CN102140953B - Method for manufacturing oxygen sensor chip - Google Patents
Method for manufacturing oxygen sensor chip Download PDFInfo
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- CN102140953B CN102140953B CN2010106149952A CN201010614995A CN102140953B CN 102140953 B CN102140953 B CN 102140953B CN 2010106149952 A CN2010106149952 A CN 2010106149952A CN 201010614995 A CN201010614995 A CN 201010614995A CN 102140953 B CN102140953 B CN 102140953B
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- zirconium oxide
- oxygen sensor
- zirconia
- sensor chip
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/40—Engine management systems
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- Measuring Oxygen Concentration In Cells (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a method for manufacturing a platy oxygen sensor chip. The method comprises the following steps of: adding terpinol and paraffin into zirconia powder, and mixing to form a solid zirconia mixed material; compressing the solid zirconia mixed material to form a laminar zirconia blank; cutting the zirconia blank into the required platy zirconia substrate and naturally cooling and molding; uniformly coating a platinum paste layer for a heating rod and a platinum paste layer for an outer electrode of an engine body on two sides of the cooled zirconia substrate respectively and compressing to form a whole platy substrate; placing the platy substrate into a zirconia powder mixed material to form the required blank, and naturally cooling to remove the zirconia powder on the electrode part; and degreasing the blank and performing sinter molding to obtain the oxygen sensor chip. The porosity of the zirconia substrate is reduced so as to improve the density of the zirconia substrate, enhance the intensity and hardness of the zirconia substrate, accelerate the response of the zirconia chip, and the energy consumption of the zirconia chip.
Description
Technical field
The present invention relates to zirconia sensor and use the integrated chip technical field, especially a kind of production method of sheet oxygen sensor chip.
Background technique
Along with the raising day by day of automobile emission regulation, also increasingly high to toxic emission control requirement, the shorter cold start-up time of demand of auto engine meets the demands for this reason.Consider the needs of energy saving simultaneously; The chip oxygen sensor that a kind of level of integration is high, volume is little, consumed power is little, toggle speed is fast becomes a kind of trend; To satisfy the requirement that gets into closed loop control after the engine electric spray system cold start-up as far as possible fast, reduce the power consumption of lambda sensor simultaneously.
Present existing sheet type sensor structure mainly is made up of 3 layers of zirconium oxide substrate and some function thick-film layers, the method moulding that the zirconium oxide substrate mainly perhaps rolls film through curtain coating, and the thick film functional layer mainly obtains through screen printing technique.The potential electrode of lambda sensor and reference electrode are formed at respectively on the inner and outer surface of substrate, wash the middle part of substrate open long and narrow openning one through impact briquetting, so that form the reference air passageways; And by the platinum disposition of heating component of ceramic insulating layer parcel on the internal surface of bottom substrate; Also to make a call to two through holes the heating element of internal surface is coupled together with the terminal heating electrode sheet of outer surface, so just constitute the integrated chip oxygen sensor structure of sensing element and heating element at the end of substrate.But this structural thickness is thick, volume is big, production process is complicated, and heating element plants in sensor internal with the parcel form, and stability is poor, and electric leakage easily.Though patent " 03136011.4 " has proposed littler a kind of structure, mainly be aspect width, to reduce, and its structure at least also want 3 layers to make up, operation is also more complicated.
