CN112723875B - Gallium oxide doped tin oxide ceramic target material and preparation method thereof - Google Patents
Gallium oxide doped tin oxide ceramic target material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a gallium oxide doped tin oxide ceramic target and a preparation method thereof, wherein the raw material comprises, by mass, 2-10% of gallium oxide and 90-98% of tin oxide, and gallium oxide high-purity nanopowder. Weighing and mixing the powder, adding ammonium polyacrylate, polyvinyl alcohol and pure water, ball-milling the mixed slurry, granulating and drying to obtain mixed powder, sequentially pressing and molding the mixed powder by using an oil press and an isostatic press, and preparing the gallium oxide doped tin oxide ceramic target material at different sintering temperatures by using a degreasing-multi-step sintering integrated sintering technology. The gallium oxide doped tin oxide target material has the advantages that the sintering performance of tin oxide ceramic is effectively improved, the density of the tin oxide ceramic target material is remarkably improved, and meanwhile, the gallium oxide doped tin oxide target material with uniform tissue and fine grains is obtained through effective control of the preparation process.
Description
Technical Field
The invention relates to the technical field of oxide target material preparation, in particular to a gallium oxide doped tin oxide ceramic target material and a preparation method thereof.
Background
Tin dioxide (SnO) 2 ) The n-type semiconductor material with a wide band gap has a forbidden bandwidth of 3.6-4.0 eV, has the characteristics of high temperature resistance, corrosion resistance, excellent high-temperature conductivity and the like, and is widely applied to the fields of gas sensitive elements, semiconductor elements, solar cells and the like due to the special photoelectric property and gas sensitive property. However, pure tin dioxide ceramics have a high resistivity and are not suitable for use as conductive ceramics. Furthermore, pure tin dioxide without additives, in addition to exhibiting poor electrical conductivity, also exhibits poor sintering properties. One of which is caused by the volatilization of tin dioxide at high temperatures. Studies have shown that tin oxide can be strongly volatilized at temperatures in excess of 1500 c. In addition, the densification mechanism of the tin dioxide ceramic does not play a role in the sintering process, and only the phenomena of pore enlargement and grain growth are caused by surface diffusion and evaporation-condensation. Pure tin dioxide ceramics therefore tend to form a loose porous structure after sintering.
In order to improve the compactness and the photoelectric property of the tin dioxide ceramic, doping treatment is often performed on the tin dioxide ceramic. The current research on tin dioxide doping is mainly focused on two aspects: on one hand, the compactness of the tin dioxide ceramic is improved by doping, the introduction of the additive is to promote the sintering of the ceramic, and the doping research of using oxides such as Cu, ag, zn, ni and the like as sintering promoters is already carried out; on the other hand, the conductivity of tin dioxide ceramics is improved by doping, and on the other hand, doping using oxides such as Sb, nb, ta, and V has been studied.
Disclosure of Invention
The invention provides a gallium oxide doped tin oxide ceramic target material and a preparation method thereof, which solve the problem that tin dioxide ceramic is difficult to densify in the sintering process so as to obtain the high-density gallium oxide doped tin dioxide ceramic target material.
The technical scheme for realizing the invention is as follows:
a preparation method of tin oxide doped ceramic comprises the following steps:
(1) Uniformly dispersing gallium oxide, tin oxide, a dispersing agent and pure water, and preparing slurry;
(2) Putting the slurry obtained in the step (1) and zirconia grinding balls into a ball milling tank, adding a certain amount of binder, and carrying out mixing and ball milling;
(3) Preparing the mixed slurry obtained in the step (2) into spherical powder by spray drying;
(4) Putting the spherical powder obtained in the step (3) into a phi 30 alloy steel die, and performing pre-pressing molding by using a hydraulic machine, wherein the process is a compression molding process, demolding after pressing to obtain a target biscuit, fully coating the biscuit by using a rubber sleeve, further pressing in an isostatic press to obtain a tin dioxide ceramic biscuit;
(5) And sintering the tin dioxide ceramic biscuit by adopting a degreasing-multi-step sintering integrated sintering technology to obtain the gallium oxide doped tin oxide ceramic target material.
