CN107858628A - The preparation method of lambda sensor dielectric substrate and fine and close diffusion layer double-decker - Google Patents

The preparation method of lambda sensor dielectric substrate and fine and close diffusion layer double-decker Download PDF

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CN107858628A
CN107858628A CN201711208999.9A CN201711208999A CN107858628A CN 107858628 A CN107858628 A CN 107858628A CN 201711208999 A CN201711208999 A CN 201711208999A CN 107858628 A CN107858628 A CN 107858628A
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fine
close
dielectric substrate
diffusion layer
powder
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刘涛
王相南
李静云
易茂义
莫扬成
于景坤
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Northeastern University China
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/409—Oxygen concentration cells

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Abstract

The present invention relates to oxygen sensor technical field, more particularly to the preparation method of lambda sensor dielectric substrate and fine and close diffusion layer double-decker.Preparation method provided by the present invention, it is that fine and close diffusion layer is formed using plasma spray coating process on electrolyte layer base, or dielectric substrate is formed using plasma spray coating process on fine and close diffusive layer base.The bond strength of dielectric substrate and fine and close diffusion layer is high in dielectric substrate and fine and close diffusion layer double-decker that the preparation method is prepared, and preparation speed is fast, suitable for large-scale production.

Description

The preparation method of lambda sensor dielectric substrate and fine and close diffusion layer double-decker
Technical field
The present invention relates to oxygen sensor technical field, more particularly to lambda sensor dielectric substrate and fine and close diffusion The preparation method of layer double-decker.
Background technology
At present, oxygen sensor is broadly divided into concentration potential type lambda sensor and limit-current type oxygen sensor.Pole Flow pattern of rationing the power supply lambda sensor is divided into pinhole type limit-current type oxygen sensor, porous type limit-current type oxygen sensor and fine and close expansion Barrier layer limit-current type oxygen sensor is dissipated, wherein, the above two, which exist, involves great expense, pore deformation and solid particle often occurs The defects of blocking.Compare, dense diffusion barrier limit-current type oxygen sensor is led as a result of oxonium ion-electronics mixing Body is as dense diffusion barrier, the problem of can overcoming pore plugging, service behaviour is more stable, the response time is sensitiveer, Life-span is longer.The cross-sectional view of dense diffusion barrier limit-current type oxygen sensor is as shown in figure 1, dense diffusion barrier A layer limit-current type oxygen sensor is hindered to generally comprise positive pole, negative pole, dense diffusion barrier (referred to as fine and close diffusion layer), solid electricity Solve matter layer (abbreviation dielectric substrate) and elevated-temperature seal glass glaze.
Dense diffusion barrier limit-current type oxygen sensor can be utilized and prepared the methods of Co-sintering and compound ceramics. Wherein, using Co-sintering method, because fine and close diffusion layer material and dielectric substrate material thermal coefficient of expansion and sintering receive Shrinkage mismatches, and easily causes sintered body cracked during co-sintering, influences the expansion of oxonium ion in the sensor Dissipate.Using ceramics composite algorithm, oxygen determination is functional, but the method long preparation period, process are cumbersome, and is prepared in normal sintering Fine and close diffusion layer contain increased number of stomata, be unfavorable for mass producing.
The content of the invention
(1) technical problems to be solved
It is an object of the invention to provide the preparation of a kind of lambda sensor dielectric substrate and fine and close diffusion layer double-decker Dielectric substrate and fine and close diffusion layer in method, the dielectric substrate prepared by the preparation method and fine and close diffusion layer double-decker Bond strength is high, and preparation speed is fast, suitable for large-scale production.
(2) technical scheme
In order to achieve the above object, the main technical schemes that the present invention uses include：
One aspect of the present invention provides the preparation method of a kind of lambda sensor dielectric substrate and fine and close diffusion layer double-decker, Comprise the following steps：S1, prepare electrolyte layer base；S2, cause is formed on electrolyte layer base using plasma spray coating process Close diffusive layer base, wherein, the process conditions of plasma spray coating process are：Arc current is 600-900A, arc voltage 40- 60V, powder feeding rate are 20-60g/min, spray distance 80-110mm, and working gas includes nitrogen and/or argon gas, powder carrier gas Including nitrogen and/or argon gas；S3, the electrolyte layer base with fine and close diffusive layer base is sintered；S4, to sintering after Electrolyte layer base with fine and close diffusive layer base is cooled down, and the fine and close diffusive layer base after cooling forms fine and close diffusion Layer, the electrolyte layer base after cooling form dielectric substrate, and fine and close diffusion layer is stacked on top of each other with dielectric substrate and is connected, and are formed double Rotating fields.
According to the present invention, in step s 2, the process conditions of plasma spray coating process are：Working gas is by nitrogen and hydrogen The gaseous mixture of gas composition, the wherein flow-rate ratio of nitrogen and hydrogen are 20:1, the pressure of working gas is 1.2-1.4MPa, work gas The flow of body is 1150-1250L/h；Arc current is 620-640A；Arc voltage is 44-48V；Powder carrier gas is argon gas, powder The pressure of last carrier gas is 0.1-0.15MPa, and the flow of powder carrier gas is 220-260L/h；Powder feeding rate is 35-40g/min；Spraying Distance is 85-90mm；Spray angle is 75 ° -90 °.
According to the present invention, step S2 includes following sub-step：S2.1, electrolyte layer base is put into and plated in membrane cavity；S2.2、 Plating membrane cavity is evacuated to vacuum as 1 × 10-3-2×10-3Pa；S2.3, inert gas is filled with into plating membrane cavity, until wherein Pressure reaches 0.3-0.4Pa；S2.4, heating electrolyte layer base are to 50-60 DEG C；S2.5, using plasma spray coating process will etc. Gas ions densification diffusion layer Powder aerosol is sprayed on electrolyte layer base, forms fine and close diffusive layer base.
According to the present invention, step S1 includes following sub-step：S1.1, dielectric substrate material powder is squeezed into dielectric substrate Flaky matrix；S1.2, dielectric substrate flaky matrix is sintered；S1.3, by after sintering dielectric substrate flaky matrix cool down To room temperature；S1.4, the sprayed surface to the dielectric substrate flaky matrix after cooling are roughened, and reach its roughness Ra0.07-0.06 μm, form electrolyte layer base.
According to the present invention, in step s 2, the particle diameter of fine and close diffusion layer powder used by fine and close diffusive layer base is formed For 50-70nm.
Another aspect of the present invention provides the preparation side of a kind of lambda sensor dielectric substrate and fine and close diffusion layer double-decker Method, comprise the following steps：S1, prepare fine and close diffusive layer base；S2, using plasma spray coating process on fine and close diffusive layer base Electrolyte layer base is formed, wherein, the process conditions of plasma spray coating process are：Arc current is 600-900A, arc voltage For 40-60V, powder feeding rate is 20-60g/min, spray distance 80-110mm, and working gas includes nitrogen and/or argon gas, powder Carrier gas includes nitrogen and/or argon gas；S3, the fine and close diffusive layer base with electrolyte layer base is sintered；S4, to sintering The fine and close diffusive layer base with electrolyte layer base afterwards is cooled down, and the fine and close diffusive layer base after cooling forms fine and close expansion Layer is dissipated, the electrolyte layer base after cooling forms dielectric substrate, and fine and close diffusion layer is stacked on top of each other with dielectric substrate and is connected, and is formed Double-decker.
According to the present invention, in step s 2, the process conditions of plasma spray coating process are：Working gas is by nitrogen and hydrogen The gaseous mixture of gas composition, the wherein flow-rate ratio of nitrogen and hydrogen are 18:1, the pressure of working gas is 1.1-1.3MPa, work gas The flow of body is 1150-1230L/h；Arc current is 625-650A；Arc voltage is 45-50V；Powder carrier gas is argon gas, powder The pressure of last carrier gas is 0.2-0.3MPa, and the flow of powder carrier gas is 235-265L/h；Powder feeding rate is 30-38g/min；Spraying away from From for 90-100mm；Spray angle is 75 ° -90 °.
According to the present invention, step S2 includes following sub-step：S2.1, fine and close diffusive layer base is put into and plated in membrane cavity； S2.2, plating membrane cavity is evacuated to vacuum as 1 × 10-3-2×10-3Pa；S2.3, inert gas is filled with into plating membrane cavity, directly Reach 0.3-0.4Pa to wherein pressure；S2.4, the fine and close diffusive layer base of heating are to 60-70 DEG C；S2.5, using plasma spraying Plasma electrolysis matter layer Powder aerosol is sprayed on fine and close diffusive layer base by technique, forms electrolyte layer base.
