CN114031376A - Preparation method of high-hardness fine-grain ZTA system complex phase ceramic material - Google Patents

Preparation method of high-hardness fine-grain ZTA system complex phase ceramic material Download PDF

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CN114031376A
CN114031376A CN202111596534.1A CN202111596534A CN114031376A CN 114031376 A CN114031376 A CN 114031376A CN 202111596534 A CN202111596534 A CN 202111596534A CN 114031376 A CN114031376 A CN 114031376A
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sintering
powder
temperature
yttria
stabilized zirconia
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李俊国
钟心宇
罗国强
蔡其旺
沈强
涂溶
张联盟
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Wuhan University of Technology WUT
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Abstract

The invention discloses a preparation method of a high-hardness and fine-grain ZTA complex phase ceramic material, which comprises the steps of material preparation, raw material treatment, mixing ball milling, powder drying, sieving and glue discharging, forming and the like, and finally sintering a green body in a discharge plasma sintering furnace, wherein in a specific sintering process, the green body is rapidly sintered under a specific temperature and pressure environment, so that the high-hardness and fine-grain ZTA complex phase ceramic material is obtained. The high-hardness and fine-grain ZTA system complex phase ceramic material prepared by the preparation method of the invention has the advantages of compact arrangement of grains, uniform and fine grain distribution, no obvious defect, minimum average grain diameter of 0.4 mu m, good hardness, fracture toughness and bending strength, simple production process, easy realization of batch production and wide application prospect, and can be used for manufacturing high-precision fields such as ceramic cleavers and the like.

Description

Preparation method of high-hardness fine-grain ZTA system complex phase ceramic material
Technical Field
The invention belongs to the technical field of preparation of complex phase ceramic materials, and particularly relates to a preparation method of a high-hardness fine-grain ZTA system complex phase ceramic material.
Background
In the semiconductor packaging industry, most of low-cost middle-grade packaging and memory chip stacking packaging processes cannot be separated from a ceramic cleaver, the ceramic cleaver is the most main consumable tool in the packaging process, the working environment of the ceramic cleaver is usually heating, pressurizing and applying ultrasonic vibration, and the requirements on the performance of a cleaver material are extremely high. At present, alumina ceramics are considered to be an excellent material for manufacturing the cleaver due to a series of advantages of large hardness, high specific gravity, fine crystal grains, high surface smoothness, high dimensional precision and the like.
However, in terms of the properties of the alumina ceramic material, the alumina ceramic material has a high melting point and strong ionic bonds, which leads to a reduction in mass point diffusion coefficient, and the high sintering temperature causes the growth of crystal grains and the mutual accumulation and connection of the crystal grains into sheets, thereby reducing the mechanical properties of the material and deteriorating the air tightness. At present, copper wires with hardness harder than gold wires are gradually used in the IC packaging process, the copper wires are more economical than the gold wires, but when the copper wires are used as bonding wires, larger ultrasonic energy needs to be used during welding, the end faces of cleavers can be subjected to larger shearing stress during welding, crystal particles are easy to fall off, and higher requirements are provided for mechanical properties of ceramic such as bending strength, wear resistance and hardness.
The prior ZTA ceramic preparation process is to prepare Al2O3Adding ZrO into the powder2The powder is obtained by granulation molding, high-temperature sintering and post processing after mechanical mixing. The preparation method has simple process and low cost, but always has ZrO2Powder of Al2O3The problems of non-uniform dispersion and agglomeration in the matrix, the problems of non-uniform distribution of a second phase in the sintered matrix, abnormal growth of partial main crystal phase particles and the like reduce the performance of the ZTA complex phase ceramic, and the large crystal grains can be caused by overhigh sintering temperature and overlong heat preservation time to influence the performance of the ceramic. The invention of patent application No. 201811435382.5 is to make the blank body at 1400-1500 deg.CSintering under normal pressure, then sintering under hot isostatic pressure at 1300-1400 ℃ in the atmosphere of protective gas to obtain alumina ceramic, and adopting a two-step sintering process to perform long-time heat preservation, so that the time required by sample sintering is increased. The invention patent of patent application No. 201810622814.7 utilizes the sintering method of hot isostatic pressing to prepare ceramics and can reach certain performance, but the sintering time is as long as several hours, the sintering time is too long, and the energy consumption is large.
