirconia (6) is respectively the internal and external electrode (8) of thick film screen printing.Wherein internal and external electrode (8) all is microcellular structures, and oxonium ion penetrates smoothly under the assurance high temperature.Well heater matrix (1) is reserved connection holes connection electrode pin (11), and the calandria slurry must possess suitable adhesion and side's resistance, so that stable heating and the suitable power of product, the power of general calandria is 6～9 watts under direct current 12V voltage.This is about half of conventional tubular lambda sensor heating power.
The responsive matrix of well heater matrix (1), reference gas channel body (4) and zirconia (6) is to be base material with 5% mole of yttrium partially stabilized zirconia of oxidation, adopts advanced at present flow casting molding technology, and the double-pole mouth is accurately controlled thickness.Idiographic flow is: at first add in fish oil, olein, castor oil, PVB, PEG, ethanol and the butanone one or more in 5% mole of yttrium partially stabilized Zirconium powder of oxidation, ball milling mixed and is prepared into casting slurry in 15～20 hours fully, the viscosity of slurry is 30～50Pa.s, pass through double-pole vocal imitation skill flow casting molding on accurate casting machine then, air dry or band auxiliary heating drying.
Calandria, interior electrode (7), external electrode (8) and electrode pin (11) are that starting material are made by pure platinum slurry, described pure platinum slurry is to add aluminium oxide and zirconia micro mist in platinum powder, and adds among fish oil, olein, castor oil, PVB and the PEG one or more and make.Aluminium oxide and zirconia micro mist are used for the resistance of the side of adjusting, adhesion and formation microcellular structure; A kind of and multiple thixotropy and the levelability that is used for regulating slurry of fish oil, olein, castor oil, PVB, PEG guarantees the carrying out of meticulous printing.
Insulation course (2), calandria, interior electrode (7), external electrode (8) and electrode pin (11) adopt the thick film screen printing technique to be molded over respectively on the responsive matrix of described well heater matrix (1), reference gas channel body (4) and zirconia (6) by level.
The two sides of the responsive matrix of zirconia (6) is respectively the internal and external electrode (8) of thick film screen printing.Wherein internal and external electrode (8) all is microcellular structures, and oxonium ion penetrates smoothly under the assurance high temperature.Well heater matrix (1) is reserved connection holes connection electrode pin (11), and the calandria slurry must possess suitable adhesion and side's resistance, so that stable heating and the suitable power of product, the power of general calandria is 6～9 watts under direct current 12V voltage.This is about half of conventional tubular lambda sensor heating power.
Insulation course (2) is made by the aluminium oxide of high temperature resistance function admirable, adopts the technology and the technology of thick film serigraphy, is molded over the two sides of calandria, prevents that calandria under the high temperature (3) leakage of current from influencing external electrode (8) and interior electrode (7).
Porous protective layer (10) is to be raw material with the magnesium aluminate spinel micro mist high temperature resistant, that structure is good, and the method by high temperature sintering or plasma sputtering forms porous protective layer (10) at external electrode (8) upper surface.Porous protective layer (10) can alleviate external electrode (8) poison deactivation phenomenon effectively, prolongs product serviceable life.
Claims (10)
1; a kind of chip oxygen sensor and preparation method thereof; chip oxygen sensor comprises well heater (9) and oxygen sensing probe (13); it is characterized in that; described well heater (9) comprises well heater matrix (1); be located at the insulation course (2) on described well heater matrix (1) top and be located at the inner some calandrias (3) of described insulation course (2); described oxygen sensing probe (13) comprises the reference gas channel body (4) that is located at described well heater (9) top; be located at the responsive matrix (6) of zirconia on described reference gas channel body (4) top; be located at the external electrode (8) and the interior electrode (7) of responsive matrix (6) upper and lower surface of described zirconia respectively; the two ends of described each calandria (3) stretch out respectively and converge and finally form in described well heater matrix (1) bottom two conductive pins (12); be provided with porous protective layer (10) at described external electrode (8) upper surface; described external electrode (8) and interior electrode (7) stretch out respectively and finally form separately electrode pin (11) on described porous protective layer (10) top; be provided with reference gas passage (5) in described reference gas channel body (4), described reference gas passage (5) is communicated with described interior electrode (7) space, place and atmosphere simultaneously.
