CN116003125A - Preparation method of zirconia ceramic material for automobile exhaust sensor - Google Patents
Preparation method of zirconia ceramic material for automobile exhaust sensor Download PDFInfo
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- CN116003125A CN116003125A CN202211553803.0A CN202211553803A CN116003125A CN 116003125 A CN116003125 A CN 116003125A CN 202211553803 A CN202211553803 A CN 202211553803A CN 116003125 A CN116003125 A CN 116003125A
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- montmorillonite
- deionized water
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229920001661 Chitosan Polymers 0.000 claims abstract description 76
- 238000001354 calcination Methods 0.000 claims abstract description 51
- 239000000843 powder Substances 0.000 claims abstract description 32
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 238000000498 ball milling Methods 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 16
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 93
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- 239000008367 deionised water Substances 0.000 claims description 63
- 229910021641 deionized water Inorganic materials 0.000 claims description 63
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 47
- 238000001035 drying Methods 0.000 claims description 41
- 239000000725 suspension Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002244 precipitate Substances 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 15
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 14
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 14
- 238000007873 sieving Methods 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000000919 ceramic Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 239000011669 selenium Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 17
- 230000000052 comparative effect Effects 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 3
- 238000003287 bathing Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- -1 zrOCl 2 .8H 2 O Inorganic materials 0.000 description 1
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Abstract
A preparation method of a zirconia ceramic material for an automobile exhaust sensor comprises the steps of adding a montmorillonite-chitosan compound into yttria-stabilized zirconia powder, ball milling, and then carrying out sectional calcination, wherein the sectional calcination is divided into three sections of sequentially increasing temperatures for calcination, the first section of temperature is 400-450 ℃, the calcination time is 50-70min, the second section of temperature is 550-650 ℃, the calcination time is 30-60min, the third section of temperature is 850-900 ℃, and the calcination time is 5-7h. According to the invention, the zirconia ceramic material is prepared by adding the montmorillonite-chitosan composite, so that the conductivity of the zirconia ceramic material is improved, the conductivity stability under high temperature change is excellent, the temperature change is effectively adapted, the conductivity of the zirconia ceramic material is kept at 93.75% of the initial conductivity of 0.033S/cm after the zirconia ceramic material is recycled 20000 times, the zirconia ceramic material has excellent circulation stability, and long-time stable operation under a high-temperature environment can be ensured.
Description
Technical Field
The invention relates to the technical field of preparation of sensing materials, in particular to a preparation method of a zirconia ceramic material for an automobile exhaust sensor.
Background
The oxygen sensor is a measuring element which utilizes zirconia ceramic sensitive elements to measure oxygen potential in various heating furnaces or exhaust pipelines, calculates corresponding oxygen concentration according to a chemical balance principle, monitors and controls air-fuel ratio of a combustion process, ensures product quality and tail gas emission to reach standards, and is widely applied to atmosphere control of combustion processes such as various coal combustion, oil combustion, gas combustion and the like. In the aspect of automobile sensor application, yttria-stabilized zirconia is very popular, and an oxygen sensor can only fully reflect the characteristics at high temperature (above 300 ℃), can output voltage, and has the fastest reaction to the change of mixed gas at about 800 ℃. The zirconia sensor is therefore effectively used in measuring gasoline vehicle emissions. The method is an optimal combustion atmosphere measuring mode at present, and has the advantages of simple structure, quick response, easy maintenance, convenient use and the like.
However, the service life of the zirconia sensor is shorter, and for yttria-stabilized zirconia, the zirconia cannot adapt to the temperature change and long-time working in a high-temperature environment due to the higher working temperature of the oxygen sensor, and the conductivity of the zirconia can also change along with the temperature change, so that the stability is poor, and the sensitivity and the accuracy of the sensor are affected. In addition, in the course of repeated cycles, as the number of cycles increases, its electrical conductivity decreases, resulting in a decay in its lifetime.
Therefore, the zirconia is ensured to be stable and unchanged in conductivity under higher temperature change, and meanwhile, the conductivity is stable and not attenuated under multiple cycle operation, and the maintenance of excellent stability is extremely important for the oxygen sensor.
Disclosure of Invention
The invention aims to provide a preparation method of a zirconia ceramic material for an automobile exhaust sensor, wherein the prepared zirconia ceramic material has the advantages of increased temperature change and cycle use times and excellent conductivity stability.