Disclosure of Invention
The invention aims to provide a preparation method of a high-hardness and fine-grain ZTA system complex phase ceramic material which has short sintering time, higher fracture toughness, better wear resistance and higher hardness and bending strength.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the high-hardness fine-grain ZTA complex-phase ceramic material comprises the following steps:
1) mixing alumina powder and yttria-stabilized zirconia (3Y-ZrO)2) The powder is respectively soaked in water, centrifuged and dried to complete the pretreatment of the raw material;
2) adding a dispersing agent into the alumina powder and the yttria-stabilized zirconia powder pretreated in the step 1), ball-milling, vacuum drying, sieving, removing glue, and shaping to obtain a blank;
3) placing the green body obtained in the step 2) into a spark plasma sintering furnace for sintering, wherein the sintering comprises a sintering early stage, a sintering middle stage and a sintering late stage, and the specific sintering process comprises the following steps:
and (3) sintering earlier stage: raising the temperature from room temperature to 600-800 ℃, wherein the temperature raising rate is 50-150 ℃/min, and the sintering pressure is 0 MPa;
in the middle stage of sintering: continuously heating to 1170-1200 ℃ on the basis of the temperature at the early stage of sintering, wherein the heating rate is 100-200 ℃/min, the sintering pressure gradually rises to 20-40 MPa in the heating process, the temperature is kept for 3-5 min after the heating is finished, and the pressure is gradually increased while the temperature is kept until the sintering pressure reaches 45-60 MPa;
and (3) at the later stage of sintering: after the heat preservation in the middle sintering stage is finished, heating the temperature to 1300-1400 ℃ on the basis of the temperature in the middle sintering stage, wherein the heating rate is 50-100 ℃/min, and preserving the heat for 3-5 min, and in the process, continuously maintaining the pressure to be consistent with the pressure in the middle sintering stage;
and after the heat preservation in the later sintering stage is finished, stopping heating and pressurizing, and cooling to room temperature along with the furnace to obtain the high-hardness fine-grain ZTA system complex-phase ceramic material.
According to the scheme, in the step 1), the mass ratio of the alumina powder to the yttria-stabilized zirconia powder is (60-90): (10-40).
According to the scheme, in the step 1), the purity of the alumina powder is more than 99.99%, and the particle size is 30-80 nm; the purity of the yttria-stabilized zirconia powder is more than 99.99 percent, and the particle size is 30-80 nm.
According to the scheme, in the step 1), the three steps of water immersion, centrifugation and vacuum drying pretreatment are sequentially repeated for 2-3 times.
According to the scheme, in the step 1), the pretreatment process comprises the following steps:
water leaching: adding deionized water with the mass being 3-5 times that of the alumina powder or yttria-stabilized zirconia powder into the alumina powder or yttria-stabilized zirconia powder, and stirring for 40-80 min under the magnetic stirring of 300-800 r/min to finish water leaching;
centrifuging: centrifuging the alumina powder or yttria-stabilized zirconia powder subjected to water leaching at a centrifugation rate of 5000-7000 r/min for 20-60 min to finish centrifuging;
and (3) vacuum drying: and drying the centrifuged alumina powder or yttria-stabilized zirconia powder at the temperature of 100-120 ℃ for 12-24 hours to complete vacuum drying, thereby obtaining pretreated raw material alumina powder or yttria-stabilized zirconia powder.
According to the scheme, in the step 2), the adding amount of the dispersing agent is 0.01-0.2% of the total mass of the raw material alumina powder and the yttrium oxide stabilized zirconia powder.