In order to address the above problem; Chinese patent number " 201010147931.6 " provides a kind of integrated chip type oxygen sensor and preparation method thereof, and its applying date is on April 16th, 2010, and open day is on August 18th, 2010; Its preparation method may further comprise the steps: the first step; The same PVB of the Zirconium oxide powder of 5% mole of yittrium oxide, terpineol and dibutyl phthalate (DBP) are prepared into slurry with the quality of 70～86:6～12:4～9:4～9 than mixing and ball milling, through double-pole vocal imitation skill flow casting molding, process zirconium oxide green compact band after the air dry then; Become the substrate base substrate through die stamping again, i.e. upper strata zirconium oxide substrate; The electrode slurry of 70%～90% platinum powder and the inner and outer surface that electrocondution slurry is printed on upper strata zirconium oxide substrate be will contain then, potential electrode and reference electrode formed; Inner surface electrode links to each other with the interior electrode connecting piece (19) of outer surface through the electrode connecting through hole that zirconium oxide substrate terminal punching press in upper strata forms; Second step, plumbago, PVB, terpineol and Softness Agent are mixed fully with the mass ratio of 30～46:20～30:16～24:10～24, but form the silk-screen printing slurry, and with this slurry printing and in covering on the electrode surface; This reference air diffusion slit printing layer width will be between upper strata zirconium oxide substrate and reference electrode width, and thickness will reach 15 to 50 microns, will form long and narrow slit behind the sintering; The 3rd step; The same PVB of the Zirconium oxide powder of 5% mole of yittrium oxide, terpineol and dibutyl phthalate (DBP) are prepared into slurry with the quality of 70～86:6～12:4～9:4～9 than mixing and ball milling; Then through double-pole vocal imitation skill flow casting molding; Process zirconium oxide green compact band after the air dry, become the substrate base substrate through die stamping again, be i.e. lower floor's zirconium oxide substrate; To contain the outer surface that slurry that purity reaches the alumina powder more than 97% is printed on lower floor's zirconium oxide substrate, the preparation alumina ceramic insulating layer; The electrocondution slurry that will contain platinum powder then is printed on this alumina ceramic insulating layer, and one-step print forms platinum heating element and heating electrode sheet; The 4th step; Next; With the tackiness agent that contains zirconia powder upper strata zirconium oxide substrate and lower floor zirconium oxide matrix plate stack are in the same place; Be heated to 40～60 degree and press closely simultaneously, the potential electrode end is immersed in the slurry contain magnesium aluminate spinel lift again, form the porous ceramics protective layer of parcel one; The 5th step merged parcel all-in-one-piece green compact and spends high temperature sinterings 1～3 hour 1300～1500, prepared integrated chip type oxygen sensor.But should technology also have following deficiency: one, owing to adopt low molecular mixing agent to carry out mixing and ball milling, voids is bigger on the formed mixture structure of molecule, thereby makes the zirconium body intensity of working it out not reach the needed strength demand of flow casting molding.Two, low molecule mixture is after making semi-finished product, because compactness does not reach requirement, thermal shock resistance is on the low side relatively, has a strong impact on its working life.Three, slurry is in the flow casting molding process, and the aforesaid operations temperature is prone to form stream shape thing and is difficult to excision forming between 40 ~ 60 degree.Four, coat in the electrode process owing to adopt 70% ~ 90% platinum powder mixture, be prone to make and cause electrode to interrupt in the screen printing process, increase reject rate.Five, in working process, adopting magnesium aluminate spinel to lift, is to be difficult to co-sintering with the formed matrix of Zirconium oxide powder.
Summary of the invention
The objective of the invention is to overcome the problems referred to above of the making method existence that has chip oxygen sensor now; A kind of production method of sheet oxygen sensor chip is provided; The present invention is through the porosity ratio in the reduction zirconium oxide matrix, thus the density of increase zirconium oxide matrix, the intensity of oxidation reinforced zirconium matrix and hardness; The response time of zirconium oxide core is accelerated, and reduced the energy consumption of zirconium oxide core.
For realizing above-mentioned purpose, the technological scheme that the present invention adopts is following:
A kind of production method of sheet oxygen sensor chip is characterized in that, comprises the steps:
A, Zirconium oxide powder is added down the zirconium oxide mixture that terpineol, paraffin mix the formation solid state at 120 ~ 180 degree, the mole proportioning of Zirconium oxide powder, terpineol and paraffin is 70 ~ 80:10 ~ 20:20 ~ 30;
B, the zirconium oxide mixture with solid state is pressed into laminar zirconium oxide idiosome again;
C, the zirconium oxide idiosome is cut into needed flaky zirconia matrix, natural cooling moulding;
D, evenly coat respectively in cooled zirconium oxide matrix both sides heating stick with platinum slurry layer and body external electrode with platinum slurry layer, be pressed into whole flaky matrix again;
E, flaky matrix is put into the Zirconium oxide powder mixture form required blank, remove the Zirconium oxide powder of electrode part office behind the natural cooling;
F, again with blank degreasing, sinter molding oxygen sensor chip.
