CN114573341A - Preparation method of zirconium dioxide-based conductive ceramic - Google Patents
Preparation method of zirconium dioxide-based conductive ceramic Download PDFInfo
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Abstract
A preparation method of zirconium dioxide-based conductive ceramic belongs to the technical field of ceramic material preparation, and comprises zirconium oxide powder pretreatment, slurry preparation, spray granulation, isostatic pressing, drying, curing and sintering; the method disclosed by the invention can be used for obtaining the zirconium dioxide-based conductive ceramic with high density, high hardness, high bending strength and good conductivity at the sintering temperature of 1600-1900 ℃; the obtained zirconium dioxide-based conductive ceramic has the compactness of 98.51-99.09%, the 3-point bending strength of 803-820 MPa, the Vickers hardness of 1204-1267 HV and the resistance of 0.14-0.21 omega.
Description
Technical Field
The invention relates to a preparation method of zirconium dioxide-based conductive ceramic, belonging to the technical field of ceramic material preparation.
Background
The zirconium dioxide ceramic has good thermal stability and chemical stability, excellent high-temperature conductivity, higher high-temperature strength and toughness, and good stability and corrosion resistance, is a special ceramic material which is developed rapidly at present, and can be used as high-temperature structural ceramic, electronic ceramic, biological ceramic and the like.
Chinese patent CN105174945A discloses a conductive ceramic material and a preparation method thereof, wherein the conductive ceramic material is composed of zirconium dioxide, aluminum nitride, diatomite, tribasic lead sulfate, germanium, copper, nickel foam, molybdenum, polyethylenedioxythiophene, aluminum oxide and N- β - (aminoethyl) - γ -aminopropylmethyldimethoxysilane. The conductive ceramic prepared by the patent has low hardness and poor bending strength.
Chinese patent CN107915483A discloses a piezoelectric ceramic material and a preparation method thereof, which takes cactus powder, zirconium dioxide, silicon dioxide, manganese dioxide, conductive slurry, molybdenum disulfide, tourmaline powder, calcium carbonate whisker, magnesium oxide, aluminum oxide, a dispersant, polyaluminosiloxane and sepiolite powder as raw materials. The conductive ceramic prepared by the patent has low density, poor conductivity and poor hardness and strength.
As can be seen from the above, the existing zirconium dioxide-based conductive ceramic still has the problems of low density, poor hardness and bending strength, poor conductivity and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of zirconium dioxide-based conductive ceramic, which realizes the following purposes: the zirconium dioxide-based conductive ceramic with high density, high hardness, high bending strength and good conductivity is obtained at a lower sintering temperature.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a process for preparing the zirconium dioxide-base electrically conducting ceramic includes pretreating zirconium oxide powder, preparing slurry, spray granulating, isostatic pressing, drying, solidifying and sintering.
The following is a further improvement of the above technical solution:
step 1, pretreatment of zirconia powder
At a stirring speed of 3500-6000 rpm, adding Y2O3Stabilized ZrO2Slowly adding the powder into the mixed solution, uniformly dispersing, reducing the stirring speed to 900-1300 rpm, heating to 110-130 ℃, refluxing at constant temperature for 3-6 hours, performing centrifugal separation, and drying the obtained solid at 50-90 ℃ for 2-4 hours to obtain pretreated zirconia powder;
said Y is2O3Stable ZrO2Powder with a particle size of 30nm, wherein Y2O3The mass fraction of (B) is 5.3 wt%;
the mixed solution consists of stearic acid, isopropanol and toluene;
the mass ratio of stearic acid to isopropanol to toluene is 1-9: 3-10: 70-130;
said Y is2O3Stabilized ZrO2The mass ratio of the powder to the mixed liquid is 1-4: 25.
Step 2, preparation of slurry
Mixing pretreated zirconium oxide powder, molybdenum disilicide powder, zirconium boride powder, titanium carbide powder, magnesium oxide powder, high-purity silicon powder, water-soluble phenolic resin, sodium polyacrylate, oxalic acid and deionized water into a slurry state, putting the obtained slurry into a ball mill, ball-milling zirconium dioxide serving as a ball-milling medium until the average particle size of the powder in the slurry is 0.5-2 mu m, and discharging to obtain slurry;
the particle size of the molybdenum disilicide powder is 1-5 microns, and the purity is 99.95%;
the particle size of the zirconium boride powder is 2-8 mu m, and the purity is 99.6%;
the particle size of the titanium carbide powder is 2-7 mu m, and the purity is 99.5%;
the particle size of the magnesium oxide powder is 3-8 mu m, and the purity is 99.5%;
the particle size of the high-purity silicon powder is 2-9 mu m, and the purity is 99.99%;
the viscosity of the water-soluble phenolic resin at normal temperature is 260-600 mPa & s;
the molecular weight of the sodium polyacrylate is 5000-8000 g/mol;
the mass ratio of the pretreated zirconia powder, molybdenum disilicide powder, zirconium boride powder, titanium carbide powder, magnesia powder, high-purity silicon powder, water-soluble phenolic resin, sodium polyacrylate, oxalic acid and deionized water is 60-90: 2-6: 4-12: 1-3: 2-6: 0.5-1.5: 4-8: 1-3: 0.8-1.5: 70-110.