The invention aims at realizing the following technical scheme:
a preparation method of a zirconia ceramic material for an automobile exhaust sensor is characterized by comprising the following steps: adding montmorillonite chitosan compound into yttria stabilized zirconia, ball milling, and performing sectional calcination, wherein the sectional calcination is divided into three sections of sequentially increasing temperatures for calcination, the first section of temperature is 400-450 ℃, the calcination time is 50-70min, the second section of temperature is 550-650 ℃, the calcination time is 30-60min, the third section of temperature is 850-900 ℃, and the calcination time is 5-7h.
Further, the first temperature is raised at 5-8 ℃/min, the second temperature is raised at 4-6 ℃/min, and the third temperature is raised at 5-8 ℃/min.
Further, the mass ratio of the montmorillonite-chitosan complex to the yttria-stabilized zirconia is 3-8:75-85.
Further, the ball milling speed of the ball milling is 300-400rpm, and the ball milling time is 15-18h.
Further, the montmorillonite-chitosan compound is prepared by adding deionized water into montmorillonite powder prepared by montmorillonite pretreatment to prepare a montmorillonite suspension, adding dilute hydrochloric acid into chitosan to obtain a chitosan solution, adding the montmorillonite suspension into the chitosan solution, stirring and heating to 90-100 ℃, preserving heat for 10-12h, centrifugally collecting solids, washing and drying, and then crushing and sieving to obtain the montmorillonite-chitosan compound.
Further, the mass ratio of the montmorillonite suspension to the chitosan solution is 1:0.2-0.4.
Further, the mass ratio of chitosan and dilute hydrochloric acid in the chitosan solution is 1:120-150, and the chitosan and the dilute hydrochloric acid are stirred and dissolved at 80-100rpm, wherein the mass fraction of the dilute hydrochloric acid is 5%.
Further, the centrifugal speed is 10000-20000rpm.
Further, the drying temperature is 100-110 ℃, and the drying is 15-18 hours.
Further, the montmorillonite powder is prepared by drying crushed and sieved montmorillonite, adding deionized water in two steps, and then adding EDTA-2Na and EDTA-2NaNaHCO 3 Stirring and standing to obtain suspension, adding edible salt, standing, centrifuging to collect precipitate, washing and drying the precipitate, ball milling, adding dilute hydrochloric acid, water bath treatment, and drying to obtain montmorillonite powder.
Further, the mass ratio of the precipitation after ball milling to the dilute hydrochloric acid is 1:30-40, and the mass fraction of the dilute hydrochloric acid is 5%.
Further, the deionized water is added into montmorillonite, soaked for 36-40h, stirred for 20-30h at 150-200rpm, and then added, wherein the mass ratio of montmorillonite to the deionized water added for two times is 1:20-30:200-250.
Further, the montmorillonite, EDTA-2Na and NaHCO 3 The mass ratio of (2) is 1:0.05-0.08:0.12-0.15.
Further, the edible salt accounts for 10-15% of the mass of the suspension.
Further, the crushing, sieving and montmorillonite drying is to crush and sieve montmorillonite with 100 mesh sieve, and then dry at 90-100 ℃ for 24-36h.
Further, the yttria-stabilized zirconia is zirconia chloride (ZrOCl) 2 .8H 2 O) and yttrium nitrate (Y (NO) 3 ) 3 ) Mixing, dissolving in deionized water, adding polyethylene glycol 200, heating to 40-50deg.C, adding hydrochloric acid to adjust pH to 2.0-3.5 within 5-8min, adding sodium hydroxide to adjust pH to 9.5-10.0, standing to form gel, drying, and calcining at 450-500deg.C for 2-3 hr.
Further, zrOCl 2 .8H 2 O、Y(NO 3 ) 3 The mass ratio of polyethylene glycol 200 to deionized water is as follows: 2.48:0.054:0.027:7.8.
further, the volume fraction of the hydrochloric acid is 5-8%, and the concentration of sodium hydroxide is 0.5mol/L.