According to the present invention, step S1 includes following sub-step：S1.1, fine and close diffusion layer material powder is squeezed into fine and close expansion Dissipate lamellar matrix；S1.2, fine and close diffusion layer flaky matrix is sintered；S1.3, by the fine and close diffusion lamellar after sintering Matrix is cooled to room temperature；S1.4, the sprayed surface to the fine and close diffusion layer flaky matrix after cooling are roughened, and make it Roughness reaches Ra0.07-0.06 μm, forms fine and close diffusive layer base.
According to the present invention, in step s 2, the particle diameter for forming dielectric substrate powder used by electrolyte layer base is 45- 75nm。
(3) beneficial effect
The beneficial effects of the invention are as follows：
In the lambda sensor dielectric substrate of the present invention and the preparation method of fine and close diffusion layer double-decker, using plasma Spraying coating process forms fine and close diffusive layer base on electrolyte layer base, or using plasma spray coating process in fine and close diffusive layer Electrolyte layer base is formed on base, makes the bond strength of fine and close diffusion layer and dielectric substrate high, while it is especially fast to prepare speed, greatly Raise labour productivity greatly, so as to obtain considerable economic results in society, suitable for large-scale production.
Brief description of the drawings
Fig. 1 is the structural representation of dense diffusion barrier limit-current type oxygen sensor in the prior art；
Fig. 2 is the preparation side of the lambda sensor dielectric substrate that following examples 1 provide and fine and close diffusion layer double-decker The flow chart of method；
Lambda sensor dielectric substrate and fine and close diffusion layer prepared by the preparation method that Fig. 3 is provided by following examples 1 The local SEM figures of double-decker；
Fig. 4 is that the SEM in the section of double-decker made from conventional sintering technique schemes；
Fig. 5 is the oxygen determination I-V curve of a fine and close Diffusion Barrier type limit-current type oxygen sensor, and the dense diffusion barrier hinders type Limit-current type oxygen sensor includes lambda sensor dielectric substrate and cause prepared by the preparation method that following examples 1 are provided Close diffusion layer double-decker.
Lambda sensor dielectric substrate and fine and close diffusion layer prepared by the preparation method that Fig. 6 is provided by following examples 2 The local SEM figures of double-decker；
Fig. 7 is the preparation side of the lambda sensor dielectric substrate that following examples 3 provide and fine and close diffusion layer double-decker The flow chart of method.
【Description of reference numerals】
1：Negative pole；2：Fine and close diffusion layer；3：Dielectric substrate；4：Positive pole；5：Elevated-temperature seal glass glaze.
Embodiment
In order to preferably explain the present invention, in order to understand, below in conjunction with the accompanying drawings, by embodiment, to this hair It is bright to be described in detail.
Embodiment 1
Reference picture 2, the present embodiment provide the preparation of a kind of lambda sensor dielectric substrate and fine and close diffusion layer double-decker Method, specifically comprise the following steps：
S1, electrolyte layer base is prepared, the main component of the electrolyte layer base is YSZ.
Specifically, above-mentioned steps S1 includes following sub-step in the present embodiment：
S1.1, dielectric substrate material powder (being in the present embodiment YSZ powder) is squeezed into circular electrolyte synusia Shape matrix.
S1.2, dielectric substrate flaky matrix is placed in high temperature furnace, dielectric substrate flaky matrix is sintered, sintering temperature Spend for 1200 DEG C, sintering time 8h.
S1.3, cool to the dielectric substrate flaky matrix after sintering with the furnace room temperature.Due to subsequently carrying out plasma spray Plasma densification diffusion layer Powder aerosol is sprayed on electrolyte layer base when applying technique, the process can be to electrolyte Base produces powerful impulsive force layer by layer, and therefore, the intensity of electrolyte layer base there are certain requirements, and otherwise spraying easily causes electrolysis The destruction of matter base layer by layer, influences spraying effect.So first carried out when preparing electrolyte layer base it is once sintered, to ensure electricity Base possesses enough intensity to receive spraying to solution matter layer by layer.
S1.4, the sprayed surface to the dielectric substrate flaky matrix after cooling (will subsequently connect with fine and close diffusive layer base The surface of conjunction) it is roughened, polished in the present embodiment using diamond, its roughness is reached Ra0.07- 0.06 μm, electrolyte layer base is formed, the thickness of electrolyte layer base is 4.85mm, a diameter of 9.7mm of electrolyte layer base. The step enables fills when follow-up plasma densification diffusion layer Powder aerosol strikes the surface of electrolyte layer base Divide and deform, sprawl, discharging gas, and then reduce porosity, more preferable with reference to effect, micro-crack significantly reduces.
Wherein, the YSZ powder employed in step S1.1 is preferably made by following steps：
A1, in molar ratio, Y (NO3)3·6H2O ﹕ ZrOCl2·8H2O=(6.5-10) ﹕ (93.5-90) carry out dispensing, its In, Y (NO3)3·6H2O molar concentration is 7-9mol%；
A2, by Y (NO3)3·6H2O and Y (NO3)3·6H2O is dissolved separately in deionized water, is filtered to remove insoluble miscellaneous Y (NO are made after matter3)3The aqueous solution and ZrOCl2The aqueous solution, wherein, the addition of deionized water is so that raw material fully dissolves is defined；
A3, by Y (NO3)3The aqueous solution and ZrOCl2The aqueous solution mixes, and mixed solution, the molar concentration position of mixed solution is made In the range of 0.6-1.1mol/L；
A4, ammoniacal liquor is added dropwise while stirring into mixed solution, until the pH value of mixed solution stops that ammonia is added dropwise when reaching 9 Water, presoma sediment is made, wherein, the concentration of ammoniacal liquor is located at 25-28wt%；
A5, presoma sediment is placed in drying box, presoma sediment is dried, drying temperature is located at 60- In the range of 80 DEG C, drying time is in more than 20h；
A6, presoma sediment after drying is placed in high temperature furnace, dried presoma sediment is calcined, forged Temperature is burnt in the range of 600-1600 DEG C, and solid-solution powder is made in the range of 6-7h in calcination time；
A7, solid-solution powder is ground in agate mortar, milling time is located in the range of 2-4h, and YSZ is made Powder, granularity≤100nm of YSZ powder.
Certainly, this is not limited to, the dielectric substrate material powder employed in step S1.1 can also be commercial 8YSZ.
Further, the preparation of above-mentioned YSZ powder in the present embodiment comprises the following steps：
A1, in molar ratio, Y (NO3)3·6H2O ﹕ ZrOCl2·8H2O=(9) ﹕ (91) carry out dispensing, wherein, Y (NO3)3· 6H2O molar concentration is 8mol%；
A2, by Y (NO3)3·6H2O and Y (NO3)3·6H2O is dissolved separately in deionized water, is filtered to remove insoluble miscellaneous Y (NO are made after matter3)3The aqueous solution and ZrOCl2The aqueous solution, wherein, the addition of deionized water is so that raw material fully dissolves is defined；
A3, by Y (NO3)3The aqueous solution and ZrOCl2The aqueous solution mixes, and mixed solution is made, and the molar concentration of mixed solution is 0.9mol/L；
A4, ammoniacal liquor is added dropwise while stirring into mixed solution, until the pH value of mixed solution stops that ammonia is added dropwise when reaching 9 Water, presoma sediment is made, wherein, the concentration of ammoniacal liquor is located at 26wt%；
A5, presoma sediment being placed in drying box, presoma sediment is dried, drying temperature is 75 DEG C, Drying time is 22.5h；
A6, presoma sediment after drying is placed in high temperature furnace, dried presoma sediment is calcined, forged It is 1200 DEG C, calcination time 6h to burn temperature, and solid-solution powder is made；
A7, solid-solution powder is ground in agate mortar, milling time 3h, YSZ powder, YSZ powder is made Granularity≤100nm.
Drawn by theory analysis and lot of experiment validation, when the condition that YSZ powder is used by the present embodiment prepares When, combined with the fine and close diffusion layer powder being subsequently sprayed at thereon more preferable, and then increase electrolyte layer base and spread with fine and close The bond strength of base layer by layer, make combine it is even closer, the double-decker for making to prepare possesses more excellent performance.
S2, plasma densification diffusion layer Powder aerosol is sprayed on by above-mentioned dielectric substrate using plasma spray coating process On layer base, fine and close diffusive layer base is formed on electrolyte layer base.