In the said A step, the hardness HRA of the zirconium oxide mixture of solid state>30.
In the said A step, contain 3-8mol yittrium oxide in the Zirconium oxide powder.
In the said B step, the zirconium oxide mixture of solid state is pressed into laminar zirconium oxide idiosome repeatedly for 3 ~ 5 times.
Adopt the mode of punching press to suppress in the said B step, pressure is 1 ~ 2 ton.
The thickness of laminar zirconium oxide idiosome should remain in 1 millimeter in the said B step.
In the said C step, be to be slit into needed flaky zirconia matrix through die cuts with the zirconium oxide idiosome, cutting pressure is 120-180 tons.
Heating stick in the said D step uses platinum slurry layer and body external electrode to use the resistance value of platinum slurry layer to be 8-10 ohm.
Pressure in the said D step is 1 ~ 2 ton.
In the said F step, be 300 ~ 1450 ℃ in temperature and carry out degreasing, sintering.
In the said F step, degreasing, sintering carry out in protection compression ring border.
Employing the invention has the advantages that:
One, the present invention can reduce the porosity ratio in the zirconium oxide matrix, thereby increases the density of zirconium oxide matrix, the intensity of oxidation reinforced zirconium matrix and hardness; The response time of zirconium oxide core is accelerated; And reduced the energy consumption of zirconium oxide core, improved the working life of zirconium oxide chip, technology of the present invention has effectively reduced cost of production; Simplify preparation process, be suitable for producing in batches.
Two, adopt the oxygen sensor chip of the present invention's preparation, can reduce emission of automobile wastes and pollute, increase the burning degree of atmosphere in the BBG; Practiced thrift the burning cost of gasoline, oxygen sensor chip has simple in structure, the response time short (being less than 10 seconds); Measuring range wide (from ppm to the percentage composition), serviceability temperature high (350～800 ℃), reliable; Easy for installation, therefore advantage such as maintenance is little is widely used on automobile.
Three, among the present invention; The Zirconium oxide powder mixture that will contain 3-8mol yittrium oxide composition passes through the zirconium oxide mixture that the proportioning suitable adhesive forms solid state under 120 ~ 180 temperature; The zirconium oxide mixture of solid state has certain rigidity, is suitable for producing ceramic matrix and uses.
Four, among the present invention; The zirconium oxide mixture of solid state is pressed into laminar zirconium oxide idiosome; Make the zirconium oxide idiosome of producing possess very high intensity and hardness, it is not enough to have solved casting molding processes produces in the tratitional technology idiosome intensity, hardness, the difficulty of processing that is produced.
Five, among the present invention, the zirconium oxide idiosome is cut into needed flaky zirconia matrix, natural cooling moulding; Solve the deficiency that the air-dry cooling of slurry exists in the tratitional technology, made the zirconium oxide material have certain intensity, reduced manufacturing process steps; Reduce production costs easy-to-operat.
Six, among the present invention; Evenly coat heating stick in cooled zirconium oxide matrix both sides respectively and starch layer with platinum, be pressed into whole flaky matrix again, the platinum slurry evenly is coated with on the zirconium oxide stock with platinum slurry layer and body external electrode; Heater band electrode and probe electrode are separated compacting; Stopped the influence of double-disk zirconium oxide core heater band electrode pair internal and external electrode signal, and it is long to have solved the corresponding time of startup that tubular type zirconium oxide core exists, reaction velocity waits a series of problems slowly.
Seven, among the present invention; Flaky matrix is put into the Zirconium oxide powder mixture; Lift into required blank, remove the Zirconium oxide powder of electrode part office behind the natural cooling, owing to adopt and the equal raw material of zirconium oxide matrix; Make the zirconium oxide sheet be easier to co-sintering, solved other technology co-sintering sheet matrixes and rim charge sintering and peeled off the problem that produces the space.