According to the scheme, in the step 2), the dispersing agent is Isobam104 (copolymer of isobutene and maleic anhydride).
According to the scheme, in the step 2),
ball milling: the ball milling time is 12-24 h, the ball milling speed is 150-300 r/min, and uniform powder is obtained;
and (3) vacuum drying: the drying time is 12-24 h, and the drying temperature is 60-100 ℃;
sieving and removing glue: and a 150-mesh sieve is adopted, the glue discharging environment is a vacuum environment, the glue discharging temperature is 400-500 ℃, and the glue discharging time is 2-4 hours.
According to the scheme, the step 2) further comprises adding chromium oxide powder in the ball milling process, namely adding a dispersing agent and chromium oxide powder into the pretreated aluminum oxide powder and yttrium oxide stabilized zirconia powder and then carrying out ball milling.
Preferably, the purity of the chromium oxide powder is more than 99.99%, and the particle size is 30-50 nm.
Preferably, the addition amount of the chromium oxide powder is 1-20% of the total mass of the raw material aluminum oxide powder and the yttrium oxide stabilized zirconia powder; preferably 1 to 10%.
The invention provides a preparation method of a ZTA complex phase ceramic material, which adopts a spark plasma sintering technology to sinter, designs three-stage sintering processes of the early stage, the middle stage and the later stage of sintering, and designs different temperatures and pressures for sintering at different stages; wherein:
on one hand, the Spark Plasma Sintering (SPS) technology has higher thermal efficiency, and can realize rapid heating and cooling of a sample, so that the growth of crystal grains in the temperature rise process can be effectively inhibited, and meanwhile, the sintering process can be assisted by applying external axial pressure, so that the rapid densification of the material can be realized, the possible component volatilization is reduced, and the occurrence of poor phase change is inhibited. When non-conductive ZTA raw material is subjected to SPS sintering, although discharge and plasma powerful experiments are not proved in the sintering process, the purpose of rapid sintering can be achieved through the design of the sintering process, and a sintered body with the same or even higher performance as other sintering modes can be obtained in a time far shorter than other sintering modes.
On the other hand, different pressures and temperatures are designed in different sintering stages: the lower temperature, the heating rate and the axial pressure are controlled in the early stage of sintering, so that the residual water and organic matters in the powder are completely discharged as far as possible, and the density of a sintered body is favorably improved; in the middle stage of sintering, the temperature is quickly raised to the expected temperature, the sintered body is obviously shrunk in volume, and meanwhile, the pressure is increased to help hinder the movement of a grain boundary so as to achieve the purpose of controlling the grain size; then, heat preservation is carried out, the heat preservation is favorable for controlling temperature difference, the pressure is increased to the required maximum value during the heat preservation, so that the phase transformation in the zirconia is more sufficient, and certain internal stress is kept in a sintered body; the heating rate is reduced in the later stage of sintering, the temperature is continuously increased to the expected maximum value and is kept, the temperature of each part of the sintered body is controlled to be uniform, the grain sizes of the center and the edge of the sintered body are ensured not to have large difference, the improvement of the overall performance is facilitated, meanwhile, the pressure is kept consistent with the maximum value of the pressure in the middle stage of sintering, and the grain size in the later stage of sintering can be effectively controlled.
The invention has the following beneficial effects:
1. the invention provides a preparation method of a ZTA system complex phase ceramic material, which takes alumina powder and yttria stabilized zirconia powder as main raw materials, ball milling is carried out after the raw materials are pretreated, vacuum drying, sieving, binder removal and sizing are carried out, the obtained blank is sintered by adopting a spark plasma sintering technology, three-stage sintering processes of the early stage, the middle stage and the later stage of sintering are designed, different stages are matched with different temperatures and pressures, the temperature and pressure are increased by stages, and the sintering process is more facilitated; the ZTA system complex phase ceramic material prepared by the invention by designing a reasonable sintering process takes Zirconia Toughened Alumina (ZTA) as a matrix, the particles are closely arranged, the crystal grains are uniformly distributed and fine, no obvious defect exists, the minimum average particle size is 0.4 mu m, the high hardness, fracture toughness and bending strength are realized, the high precision fields such as ceramic cleavers can be manufactured, the production process is simple, the sintering temperature is low, the mass production is easy to realize, and the application prospect is wide.