The preparation method of the zirconia ceramic material for the automobile exhaust sensor is characterized by comprising the following steps of:
step one: preparation of yttria-stabilized zirconia
Zirconium oxychloride (ZrOCl) 2 .8H 2 O) and yttrium nitrate (Y (NO) 3 ) 3 ) Mixing and adding deionized water, stirring for 10-15min, adding polyethylene glycol 200, heating to 40-50deg.C, adding 5-8% hydrochloric acid to adjust pH to 2.0-3.5 in 5-8min, adding 0.5mol/L sodium hydroxide to adjust pH to 9.5-10.0, standing for 8-12 hr to form gel, drying at vacuum degree of-0.05 to-0.08 MPa and temperature of 60-80deg.C for 2-3 hr, calcining at 450-500deg.C for 2-3 hr to obtain yttria-stabilized zirconia, zrOCl 2 .8H 2 O、Y(NO 3 ) 3 The mass ratio of polyethylene glycol 200 to deionized water is as follows: 2.48:0.054:0.027:7.8;
step two: preparation of montmorillonite-chitosan composite material
(1) Pretreatment of montmorillonite
Drying montmorillonite crushed by 100 mesh sieve at 90-100deg.C for 24-36 hr, soaking in deionized water for 36-40 hr at 150-200rpm, and sequentially adding deionized water, EDTA-2Na and NaHCO 3 Wherein the mass ratio of montmorillonite to deionized water added for two times is 1:20-30:200-250, montmorillonite, EDTA-2Na and NaHCO 3 The mass ratio of the solution is 1:0.05-0.08:0.12-0.15, stirring and standing to obtain suspension, adding edible salt, wherein the edible salt accounts for 10-15% of the mass of the suspension, standing for 1-2h, centrifuging at 8000-10000rpm, collecting precipitate, repeatedly washing the precipitate with deionized water for 3-5 times, drying selenium at 90-100 ℃ until the water content is lower than 0.2%, ball milling, adding 5% of dilute hydrochloric acid, stirring the precipitate and the dilute hydrochloric acid for 10-12h at 80-100rpm while water bath at 85-90 ℃, filtering and collecting precipitate after cooling, washing with deionized water, drying at-0.05-0.08 MPa and 70-80 ℃, crushing, and sieving with a 200-mesh sieve to obtain montmorillonite powder;
(2) Composite montmorillonite chitosan
Adding deionized water into montmorillonite powder, stirring for 10-15min at 60-80rpm to form a montmorillonite suspension, wherein the mass ratio of the montmorillonite powder to the deionized water is 1:80-100, adding 5% of diluted hydrochloric acid into chitosan to obtain a chitosan solution, adding the montmorillonite suspension into the chitosan solution, stirring and heating to 90-100 ℃, preserving heat for 10-12h, wherein the mass ratio of the montmorillonite suspension to the chitosan solution is 1:0.2-0.4, centrifuging at 10000-12000rpm to collect solids, washing for 3-5 times with deionized water, drying at 100-110 ℃ for 15-18h, and then crushing and sieving with a 200-mesh sieve to obtain a montmorillonite chitosan compound;
step three: preparation of zirconia ceramic powder
Adding a montmorillonite chitosan compound into the yttria-stabilized zirconia prepared in the step one, ball milling, and then performing sectional calcination, wherein the sectional calcination is divided into three sections of temperatures which are gradually increased, the first section of temperature is heated to 400-450 ℃ at 5-8 ℃/min, the calcination is performed for 50-70min, the second section of temperature is heated to 550-650 ℃ at 4-6 ℃/min, the calcination is performed for 30-60min, the third section of temperature is heated to 850-900 ℃ at 5-8 ℃/min, and the calcination is performed for 5-7h, wherein the mass ratio of the montmorillonite chitosan compound to the yttria-stabilized zirconia is 3-8:75-85.
In the prior art, the montmorillonite-chitosan composite is usually used as an adsorption material, and the adsorption performance of the montmorillonite-chitosan composite is researched, and the stability of the zirconia ceramic material is effectively improved by adding the montmorillonite-chitosan composite and combining three-stage heating and calcining treatment, so that the stability of the zirconia ceramic material in a high-temperature working environment is enhanced, the deformation is small, and the stability of the conductivity and other performances of the zirconia ceramic material under high-temperature change and the performance stability of repeated recycling are improved.
The invention has the following technical effects:
according to the invention, the zirconia ceramic material is prepared by adding the montmorillonite-chitosan composite, so that the conductivity of the zirconia ceramic material is improved, the conductivity stability under high temperature change is excellent, the temperature change is effectively adapted, the conductivity of the zirconia ceramic material is kept at 93.75% of the initial conductivity of 0.033S/cm after the zirconia ceramic material is recycled 20000 times, the zirconia ceramic material has excellent circulation stability, and long-time stable operation under a high-temperature environment can be ensured.
