CN116969758A - Preparation method of high-stability zirconia ceramic material - Google Patents
Preparation method of high-stability zirconia ceramic material Download PDFInfo
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- CN116969758A CN116969758A CN202310988995.6A CN202310988995A CN116969758A CN 116969758 A CN116969758 A CN 116969758A CN 202310988995 A CN202310988995 A CN 202310988995A CN 116969758 A CN116969758 A CN 116969758A
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- montmorillonite
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 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 abstract description 65
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 65
- 229920001661 Chitosan Polymers 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000008367 deionised water Substances 0.000 claims abstract description 38
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 31
- 239000000725 suspension Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 21
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000002244 precipitate Substances 0.000 description 15
- 239000002131 composite material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- 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 description 8
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 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 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000008187 granular material Substances 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 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
- 230000000630 rising effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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Abstract
A preparation method of a high-stability zirconia ceramic material comprises the steps of adding a montmorillonite chitosan compound into yttria stabilized zirconia, ball milling and then calcining in sections, wherein the montmorillonite chitosan compound is prepared by adding montmorillonite powder 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 solution, stirring and heating to 90-100 ℃, preserving heat for 10-12h, and centrifugally collecting solids, the section calcining is divided into three sections, the temperature of the first section is 400-450 ℃, the temperature of the second section is 550-650 ℃, and the temperature of the third section is 850-900 ℃. The zirconia ceramic material prepared by the method improves the conductivity of the zirconia ceramic material, and has excellent conductivity stability under high-temperature change.
Description
The invention relates to a divisional application of patent application number 202211553803.0 with the name of 'a preparation method of zirconia ceramic material for an automobile exhaust sensor'.
Technical Field
The invention relates to the technical field of ceramic material preparation, in particular to a preparation method of a high-stability zirconia ceramic material.
Background
The yttria stabilized zirconia is very commonly applied to an automobile oxygen sensor, and the zirconia sensor is effectively applied to measuring the emission of a gasoline automobile, is the current optimal combustion atmosphere measuring mode, and has the advantages of simple structure, rapidness, easiness in maintenance, convenience in 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 high-stability zirconia ceramic material, which is free from attenuation of conductivity along with temperature change and increase of cycle times and has excellent conductivity stability.
The invention aims at realizing the following technical scheme:
a preparation method of a high-stability zirconia ceramic material is characterized by comprising the following steps: adding a montmorillonite chitosan compound into yttria stabilized zirconia, ball milling, and then carrying out sectional calcination, wherein 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.
Further, in the sectional calcination, the temperature of the first stage is raised to 400-450 ℃ at 5-8 ℃/min, the calcination time is 50-70min, the temperature of the second stage is raised to 550-650 ℃ at 4-6 ℃/min, the calcination time is 30-60min, and the temperature of the third stage is raised to 850-900 ℃ at 5-8 ℃/min, and the calcination time is 5-7h.
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.
Further, the ball milling speed of the ball milling is 300-400rpm, and the ball milling time is 15-18h.
Further, the drying temperature is 100-110 ℃, and the drying is 15-18 hours.
Further, the mass ratio of the montmorillonite suspension to the chitosan solution is 1:0.2-0.4, the mass ratio of the chitosan in the chitosan solution to the diluted hydrochloric acid is 1:120-150, the mixture is stirred and dissolved at 80-100rpm, the mass fraction of the diluted hydrochloric acid is 5%, and the centrifugal speed is 10000-20000rpm.
Further, the mass ratio of the montmorillonite-chitosan complex to the yttria-stabilized zirconia is 3-8:75-85.
Further, the pretreatment is to dry the crushed and sieved montmorillonite, then add deionized water in two steps, and then add EDTA-2Na and NaHCO 3 Stirring, standing to obtain suspension, adding edible salt, standing, and separatingAnd (3) collecting the precipitate, washing and drying the precipitate, ball-milling the precipitate, adding dilute hydrochloric acid, performing water bath treatment, and drying to obtain montmorillonite powder.