Step 3, spray granulation
Performing spray granulation on the slurry, wherein the inlet temperature is controlled to be 150-190 ℃, and the outlet temperature is controlled to be 80-100 ℃ to obtain granules;
the water content of the aggregate is 0.8-1.7 wt%, and the particle size is 10-26 μm.
Step 4, isostatic pressing forming
And putting the granules into a mould, and carrying out isostatic pressing under the pressure of 400-500 MPa to obtain a biscuit.
Step 5, drying and curing
Drying the biscuit at 80-110 ℃ for 2-4 hours, then heating to 180-220 ℃ for curing for 1-3 hours, and cooling to room temperature to obtain the cured biscuit.
Step 6, sintering
And heating the solidified element blank to 1600-1900 ℃ at the speed of 2-4 ℃/min under the protection of high-purity argon, sintering at constant temperature for 1-2.5 hours, and cooling to room temperature to obtain the zirconium dioxide-based conductive ceramic.
Compared with the prior art, the invention has the following beneficial effects:
1. the method disclosed by the invention can be used for obtaining the zirconium dioxide-based conductive ceramic with high density, high hardness, high bending strength and good conductivity at the sintering temperature of 1600-1900 ℃;
2. the zirconium dioxide-based conductive ceramic obtained by the invention has the density of 98.51-99.09%, the 3-point bending strength of 803-820 MPa, the Vickers hardness of 1204-1267 HV and the resistance of 0.14-0.21 omega;
3. y used in the invention2O3Stabilized ZrO2The powder has the particle size of 30nm, and if the powder is not pretreated, the powder is easy to agglomerate in the preparation process of the slurry, so that the compactness and the strength of the finally prepared ceramic are influenced; invention pair Y2O3Stabilized ZrO2The powder is pretreated to increase Y2O3Stabilized ZrO2The dispersion performance of the powder enables the powder to be uniformly dispersed in the slurry in a nanoscale scale in the slurry preparation process, and finally the compactness and strength performance of the ceramic are improved;
4. the conductive ceramic in the prior art generally adopts polyvinyl alcohol as a binder, the polyvinyl alcohol can be decomposed in the sintering process to generate gas, the gas overflow process can cause the porosity of the ceramic to be increased, and the density and the strength of the ceramic are reduced;
according to the invention, water-soluble phenolic resin is used as a binder, and in the drying and curing process, the water-soluble phenolic resin is subjected to crosslinking curing under the catalytic action of oxalic acid to generate thermosetting phenolic resin; the thermosetting phenolic resin is carbonized in the sintering process, and the residual carbon and high-purity silicon powder after carbonization generate silicon carbide, so that the density and the strength of the ceramic are finally improved.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1: preparation method of zirconium dioxide-based conductive ceramic
The method comprises the following steps:
1. pretreatment of zirconia powder
Stirring at 5000 rpm for Y2O3Stabilized ZrO2Slowly adding the powder into the mixed solution, uniformly dispersing, reducing the stirring speed to 1100 r/min, heating to 120 ℃, refluxing at constant temperature for 5 hours, performing centrifugal separation, and drying the obtained solid at 70 ℃ for 3 hours to obtain pretreated zirconium oxide powder;
said Y is2O3Stabilized ZrO2Powder with a particle size of 30nm, wherein Y2O3The mass fraction of (B) is 5.3 wt%;
the mixed solution consists of stearic acid, isopropanol and toluene;
the mass ratio of stearic acid to isopropanol to toluene is 5:8: 100;
said Y is2O3Stabilized ZrO2The mass ratio of the powder to the mixed solution is 2: 25.