Drawings
Fig. 1: a graph of the conductivity change of the zirconia ceramic material with temperature change.
Fig. 2: the zirconia ceramic material is circularly used for 20000 times of conductivity change curve graphs.
Detailed Description
The present invention is described in detail below by way of examples, which are necessary to be pointed out herein for further illustration of the invention and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and adaptations of the invention will be to those skilled in the art in light of the foregoing disclosure.
Example 1
The preparation method of the zirconia ceramic material for the automobile exhaust sensor comprises the following steps:
step one: preparation of yttria-stabilized zirconia
Zirconium oxychloride (ZrOCl) 2 .8H 2 O) and yttrium nitrate (Y (NO) 3 ) 3 ) Mixing, adding deionized water, stirring for 10min, adding polyethylene glycol 200, heating to 40deg.C, adding 5% hydrochloric acid to adjust pH to 3.5 within 5min, adding 0.5mol/L sodium hydroxide to adjust pH to 9.5, standing for 8 hr to form gel, drying at-0.05 to-0.08 MPa and 60deg.C for 3 hr, calcining at 450deg.C for 3 hr, and ZrOCl 2 .8H 2 O、Y(NO 3 ) 3 The mass ratio of polyethylene glycol 200 to deionized water is as follows: 2.48:0.054:0.027:7.8;
step two: preparation of montmorillonite-chitosan composite material
(1) Pretreatment of montmorillonite
Drying montmorillonite crushed by 100 mesh sieve at 100deg.C for 24 hr, soaking in deionized water for 40 hr, adding deionized water, EDTA-2Na and NaHCO sequentially at 200rpm 3 And stirring continuously for 15-20h, wherein the mass ratio of montmorillonite to deionized water added for two times is 1:30:250, and the mass ratio of montmorillonite, EDTA-2Na and NaHCO is 1:30:250 3 Stirring and standing to obtain suspension, adding edible salt, standing for 1 hr until the mass of the suspension is 15%, centrifuging at 10000rpm, collecting precipitate, repeatedly washing the precipitate with deionized water for 5 times, and drying selenium at 90deg.C until the water content is lower than 02%, ball milling, adding dilute hydrochloric acid, wherein the mass ratio of the precipitate to the dilute hydrochloric acid is 1:30, carrying out water bath at 90 ℃, stirring at 100rpm for 10 hours, cooling, filtering, collecting the precipitate, washing with deionized water, drying at the vacuum degree of-0.05 to-0.08 MPa and the drying temperature of 80 ℃, crushing, and sieving with a 200-mesh sieve to obtain montmorillonite powder;
(2) Composite montmorillonite chitosan
Adding montmorillonite powder into deionized water, stirring at 60rpm for 15min to form montmorillonite suspension, wherein the mass ratio of the montmorillonite powder to the deionized water is 1:80, adding 5% of diluted hydrochloric acid into chitosan to obtain chitosan solution, wherein the mass ratio of the chitosan to the diluted hydrochloric acid is 1:150, adding the montmorillonite suspension into the chitosan solution, stirring and heating to 90 ℃, preserving heat for 12h, wherein the mass ratio of the montmorillonite suspension to the chitosan solution is 1:0.4, centrifuging at 10000rpm to collect solids, washing with deionized water for 5 times, drying at 100 ℃ for 18h, crushing and sieving with a 200-mesh sieve to obtain a montmorillonite-chitosan compound;
step three: preparation of zirconia ceramic powder
Adding a montmorillonite chitosan compound into the yttria-stabilized zirconia prepared in the step one, ball milling, and then performing sectional calcination, wherein the sectional calcination is divided into three sections of temperatures which are gradually increased, the first section of temperature is heated to 400 ℃ at 5 ℃/min and is calcined for 70min, the second section of temperature is heated to 550 ℃ at 4 ℃/min and is calcined for 60min, the third section of temperature is heated to 900 ℃ at 5 ℃/min and is calcined for 5h, and the mass ratio of the montmorillonite chitosan compound to the yttria-stabilized zirconia is 3:85.
The sensor prepared by the zirconia ceramic material prepared by the embodiment has the conductivity of 0.031S/cm, excellent conductivity stability at 400-900 ℃, basically unchanged conductivity after 20000 times of circulation, 93.16% of initial conductivity still maintained, and excellent circulation stability.