In the present embodiment, step S2 includes following sub-step in the present embodiment：
S2.1, electrolyte layer base is put into the plating membrane cavity of plasma spray apparatus.Specifically, plasma spray apparatus Contain plating membrane cavity, spray gun, material powder feeder and supporting plate.Gun slot and material powder feeder ejiction opening stretch into plated film In chamber, and the ejiction opening of material powder feeder is correspondingly arranged with gun slot, and supporting plate is arranged in plating membrane cavity and is interval in Gun slot.Negative electrode, anode and working gas feeder are provided with spray gun.Electrolyte layer base is fixed on supporting plate, alignment spray Muzzle.
S2.2, plating membrane cavity is evacuated to vacuum as 1.5 × 10-3Pa。
S2.3, inert gas (the present embodiment is helium) is filled with into plating membrane cavity, until wherein pressure reaches 0.3Pa.Such as This, forms low pressure spray in follow-up spraying process, can so substantially reduce the resistance of particle flight, the fine and close diffusion of plasma The speed of layer Powder aerosol can be greatly improved, and the binding ability of the fine and close diffusion layer powder with kinetic energy is significantly Strengthen, improve the adhesion of dielectric substrate and fine and close diffusion layer.
S2.4, heating electrolyte layer base in the present embodiment, are heated to 50 DEG C using plasma flame flow.
S2.5, plasma densification diffusion layer Powder aerosol is sprayed on by electrolyte layer using plasma spray coating process On base.
Specifically, in above-mentioned plasma spray apparatus, make electric arc occurs between negative electrode and anode, and supplied from working gas To device to injecting working gas at electric arc.Working gas and plasma, is changed into plasma jet from gun slot by electric arc Spray.Powder carrier gas carries fine and close diffusion layer powder and sprayed from material powder feeder, forms fine and close diffusion layer Powder aerosol, Fine and close diffusion layer Powder aerosol puts into plasma jet.Fine and close diffusion layer powder is melted due to the heat of plasma jet Melt, form plasma densification diffusion layer Powder aerosol, the plasma densification diffusion layer Powder aerosol strikes electrolysis Matter is layer by layer on base surface, and the kinetic energy of fine and close diffusion layer powder therein transforms into heat energy and deformation energy, and heat energy is delivered to electrolysis Base, particle are adhered to electrolyte layer base surface to matter layer by layer, and plastic deformation and mutually clasp joint shape are relied between each particle Into fine and close diffusive layer base, so as to obtain good adhesion and compactness.In the present embodiment, the thickness of fine and close diffusive layer base Spend for 2mm, a diameter of 9.7mm.Wherein, working gas is the gaseous mixture (flow of nitrogen and hydrogen being made up of nitrogen and hydrogen Than for 20:1), the pressure of working gas is 1.2MPa, and the flow of working gas is 1200L/h；Arc current is 640A；Electric arc Voltage is 44V；Powder carrier gas is argon gas, and the pressure of powder carrier gas is 0.15MPa, and the flow of powder carrier gas is 250L/h；Powder feeding Rate is 38g/min；Spray distance (i.e. the distance of gun slot to electrolyte layer base surface) is 90mm；Spray angle (i.e. spray gun Angle between the sensing of mouth and electrolyte layer base surface) it is 85 °.
Further, the fine and close diffusion layer powder employed in above-mentioned steps is LSM powder, and preferably preparation method is as follows：
B1, in molar ratio, La (NO3)3·Sr(NO3)2·Mn(NO3)2The ﹕ 1 of=0.8 ﹕ 0.2 carry out dispensing；
B2, by La (NO3)3、Sr(NO3)2With Mn (NO3)2It is dissolved separately in deionized water, is filtered to remove insoluble impurities After obtain La (NO3)3The aqueous solution, Sr (NO3)2The aqueous solution and Mn (NO3)2The aqueous solution, wherein, the addition of deionized water is so that original Material fully dissolving is defined；
B3, by La (NO3)3The aqueous solution, Sr (NO3)2The aqueous solution and Mn (NO3)2The aqueous solution mixes, and mixed solution is made；
B4, add citric acid solution citric acid while stirring into mixed solution, after stirring, add ethylene glycol, stir Ammoniacal liquor is added dropwise after mixing uniformly, until the pH value of mixed solution stops that ammoniacal liquor is added dropwise when being located at 8.0-9.5, collosol and gel forerunner is made Body, wherein, the mass concentration of citric acid solution citric acid is located in the range of 10-20%, and the mass concentration of ammoniacal liquor is located at 20- In the range of 30%, in molar ratio, Jin belongs to Yang Li ﹕ Ning Meng Suan ﹕ ethylene glycol=﹕ 1.2 of 1 ﹕ 4.8 in mixed solution；
B5, sol-gel precursor is placed in drying oven, sol-gel precursor is dried, drying temperature is located at In the range of 70-90 DEG C；
B6, dried sol-gel precursor is placed in high temperature furnace, to dried sol-gel precursor is entered Row calcining, calcining heat are located in the range of 500-1000 DEG C, and calcination time is located in the range of 5-6h, and solid solution powder is made End；
B7, solid-solution powder is placed in agate mortar, solid-solution powder is ground, milling time is located at 2-3h's In the range of, LSM powder is made, the granularity of LSM powder is located in the range of 50-70nm, purity 99.99%.
Further, the preparation of the LSM powder used in the present embodiment comprises the following steps：
B1, in molar ratio, La (NO3)3·Sr(NO3)2·Mn(NO3)2The ﹕ 1 of=0.8 ﹕ 0.2 carry out dispensing；
B2, by La (NO3)3、Sr(NO3)2With Mn (NO3)2It is dissolved separately in deionized water, is filtered to remove insoluble impurities After obtain La (NO3)3The aqueous solution, Sr (NO3)2The aqueous solution and Mn (NO3)2The aqueous solution, wherein, the addition of deionized water is so that original Material fully dissolving is defined；
B3, by La (NO3)3The aqueous solution, Sr (NO3)2The aqueous solution and Mn (NO3)2The aqueous solution mixes, and mixed solution is made；
B4, add citric acid solution citric acid while stirring into mixed solution, after stirring, add ethylene glycol, stir Ammoniacal liquor is added dropwise after mixing uniformly, until the pH value of mixed solution stops that ammoniacal liquor is added dropwise when being located at 9.0, sol-gel precursor is made, Wherein, the mass concentration of citric acid solution citric acid is 12%, and the mass concentration of ammoniacal liquor is 30%, in molar ratio, mixed solution Middle Jin category Yang Li ﹕ Ning Meng Suan ﹕ ethylene glycol=﹕ 1.2 of 1 ﹕ 4.8；
B5, sol-gel precursor is placed in drying oven, sol-gel precursor is dried, drying temperature 85 ℃；
B6, dried sol-gel precursor is placed in high temperature furnace, to dried sol-gel precursor is entered Row calcining, calcining heat are 950 DEG C, calcination time 6h, and solid-solution powder is made；
B7, solid-solution powder is placed in agate mortar, solid-solution powder is ground, milling time 3h, is made LSM powder, the granularity of LSM powder are located in the range of 50-70nm, purity 99.99%.
Also, the nano particle of the fine and close diffusion layer powder obtained by the above method is spherical, and passes through dry and high temperature Moisture containing below 0.001g in every 100g powder in the fine and close diffusion layer powder that sintering guarantee finally obtains.
Drawn by theory analysis and lot of experiment validation, when LSM powder is prepared by the above-mentioned condition of the present embodiment When, it can be easier to when using plasma spray coating process by carrier gas conveying and be capable of the ejection of more smooth smoothness, so as to carry Height prepares speed, greatly improves labor productivity, so as to obtain considerable economic results in society, suitable for large-scale production.
In addition, using dry nanoscale densification diffusion layer powder, on the one hand, " refined crystalline strengthening " effect of nano-particle has Help the raising of the hardness and intensity of fine and close diffusion layer；On the other hand, fully dry nanoscale densification diffusion layer powder and Its ball shape is advantageous to the fluency of spraying, with reference to air pressure selected in the present embodiment, the stream of working gas The proportioning of amount, powder nebulizer gas pressure, powder carrier gas flux and powder feeding rate, the fluency of spraying is can further improve, improve spraying Effect.
S3, the electrolyte layer base with fine and close diffusive layer base is placed in high temperature furnace be sintered, sintering temperature is 1400℃.In the present embodiment, 1000 DEG C first are warming up to by 10 DEG C/min heating rate in sintering, then by 5 DEG C/min Heating rate be warming up to 1400 DEG C, persistently sinter 10h at this temperature afterwards.Heated up at a slow speed again using this be first rapidly heated Staged sinter and substitute original Isothermal sinter mode, can further improve the consistency of fine and close diffusion layer.