2. The invention has short sintering time, can complete the whole sintering process within half an hour, has low sintering temperature, can obtain a high-quality ceramic body at the temperature of 1350 ℃ at most, can effectively improve the efficiency and reduce the energy consumption and the cost.
3. Further, chromium oxide and oxygen are added in the ball milling processThe chromium is mixed with the raw materials in advance and then sintered in an auxiliary way, so that the ZTA structure is more uniform and refined, and Cr2O3With Al2O3Simultaneously, the corundum structure can form a substitutional solid solution and large-size Cr3+Ion substituted Al3+The local pressure stress caused by the lattice distortion caused by ions hinders the permeation of cracks through a grain boundary, and simultaneously, the pressure stress also hinders the growth of grains, the refinement of the grains and the further improvement of the strengthening performance of the material.
Drawings
FIG. 1 is a microscopic structure of the products prepared in comparative example 2 and example 3 according to the present invention, wherein (a) corresponds to the product prepared in comparative example 2 and (b) corresponds to the product prepared in example 3.
Fig. 2 is a temperature-pressure curve of the sintering process used in the examples and comparative examples of the present invention, wherein (a) corresponds to the temperature-pressure curve of the sintering process 1, (b) corresponds to the temperature-pressure curve of the sintering process 2, and (c) corresponds to the temperature-pressure curve of the sintering process 3.
FIG. 3 is an XRD pattern of a product prepared in example 3 of the present invention.
FIG. 4 shows Cr values corresponding to products prepared in examples 1 to 5 of the present invention2O3Is in the different concentrations, and is an enlarged view of the diffraction peak corresponding to the crystal face.
FIG. 5 shows Cr values corresponding to products prepared in examples 1 to 5 of the present invention2O3The microscopic structure chart with different concentrations of doping amount of (1) is a microscopic structure chart with different concentrations.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
In the following examples, the additive is chromium oxide powder, the dispersant is Isobam104 (copolymer of isobutylene and maleic anhydride), and the aluminum oxide powder has a purity of 99.99% and a particle size of 30-80 nm; the yttria-stabilized zirconia (3Y-ZrO)2) The purity of the powder is more than 99.99 percent, and the particle size is 30-80 nm; the purity of the chromium oxide powder is more than 99.99%, and the particle size is 30-50 nm.
Example 1
The preparation method of the high-hardness fine-grain ZTA complex-phase ceramic material comprises the following steps:
1) pretreatment of raw materials
Weighing alumina powder and yttria-stabilized zirconia (3Y-ZrO) according to the mass ratio of 4:12) Powder, namely respectively carrying out water immersion, centrifugation and drying on alumina powder and yttria-stabilized zirconia powder to obtain treated raw material aluminum powder and raw material zirconium powder; completing the treatment of the main raw materials, wherein:
water immersion: respectively putting alumina powder and yttria-stabilized zirconia powder into different beakers, adding deionized water with the mass ratio of 4 times of that of each powder, and stirring for 60min under the magnetic stirring of 500r/min to finish water immersion; the water immersion step mainly cleans the alumina powder and the yttria-stabilized zirconia powder.
Centrifuging: respectively centrifuging the alumina powder and the yttria-stabilized zirconia powder after the completion of water leaching at a centrifugation speed of 6000r/min for 30min to complete centrifugation; completely removing water from the soaked materials.
And (3) vacuum drying: respectively putting the centrifuged alumina powder and yttria-stabilized zirconia powder into a vacuum drying oven, drying for 24 hours at the temperature of 105 ℃, and finishing vacuum drying to obtain raw material aluminum powder and raw material zirconium powder; the dried powder can meet the requirement of subsequent actual use.