Example 2
The preparation method of the zirconia ceramic material for the automobile exhaust sensor comprises the following steps:
step one: preparation of yttria-stabilized zirconia
Zirconium oxychloride (ZrOCl) 2 .8H 2 O) and yttrium nitrate (Y (NO) 3 ) 3 ) Mixing, adding deionized water, stirring for 15min, adding polyethylene glycol 200, heating to 50deg.C, adding 8% hydrochloric acid to adjust pH to 2.0 within 8min, adding 0.5mol/L sodium hydroxide to adjust pH to 10.0, standing for 12 hr to form gel, drying at-0.05 to-0.08 MPa and 80deg.C for 2 hr, calcining at 500deg.C for 2 hr, and ZrOCl 2 .8H 2 O、Y(NO 3 ) 3 The mass ratio of polyethylene glycol 200 to deionized water is as follows: 2.48:0.054:0.027:7.8;
step two: preparation of montmorillonite-chitosan composite material
(1) Pretreatment of montmorillonite
Drying montmorillonite crushed by 100 mesh sieve at 90deg.C for 36h, adding deionized water, soaking for 36h, sequentially adding deionized water, EDTA-2Na and NaHCO at 150rpm 3 And stirring continuously for 20h, wherein the mass ratio of montmorillonite to deionized water added for two times is 1:20:200, and the mass ratio of montmorillonite, EDTA-2Na and NaHCO is 1:20:200 3 Stirring and standing to obtain a suspension, adding edible salt, wherein the edible salt accounts for 10% of the mass of the suspension, standing for 2 hours, centrifuging at 8000rpm, collecting precipitate, repeatedly washing the precipitate with deionized water for 3 times, drying selenium at 100 ℃ until the water content is lower than 0.2%, ball-milling, adding 5% of dilute hydrochloric acid, wherein the mass ratio of the precipitate to the dilute hydrochloric acid is 1:40, water-bathing at 85 ℃, stirring at 80rpm for 12 hours, filtering and collecting the precipitate after cooling, washing with deionized water, drying at-0.05 to-0.08 MPa and 70 ℃ of drying temperature, and sieving with a 200-mesh sieve to obtain montmorillonite powder;
(2) Composite montmorillonite chitosan
Adding montmorillonite powder into deionized water, stirring for 10min at 80rpm to form montmorillonite suspension, wherein the mass ratio of the montmorillonite powder to the deionized water is 1:100, adding 5% of diluted hydrochloric acid into chitosan to obtain chitosan solution, wherein the mass ratio of the chitosan to the diluted hydrochloric acid is 1:150, adding the montmorillonite suspension into the chitosan solution, stirring and heating to 100 ℃, preserving heat for 10h, wherein the mass ratio of the montmorillonite suspension to the chitosan solution is 1:0.2, centrifuging at 12000rpm to collect solids, washing for 3 times with deionized water, drying at 110 ℃ for 15h, and crushing and sieving with a 200-mesh sieve to obtain a montmorillonite-chitosan compound;
step three: preparation of zirconia ceramic powder
Adding a montmorillonite chitosan compound into the yttria-stabilized zirconia prepared in the step one, ball milling, and then performing sectional calcination, wherein the sectional calcination is divided into three sections of temperatures which are gradually increased, the first section of temperature is heated to 450 ℃ at 8 ℃/min, the calcination is performed for 50min, the second section of temperature is heated to 650 ℃ at 6 ℃/min, the calcination is performed for 30min, the third section of temperature is heated to 850 ℃ at 8 ℃/min, and the calcination is performed for 5h, wherein the mass ratio of the montmorillonite chitosan compound to the yttria-stabilized zirconia is 8:75.
The sensor prepared by the zirconia ceramic material prepared by the embodiment has the conductivity of 0.032S/cm, excellent stability at 400-900 ℃, basically unchanged conductivity after 20000 times of circulation, and excellent circulation stability, wherein the conductivity is still kept at 92.49% of the initial conductivity.