S4, the electrolyte layer base with fine and close diffusive layer base after sintering is cooled down, the fine and close expansion after cooling Dissipate base layer by layer and form fine and close diffusion layer, the electrolyte layer base after cooling forms dielectric substrate, fine and close diffusion layer and dielectric substrate It is stacked on top of each other and connected, double-decker is formed, the wherein thickness of dielectric substrate is 4.7mm, a diameter of 9.5mm, fine and close diffusion layer Thickness be 1.9mm, a diameter of 9.51mm.
Reference picture 3 and Fig. 4, Fig. 3 are lambda sensor dielectric substrate prepared by the preparation method provided in the present embodiment And the local SEM of fine and close diffusion layer double-decker schemes, downside is dielectric substrate in Fig. 3, and upside is fine and close diffusion layer.Fig. 4 is biography The SEM in the section of double-decker schemes made from system sintering process, and downside is dielectric substrate in Fig. 4, and upside is fine and close diffusion layer.
Comparison diagram 3 and Fig. 4 can be seen that the fine and close diffusion layer formed using above-mentioned plasma spray coating process, compared to existing There is the fine and close diffusion layer prepared in technology using conventional sintering method, dense structure is uniform, stomata is few, and consistency is improved, and And can be minimized by the heat affected area scope of dielectric substrate and deformation, and the width of fine and close diffusion layer and thickness can Accurate control, wherein, the thickness of fine and close diffusion layer can be controlled by limiting the spray time of plasma spraying, and then include this The oxygen determination performance of the lambda sensor of fine and close diffusion layer is improved.It should be noted that Fig. 3 is to break obtained double-decker into two with one's hands The Local map shot afterwards, the pit on fine and close diffusion layer in Fig. 3 are formed when double-decker is broken into two with one's hands, are not to spray During formed.
Further, reference picture 5, lambda sensor will be fabricated to by double-decker made of above-mentioned preparation method, i.e., such as Fig. 1 In include negative pole 1, dense diffusion barrier (referred to as fine and close diffusion layer 2), solid electrolyte layer (abbreviation dielectric substrate 3), positive pole 4 With elevated-temperature seal glass glaze 5.After tested, oxygen determination scope is 0-19.3vol%.
To sum up, fine and close diffusion layer is formed using plasma spray coating process, dense structure is uniform, stomata is few, and consistency is able to Improve, and then the oxygen determination performance of the lambda sensor comprising the fine and close diffusion layer is improved.Secondly, using plasma spray coating process Make the bond strength of fine and close diffusion layer and dielectric substrate high, and be not easy cracked, further increase comprising the densification The oxygen determination performance of the lambda sensor of diffusion layer.Again, the process of the preparation method is simple, and preparation speed is fast, is adapted to high-volume raw Production.In addition, the oxygen determination scope for the lambda sensor that the double-decker formed by the preparation method of the present invention is formed is improved.By This, present embodiments provides the preparation of a kind of new beneficial lambda sensor dielectric substrate and fine and close diffusion layer double-decker Method.
Embodiment 2
Reference picture 2, the present embodiment provide the preparation of a kind of lambda sensor dielectric substrate and fine and close diffusion layer double-decker Method, specifically comprise the following steps：
S1, electrolyte layer base is prepared, the main component of the electrolyte layer base is YSZ.
Specifically, above-mentioned steps S1 includes following sub-step in the present embodiment：
S1.1, by dielectric substrate material powder (being in the present embodiment YSZ powder, preparation method is with embodiment 1) extrude Into the dielectric substrate flaky matrix of circle.
S1.2, dielectric substrate flaky matrix is placed in high temperature furnace, dielectric substrate flaky matrix is sintered, sintering temperature Spend for 1300 DEG C, sintering time 7.5h.
S1.3, cool to the dielectric substrate flaky matrix after sintering with the furnace room temperature.
S1.4, the sprayed surface to the dielectric substrate flaky matrix after cooling are roughened, and are adopted in the present embodiment Polished with diamond, its roughness is reached Ra0.07-0.06 μm, form electrolyte layer base, electrolyte layer base Thickness is 2.89mm, a diameter of 9.71mm of electrolyte layer base.
S2, plasma densification diffusion layer Powder aerosol is sprayed on by above-mentioned dielectric substrate using plasma spray coating process On layer base, fine and close diffusive layer base is formed on electrolyte layer base.
In the present embodiment, step S2 includes following sub-step in the present embodiment：
S2.1, electrolyte layer base is put into the plating membrane cavity of plasma spray apparatus.Specifically, plasma spray apparatus Contain plating membrane cavity, spray gun, material powder feeder and supporting plate.Gun slot and material powder feeder ejiction opening stretch into plated film In chamber, and the ejiction opening of material powder feeder is correspondingly arranged with gun slot, and supporting plate is arranged in plating membrane cavity and is interval in Gun slot.Negative electrode, anode and working gas feeder are provided with spray gun.Electrolyte layer base is fixed on supporting plate, alignment spray Muzzle.
S2.2, plating membrane cavity is evacuated to vacuum as 2 × 10-3Pa。
S2.3, inert gas (the present embodiment is helium) is filled with into plating membrane cavity, until wherein pressure reaches 0.4Pa.
S2.4, heating electrolyte layer base in the present embodiment, are heated to 55 DEG C using plasma flame flow.
S2.5, plasma densification diffusion layer Powder aerosol is sprayed on by electrolyte layer using plasma spray coating process On base.The thickness of the fine and close diffusive layer base of formation is 1mm, a diameter of 9.71mm.Wherein, working gas is by nitrogen and hydrogen (flow-rate ratio of nitrogen and hydrogen is 20 to the gaseous mixture of composition:1), the pressure of working gas is 1.3MPa, the flow of working gas For 1250L/h；Arc current is 625A；Arc voltage is 47V；Powder carrier gas is argon gas, and the pressure of powder carrier gas is 0.12MPa, the flow of powder carrier gas is 220L/h；Powder feeding rate is 35g/min；Spray distance is 85mm；Spray angle is 90 °. Wherein, the fine and close diffusion layer powder employed in the step is LSM powder, and preparation method repeats no more with embodiment 1.
S3, the electrolyte layer base with fine and close diffusive layer base is placed in high temperature furnace be sintered, sintering temperature is 1500℃.In the present embodiment, 1000 DEG C first are warming up to by 10 DEG C/min heating rate in sintering, then by 5 DEG C/min Heating rate be warming up to 1500 DEG C, persistently sinter 9.5h at this temperature afterwards.
S4, the electrolyte layer base with fine and close diffusive layer base after sintering is cooled down, the fine and close expansion after cooling Dissipate base layer by layer and form fine and close diffusion layer, the electrolyte layer base after cooling forms dielectric substrate, fine and close diffusion layer and dielectric substrate It is stacked on top of each other and connected, double-decker is formed, the wherein thickness of dielectric substrate is 2.81mm, a diameter of 9.49mm, and densification is spread The thickness of layer is 0.92mm, a diameter of 9.49mm.
Lambda sensor will be fabricated to made of above-mentioned preparation method by double-decker, i.e., as included negative pole 1, densification in Fig. 1 Diffusion barrier layer (referred to as fine and close diffusion layer 2), solid electrolyte layer (abbreviation dielectric substrate 3), positive pole 4 and elevated-temperature seal glass glaze 5.After tested, oxygen determination scope is 0-20.1vol%.
Reference picture 6, Fig. 6 are lambda sensor dielectric substrate and densification prepared by the preparation method provided in the present embodiment The local SEM of diffusion layer double-decker schemes, and downside is dielectric substrate in Fig. 6, and upside is fine and close diffusion layer.Comparison diagram 6 and Fig. 4 can To find out, the fine and close diffusion layer that is formed using above-mentioned plasma spray coating process, compared to using conventional sintering method in the prior art The fine and close diffusion layer of preparation, dense structure is uniform, stomata is few, and consistency is improved, and can make the heat affecting of dielectric substrate Area's scope and deformation are minimized by.It should be noted that Fig. 6 is the part shot after obtained double-decker is broken into two with one's hands Scheme, the pit on fine and close diffusion layer in Fig. 6 is formed when double-decker is broken into two with one's hands, is formed in spraying process 's.
To sum up, fine and close diffusion layer being formed using plasma spraying, dense structure is uniform, stomata is few, and consistency is improved, And then the oxygen determination performance of the lambda sensor comprising the fine and close diffusion layer is improved.Secondly, fine and close expansion is made using plasma spraying It is high to dissipate the bond strength of layer and dielectric substrate, and is not easy cracked, further increases comprising the fine and close diffusion layer The oxygen determination performance of lambda sensor.Again, the process of the preparation method is simple, and preparation speed is fast, is adapted to produce in enormous quantities.In addition, The oxygen determination scope for the lambda sensor that the double-decker formed by the preparation method of the present invention is formed is improved.Thus, this reality Apply the preparation method that example provides a kind of new beneficial lambda sensor dielectric substrate and fine and close diffusion layer double-decker.