Eight, among the present invention, carry out degreasing, sinter molding oxygen sensor chip, degreasing, sintering process are combined, increased the yield rate of sinter molding, reach batch production requirements.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Embodiment 1
A kind of production method of sheet oxygen sensor chip comprises the steps:
A, Zirconium oxide powder is added down the zirconium oxide mixture that terpineol, paraffin mix the formation solid state at 120 degree, the mole proportioning of Zirconium oxide powder, terpineol and paraffin is 70:10:20;
B, the zirconium oxide mixture with solid state is pressed into laminar zirconium oxide idiosome again;
C, the zirconium oxide idiosome is cut into needed flaky zirconia matrix, natural cooling moulding;
D, evenly coat respectively in cooled zirconium oxide matrix both sides heating stick with platinum slurry layer and body external electrode with platinum slurry layer, be pressed into whole flaky matrix again;
E, flaky matrix is put into the Zirconium oxide powder mixture form required blank, remove the Zirconium oxide powder of electrode part office behind the natural cooling;
F, again blank is carried out degreasing, sinter molding oxygen sensor chip.
Optimal way of the present invention does, in the A step, and the hardness HRA of the zirconium oxide mixture of solid state>30.
Optimal way of the present invention is in the A step, to contain the 3mol yittrium oxide in the Zirconium oxide powder.
Optimal way of the present invention does, in the B step, the zirconium oxide mixture of solid state is pressed into laminar zirconium oxide idiosome repeatedly for 3 times.Reach the corresponding thickness requirement through suppressing repeatedly, and reduce the quantity of solid mixture inner air vent.
Optimal way of the present invention does, adopts the mode of punching press to suppress in the B step, and pressure is 1 ton.
Optimal way of the present invention is that the thickness of laminar zirconium oxide idiosome should remain in 1 millimeter in the B step.
Optimal way of the present invention does, in the C step, is to be slit into needed flaky zirconia matrix through die cuts with the zirconium oxide idiosome, and cutting pressure is 120 tons.
Optimal way of the present invention is that it is 8 ohm that the heating stick in the D step uses platinum slurry layer and body external electrode to use the resistance value of platinum slurry layer.
Optimal way of the present invention is that the pressure in the D step is 1 ton.
Optimal way of the present invention does, in the F step, is 300 ℃ in temperature and carries out degreasing, sintering, and degreasing, sintering process are identical with existing technology.
Optimal way of the present invention is that in the F step, degreasing, sintering carry out in protection compression ring border.
Embodiment 2
A kind of production method of sheet oxygen sensor chip comprises the steps:
A, Zirconium oxide powder is added down the zirconium oxide mixture that terpineol, paraffin mix the formation solid state at 180 degree, the mole proportioning of Zirconium oxide powder, terpineol and paraffin is 80:20:30;
B, the zirconium oxide mixture with solid state is pressed into laminar zirconium oxide idiosome again;
C, the zirconium oxide idiosome is cut into needed flaky zirconia matrix, natural cooling moulding;
D, evenly coat respectively in cooled zirconium oxide matrix both sides heating stick with platinum slurry layer and body external electrode with platinum slurry layer, be pressed into whole flaky matrix again;
E, flaky matrix is put into the Zirconium oxide powder mixture form required blank, remove the Zirconium oxide powder of electrode part office behind the natural cooling;
F, again with blank degreasing, sinter molding oxygen sensor chip.
Optimal way of the present invention does, in the A step, and the hardness HRA of the zirconium oxide mixture of solid state>30.
Optimal way of the present invention is in the A step, to contain the 8mol yittrium oxide in the Zirconium oxide powder.
Optimal way of the present invention does, in the B step, the zirconium oxide mixture of solid state is pressed into laminar zirconium oxide idiosome repeatedly for 5 times.
Optimal way of the present invention does, adopts the mode of punching press to suppress in the B step, and pressure is 2 tons.
Optimal way of the present invention is that the thickness of laminar zirconium oxide idiosome should remain in 1 millimeter in the B step.
Optimal way of the present invention does, in the C step, is to be slit into needed flaky zirconia matrix through die cuts with the zirconium oxide idiosome, and cutting pressure is 180 tons.
Optimal way of the present invention is that it is 10 ohm that the heating stick in the D step uses platinum slurry layer and body external electrode to use the resistance value of platinum slurry layer.
Optimal way of the present invention is that the pressure in the D step is 2 tons.
Optimal way of the present invention is in the F step, to be 1450 ℃ in temperature and to carry out degreasing, sintering.