2, a kind of chip oxygen sensor according to claim 1 and preparation method thereof is characterized in that, the width of described reference gas passage (5) and highly be respectively 0.5mm and 0.4mm.
3, a kind of chip oxygen sensor and preparation method thereof is characterized in that, described chip oxygen sensor is prepared by following method:
A, employing flow casting molding technology and double-pole vocal imitation skill are made the responsive matrix (6) of described well heater matrix (1), reference gas channel body (4) and zirconia;
B, employing thick film screen printing technique are gone up at described well heater matrix (1) and are printed calandria (3), and draw conductive pin (12) at the back side of well heater matrix (1);
C, employing thick film screen printing technique are printed described insulation course (2) on described calandria (3) outside surface;
D, employing thick film screen printing technique electrode (7) and external electrode (8) in the responsive matrix of described zirconia (6) is gone up printing;
E, make described porous protective layer (10) at external electrode (8) outside surface;
F, employing thick film screen printing technique are printed described electrode pin (11) and are made it to be communicated with interior electrode (7) and external electrode (8) respectively on described porous protective layer (10);
G, described well heater matrix (1), reference gas channel body (4) and the responsive matrix of zirconia (6) accurately are stacked according to level, form whole slab construction after, sinter molding after insulation a period of time in high temperature furnace.
4, a kind of chip oxygen sensor according to claim 3 and preparation method thereof, it is characterized in that, described well heater matrix (1), the responsive matrix of reference gas channel body (4) and zirconia (6) is made in conjunction with the double-pole vocal imitation skill by the flow casting molding technology, idiographic flow is: at first add auxiliary material in 5% mole of yttrium partially stabilized Zirconium powder of oxidation, ball milling mixed and is prepared into casting slurry in 15～20 hours fully, the viscosity of slurry is controlled to be 30～50Pa.s, pass through double-pole vocal imitation skill flow casting molding on accurate casting machine then, air dry or band auxiliary heating drying.
5, a kind of chip oxygen sensor according to claim 4 and preparation method thereof is characterized in that, described auxiliary material are one or more the potpourri in fish oil, olein, castor oil, PVB, PEG, ethanol and the butanone.
6, a kind of chip oxygen sensor according to claim 3 and preparation method thereof, it is characterized in that, described calandria (3), interior electrode (7), external electrode (8) and electrode pin (11) are to add aluminium oxide and the zirconia micro mist is made pure platinum slurry in platinum powder, adopt the thick film screen printing technique to be printed on separately the matrix then.
7, a kind of chip oxygen sensor according to claim 6 and preparation method thereof is characterized in that, adds one or more the potpourri among fish oil, olein, castor oil, PVB and the PEG in described pure platinum slurry.
8, a kind of chip oxygen sensor according to claim 3 and preparation method thereof is characterized in that, described insulation course (2) is to be that starting material adopt the thick film screen printing technique to be molded over calandria (3) outside surface with the aluminium oxide.
9, a kind of chip oxygen sensor according to claim 3 and preparation method thereof, it is characterized in that, after the responsive matrix of described well heater matrix (1), reference gas channel body (4) and zirconia (6) accurately is stacked according to level, at 50-100 ℃, the pressure of 25～50MPa is incubated 1～3 hour sinter molding after forming whole slab construction down in 1400～1500 ℃ high temperature furnace.
10 a kind of chip oxygen sensors according to claim 3 and preparation method thereof is characterized in that, described porous protective layer (10) is to be raw material with the aluminate micro mist, and the method by high temperature sintering or plasma sputtering forms at external electrode (8) upper surface.
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