The three steps of water soaking, centrifuging and vacuum drying are sequentially repeated for 2 times, and are repeated for two times, so that the raw materials do not contain other impurities and are purer.
2) Mixed ball mill
Mixing and ball milling: adding a dispersing agent into the pretreated alumina powder and yttria-stabilized zirconia powder in the step 1) to mix into mixed powder, wherein the adding mass of the dispersing agent is 0.2% of the total mass of the raw materials of the alumina powder and the yttria-stabilized zirconia powder, then putting the mixed powder into a ball milling tank, adding zirconia ball milling balls with the mass being 3 times of that of the mixed powder, and carrying out ball milling, wherein the ball milling time is 12 hours, and the ball milling speed is 300 r/min. Obtaining uniform powder.
3) Drying, sieving, removing glue and shaping
Drying powder: and (3) placing the uniform powder subjected to ball milling in the step 2) into a dryer, wherein the drying environment is vacuum, specifically, the dryer adopts a vacuum dryer, the drying time is 24 hours, and the drying temperature is 80 ℃, so as to obtain dry powder.
Sieving and removing glue: sieving the dry powder, adopting a 150-mesh sieve, putting the sieved dry powder into a crucible, and feeding the powder into a glue discharging furnace for glue discharging, wherein the glue discharging environment is a vacuum environment, the glue discharging temperature is 475 ℃, and the glue discharging time is 3 hours.
Shaping: and injecting the dried powder after the binder removal into a graphite mold for shaping to obtain a blank shaped in the graphite mold.
4) Sintering
Placing the green body obtained in the step 3) into a discharge plasma sintering furnace, sealing the discharge plasma sintering furnace and vacuumizing, wherein the temperature in the discharge plasma sintering furnace is room temperature, the environment is vacuum, sintering is started, the sintering process is divided into a sintering early stage, a sintering middle stage and a sintering late stage, and the sintering process is named as a sintering process 3, and specifically comprises the following steps:
and (3) sintering earlier stage: heating the discharge plasma sintering furnace, raising the temperature of the discharge plasma sintering furnace from room temperature to 700 ℃, wherein the temperature raising rate is 100 ℃/min, and the sintering pressure is 0MPa in the process.
The temperature is increased from room temperature to 700 ℃, the temperature rising rate is not suitable to be too fast (100 ℃/min), water and organic matters remained in a blank body in the early stage of sintering are discharged in the form of gas, if the temperature rising rate in the sintering is too fast, the water and the organic matters can not be well vaporized or decomposed, the gas can remain in a matrix along with the continuous temperature rising, the compactness degree of a sintered body is reduced, the mechanical property is finally greatly reduced, meanwhile, lower axial pressure is kept in the early stage of sintering, the gas in the blank body can be continuously discharged under the action of vacuum, the gas in the powder body can be discharged in the early stage of sintering by keeping the lower axial pressure, and if higher pressure is applied in the early stage of sintering, the gas generated in the center of the powder body can not be well discharged due to the blockage of a capillary channel caused by the axial pressure.
In the middle stage of sintering: and (3) heating the temperature of the discharge plasma sintering furnace from 700 ℃ to 1170 ℃, wherein the heating rate is 150 ℃/min, the sintering pressure is gradually increased to 37.5MPa in the heating process, the medium-temperature heat preservation is carried out for 3min after the heating is finished, and the pressure is gradually increased while the medium-temperature heat preservation is carried out until the sintering pressure reaches 50 MPa.