Optimal way of the present invention is that in the F step, degreasing, sintering carry out in protection compression ring border.
Embodiment 3
A kind of production method of sheet oxygen sensor chip comprises the steps:
A, Zirconium oxide powder is added down the zirconium oxide mixture that terpineol, paraffin mix the formation solid state at 150 degree, the mole proportioning of Zirconium oxide powder, terpineol and paraffin is 75:15:25;
B, the zirconium oxide mixture with solid state is pressed into laminar zirconium oxide idiosome again;
C, the zirconium oxide idiosome is cut into needed flaky zirconia matrix, natural cooling moulding;
D, evenly coat respectively in cooled zirconium oxide matrix both sides heating stick with platinum slurry layer and body external electrode with platinum slurry layer, be pressed into whole flaky matrix again;
E, flaky matrix is put into the Zirconium oxide powder mixture form required blank, remove the Zirconium oxide powder of electrode part office behind the natural cooling;
F, again with blank degreasing, sinter molding oxygen sensor chip.
In the said A step, the hardness HRA of the zirconium oxide mixture of solid state>30.
Optimal way of the present invention is in the A step, to contain the 5mol yittrium oxide in the Zirconium oxide powder.
Optimal way of the present invention does, in the B step, the zirconium oxide mixture of solid state is pressed into laminar zirconium oxide idiosome repeatedly for 4 times.
Optimal way of the present invention does, adopts the mode of punching press to suppress in the B step, and pressure is 1.5 tons.
Optimal way of the present invention is that the thickness of laminar zirconium oxide idiosome should remain in 1 millimeter in the B step.
Optimal way of the present invention does, in the C step, is to be slit into needed flaky zirconia matrix through die cuts with the zirconium oxide idiosome, and cutting pressure is 150 tons.
Optimal way of the present invention is that it is 9 ohm that the heating stick in the D step uses platinum slurry layer and body external electrode to use the resistance value of platinum slurry layer.
Optimal way of the present invention is that the pressure in the D step is 1.2 tons.
Optimal way of the present invention is in the F step, to be 1000 ℃ in temperature and to carry out degreasing, sintering.
Optimal way of the present invention is that in the F step, degreasing, sintering carry out in protection compression ring border.
Embodiment 4
A kind of production method of sheet oxygen sensor chip comprises the steps:
A, the Zirconium oxide powder that will contain the 6mol yittrium oxide add the zirconium oxide mixture that terpineol, paraffin mix the formation solid state down at 160 degree, and the mole proportioning of Zirconium oxide powder, terpineol and paraffin is 76:16:26;
B, the zirconium oxide mixture with solid state is pressed into laminar zirconium oxide idiosome again, and pressure should guarantee evenly, and pressure is at 2 tons, and suppresses with the mode of punching press, and sheet thickness should remain in 1 millimeter;
C, the zirconium oxide idiosome is cut into needed flaky zirconia matrix, natural cooling moulding;
D, evenly coat respectively in cooled zirconium oxide matrix both sides heating stick with platinum slurry layer and body external electrode with platinum slurry layer; And the resistance value that makes heating stick starch layer with platinum slurry layer and body external electrode with platinum reaches in 8-10 ohm, presses down at 2 tons of pressure and processes whole flaky matrix;
E, flaky matrix is put into the Zirconium oxide powder mixture form required blank, in the Zirconium oxide powder mixture that flaky matrix was wrapped in contain 3-8mol yittrium oxide, remove the Zirconium oxide powder of electrode part office behind the natural cooling;
F, carry out degreasing, sinter molding oxygen sensor chip again, carry out degreasing, sintering at persistently overheating 300 ~ 1450 ℃.
In the A step, the hardness of the zirconium oxide mixture of solid state is HRA>30.
In the B step, the zirconium oxide mixture of solid state is pressed into laminar zirconium oxide idiosome repeatedly for 4 times.Reach the corresponding thickness requirement through suppressing repeatedly, and reduce the quantity of solid mixture inner air vent.
In the C step, with the zirconium oxide idiosome through cutting into needed flaky zirconia matrix under the die-cut.In the F step, degreasing, sintering carry out in protection compression ring border.