Certainly the present invention forms fine and close diffusive layer base on electrolyte layer base, and then sintering is cooled into double-decker Preparation method in be not limited to above-described embodiment：
In step sl, the main component of electrolyte layer base is to be not limited only to YSZ powder or LSGM powder End；The step of preparing electrolyte layer base is also not limited to step S1.1 to S1.4, can also use other modes；Prepare YSZ The step of powder, is also not limited to a1 to a7, can also use other modes or directly be obtained with buying pattern；In step The thickness of dielectric substrate flaky matrix is preferably any value in 3-5mm in S1.1, and diameter is preferably any in 10-15mm Value.
In step s 2, fine and close diffusion layer powder is also not limited to only LSM powder or LSC powder or LSF Powder；Any value of the particle diameter of fine and close diffusion layer powder preferably in 50-70nm, due to the particle size of fine and close diffusion layer powder Very big influence is played with the effect of its concentration microstructure of plasma sprayed, by experimental results demonstrate when fine and close diffusion layer powder It when particle diameter is more than 70nm, can cause to spray uneven, not smooth, the compactness of the fine and close diffusive layer base of formation is affected, And can then increase difficulty of processing when particle diameter is less than 50nm, the process such as increase grinding, and then productivity ratio is reduced, therefore, densification is expanded The particle diameter of layer powder is dissipated preferably in 50-70nm；Working gas includes nitrogen and/or argon gas, and powder carrier gas includes nitrogen and/or argon Gas；The pressure of working gas is preferably any value in 1.2-1.4MPa, and the flow of working gas is preferably 1150-1250L/h In any value；Arc current is preferably any value in 600-900A, and arc current is more preferably appointing in 620-640A One value；Arc voltage is preferably any value in 40-60V, and arc voltage is more preferably any value in 44-48V；Powder carries The pressure of gas is preferably any value in 0.1-0.15MPa, and the flow of powder carrier gas is preferably any value in 220-260L/h； Powder feeding rate is preferably any value in 20-60g/min, and powder feeding rate is more preferably any value in 35-40g/min；Spraying away from From any value in preferably 80-110mm, spray distance is more preferably any value in 85-90mm；Spray angle is preferably Any value in 75 ° -90 °；The vacuum that membrane cavity is plated in step S2.2 is preferably 1 × 10-3-2×10-3Any value in Pa；Step The pressure of plating membrane cavity preferably reaches any value in 0.3-0.4Pa in rapid S2.3, is consequently formed suitable environment under low pressure；Step Electrolyte layer base is heated in S2.4 preferably to any value in 50-60 DEG C, can occur sintering effect ahead of time as heating-up temperature is too high Fruit, again bond effect can be caused bad as heating-up temperature is inadequate, therefore 50-60 DEG C most appropriate；The fine and close diffusive layer of formation The thickness of base can voluntarily control coating thickness as needed, and the thickness of general fine and close diffusive layer base is preferably in 1-2mm Any value.
In step s3, any value of the sintering temperature preferably in 1000-1600 DEG C；Further, it is preferable to using first fast The staged sintering method that speed heating heats up at a slow speed again, it is preferably：First heated up during sintering by 10 DEG C/min heating rate Any value into 950-1000 DEG C, any value being then warming up to by 5 DEG C/min heating rate in 1000-1600 DEG C, so After sinter 8-10h.
Meanwhile in lambda sensor dielectric substrate of the invention and the preparation method of fine and close diffusion layer double-decker, use Plasma spraying, this method can make the preparation technology mechanization, serialization, reduction waste product of fine and close diffusion layer and dielectric substrate Rate, excellent coating performance is obtained, and then obtain well stable electric property, preparation speed is especially fast, greatly improves work Productivity ratio, so as to obtain considerable economic results in society, suitable for large-scale production.In spraying, spraying is uniform simultaneously and bonds Power is strong, makes the bond strength of fine and close diffusion layer and dielectric substrate high, and the deformation of dielectric substrate and fine and close diffusion layer is decreased to minimum Degree, crackle is less prone to, and the dense structure of final obtained fine and close diffusion layer and dielectric substrate is uniform, stomata significantly subtracts It is few, the performance of the lambda sensor comprising the double-decker can be improved.
Embodiment 3
Reference picture 7, the present embodiment provide the preparation of a kind of lambda sensor dielectric substrate and fine and close diffusion layer double-decker Method, specifically comprise the following steps：
S1, fine and close diffusive layer base is prepared, the main component of the fine and close diffusive layer base is LSM.
Specifically, above-mentioned steps S1 includes following sub-step in the present embodiment：
S1.1, fine and close diffusion layer material powder (being in the present embodiment LSM powder) is squeezed into circular fine and close diffusion Lamellar matrix.Wherein, the narration of the preparation method of the LSM powder such as embodiment 1, simply final LSM powder mulls to granularity ≤ 100nm, without being limited to 50-70nm.
S1.2, fine and close diffusion layer flaky matrix is placed in high temperature furnace, fine and close diffusion layer flaky matrix is sintered, burnt Junction temperature is 1300 DEG C, sintering time 7h.
S1.3, cool to the fine and close diffusion layer flaky matrix after sintering with the furnace room temperature.Due to subsequently carrying out plasma Plasma electrolysis matter layer Powder aerosol is sprayed on fine and close diffusive layer base during spraying, the process can spread to densification Base produces powerful impulsive force layer by layer, and therefore, the intensity of fine and close diffusive layer base there are certain requirements, and otherwise spraying easily causes cause The destruction of close diffusive layer base, influences spraying effect.So first carried out when preparing fine and close diffusive layer base it is once sintered, with Ensure that fine and close diffusive layer base possesses enough intensity to receive spraying.
S1.4, the sprayed surface to the fine and close diffusion layer flaky matrix after cooling (will subsequently connect with electrolyte layer base The surface of conjunction) it is roughened, polished in the present embodiment using diamond, its roughness is reached Ra0.07- 0.06 μm, form fine and close diffusive layer base, the thickness of fine and close diffusive layer base is 4.88mm, fine and close diffusive layer base it is a diameter of 9.75mm.The step causes when follow-up plasma electrolysis matter layer Powder aerosol strikes the surface of fine and close diffusive layer base Can fully deformed, sprawl, discharge gas, and then reduce porosity, more preferable with reference to effect, micro-crack significantly reduces.
S2, plasma electrolysis matter layer Powder aerosol be sprayed on by above-mentioned fine and close diffusion layer using plasma spray coating process On layer base, electrolyte layer base is formed on fine and close diffusive layer base.
In the present embodiment, step S2 includes following sub-step in the present embodiment：
S2.1, fine and close diffusive layer base is put into the plating membrane cavity of plasma spray apparatus.Specifically, plasma spray application Put containing plating membrane cavity, spray gun, material powder feeder and supporting plate.Gun slot and material powder feeder ejiction opening stretch into plating In membrane cavity, and the ejiction opening of material powder feeder is correspondingly arranged with gun slot, and supporting plate is arranged in plating membrane cavity and is spaced In gun slot.Negative electrode, anode and working gas feeder are provided with spray gun.Fine and close diffusive layer base is fixed on supporting plate, right Quasi- gun slot.
S2.2, plating membrane cavity is evacuated to vacuum as 1.5 × 10-3Pa。
S2.3, inert gas (the present embodiment is helium) is filled with into plating membrane cavity, until wherein pressure reaches 0.3Pa.Such as This, forms low pressure spray in follow-up spraying process, can so substantially reduce the resistance of particle flight, plasma electrolysis matter layer The speed of Powder aerosol can be greatly improved, and the dielectric substrate powder binding ability with kinetic energy greatly reinforces, Improve the adhesion of dielectric substrate and fine and close diffusion layer.
S2.4, the fine and close diffusive layer base of heating in the present embodiment, are heated to 65 DEG C using plasma flame flow.
S2.5, plasma electrolysis matter layer Powder aerosol be sprayed on by fine and close diffusive layer using plasma spray coating process On base.