The gallium oxide and the tin oxide are respectively in mass percent: 2-10% of gallium oxide and 90-98% of tin oxide; the dispersant is ammonium polyacrylate, the binder is polyvinyl alcohol, the addition amount of the dispersant and the binder is 0.5 to 2 percent and the addition amount of the water is 65 to 75 percent based on the total mass of the gallium oxide and the tin oxide.
In the step (2), the rotating speed of the ball mill is 160-260r/min, the zirconia grinding balls are phi 5, phi 3 and phi 1 respectively, and the mass ratio of the three balls is 1:1:2; the ball-material ratio is 3, the ball milling time is 24-48h, and the maximum charging amount does not exceed three fifths of the volume of the tank.
In the step (3), the spray drying temperature is 200-240 ℃, the feeding rate is 10-20mL/min, and the frequency of a centrifugal machine is 30-45Hz.
And (4) pre-pressing and forming at 25-75MPa for 2-8min, and isostatic pressing at 200-250MPa for 3-15min.
The degreasing-multi-step sintering integrated sintering technology in the step (5) specifically comprises the following steps: firstly, slowly heating from room temperature to 600-650 ℃ to completely degrease the biscuit, wherein the heating rate is 0.5-1 ℃/min; increasing the heating rate at 600-650 deg.C or above, keeping the temperature for 1-3h when the temperature rises to 850-950 deg.C, then keeping the temperature for 4-10h when the temperature rises to 1350-1450 deg.C, stopping heating, and slowly cooling to room temperature at a cooling rate of 1-3 deg.C/min.
In the step (1), the grain diameter of the tin oxide is 20-100 nm, and the purity is 4N; the grain diameter of the gallium oxide is 2-5 μm, and the purity is 4N.
The relative density of the ceramic target material is 98-99.5%, and the average grain diameter of the crystal grains is 2-3.5 μm.
The invention has the beneficial effects that: in order to improve the compactness and the electrical property of the tin dioxide ceramic, metal oxide is usually added for doping and sintering, and the invention provides a preparation method of a gallium oxide doped tin oxide ceramic target material with high compactness and uniform tissue. By introducing the gallium oxide, the densification temperature of the tin dioxide ceramic is effectively reduced, the volatilization of the tin dioxide at high temperature is weakened, and the density of the tin dioxide ceramic is improved; meanwhile, the doped tin oxide target material with uniform grain structure is obtained through the effective control of powder treatment and sintering process; in addition, gallium oxide can be pinned at the crystal boundary of tin dioxide to prevent crystal grains from growing, and the doped tin oxide target with fine crystal grains is obtained.
Therefore, the doped tin oxide ceramic target material with high compactness and uniform tissue distribution is effectively prepared by introducing gallium oxide into the tin dioxide matrix.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a scanning electron micrograph of a polished surface of gallium oxide-doped tin dioxide ceramic in example 1.
FIG. 2 is a scanning electron micrograph of a cross section of the gallium oxide-doped tin dioxide ceramic of example 1.