Example 3
The preparation method of the zirconia ceramic material for the automobile exhaust sensor comprises the following steps:
step one: preparation of yttria-stabilized zirconia
Zirconium oxychloride (ZrOCl) 2 .8H 2 O) and yttrium nitrate (Y (NO) 3 ) 3 ) Mixing, adding deionized water, stirring for 12min, adding polyethylene glycol 200, heating to 45deg.C, adding 6% hydrochloric acid to adjust pH to 3.0 within 5-8min, adding 0.5mol/L sodium hydroxide to adjust pH to 9.8, standing for 10 hr to form gel, drying at-0.05-0.08 MPa under 70 deg.C for 2.5 hr, calcining at 480 deg.C for 2.5 hr, and ZrOCl 2 .8H 2 O、Y(NO 3 ) 3 The mass ratio of polyethylene glycol 200 to deionized water is as follows: 2.48:0.054:0.027:7.8;
step two: preparation of montmorillonite-chitosan composite material
(1) Pretreatment of montmorillonite
Drying montmorillonite crushed by 100 mesh sieve at 95deg.C for 28 hr, soaking in deionized water for 38 hr, adding deionized water, EDTA-2Na and NaHCO sequentially at 180rpm 3 And stirring continuously for 18h, wherein the mass ratio of montmorillonite to deionized water added for two times is 1:25:230, and the mass ratio of montmorillonite, EDTA-2Na and NaHCO is 1:25:230 3 Stirring and standing to obtain a suspension, adding edible salt, wherein the edible salt accounts for 12% of the mass of the suspension, standing for 1.5h, centrifuging at 9000rpm, collecting precipitate, repeatedly washing the precipitate with deionized water for 4 times, drying selenium at 95 ℃ until the water content is lower than 0.2%, ball-milling, adding 5% of dilute hydrochloric acid, wherein the mass ratio of the precipitate to the dilute hydrochloric acid is 1:35, water-bathing at 90 ℃, stirring at 90rpm for 11h, cooling, filtering, collecting precipitate, washing with deionized water, drying at a vacuum degree of-0.05 to-0.08 MPa and a drying temperature of 75 ℃, and sieving with a 200-mesh sieve to obtain montmorillonite powder;
(2) Composite montmorillonite chitosan
Adding montmorillonite powder into deionized water, stirring at 70rpm for 12min to form montmorillonite suspension, wherein the mass ratio of the montmorillonite powder to the deionized water is 1:90, adding 5% of diluted hydrochloric acid into chitosan to obtain chitosan solution, wherein the mass ratio of the chitosan to the diluted hydrochloric acid is 1:130, adding the montmorillonite suspension into the chitosan solution, stirring and heating to 95 ℃, preserving heat for 11h, wherein the mass ratio of the montmorillonite suspension to the chitosan solution is 1:0.3, centrifuging at 11000rpm to collect solids, washing with deionized water for 4 times, drying at 105 ℃ for 16h, and crushing and sieving with a 200-mesh sieve to obtain a montmorillonite-chitosan compound;
step three: preparation of zirconia ceramic powder
Adding a montmorillonite chitosan compound into the yttria-stabilized zirconia prepared in the step one, ball milling, and then performing sectional calcination, wherein the sectional calcination is divided into three sections of temperatures which are gradually increased, the first section of temperature is heated to 420 ℃ at 6 ℃/min, the second section of temperature is heated to 600 ℃ at 5 ℃/min, the calcination is performed for 50min, the third section of temperature is heated to 880 ℃ at 6 ℃/min, and the calcination is performed for 6h, wherein the mass ratio of the montmorillonite chitosan compound to the yttria-stabilized zirconia is 5:80.
Comparative example 1:
unlike example 3, after the yttria-stabilized zirconia was prepared in step one, the three-stage temperature-rising calcination treatment in step three was directly performed, i.e., without adding the montmorillonite-chitosan composite. The remaining steps and parameters remain the same as in example 3.
Comparative example 2:
compared with the embodiment 3, the third step adopts a one-stage temperature calcination treatment, specifically, calcination is carried out for 10 hours at 850-900 ℃, and the zirconia ceramic powder is obtained after cooling.
Performance test:
the zirconia ceramic powders prepared in example 3, comparative example 1 and comparative example 2 were processed to prepare electrodes, and performance test was performed. The method comprises the following steps:
removing zirconia ceramic powder, adding PVA solution with the mass fraction of 25%, preparing granules, and sieving with a 200-mesh sieve, wherein the mass ratio of the zirconia powder to the PVA is 1:0.2; pressing into a blank sheet under 25MPa, wherein the pressing density is 3.6g/cm < 2 >; sintering the blank, and printing the blank into an electrode by using a screen.