Specifically, in above-mentioned plasma spray apparatus, make electric arc occurs between negative electrode and anode and supplied from working gas To device to injecting working gas at electric arc.Working gas and plasma, is changed into plasma jet from gun slot by electric arc Spray.Powder carrier gas carries dielectric substrate powder and sprayed from material powder feeder, forms dielectric substrate Powder aerosol, electrolysis Matter layer Powder aerosol puts into plasma jet.Dielectric substrate powder is melted due to the heat of plasma jet, is formed Plasma electrolysis matter layer Powder aerosol, the plasma dielectric substrate Powder aerosol strike fine and close diffusive layer base table On face, the kinetic energy of dielectric substrate powder therein transforms into heat energy and deformation energy, and heat energy is delivered to fine and close diffusive layer base, Grain is adhered to fine and close diffusive layer base surface, and by plastic deformation, mutual clasp joint forms dielectric substrate between each particle Layer base, so as to obtain good adhesion and compactness.In the present embodiment, the thickness of electrolyte layer base is 2mm, a diameter of 9.75mm.Wherein, working gas is that (flow-rate ratio of nitrogen and hydrogen is 18 for the gaseous mixture that is made up of nitrogen and hydrogen:1), work The pressure of gas is 1.1MPa, and the flow of working gas is 1220L/h；Arc current is 630A；Arc voltage is 47V；Powder Carrier gas is argon gas, and the pressure of powder carrier gas is 0.25MPa, and the flow of powder carrier gas is 255L/h；Powder feeding rate is 38g/min；Spray It is 95mm to apply distance (i.e. the distance of gun slot to fine and close diffusive layer base surface)；Spray angle (the i.e. sensing and cause of gun slot Angle between close diffusive layer base surface) it is 85 °.Wherein, used dielectric substrate powder is YSZ powder, YSZ powder The narration of preparation method such as embodiment 1, simply most YSZ powder mulls to granularity is 45-75nm at last.Also, by the above method The nano particle of the dielectric substrate powder of acquisition is spherical, and the dielectric substrate by drying and high temperature sintering guarantee finally obtains Moisture containing below 0.001g in every 100g powder in powder.
S3, the fine and close diffusive layer base with electrolyte layer base is placed in high temperature furnace be sintered, sintering temperature is 1400℃.In the present embodiment, 1000 DEG C first are warming up to by 10 DEG C/min heating rate in sintering, then by 5 DEG C/min Heating rate be warming up to 1400 DEG C, persistently sinter 10h at this temperature afterwards.Heated up at a slow speed again using this be first rapidly heated Staged sinter and substitute original Isothermal sinter mode, can further improve the consistency of fine and close diffusion layer.
S4, the fine and close diffusive layer base with electrolyte layer base after sintering is cooled down, the electrolyte after cooling Base forms fine and close diffusion layer layer by layer, and the fine and close diffusive layer base after cooling forms dielectric substrate, fine and close diffusion layer and dielectric substrate It is stacked on top of each other and connected, double-decker is formed, the wherein thickness of dielectric substrate is 1.92mm, a diameter of 9.34mm, and densification is spread The thickness of layer is 4.67mm, a diameter of 9.32mm.
Lambda sensor will be fabricated to made of above-mentioned preparation method by double-decker, i.e., as included negative pole 1, densification in Fig. 1 Diffusion barrier layer (referred to as fine and close diffusion layer 2), solid electrolyte layer (abbreviation dielectric substrate 3), positive pole 4 and elevated-temperature seal glass glaze 5.After tested, oxygen determination scope is 0-20.4vol%.
To sum up, dielectric substrate is formed using plasma spraying, dense structure is uniform, stomata is few, and consistency is improved, and is entered And the oxygen determination performance of the lambda sensor comprising the dielectric substrate is improved.Secondly, fine and close diffusion layer is made using plasma spraying It is high with the bond strength of dielectric substrate, and it is not easy cracked, further increase the oxygen sensing comprising the dielectric substrate The oxygen determination performance of device.Again, the process of the preparation method is simple, and preparation speed is fast, is adapted to produce in enormous quantities.In addition, by this hair The oxygen determination scope for the lambda sensor that the double-decker that bright preparation method is formed is formed is improved.Thus, the present embodiment carries For the preparation method of a kind of new beneficial lambda sensor dielectric substrate and fine and close diffusion layer double-decker.
Embodiment 4
Reference picture 7, the present embodiment provide the preparation of a kind of lambda sensor dielectric substrate and fine and close diffusion layer double-decker Method, specifically comprise the following steps：
S1, fine and close diffusive layer base is prepared, the main component of the fine and close diffusive layer base is LSM.
Specifically, above-mentioned steps S1 includes following sub-step in the present embodiment：
S1.1, fine and close diffusion layer material powder (being in the present embodiment LSM powder) is squeezed into circular fine and close diffusion Lamellar matrix.Wherein, the narration of the preparation method of the LSM powder such as embodiment 1, simply final LSM powder mulls to granularity ≤ 100nm, without being limited to 50-70nm.
S1.2, fine and close diffusion layer flaky matrix is placed in high temperature furnace, fine and close diffusion layer flaky matrix is sintered, burnt Junction temperature is 1350 DEG C, sintering time 7h.
S1.3, cool to the fine and close diffusion layer flaky matrix after sintering with the furnace room temperature.Due to subsequently carrying out plasma Plasma electrolysis matter layer Powder aerosol is sprayed on fine and close diffusive layer base during spraying, the process can spread to densification Base produces powerful impulsive force layer by layer, and therefore, the intensity of fine and close diffusive layer base there are certain requirements, and otherwise spraying easily causes cause The destruction of close diffusive layer base, influences spraying effect.So first carried out when preparing fine and close diffusive layer base it is once sintered, with Ensure that fine and close diffusive layer base possesses enough intensity and can receive spraying.
S1.4, the sprayed surface to the fine and close diffusion layer flaky matrix after cooling (will subsequently connect with electrolyte layer base The surface of conjunction) it is roughened, polished in the present embodiment using diamond, its roughness is reached Ra0.07- 0.06 μm, form fine and close diffusive layer base, the thickness of fine and close diffusive layer base is 2.86mm, fine and close diffusive layer base it is a diameter of 9.73mm.The step causes when follow-up plasma electrolysis matter layer Powder aerosol strikes the surface of fine and close diffusive layer base Can fully deformed, sprawl, discharge gas, and then reduce porosity, more preferable with reference to effect, micro-crack significantly reduces.
S2, plasma electrolysis matter layer Powder aerosol be sprayed on by above-mentioned fine and close diffusion layer using plasma spray coating process On layer base, electrolyte layer base is formed on fine and close diffusive layer base.
In the present embodiment, step S2 includes following sub-step in the present embodiment：
S2.1, fine and close diffusive layer base is put into the plating membrane cavity of plasma spray apparatus.Specifically, plasma spray application Put containing plating membrane cavity, spray gun, material powder feeder and supporting plate.Gun slot and material powder feeder ejiction opening stretch into plating In membrane cavity, and the ejiction opening of material powder feeder is correspondingly arranged with gun slot, and supporting plate is arranged in plating membrane cavity and is spaced In gun slot.Negative electrode, anode and working gas feeder are provided with spray gun.Fine and close diffusive layer base is fixed on supporting plate, right Quasi- gun slot.
S2.2, plating membrane cavity is evacuated to vacuum as 1 × 10-3Pa。
S2.3, inert gas (the present embodiment is helium) is filled with into plating membrane cavity, until wherein pressure reaches 0.4Pa.Such as This, forms low pressure spray in follow-up spraying process, can so substantially reduce the resistance of particle flight, plasma electrolysis matter layer The speed of Powder aerosol can be greatly improved, and the dielectric substrate powder binding ability with kinetic energy greatly reinforces, Improve the adhesion of dielectric substrate and fine and close diffusion layer.
S2.4, the fine and close diffusive layer base of heating in the present embodiment, are heated to 70 DEG C using plasma flame flow.
S2.5, plasma electrolysis matter layer Powder aerosol be sprayed on by fine and close diffusive layer using plasma spray coating process On base.