Figure 3 is an XRD spectrum of the gallium oxide doped tin dioxide ceramic of example 1.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The preparation method of the high-density tin oxide doped ceramic and the pressureless sintering thereof comprises the following steps:
firstly, preparing high-density tin oxide doped ceramic from the following raw materials in percentage by mass: 95% of nano-grade high-purity tin oxide powder and 5% of nano-grade high-purity gallium oxide powder. Weighing ammonium polyacrylate accounting for 0.7% of the powder by mass as a dispersing agent, weighing polyvinyl alcohol accounting for 0.8% of the powder by mass as a binder, and adding pure water accounting for 70% of the powder by mass to prepare slurry;
secondly, putting the powder mixture, ammonium polyacrylate, pure water and zirconia grinding balls with three specifications into a zirconia ball milling tank of 1L, and carrying out mixed ball milling on the powder on a ball mill, wherein the ball milling needs 48 hours, and the rotating speed of the ball mill is 260r/min; adding polyvinyl alcohol into the slurry after the ball milling is finished, and continuing the ball milling for 2 hours until the mixture is uniformly mixed; the grinding balls used in the ball milling process are respectively phi 5, phi 3 and phi 1, and the mass ratio of the three balls is 1:1:2; the ball-material ratio is 3;
and step three, taking the mixed slurry after ball milling out of the ball milling tank, and performing spray drying by using a granulator to obtain mixed spherical powder. The granulation temperature is 220 ℃, the feeding rate is 15mL/min, and the frequency of a centrifugal machine is 35Hz;
and step four, weighing a certain mass of mixed granulation powder, placing the mixed granulation powder in a phi 30 alloy steel mold, performing pre-pressing molding by using a hydraulic press at the molding pressure of 50MPa for 5min, and demolding after the pressing is finished to obtain the target biscuit. Fully coating the biscuit by using a rubber sheath, and further pressing in an isostatic pressing machine, wherein the isostatic pressing pressure is 250Mpa;
and step five, sintering the tin dioxide ceramic biscuit by adopting a degreasing-multi-step sintering integrated sintering technology, and firstly slowly heating to 650 ℃ from room temperature to completely degrease the biscuit, wherein the heating rate is 0.5 ℃/min. Increasing the heating rate at above 650 deg.C, the heating rate is 3 deg.C/min, and maintaining the temperature for 3h when the temperature is increased to 950 deg.C. And then introducing oxygen with the oxygen flow of 10L/min, continuously heating to 1400 ℃, keeping the temperature for 8h, stopping heating, slowly cooling to room temperature with the cooling rate of 1 ℃/min, and sampling to obtain the high-density gallium oxide doped tin oxide ceramic target material.
The relative density of the tin dioxide ceramic obtained in the example is 99.2%, the microstructure of the polished surface is shown in fig. 1, the average grain diameter of the grains is 2.76 μm, and the target material has no obvious pores in the grain gaps and the grains. The microscopic morphology of the fracture is shown in FIG. 2, the fracture mode is transgranular fracture, the bonding force among target grains is strong, the number of air holes is small, and the densification degree is high. To the prepared oxidationXRD phase detection of the tin target material shows that the target material component is solid solution Ga as shown in figure 3 2 O 3 SnO of (2) 2 Phase, no other phases are present. Gallium oxide is used as an additive, crystal grains of the gallium oxide are pinned in a tin oxide ceramic matrix, the existence significance of the gallium oxide hinders further growth of the tin oxide ceramic crystal grains, the crystal grain size of the ceramic matrix is refined, and the densification degree of the tin oxide target is effectively improved. The obtained gallium oxide doped tin oxide ceramic has high density, low porosity, smaller grain size and uniform grain size distribution.