Heating from 700 deg.C to 1170 deg.C, and holding at 1170 deg.C for 3min, wherein the temperature of 1170 deg.C is 3Y-ZrO2Monoclinic phase (m-ZrO)2) Tetragonal phase (t-ZrO)2) The phase transition temperature of the transformation, under which the sintered body undergoes obvious volume shrinkage, is increased to 1170 ℃ at the sintering rate (150 ℃/min) and then is kept for 3min in order to control the temperature difference between the inside and the outside of the mould, because the temperature of the green body is mainly raised by heating the graphite die when the non-conductive powder is sintered by the discharge plasma, the temperature rise rate is fast, it is important to maintain the temperature of the sintering area uniform, and as the temperature increases, the grains in the green body begin to grow, and the pressure rises from 0MPa at 700 ℃ to 37.5MPa (1.2T), at which the movement of grain boundaries is hindered, so as to achieve the purpose of controlling the grain size, and when the temperature is maintained at 1170 ℃ for 3min, the pressure rises from 37.5MPa (1.2T) to the sintering pressure of 50MPa (1.6T), and the temperature and the pressure are both maintained, so that the phase transformation in the zirconia is more sufficient, and a certain internal stress is maintained in the sintered body.
And (3) at the later stage of sintering: after the medium-temperature heat preservation is finished, the temperature of the discharge plasma sintering furnace is increased from 1170 ℃ to 1350 ℃, the temperature increase rate is 60 ℃/min, the high-temperature heat preservation is carried out for 3min, and in the process, the sintering pressure is kept at 50 MPa.
And (2) heating to 1170 ℃ to 1350 ℃ and then preserving heat for 3min, wherein the heating rate is slowed down (60 ℃/min), the temperature of each part of the sintered body is controlled to be uniform, if the temperature is raised too fast at 1350 ℃, the grain sizes of the center and the edge of the sintered body are greatly different, the performances of different areas of the sintered body are different, the overall performance of the complex phase ceramic is finally reduced, the temperature is raised, the grains continue to grow, the sintering pressure is up to 50MPa (1.6T) at 1170 ℃, the sintering pressure is kept in the subsequent heating and heat preservation processes, and the grain size at the later stage of sintering is effectively controlled.
And after the sintering is finished, stopping heating the discharge plasma sintering furnace after the high-temperature heat preservation is finished, stopping pressurizing at the same time, cooling the furnace temperature of the discharge plasma sintering furnace to room temperature, and taking out a finished product to obtain the high-hardness and fine-grain ZTA system complex-phase ceramic material.
And cleaning and polishing the surface of the high-hardness and fine-grain ZTA complex phase ceramic material to perform hardness test, cutting to obtain a rectangular sample, performing bending strength test, performing XRD phase analysis, and performing field emission scanning electron microscope microstructure analysis on the area, wherein specific results are shown in Table 1.
From Table 1, it can be seen that the porosity of the high-hardness fine-grain ZTA system complex phase ceramic material is 1.53%, and the sample density is 4.24g/cm3The Vickers hardness is 18.27GPa, and the fracture toughness is 5.32MPa1/2The average grain size of alumina with the bending strength of 629.01MPa is distributed in the range of 0.64 +/-0.1 mu m, the average grain size of zirconia is distributed in the range of 0.30 +/-0.1 mu m, and the ZTA complex phase ceramic material sample is subjected to an X-ray diffraction test, wherein the XRD diffraction peak shows that the zirconia in the sample is basically in a tetragonal phase.
Example 2
The preparation method of the high-hardness fine-grain ZTA complex-phase ceramic material comprises the following steps:
1) pretreatment of raw materials: the alumina powder and the yttria-stabilized zirconia powder were weighed in a mass ratio of 4:1, and the specific pretreatment operation was the same as in example 1.
2) Mixing and ball milling: adding a dispersing agent and an additive into the pretreated alumina powder and yttria-stabilized zirconia powder in the step 1) to form mixed powder, wherein the adding mass of the dispersing agent is 0.2% of the total mass of the raw material alumina powder and yttria-stabilized zirconia powder, the adding mass of the additive chromia powder is 1% of the total mass of the alumina powder and yttria-stabilized zirconia powder, putting the mixed powder into a ball milling tank, adding zirconia ball milling balls with the mass being 3 times that of the mixed powder, and carrying out ball milling, wherein the ball milling time is 12h, and the ball milling speed is 300 r/min. Obtaining uniform powder.