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 the edible salt to the suspension is 1:0.05-0.08:0.12-0.15, and the edible salt accounts for 10-15% of the mass of the suspension.
Further, the montmorillonite after crushing and sieving is dried by crushing the montmorillonite, sieving with a 100-mesh sieve and then drying at 90-100 ℃ for 24-36h.
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 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 invention has the following technical effects:
according to the invention, by adopting the montmorillonite-chitosan composite for adding and combining the zirconia ceramic material prepared by three-stage heating calcination, 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 circulating stability, and long-time stable operation under a high-temperature environment can be ensured.
Drawings
Fig. 1: the zirconia ceramic material prepared by the invention has a conductivity change curve graph along with the temperature change.
Fig. 2: the zirconia ceramic material prepared by the invention 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 with high stability 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 a suspension, adding edible salt, wherein the edible salt accounts for 15% of the mass of the suspension, standing for 1h, centrifuging at 10000rpm, collecting precipitate, repeatedly washing the precipitate with deionized water for 5 times, drying at 90 ℃ until the water content is lower than 0.2%, 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 ℃ while stirring at 100rpm for 10h, filtering and collecting the precipitate after cooling, washing with deionized water, drying at-0.05 to-0.08 MPa of vacuum degree and 80 ℃ of drying temperature, and sieving with 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 conductivity of the zirconia ceramic material prepared by the embodiment is 0.031S/cm, the conductivity stability is excellent at 400-900 ℃, the conductivity is basically unchanged after 20000 times of circulation, the conductivity is still kept at 93.16% of the initial conductivity, and the circulation stability is excellent.
Example 2
The preparation method of the high-stability zirconia ceramic material 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 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 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, the conductivity still maintained at 92.49% of the initial conductivity, and excellent circulation stability.
Example 3
The preparation method of the high-stability zirconia ceramic material 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 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, carrying out water bath at 90 ℃ and stirring at 90rpm for 11h, filtering and collecting precipitate after cooling, washing with deionized water, drying at the vacuum degree of-0.05 to-0.08 MPa and the 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 at 900 ℃ for 10 hours, 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:
adding 25% PVA solution into zirconia ceramic powder to prepare granules, and sieving the granules 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 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 electrodes have excellent recycling stability; the zirconia ceramic materials prepared in comparative examples 1 and 2 showed significant attenuation during the circulation process, and after 20000 times of circulation, the conductivities were 26.7% and 26.3% of the initial period, respectively, and the circulation stability was poor.
Claims (5)
1. A preparation method of a high-stability zirconia ceramic material is characterized by comprising the following steps: adding a montmorillonite chitosan compound into yttria stabilized zirconia, ball milling, and then carrying out sectional calcination, wherein 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.
2. The method for preparing the high-stability zirconia ceramic material according to claim 1, wherein the method comprises the following steps: the first stage of temperature is heated to 400-450 ℃ at 5-8 ℃/min and the calcination time is 50-70min, the second stage of temperature is heated to 550-650 ℃ at 4-6 ℃/min and the calcination time is 30-60min, and the third stage of temperature is heated to 850-900 ℃ at 5-8 ℃/min and the calcination time is 5-7h.
3. A method for preparing a high stability zirconia ceramic material according to claim 1 or 2, wherein: the ball milling speed of the ball milling is 300-400rpm, and the ball milling time is 15-18h.
4. A method for preparing a high stability zirconia ceramic material as defined in any one of claims 1 to 3, wherein: the mass ratio of the montmorillonite suspension to the chitosan solution is 1:0.2-0.4, the mass ratio of the chitosan in the chitosan solution to the diluted hydrochloric acid is 1:120-150, the mixture is stirred and dissolved at 80-100rpm, the mass fraction of the diluted hydrochloric acid is 5%, and the centrifugal speed is 10000-20000rpm.
5. A method for preparing a high stability zirconia ceramic material according to any one of claims 1 to 4, wherein: the mass ratio of the montmorillonite-chitosan complex to the yttria-stabilized zirconia is 3-8:75-85.
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