2. Slurry preparation
Mixing pretreated zirconium oxide powder, molybdenum disilicide powder, zirconium boride powder, titanium carbide powder, magnesium oxide powder, high-purity silicon powder, water-soluble phenolic resin, sodium polyacrylate, oxalic acid and deionized water into a slurry state, putting the obtained slurry into a ball mill, ball-milling zirconium dioxide serving as a ball-milling medium until the average particle size of the powder in the slurry is 1 mu m, and discharging to obtain slurry;
the particle size of the molybdenum disilicide powder is 4 microns, and the purity is 99.95%;
the particle size of the zirconium boride powder is 5 mu m, and the purity is 99.6%;
the particle size of the titanium carbide powder is 6 mu m, and the purity is 99.5%;
the particle size of the magnesium oxide powder is 4 mu m, and the purity is 99.5%;
the particle size of the high-purity silicon powder is 7 microns, and the purity is 99.99 percent;
the viscosity of the water-soluble phenolic resin is 350mPa & s at normal temperature;
the molecular weight of the sodium polyacrylate is 7500 g/mol;
the mass ratio of the pretreated zirconia powder, the molybdenum disilicide powder, the zirconium boride powder, the titanium carbide powder, the magnesia powder, the high-purity silicon powder, the water-soluble phenolic resin, the sodium polyacrylate, the oxalic acid and the deionized water is 80:4:8:2:4:1:6:2:1: 100.
3. Spray granulation
Carrying out spray granulation on the slurry, wherein the inlet temperature is controlled at 170 ℃, and the outlet temperature is controlled at 90 ℃ to obtain granules;
the water content of the pellets was 1wt%, and the particle size was 15 μm.
4. Isostatic compaction
And putting the granules into a mould, and carrying out isostatic pressing under the pressure of 450MPa to obtain a biscuit.
5. Drying and curing
Drying the biscuit at 95 ℃ for 3 hours, then heating to 200 ℃ for curing for 2 hours, and cooling to room temperature to obtain the cured biscuit.
6. Sintering
And (3) heating the solidified element blank to 1800 ℃ at the speed of 3 ℃/min under the protection of high-purity argon, sintering at constant temperature for 2 hours, and cooling to room temperature to obtain the zirconium dioxide-based conductive ceramic.
Example 2: preparation method of zirconium dioxide-based conductive ceramic
The method comprises the following steps:
1. zirconia powder pretreatment
At a stirring speed of 3500 rpm, Y is added2O3Stabilized ZrO2Slowly adding the powder into the mixed solutionAfter dispersing uniformly, reducing the stirring speed to 900 revolutions per minute, heating to 110 ℃, refluxing for 3 hours at constant temperature, centrifuging, and drying the obtained solid at 50 ℃ for 2 hours to obtain pretreated zirconia powder;
said Y is2O3Stabilized ZrO2Powder with a particle size of 30nm, wherein Y2O3The mass fraction of (A) is 5.3 wt%;
the mixed solution consists of stearic acid, isopropanol and toluene;
the mass ratio of stearic acid to isopropanol to toluene is 1:3: 70;
said Y2O3Stabilized ZrO2The mass ratio of the powder to the mixed solution is 1: 25.
2. Slurry preparation
Mixing pretreated zirconium oxide powder, molybdenum disilicide powder, zirconium boride powder, titanium carbide powder, magnesium oxide powder, high-purity silicon powder, water-soluble phenolic resin, sodium polyacrylate, oxalic acid and deionized water into a slurry state, putting the obtained slurry into a ball mill, ball-milling zirconium dioxide serving as a ball-milling medium until the average particle size of the powder in the slurry is 0.5 mu m, and discharging to obtain slurry;
the particle size of the molybdenum disilicide powder is 1 mu m, and the purity is 99.95%;
the particle size of the zirconium boride powder is 2 microns, and the purity is 99.6%;
the particle size of the titanium carbide powder is 2 mu m, and the purity is 99.5%;
the particle size of the magnesium oxide powder is 3 mu m, and the purity is 99.5%;
the particle size of the high-purity silicon powder is 2 microns, and the purity is 99.99%;
the viscosity of the water-soluble phenolic resin at normal temperature is 260mPa & s;
the molecular weight of the sodium polyacrylate is 5000 g/mol;
the mass ratio of the pretreated zirconia powder, the molybdenum disilicide powder, the zirconium boride powder, the titanium carbide powder, the magnesia powder, the high-purity silicon powder, the water-soluble phenolic resin, the sodium polyacrylate, the oxalic acid and the deionized water is 60:2:4:1: 0.5:4:1:0.8: 70.
3. Spray granulation
Carrying out spray granulation on the slurry, controlling the inlet temperature at 150 ℃ and the outlet temperature at 80 ℃ to obtain granules;
the water content of the pellets was 0.8wt%, and the particle size was 10 μm.
4. Isostatic compaction
And putting the granules into a mould, and carrying out isostatic pressing under the pressure of 400MPa to obtain a biscuit.