3) Drying, sieving, removing glue and shaping: the procedure was as in example 1.
4) And (3) sintering: the procedure was as in example 1.
The surface of the high-hardness and fine-grain ZTA system complex phase ceramic material is cleaned and polished to carry out hardness test, the surface is cut to obtain a rectangular sample to carry out bending strength test, XRD phase analysis and field emission scanning electron microscope microstructure analysis are carried out on the area, the porosity of the high-hardness and fine-grain ZTA system complex phase ceramic material is 1.17 percent, and the sample density is 4.26g/cm as shown in Table 13The Vickers hardness is 18.30GPa, and the fracture toughness is 5.64MPa1/2The bending strength is 801.01MPa, the average grain size of alumina is distributed in the range of 0.85 +/-0.1 mu m, the average grain size of zirconia is distributed in the range of 0.28 +/-0.1 mu m, and the ZTA complex phase ceramic material sample is subjected to X-ray diffraction test, wherein the XRD diffraction peak shows that the zirconia in the sample is basically tetragonal phase.
Example 3
The preparation method of the high-hardness fine-grain ZTA complex-phase ceramic material comprises the following steps:
1) pretreatment of raw materials: the alumina powder and the yttria-stabilized zirconia powder were weighed in a mass ratio of 4:1, and the specific pretreatment operation was the same as in example 1.
2) Mixing and ball milling: adding a dispersing agent and an additive into the pretreated alumina powder and yttria-stabilized zirconia powder in the step 1) to form mixed powder, wherein the adding mass of the dispersing agent is 0.2% of the total mass of the raw material alumina powder and yttria-stabilized zirconia powder, the adding mass of the additive is 5% of the total mass of the alumina powder and yttria-stabilized zirconia powder, putting the mixed powder into a ball milling tank, adding zirconia ball milling balls with the mass being 3 times that of the mixed powder, and carrying out ball milling, wherein the ball milling time is 12h, and the ball milling speed is 300 r/min. Obtaining uniform powder.
3) Drying, sieving, removing glue and shaping: the procedure was as in example 1.
4) And (3) sintering: the procedure was as in example 1.
The surface of the high-hardness and fine-grain ZTA system complex phase ceramic material is cleaned and polished to be hardThe degree is tested, the rectangular sample is obtained by cutting, the bending strength is tested, the XRD phase analysis is carried out, the area is subjected to the field emission scanning electron microscope microstructure analysis, the porosity of the high-hardness and fine-grain ZTA system complex phase ceramic material is 0.48 percent, and the sample density is 4.25g/cm as can be seen from the table 13The Vickers hardness is 20.18GPa, and the fracture toughness is 6.37MPa1/2The bending strength is 666.60MPa, the average grain size of alumina is distributed in the range of 0.4 +/-0.1 μm, the average grain size of zirconia is distributed in the range of 0.20 +/-0.1 μm, the ZTA complex phase ceramic material sample is subjected to an X-ray diffraction test, the XRD diffraction peak shows that the zirconia in the sample is basically tetragonal phase, and the XRD pattern of the product prepared in the embodiment is shown in figure 3.
Example 4
The preparation method of the high-hardness fine-grain ZTA complex-phase ceramic material comprises the following steps:
1) pretreatment of raw materials: the alumina powder and the yttria-stabilized zirconia powder were weighed in a mass ratio of 4:1, and the specific pretreatment operation was the same as in example 1.
2) Mixing and ball milling: adding a dispersing agent and an additive into the pretreated alumina powder and yttria-stabilized zirconia powder in the step 1) to form mixed powder, wherein the adding mass of the dispersing agent is 0.2% of the total mass of the raw material alumina powder and yttria-stabilized zirconia powder, the adding mass of the additive is 10% of the total mass of the alumina powder and yttria-stabilized zirconia powder, putting the mixed powder into a ball milling tank, adding zirconia ball milling balls with the mass being 3 times that of the mixed powder, and carrying out ball milling, wherein the ball milling time is 12h, and the ball milling speed is 300 r/min. Obtaining uniform powder.