Specifically, in above-mentioned plasma spray apparatus, make electric arc occurs and supplies from working gas between negative electrode and anode To device to injecting working gas at electric arc.Working gas and plasma, is changed into plasma jet from gun slot by electric arc Spray.Powder carrier gas carries dielectric substrate powder and sprayed from material powder feeder, forms dielectric substrate Powder aerosol, electrolysis Matter layer Powder aerosol puts into plasma jet.Dielectric substrate powder is melted due to the heat of plasma jet, is formed Plasma electrolysis matter layer Powder aerosol, the plasma dielectric substrate Powder aerosol strike fine and close diffusive layer base table On face, the kinetic energy of dielectric substrate powder therein transforms into heat energy and deformation energy, and heat energy is delivered to fine and close diffusive layer base, Grain is adhered to fine and close diffusive layer base surface, and by plastic deformation, mutual clasp joint forms dielectric substrate between each particle Layer base, so as to obtain good adhesion and compactness.In the present embodiment, the thickness of electrolyte layer base is 1.5mm, diameter For 9.73mm.Wherein, working gas is that (flow-rate ratio of nitrogen and hydrogen is 18 for the gaseous mixture that is made up of nitrogen and hydrogen:1), work The pressure for making gas is 1.3MPa, and the flow of working gas is 1180L/h；Arc current is 630A；Arc voltage is 46V；Powder Last carrier gas is argon gas, and the pressure of powder carrier gas is 0.2MPa, and the flow of powder carrier gas is 235L/h；Powder feeding rate is 32g/min；Spray It is 96mm to apply distance (i.e. the distance of gun slot to fine and close diffusive layer base surface)；Spray angle (the i.e. sensing and cause of gun slot Angle between close diffusive layer base surface) it is 90 °.Wherein, used dielectric substrate powder is YSZ powder, YSZ powder The narration of preparation method such as embodiment 1, simply most YSZ powder mulls to granularity is 45-75nm at last.Also, by the above method The nano particle of the dielectric substrate powder of acquisition is spherical, and the dielectric substrate by drying and high temperature sintering guarantee finally obtains Moisture containing below 0.001g in every 100g powder in powder.
S3, the fine and close diffusive layer base with electrolyte layer base is placed in high temperature furnace be sintered, sintering temperature is 1500℃.In the present embodiment, 1000 DEG C first are warming up to by 10 DEG C/min heating rate in sintering, then by 5 DEG C/min Heating rate be warming up to 1500 DEG C, persistently sinter 10h at this temperature afterwards.Heated up at a slow speed again using this be first rapidly heated Staged sinter and substitute original Isothermal sinter mode, can further improve the consistency of fine and close diffusion layer.
S4, the fine and close diffusive layer base with electrolyte layer base after sintering is cooled down, dielectric substrate after cooling Layer base forms fine and close diffusion layer, and fine and close diffusive layer base forms dielectric substrate, fine and close diffusion layer and dielectric substrate it is stacked on top of each other and It is connected, forms double-decker, the wherein thickness of dielectric substrate is 1.42mm, a diameter of 9.32mm, and the thickness of fine and close diffusion layer is 2.7mm, a diameter of 9.31mm.
Lambda sensor will be fabricated to made of above-mentioned preparation method by double-decker, i.e., as included negative pole 1, densification in Fig. 1 Diffusion barrier layer (referred to as fine and close diffusion layer 2), solid electrolyte layer (abbreviation dielectric substrate 3), positive pole 4 and elevated-temperature seal glass glaze 5.After tested, oxygen determination scope is 0-19.9vol%.
To sum up, dielectric substrate is formed using plasma spraying, dense structure is uniform, stomata is few, and consistency is improved, and is entered And the oxygen determination performance of the lambda sensor comprising the dielectric substrate is improved.Secondly, fine and close diffusion layer is made using plasma spraying It is high with the bond strength of dielectric substrate, and it is not easy cracked, further increase the oxygen sensing comprising the dielectric substrate The oxygen determination performance of device.Again, the process of the preparation method is simple, and preparation speed is fast, is adapted to produce in enormous quantities.In addition, by this hair The oxygen determination scope for the lambda sensor that the double-decker that bright preparation method is formed is formed is improved.Thus, the present embodiment carries For the preparation method of a kind of new beneficial lambda sensor dielectric substrate and fine and close diffusion layer double-decker.
Certainly the present invention forms electrolyte layer base on fine and close diffusive layer base, and then sintering is cooled into double-decker Preparation method in be not limited to above-described embodiment：
In step sl, the main component of fine and close diffusive layer base is not limited only to LSM powder or LSC powder End or LSF powder；The step of preparing fine and close diffusive layer base is also not limited to step S1.1 to S1.4, can also use other Mode；The step of preparing LSM powder is also not limited to b1 to b7, can also use other modes or directly be obtained with buying pattern Take；The thickness of fine and close diffusion layer flaky matrix is preferably any value in 3-5mm in step S1.1, and diameter is preferably 10- Any value in 15mm.
In step s 2, dielectric substrate powder is also not limited to only YSZ powder or LSGM powder；Electrolyte Any value of the particle diameter preferably in 45-75nm of layer powder, due to dielectric substrate powder particle size and its concentration equity from Son spraying effect play very big influence, by experimental results demonstrate, when the particle diameter of dielectric substrate powder is more than 75nm, meeting Cause to spray uneven, not smooth, the compactness of the electrolyte layer base of formation is affected, and when particle diameter is less than 45nm then The process such as difficulty of processing, increase grinding can be increased, and then reduce productivity ratio, therefore, the particle diameter of dielectric substrate powder is preferably in 45- 75nm；Working gas includes nitrogen and/or argon gas, and powder carrier gas includes nitrogen and/or argon gas；The pressure of working gas is preferably Any value in 1.1-1.3MPa, the flow of working gas are preferably any value in 1150-1230L/h；Arc current is preferred For any value in 600-900A, arc current is more preferably any value in 625-650A；Arc voltage is preferably 40- Any value in 60V, arc voltage are more preferably any value in 45-50V；The pressure of powder carrier gas is preferably 0.2- Any value in 0.3MPa, the flow of powder carrier gas are preferably any value in 235-265L/h；Powder feeding rate is preferably 20-60g/ Any value in min, powder feeding rate are more preferably any value in 30-38g/min；Spray distance is preferably in 80-110mm Any value, spray distance are more preferably any value in 90-100mm；Spray angle is preferably any value in 75 ° -90 °； The vacuum that membrane cavity is plated in step S2.2 is preferably 1 × 10-3-2×10-3Any value in Pa；The pressure of membrane cavity is plated in step S2.3 Power preferably reaches any value in 0.3-0.4Pa, is consequently formed suitable environment under low pressure；Fine and close diffusion layer is heated in step S2.4 Layer base preferably to any value in 60-70 DEG C, sintering effect can occur, such as heating-up temperature not enough again ahead of time as heating-up temperature is too high Bond effect can be caused bad, therefore 60-70 DEG C most appropriate；The thickness of the electrolyte layer base of formation as needed can be certainly Row control coating thickness, any value of the thickness of general electrolyte layer base preferably in 1-2mm.
In step s3, any value of the sintering temperature preferably in 1000-1600 DEG C；Further, it is preferable to using first fast The staged sintering method that speed heating heats up at a slow speed again, it is preferably：First heated up during sintering by 10 DEG C/min heating rate Any value into 950-1000 DEG C, any value being then warming up to by 5 DEG C/min heating rate in 1000-1600 DEG C, so After sinter 8-10h.
Meanwhile in lambda sensor dielectric substrate of the invention and the preparation method of fine and close diffusion layer double-decker, use Plasma spraying, this method can make the preparation technology mechanization, serialization, reduction waste product of fine and close diffusion layer and dielectric substrate Rate, excellent coating performance is obtained, and then obtain well stable electric property, preparation speed is especially fast, greatly improves work Productivity ratio, so as to obtain considerable economic results in society, suitable for large-scale production.In spraying, spraying is uniform simultaneously and bonds Power is strong, makes the bond strength of fine and close diffusion layer and dielectric substrate high, and the deformation of dielectric substrate and fine and close diffusion layer is decreased to minimum Degree, crackle is less prone to, and the dense structure of final obtained fine and close diffusion layer and dielectric substrate is uniform, stomata significantly subtracts It is few, the performance of the lambda sensor comprising the double-decker can be improved.
To sum up, the preparation method of above two lambda sensor dielectric substrate and fine and close diffusion layer double-decker, two kinds of sides Method is to form dielectric substrate and fine and close diffusion layer double-decker using plasma spraying, and be be initially formed dielectric substrate and The layer base of one in fine and close diffusion layer, then spray another layer in this layer of base upper plasma.
No matter above-mentioned any method, the combination of the dielectric substrate that can be prepared and fine and close diffusion layer double-decker is strong Degree is high, while it is especially fast to prepare speed, greatly improves labor productivity, so as to obtain considerable economic results in society, is applied to Large-scale production.Specifically, by above two method, prepared using plasma spraying, fine and close diffusion layer and electricity can be made The preparation technology mechanization, serialization, reduction percent defective of matter layer are solved, obtains excellent coating performance, and then is obtained good stable Electric property, prepare speed it is especially fast, greatly improve labor productivity, so as to obtain considerable economic results in society, be applicable In large-scale production.In spraying, spraying is uniformly simultaneously and bonding force is strong, makes the bond strength of fine and close diffusion layer and dielectric substrate Height, the deformation of dielectric substrate and fine and close diffusion layer are decreased to minimum level, are less prone to crackle, and final obtained fine and close diffusion The dense structure of layer and dielectric substrate is uniform, stomata substantially reduces, and can improve the performance of the lambda sensor comprising the double-decker.