Claims (9)
1. the production method of a sheet oxygen sensor chip is characterized in that, comprises the steps:
A, Zirconium oxide powder is added down the zirconium oxide mixture that terpineol, paraffin mix the formation solid state at 120 ~ 180 degree, the mole proportioning of Zirconium oxide powder, terpineol and paraffin is 70 ~ 80:10 ~ 20:20 ~ 30;
B, the zirconium oxide mixture with solid state is pressed into laminar zirconium oxide idiosome again;
C, the zirconium oxide idiosome is cut into needed flaky zirconia matrix, natural cooling moulding;
D, evenly coat respectively in cooled zirconium oxide matrix both sides heating stick with platinum slurry layer and body external electrode with platinum slurry layer, be pressed into whole flaky matrix again;
E, flaky matrix is put into the Zirconium oxide powder mixture form required blank, remove the Zirconium oxide powder of electrode part office behind the natural cooling;
F, again with blank degreasing, sinter molding oxygen sensor chip.
2. the production method of sheet oxygen sensor chip according to claim 1 is characterized in that: in the said A step, and the hardness HRA of the zirconium oxide mixture of solid state>30.
3. the production method of sheet oxygen sensor chip according to claim 1 and 2 is characterized in that: in the said B step, the zirconium oxide mixture of solid state is pressed into laminar zirconium oxide idiosome repeatedly for 3 ~ 5 times.
4. the production method of sheet oxygen sensor chip according to claim 3 is characterized in that: adopt the mode of punching press to suppress in the said B step, pressure is 1 ~ 2 ton.
5. the production method of sheet oxygen sensor chip according to claim 4 is characterized in that: the thickness of laminar zirconium oxide idiosome should remain in 1 millimeter in the said B step.
6. according to the production method of claim 1,2,4 or 5 described sheet oxygen sensor chips, it is characterized in that: in the said C step, the zirconium oxide idiosome is to be slit into needed flaky zirconia matrix through die cuts, and cutting pressure is 120-180 tons.
7. the production method of sheet oxygen sensor chip according to claim 6 is characterized in that: the heating stick in the said D step uses platinum slurry layer and body external electrode to use the resistance value of platinum slurry layer to be 8-10 ohm.
8. the production method of sheet oxygen sensor chip according to claim 7 is characterized in that: the pressure in the said D step is 1 ~ 2 ton.
9. the production method of sheet oxygen sensor chip according to claim 8 is characterized in that: in the said F step, be 300 ~ 1450 ℃ in temperature and carry out degreasing, sintering.
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| CN2010106149952A CN102140953B (en) | 2010-12-30 | 2010-12-30 | Method for manufacturing oxygen sensor chip |
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| CN2010106149952A CN102140953B (en) | 2010-12-30 | 2010-12-30 | Method for manufacturing oxygen sensor chip |
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| CN102140953B true CN102140953B (en) | 2012-07-11 |
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| CN103776871B (en) * | 2014-01-15 | 2016-06-29 | 深圳市普利斯通传感科技有限公司 | A kind of oxygen sensor used in vehicle based on oxide casting slurry and manufacture method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH03274451A (en) * | 1990-03-24 | 1991-12-05 | Japan Electron Control Syst Co Ltd | Manufacture of oxygen sensor for internal combustion engine |
| DE202004015400U1 (en) * | 2004-10-04 | 2004-12-16 | Aceos Gmbh | Oxygen sensor for e.g. medical equipment has electrically insulated base plate under first layer which is solid electrolyte and second layer with two electrodes |
| CN1865970A (en) * | 2006-06-13 | 2006-11-22 | 上海星华工艺书画刻字印刷商社 | Method for fabricating sheet oxygen sensor |
| CN100487444C (en) * | 2007-04-24 | 2009-05-13 | 谢光远 | Manufacturing method of plate type oxygen sensor chip |
| CN101408525B (en) * | 2008-09-09 | 2010-06-23 | 深圳市日理江澍实业有限公司 | Method for preparing oxygen sensor external platinum electrode |
| CN101718743B (en) * | 2009-11-30 | 2013-03-20 | 宁波大学 | Method for preparing mixed conductor dense diffusion barrier-type oxygen sensor |
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