Example 2
The preparation method of the high-density tin oxide doped ceramic and the pressureless sintering thereof comprises the following steps:
step one, preparing high-density tin oxide doped ceramic by using raw materials according to mass percentage, wherein the high-density tin oxide doped ceramic comprises the following components: 90% of nano-grade high-purity tin oxide powder and 10% of nano-grade high-purity gallium oxide powder. Weighing 2% of ammonium polyacrylate in the total mass as a dispersing agent, weighing 2% of polyvinyl alcohol in the total mass as a binder, and adding pure water in an amount of 70% of the powder mass to prepare slurry;
step two, putting the powder mixture, ammonium polyacrylate, pure water and zirconia grinding balls with three specifications into a zirconia ball milling tank with the volume of 1L, and carrying out mixed ball milling on the powder on a ball mill, wherein the ball milling needs 48 hours, and the rotating speed of the ball mill is 240r/min; after the ball milling is finished, adding polyvinyl alcohol into the slurry, and continuing the ball milling for 2 hours until the mixture is uniformly mixed; the grinding balls used in the ball milling process are respectively phi 5, phi 3 and phi 1, and the mass ratio of the three balls is 1:1:2; the ball-material ratio is 3;
and step three, taking the mixed slurry after ball milling out of the ball milling tank, and performing spray drying by using a granulator to obtain mixed spherical powder. The granulation temperature is 200 ℃, the feeding rate is 10mL/min, and the frequency of a centrifugal machine is 35Hz;
and step four, weighing a certain mass of mixed granulation powder, placing the mixed granulation powder in a phi 30 alloy steel mold, performing pre-pressing molding by using a hydraulic press at the molding pressure of 25MPa for 2min, and demolding after the pressing is finished to obtain the target biscuit. Fully coating the biscuit by using a rubber sleeve, and further pressing in an isostatic press, wherein the isostatic pressure is 220Mpa;
and step five, sintering the tin dioxide ceramic biscuit by adopting a degreasing-multi-step sintering integrated sintering technology, and firstly, slowly heating the temperature from room temperature to 630 ℃ to completely degrease the biscuit, wherein the heating rate is 0.75 ℃/min. Increasing the heating rate at above 630 ℃ and keeping the temperature for 2h when the temperature is increased to 900 ℃. And then introducing oxygen with the oxygen flow of 10L/min, continuously heating to 1350 ℃, preserving the heat for 10h at the temperature, stopping heating, slowly cooling to room temperature with the cooling rate of 2 ℃/min, and sampling to obtain the high-density gallium oxide doped tin oxide ceramic target material.
The relative density of the tin dioxide ceramic prepared by the embodiment is 98.14%, the average grain diameter of the grains is 2.23 μm, and a small amount of air holes exist in the grain gaps of the target material. Gallium oxide is used as an additive, crystal grains of the gallium oxide are pinned in a tin oxide ceramic matrix, the existence significance of the gallium oxide hinders further growth of the tin oxide ceramic crystal grains, the crystal grain size of the ceramic matrix is refined, and the densification degree of the tin oxide target is effectively improved. The obtained gallium oxide doped tin oxide ceramic has high density, low porosity, small crystal grain size and uniform crystal grain size distribution.
Example 3
The preparation method of the high-density tin oxide doped ceramic and the pressureless sintering thereof comprises the following steps:
firstly, preparing high-density tin oxide doped ceramic from the following raw materials in percentage by mass: 98% of nano-grade high-purity tin oxide powder and 2% of nano-grade high-purity gallium oxide powder. Weighing ammonium polyacrylate accounting for 0.5 percent of the total mass as a dispersing agent, weighing polyvinyl alcohol accounting for 0.5 percent of the total mass as a binder, and adding pure water accounting for 70 percent of the mass of the powder to prepare slurry;
step two, putting the powder mixture, ammonium polyacrylate, pure water and zirconia grinding balls with three specifications into a zirconia ball milling tank of 1L, and carrying out mixed ball milling on the powder on a ball mill, wherein the ball milling needs 48 hours, and the rotating speed of the ball mill is 160r/min; adding polyvinyl alcohol into the slurry after the ball milling is finished, and continuing the ball milling for 2 hours until the mixture is uniformly mixed; the grinding balls used in the ball milling process are phi 5, phi 3 and phi 1 respectively, and the mass ratio of the three balls is 1:1:2; the ball-material ratio is 3;
and step three, taking the mixed slurry after ball milling out of the ball milling tank, and performing spray drying by using a granulator to obtain mixed spherical powder. The granulation temperature is 240 ℃, the feeding rate is 20mL/min, and the frequency of a centrifugal machine is 35Hz;
and step four, weighing a certain mass of mixed granulation powder, placing the mixed granulation powder in a phi 30 alloy steel mold, performing pre-pressing molding by using a hydraulic press at the molding pressure of 75MPa for 8min, and demolding after the pressing is finished to obtain the target biscuit. Fully coating the biscuit by a rubber sheath, and further pressing in an isostatic press with the isostatic pressure of 200MPa.