(1) The electrodes prepared from the zirconia ceramic powders prepared in example 3, comparative example 1 and comparative example 2 were respectively subjected to conductivity test at 300 to 900 c, and the record of the change in conductivity was made every 100 c, and the experimental results are shown in table 1.
Table 1: conductivity change at different temperatures
From the above results and fig. 1, it can be seen that the zirconia ceramic materials prepared in the present invention have higher conductivity and excellent stability at different temperatures, whereas the zirconia ceramic materials prepared in comparative examples 1 and 2 have lower initial conductivity, and have a larger conductivity, a sharp rising trend and a poor temperature stability with increasing temperature.
(2) The electrodes prepared by the zirconia ceramic materials prepared in the example 3, the comparative example 1 and the comparative example 2 are recycled 20000 times at 800 ℃, the conductivity change of the electrodes is shown in figure 2, and it can be seen that the conductivity of the sensor prepared by the zirconia ceramic material prepared in the invention is basically unchanged after being recycled 20000 times, the conductivity is still maintained at 93.75% of the original conductivity, and the sensor has excellent recycling stability; the sensors prepared from the zirconia ceramic materials prepared in comparative examples 1 and 2 all have obvious attenuation in the circulating process, after 20000 times of circulation, the conductivities are 26.7% and 26.3% of the initial conductivities respectively, and the circulating stability is poor.
Claims (9)
1. A preparation method of a zirconia ceramic material for an automobile exhaust sensor is characterized by comprising the following steps: adding a montmorillonite chitosan compound into yttria-stabilized zirconia, ball milling, and then performing segmented calcination, wherein the segmented calcination is divided into three sections of sequentially increasing temperatures for calcination, the first section of temperature is 400-450 ℃, the calcination time is 50-70min, the second section of temperature is 550-650 ℃, the calcination time is 30-60min, the third section of temperature is 850-900 ℃, the calcination time is 5-7h, the mass ratio of the montmorillonite chitosan compound to the yttria-stabilized zirconia is 3-8:75-85, the montmorillonite chitosan compound is prepared by adding montmorillonite powder prepared by montmorillonite pretreatment into deionized water to prepare a montmorillonite suspension, adding dilute hydrochloric acid into chitosan to obtain a chitosan solution, adding the montmorillonite suspension into the chitosan suspension, stirring the mixture to the temperature of 90-100 ℃, preserving the temperature for 10-12h, centrifuging, collecting solids, washing, drying, and then crushing and sieving.
2. The method for preparing a zirconia ceramic material for an automobile exhaust gas sensor according to claim 1, wherein: the mass ratio of chitosan to dilute hydrochloric acid in the chitosan solution is 1:120-150, and the chitosan and the dilute hydrochloric acid are stirred and dissolved at 80-100rpm, wherein the mass fraction of the dilute hydrochloric acid is 5%.
3. A method for producing a zirconia ceramic material for an automobile exhaust gas sensor according to claim 1 or 2, characterized in that: the Mongolian alopeciaThe stone powder is prepared by drying montmorillonite, adding deionized water, EDTA-2Na and NaHCO 3 Stirring and standing to obtain suspension, adding edible salt, standing, centrifuging to collect precipitate, washing and drying the precipitate, ball milling, adding dilute hydrochloric acid, water bath treatment, and drying to obtain montmorillonite powder.
4. A method for preparing a zirconia ceramic material for an automobile exhaust gas sensor according to any one of claims 1 to 3, wherein: the montmorillonite, EDTA-2Na and NaHCO 3 The mass ratio of (2) is 1:0.05-0.08:0.12-0.15.
5. The method for preparing the zirconia ceramic material for the automobile exhaust gas sensor according to claim 4, wherein: the two-step deionized water adding is to add deionized water into montmorillonite, soak for 36-40h, stir for 20-30h at 150-200rpm, and then add deionized water, wherein the mass ratio of montmorillonite to the two-time deionized water is 1:20-30:200-250.
6. The method for preparing the zirconia ceramic material for the automobile exhaust gas sensor according to claim 5, wherein: the edible salt accounts for 10-15% of the mass of the suspension.
7. The method for preparing the zirconia ceramic material for the automobile exhaust gas sensor according to claim 6, wherein: the yttria-stabilized zirconia is zirconia chloride (ZrOCl) 2 .8H 2 O) and yttrium nitrate (Y (NO) 3 ) 3 ) Mixing, adding polyethylene glycol 200, heating to 40-50deg.C, adding hydrochloric acid to adjust pH to 2.0-3.5 within 5-8min, adding sodium hydroxide to adjust pH to 9.5-10.0, standing to form gel, drying, and calcining at 450-500deg.C for 2-3 hr.