5. Drying and curing
Drying the biscuit at 80 ℃ for 2 hours, then heating to 180 ℃ for curing for 1 hour, and cooling to room temperature to obtain the cured biscuit.
6. Sintering
And under the protection of high-purity argon, heating the solidified element blank to 1600 ℃ at the speed of 2 ℃/min, sintering at constant temperature for 1 hour, and cooling to room temperature to obtain the zirconium dioxide-based conductive ceramic.
Example 3: preparation method of zirconium dioxide-based conductive ceramic
The method comprises the following steps:
1. pretreatment of zirconia powder
Stirring at 6000 rpm, adding Y2O3Stabilized ZrO2Slowly adding the powder into the mixed solution, uniformly dispersing, reducing the stirring speed to 1300 r/min, heating to 130 ℃, refluxing at constant temperature for 6 hours, performing centrifugal separation, and drying the obtained solid at 90 ℃ for 4 hours to obtain pretreated zirconium oxide powder;
said Y is2O3Stabilized ZrO2Powder with a particle size of 30nm, wherein Y2O3The mass fraction of (B) is 5.3 wt%;
the mixed solution consists of stearic acid, isopropanol and toluene;
the mass ratio of stearic acid to isopropanol to toluene is 9:10: 130;
said Y is2O3Stabilized ZrO2The mass ratio of the powder to the mixed solution was 4: 25.
2. Slurry preparation
Mixing pretreated zirconium oxide powder, molybdenum disilicide powder, zirconium boride powder, titanium carbide powder, magnesium oxide powder, high-purity silicon powder, water-soluble phenolic resin, sodium polyacrylate, oxalic acid and deionized water into a slurry state, putting the obtained slurry into a ball mill, ball-milling zirconium dioxide serving as a ball-milling medium until the average particle size of the powder in the slurry is 2 microns, and discharging to obtain slurry;
the particle size of the molybdenum disilicide powder is 5 microns, and the purity is 99.95%;
the particle size of the zirconium boride powder is 8 mu m, and the purity is 99.6%;
the particle size of the titanium carbide powder is 7 mu m, and the purity is 99.5%;
the particle size of the magnesium oxide powder is 8 mu m, and the purity is 99.5%;
the particle size of the high-purity silicon powder is 9 microns, and the purity is 99.99 percent;
the viscosity of the water-soluble phenolic resin at normal temperature is 600mPa & s;
the molecular weight of the sodium polyacrylate is 8000 g/mol;
the mass ratio of the pretreated zirconia powder, the molybdenum disilicide powder, the zirconium boride powder, the titanium carbide powder, the magnesia powder, the high-purity silicon powder, the water-soluble phenolic resin, the sodium polyacrylate, the oxalic acid and the deionized water is 90:6:12:3: 1.5:8:3:1.5: 110.
3. Spray granulation
Carrying out spray granulation on the slurry, controlling the inlet temperature at 190 ℃ and the outlet temperature at 100 ℃ to obtain granules;
the water content of the pellets was 1.7wt%, and the particle size was 26 μm.
4. Isostatic compaction
And putting the granules into a mould, and carrying out isostatic pressing under the pressure of 500MPa to obtain a biscuit.
5. Drying and curing
Drying the biscuit at 110 ℃ for 4 hours, heating to 220 ℃ for curing for 3 hours, and cooling to room temperature to obtain the cured biscuit.
6. Sintering
Under the protection of high-purity argon, the solidified element blank is heated to 1900 ℃ at the speed of 4 ℃/min, sintered for 2.5 hours at constant temperature, and cooled to room temperature to obtain the zirconium dioxide-based conductive ceramic.
Comparative example 1: example 1 based on the absence of a zirconium oxide powder pretreatment step
Step 1 is not carried out;
in step 2, the pretreated zirconia powder was replaced with Y in equal amounts2O3Stabilized ZrO2Powder, otherwise the same procedure as in example 1;
steps 3, 4, 5, 6 were performed as in example 1.
Comparative example 2: example 1 in addition, the water-soluble phenol resin was replaced with the same amount of polyvinyl alcohol
Step 1 was performed as in example 1;
in the step 2, 6 parts of water-soluble phenolic resin is replaced by 6 parts of polyvinyl alcohol, and the other operations are the same as those in the example 1;
the molecular weight of the polyvinyl alcohol is 26000 g/mol;
steps 3, 4, 5, 6 were performed as in example 1.