More than, only it is presently preferred embodiments of the present invention, is not the limitation that other forms are done to invention, it is any to be familiar with Professional and technical personnel is changed or is modified as the equivalence enforcement of equivalent variations possibly also with the technology contents of the disclosure above Example.But it is every without departing from technical solution of the present invention content, what the technical spirit according to the present invention was made to above example appoints What simple modification, equivalent variations and remodeling, still fall within the protection domain of technical solution of the present invention.

Claims (10)

1. the preparation method of a kind of lambda sensor dielectric substrate and fine and close diffusion layer double-decker, it is characterised in that including such as Lower step：
S1, prepare electrolyte layer base；
S2, fine and close diffusive layer base formed on the electrolyte layer base using plasma spray coating process, wherein, plasma spray Apply technique process conditions be：Arc current is 600-900A, and arc voltage 40-60V, powder feeding rate is 20-60g/min, spray It is 80-110mm to apply distance, and working gas includes nitrogen and/or argon gas, and powder carrier gas includes nitrogen and/or argon gas；
S3, the electrolyte layer base with fine and close diffusive layer base is sintered；
S4, the electrolyte layer base with fine and close diffusive layer base after sintering is cooled down, the fine and close diffusion layer after cooling Layer base forms fine and close diffusion layer, and the electrolyte layer base after cooling forms dielectric substrate, the fine and close diffusion layer and the electrolysis Matter layer is stacked on top of each other and connected, forms double-decker.
2. the preparation method of lambda sensor dielectric substrate according to claim 1 and fine and close diffusion layer double-decker, its It is characterised by,
In step s 2, the process conditions of plasma spray coating process are：
The working gas is the gaseous mixture being made up of nitrogen and hydrogen, and wherein the flow-rate ratio of nitrogen and hydrogen is 20:1, work The pressure of gas is 1.2-1.4MPa, and the flow of working gas is 1150-1250L/h；
The arc current is 620-640A；
The arc voltage is 44-48V；
The powder carrier gas is argon gas, and the pressure of the powder carrier gas is 0.1-0.15MPa, and the flow of the powder carrier gas is 220-260L/h；
The powder feeding rate is 35-40g/min；
The spray distance is 85-90mm；
Spray angle is 75 ° -90 °.
3. the preparation method of lambda sensor dielectric substrate according to claim 2 and fine and close diffusion layer double-decker, its It is characterised by,
Step S2 includes following sub-step：
S2.1, the electrolyte layer base is put into and plated in membrane cavity；
S2.2, the plating membrane cavity is evacuated to vacuum as 1 × 10-3-2×10-3Pa；
S2.3, inert gas is filled with into the plating membrane cavity, until wherein pressure reaches 0.3-0.4Pa；
S2.4, the heating electrolyte layer base are to 50-60 DEG C；
S2.5, plasma densification diffusion layer Powder aerosol is sprayed on by the electrolyte layer using plasma spray coating process On base, fine and close diffusive layer base is formed.
4. the preparation method of lambda sensor dielectric substrate according to claim 1 and fine and close diffusion layer double-decker, its It is characterised by,
Step S1 includes following sub-step：
S1.1, dielectric substrate material powder is squeezed into dielectric substrate flaky matrix；
S1.2, the dielectric substrate flaky matrix is sintered；
S1.3, the dielectric substrate flaky matrix after sintering is cooled to room temperature；
S1.4, the sprayed surface to the dielectric substrate flaky matrix after cooling are roughened, and reach its roughness Ra0.07-0.06 μm, form electrolyte layer base.
5. the preparation method of lambda sensor dielectric substrate according to claim 1 and fine and close diffusion layer double-decker, its It is characterised by,
In step s 2, the particle diameter for forming fine and close diffusion layer powder used by fine and close diffusive layer base is 50-70nm.
6. the preparation method of a kind of lambda sensor dielectric substrate and fine and close diffusion layer double-decker, it is characterised in that including such as Lower step：
S1, prepare fine and close diffusive layer base；
S2, electrolyte layer base formed on the fine and close diffusive layer base using plasma spray coating process, wherein, plasma spray Apply technique process conditions be：Arc current is 600-900A, and arc voltage 40-60V, powder feeding rate is 20-60g/min, spray It is 80-110mm to apply distance, and working gas includes nitrogen and/or argon gas, and powder carrier gas includes nitrogen and/or argon gas；
S3, the fine and close diffusive layer base with electrolyte layer base is sintered；
S4, the fine and close diffusive layer base with electrolyte layer base after sintering is cooled down, the fine and close diffusion layer after cooling Layer base forms fine and close diffusion layer, and the electrolyte layer base after cooling forms dielectric substrate, the fine and close diffusion layer and the electrolysis Matter layer is stacked on top of each other and connected, forms double-decker.
7. the preparation method of lambda sensor dielectric substrate according to claim 6 and fine and close diffusion layer double-decker, its It is characterised by,
In step s 2, the process conditions of plasma spray coating process are：
The working gas is the gaseous mixture being made up of nitrogen and hydrogen, and wherein the flow-rate ratio of nitrogen and hydrogen is 18:1, it is described The pressure of working gas is 1.1-1.3MPa, and the flow of the working gas is 1150-1230L/h；
The arc current is 625-650A；
The arc voltage is 45-50V；
The powder carrier gas is argon gas, and the pressure of the powder carrier gas is 0.2-0.3MPa, and the flow of the powder carrier gas is 235-265L/h；
The powder feeding rate is 30-38g/min；
The spray distance is 90-100mm；
Spray angle is 75 ° -90 °.
8. the preparation method of lambda sensor dielectric substrate according to claim 7 and fine and close diffusion layer double-decker, its It is characterised by,
Step S2 includes following sub-step：
S2.1, fine and close diffusive layer base is put into and plated in membrane cavity；
S2.2, the plating membrane cavity is evacuated to vacuum as 1 × 10-3-2×10-3Pa；
S2.3, inert gas is filled with into the plating membrane cavity, until wherein pressure reaches 0.3-0.4Pa；
S2.4, the heating fine and close diffusive layer base are to 60-70 DEG C；
S2.5, plasma electrolysis matter layer Powder aerosol be sprayed on by the fine and close diffusive layer using plasma spray coating process On base, electrolyte layer base is formed.
9. the preparation method of lambda sensor dielectric substrate according to claim 6 and fine and close diffusion layer double-decker, its It is characterised by,
Step S1 includes following sub-step：
S1.1, fine and close diffusion layer material powder is squeezed into fine and close diffusion layer flaky matrix；
S1.2, the fine and close diffusion layer flaky matrix is sintered；
S1.3, the fine and close diffusion layer flaky matrix after sintering is cooled to room temperature；
S1.4, the sprayed surface to the fine and close diffusion layer flaky matrix after cooling are roughened, and reach its roughness Ra0.07-0.06 μm, form fine and close diffusive layer base.
10. the preparation method of lambda sensor dielectric substrate according to claim 6 and fine and close diffusion layer double-decker, its It is characterised by,
In step s 2, the particle diameter for forming dielectric substrate powder used by electrolyte layer base is 45-75nm.
CN201711208999.9A 2017-11-27 2017-11-27 The preparation method of lambda sensor dielectric substrate and fine and close diffusion layer double-decker Pending CN107858628A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57147049A (en) * 1981-03-06 1982-09-10 Nissan Motor Co Ltd Oxygen sensor element
CN1731616A (en) * 2005-08-15 2006-02-08 西安交通大学 Method for manufacturing solid oxide fuel cell electrolyte
CN106996952A (en) * 2017-04-24 2017-08-01 东北大学 The preparation method of lambda sensor dielectric substrate and fine and close diffusion layer double-decker
CN107389770A (en) * 2017-06-29 2017-11-24 东北大学 The preparation method of lambda sensor dielectric substrate and fine and close diffusion layer double-decker

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57147049A (en) * 1981-03-06 1982-09-10 Nissan Motor Co Ltd Oxygen sensor element
CN1731616A (en) * 2005-08-15 2006-02-08 西安交通大学 Method for manufacturing solid oxide fuel cell electrolyte
CN106996952A (en) * 2017-04-24 2017-08-01 东北大学 The preparation method of lambda sensor dielectric substrate and fine and close diffusion layer double-decker
CN107389770A (en) * 2017-06-29 2017-11-24 东北大学 The preparation method of lambda sensor dielectric substrate and fine and close diffusion layer double-decker

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