8. The method for preparing a zirconia ceramic material for an automobile exhaust gas sensor according to claim 7, wherein: the ZrOCl 2 .8H 2 O、Y(NO 3 ) 3 The mass ratio of polyethylene glycol 200 to deionized water is as follows: 2.48:0.054:0.027:7.8.
9. the preparation method of the zirconia ceramic material for the automobile exhaust sensor is characterized by comprising the following steps of:
step one: preparation of yttria-stabilized zirconia
Zirconium oxychloride (ZrOCl) 2 .8H 2 O) and yttrium nitrate (Y (NO) 3 ) 3 ) Mixing deionized water, stirring for 10-15min, adding polyethylene glycol 200, heating to 40-50deg.C, adding 5-8% hydrochloric acid to adjust pH to 2.0-3.5 in 5-8min, adding 0.5mol/L sodium hydroxide to adjust pH to 9.5-10.0, standing for 8-12 hr to form gel, drying at vacuum degree of-0.05 to-0.08 MPa and temperature of 60-80deg.C for 2-3 hr, calcining at 450-500deg.C for 2-3 hr, and ZrOCl 2 .8H 2 O、Y(NO 3 ) 3 The mass ratio of polyethylene glycol 200 to deionized water is as follows: 2.48:0.054:0.027:7.8;
step two: preparation of montmorillonite-chitosan composite material
(1) Pretreatment of montmorillonite
Drying montmorillonite crushed by 100 mesh sieve at 90-100deg.C for 24-36 hr, soaking in deionized water for 36-40 hr, sequentially adding deionized water, EDTA-2Na and NaHCO at 150-200rpm 3 And continuously stirring for 15-20h, wherein the mass ratio of montmorillonite to deionized water added for two times is 1:20-30:200-250, and the mass ratio of montmorillonite, EDTA-2Na and NaHCO is 1:20-30:200 3 The mass ratio of the solution is 1:0.05-0.08:0.12-0.15, stirring and standing to obtain a suspension, adding edible salt, wherein the edible salt accounts for 10-15% of the mass of the suspension, standing for 1-2h, centrifuging at 8000-10000rpm, collecting precipitate, repeatedly washing the precipitate with deionized water for 3-5 times, drying selenium at 90-100 ℃ until the water content is lower than 0.2%, ball milling, adding dilute hydrochloric acid, wherein the mass ratio of chitosan to hydrochloric acid is 1:30-40, stirring at 85-90 ℃ for 10-12h at 80-100rpm while in a water bath, cooling, filtering, collecting precipitate, washing with deionized water, and drying at vacuum degree of-0.05-0.08 MPaDrying at 70-80 ℃, crushing, and sieving with a 200-mesh sieve to obtain montmorillonite powder;
(2) Composite montmorillonite chitosan
Adding deionized water into montmorillonite powder, stirring for 10-15min at 60-80rpm to form a montmorillonite suspension, wherein the mass ratio of the montmorillonite powder to the deionized water is 1:80-100, adding 5% of diluted hydrochloric acid into chitosan to obtain a chitosan solution, adding the montmorillonite suspension into the chitosan solution, stirring and heating to 90-100 ℃, preserving heat for 10-12h, wherein the mass ratio of the montmorillonite suspension to the chitosan solution is 1:0.2-0.4, centrifuging at 10000-12000rpm to collect solids, washing for 3-5 times with deionized water, drying at 100-110 ℃ for 15-18h, and then crushing and sieving with a 200-mesh sieve to obtain a montmorillonite chitosan compound;
step three: preparation of zirconia ceramic powder
Adding a montmorillonite chitosan compound into the yttria-stabilized zirconia prepared in the step one, ball milling, and then performing sectional calcination, wherein the sectional calcination is divided into three sections of temperatures which are gradually increased to perform calcination, the first section of temperature is 400-450 ℃, the calcination is performed for 50-70min, the second section of temperature is 550-650 ℃, the calcination is performed for 30-60min, the third section of temperature is 850-900 ℃, and the calcination is performed for 5-7h, wherein the mass ratio of the montmorillonite chitosan compound to the yttria-stabilized zirconia is 3-8:75-85.
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