And (3) performance testing:
the ceramic samples obtained in examples 1, 2 and 3 and comparative examples 1 and 2 were tested for compactness, 3-point bending strength, Vickers hardness and electric resistance in the following manner;
1. and (3) density testing: the method is characterized in that the actual density of a sample is tested by adopting an Archimedes drainage method, the theoretical density of the sample is calculated according to the mixture ratio of raw materials, and the calculation formula comprises the following steps: density is (actual density/theoretical density) × 100%;
2. 3-point bending strength test: measuring the 3-point bending strength of a sample by using a universal testing machine, wherein the sample has the advantages of wide size, high length and span of 4 multiplied by 3 multiplied by 36mm, 30mm and 2mm/min of loading rate;
3. vickers hardness test: measuring the Vickers hardness of the sample by using a Vickers hardness meter, and testing the pressure at 3000g for 15S;
4. and (3) resistance testing: measuring the resistance of the sample by using a universal meter;
the results of the above tests are shown in the following table:
Claims (7)
1. a preparation method of zirconium dioxide-based conductive ceramic is characterized by comprising the following steps: comprises the steps of zirconium oxide powder pretreatment, slurry preparation, spray granulation, isostatic pressing, drying, solidification and sintering;
the zirconium oxide powder is pretreated by stirring Y at 3500-6000 rpm2O3Stabilized ZrO2Slowly adding the powder into the mixed solution, uniformly dispersing, reducing the stirring speed to 900-1300 rpm, heating to 110-130 ℃, refluxing at constant temperature for 3-6 hours, performing centrifugal separation, and drying the obtained solid at 50-90 ℃ for 2-4 hours to obtain pretreated zirconium oxide powder;
said Y is2O3Stabilized ZrO2Powder of 30nm particle size, wherein Y2O3The mass fraction of (B) is 5.3 wt%;
the mixed solution consists of stearic acid, isopropanol and toluene;
the mass ratio of stearic acid to isopropanol to toluene is 1-9: 3-10: 70-130;
said Y is2O3Stabilized ZrO2The mass ratio of the powder to the mixed liquid is 1-4: 25;
the preparation method of the slurry comprises the steps of mixing pretreated zirconium oxide powder, molybdenum disilicide powder, zirconium boride powder, titanium carbide powder, magnesium oxide powder, high-purity silicon powder, water-soluble phenolic resin, sodium polyacrylate, oxalic acid and deionized water into a slurry state, putting the obtained slurry into a ball mill, performing ball milling until the average particle size of the powder in the slurry is 0.5-2 mu m, and discharging to obtain the slurry;
the medium of the ball mill is zirconium dioxide;
the mass ratio of the pretreated zirconia powder, molybdenum disilicide powder, zirconium boride powder, titanium carbide powder, magnesia powder, high-purity silicon powder, water-soluble phenolic resin, sodium polyacrylate, oxalic acid and deionized water is 60-90: 2-6: 4-12: 1-3: 2-6: 0.5-1.5: 4-8: 1-3: 0.8-1.5: 70-110;
the isostatic compaction method comprises the steps of putting granules obtained by spray granulation into a mould, and carrying out isostatic compaction under the pressure of 400-500 MPa to obtain a blank.
2. The method of claim 1, wherein:
the particle size of the molybdenum disilicide powder is 1-5 microns, and the purity is 99.95%;
the particle size of the zirconium boride powder is 2-8 mu m, and the purity is 99.6%;
the particle size of the titanium carbide powder is 2-7 mu m, and the purity is 99.5%;
the particle size of the magnesium oxide powder is 3-8 mu m, and the purity is 99.5%;
the particle size of the high-purity silicon powder is 2-9 mu m, and the purity is 99.99%.
3. The method of claim 1, wherein:
the viscosity of the water-soluble phenolic resin at normal temperature is 260-600 mPa & s;
the molecular weight of the sodium polyacrylate is 5000-8000 g/mol.
4. The method of claim 1, wherein:
the spray granulation method comprises the steps of carrying out spray granulation on the slurry, controlling the inlet temperature to be 150-190 ℃ and the outlet temperature to be 80-100 ℃ to obtain granules.
5. The method according to claim 4, wherein the zirconia-based conductive ceramic comprises:
the water content of the aggregate is 0.8-1.7 wt%, and the particle size is 10-26 μm.
6. The method of claim 1, wherein:
and drying and curing the biscuit at 80-110 ℃ for 2-4 hours, then heating to 180-220 ℃ for curing for 1-3 hours, and cooling to room temperature to obtain the cured biscuit.
7. The method of claim 1, wherein:
the sintering method comprises the steps of heating the solidified biscuit to 1600-1900 ℃ at the speed of 2-4 ℃/min under the protection of high-purity argon, sintering at constant temperature for 1-2.5 hours, and cooling to room temperature to obtain the zirconium dioxide-based conductive ceramic.
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