Step five, sintering the tin dioxide ceramic biscuit by adopting a degreasing-multi-step sintering integrated sintering technology, and firstly, slowly heating the temperature from room temperature to 600 ℃ to completely degrease the biscuit, wherein the heating rate is 1 ℃/min; and (2) increasing the heating rate at the temperature of more than 600 ℃, keeping the temperature for 1h when the temperature is increased to 850 ℃, introducing oxygen with the flow rate of 10L/min, continuing to increase the temperature to 1450 ℃, keeping the temperature for 4h at the temperature, stopping heating, slowly cooling to room temperature with the cooling rate of 3 ℃/min, and sampling to obtain the high-density gallium oxide doped tin oxide ceramic target material.
The relative density of the tin dioxide ceramic prepared in this example was 98.82%. The average grain size of the crystal grains was 3.16. Mu.m. The target material has no obvious air holes in the grain gaps and the grains, the gallium oxide is used as an additive, the grains are pinned in the tin oxide ceramic matrix, the existence significance of the gallium oxide hinders the further growth of the tin oxide ceramic grains, refines the grain size of the ceramic matrix and effectively improves the densification degree of the tin oxide target material. The obtained gallium oxide doped tin oxide ceramic has high density, low porosity, smaller grain size and uniform grain size distribution.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (4)
1. The preparation method of the tin oxide doped ceramic is characterized by comprising the following steps of:
(1) Uniformly dispersing gallium oxide, tin oxide and a dispersing agent, and adding water to prepare slurry, wherein the particle size of the gallium oxide is 2-5 μm, the purity is 4N, and the mass percent is 2-10%, the particle size of the tin oxide is 20-100 nm, the purity is 4N, and the mass percent is 90-98%, the dispersing agent is ammonium polyacrylate, the adding amount of the ammonium polyacrylate is 0.5-2% of the total mass of the gallium oxide and the tin oxide, and the adding amount of the water is 65-75% of the total mass of the gallium oxide and the tin oxide;
(2) Filling the slurry and zirconia grinding balls in the step (1) into a ball-milling tank, adding a binder, mixing and ball-milling, wherein the binder is polyvinyl alcohol, and the addition amount of the polyvinyl alcohol is 0.5-2% of the total mass of gallium oxide and tin oxide;
(3) Preparing the mixed slurry obtained in the step (2) into spherical powder by spray drying;
(4) Placing the spherical powder obtained in the step (3) in a mould, performing prepressing molding by using a hydraulic press, demolding after pressing to obtain a target biscuit, fully coating the biscuit by using a rubber sheath, further pressing in an isostatic press, and pressing to obtain a tin dioxide ceramic biscuit;
(5) Sintering the tin dioxide ceramic biscuit by adopting a degreasing-multi-step sintering integrated sintering technology, wherein the temperature is slowly increased from room temperature to 600-650 ℃, and the temperature increase rate is 0.5-1 ℃/min; raising the temperature rise rate at a temperature of more than 600-650 ℃, keeping the temperature for 1-3h when the temperature rises to 850-950 ℃, introducing oxygen, continuing to raise the temperature until 1350-1450 ℃, keeping the temperature for 4-10h, stopping heating, and slowly cooling to room temperature at a temperature of 1-3 ℃/min to obtain the gallium oxide doped tin oxide ceramic target material with the average grain size of 2-3.5 mu m and the relative density of 98-99.5%.
2. The production method according to claim 1, characterized in that: in the step (2), the rotating speed of the ball mill is 160-260r/min, the zirconia grinding balls are phi 5, phi 3 and phi 1 respectively, and the mass ratio of the three balls is 1:1:2; the ball-material ratio is 3.
3. The method of claim 1, wherein: in the step (3), the spray drying temperature is 200-240 ℃, the feeding rate is 10-20mL/min, and the frequency of a centrifugal machine is 30-45Hz.
4. The method of claim 1, wherein: and (4) pre-pressing and forming at 25-75MPa for 2-8min, and isostatic pressing at 200-250MPa for 3-15min.
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