3) Drying, sieving, removing glue and shaping: the procedure was as in example 1.
4) And (3) sintering: the procedure was as in example 1.
Cleaning and polishing the surface of the high-hardness and fine-grain ZTA complex phase ceramic material to perform hardness test, cutting to obtain a rectangular sample, performing bending strength test, XRD phase analysis, and performing field emission scanning electron microscope microstructure analysis on the region, wherein the high-hardness material can be obtained from Table 1The porosity of the fine-grain ZTA system complex phase ceramic material is 0.74 percent, and the sample density is 4.28g/cm3The Vickers hardness is 19.02GPa, and the fracture toughness is 5.54MPa1/2The bending strength is 795.84MPa, the average grain size of alumina is distributed in the range of 0.58 +/-0.1 mu m, the average grain size of zirconia is distributed in the range of 0.24 +/-0.1 mu m, and the ZTA complex phase ceramic material sample is subjected to X-ray diffraction test, and the XRD diffraction peak shows that the zirconia in the sample is basically tetragonal phase.
Example 5
The preparation method of the high-hardness fine-grain ZTA complex-phase ceramic material comprises the following steps:
1) pretreatment of raw materials: the alumina powder and the yttria-stabilized zirconia powder were weighed in a mass ratio of 4:1, and the specific pretreatment operation was the same as in example 1.
2) Mixing and ball milling: adding a dispersing agent and an additive into the pretreated alumina powder and yttria-stabilized zirconia powder in the step 1) to form mixed powder, wherein the adding mass of the dispersing agent is 0.2% of the total mass of the raw material alumina powder and yttria-stabilized zirconia powder, the adding mass of the additive is 20% of the total mass of the alumina powder and yttria-stabilized zirconia powder, putting the mixed powder into a ball milling tank, adding zirconia ball milling balls with the mass being 3 times that of the mixed powder, and carrying out ball milling, wherein the ball milling time is 12h, and the ball milling speed is 300 r/min. Obtaining uniform powder.
3) Drying, sieving, removing glue and shaping: the procedure was as in example 1.
4) And (3) sintering: the procedure was as in example 1.
The surface of the high-hardness and fine-grain ZTA system complex phase ceramic material is cleaned and polished to carry out hardness test, the surface is cut to obtain a rectangular sample to carry out bending strength test, XRD phase analysis and field emission scanning electron microscope microstructure analysis are carried out on the area, the porosity of the high-hardness and fine-grain ZTA system complex phase ceramic material is 0.50 percent, and the sample density is 4.29g/cm as shown in Table 13The Vickers hardness is 18.53GPa, and the fracture toughness is 4.79MPa1/2The bending strength is 537.69MPa, and the ZTA complex phase ceramic material sample is subjected to XAnd (4) performing ray diffraction test, wherein the zirconium oxide in the sample is basically tetragonal as can be seen from XRD diffraction peaks.
Comparative example 1
Provides a preparation method of a ZTA complex phase ceramic material, which comprises the following steps:
1) pretreatment of raw materials: weighing alumina powder and yttria-stabilized zirconia (3Y-ZrO) according to the mass ratio of 4:12) The powder pretreatment was carried out in the same manner as in example 1.
2) Mixing and ball milling: adding a dispersing agent and an additive into the pretreated alumina powder and yttria-stabilized zirconia powder in the step 1) to form mixed powder, wherein the adding mass of the dispersing agent is 0.2% of the total mass of the raw material alumina powder and yttria-stabilized zirconia powder, the adding mass of the additive is 5% of the total mass of the alumina powder and yttria-stabilized zirconia powder, putting the mixed powder into a ball milling tank, adding zirconia ball milling balls with the mass being 3 times that of the mixed powder, and carrying out ball milling, wherein the ball milling time is 12h, and the ball milling speed is 300 r/min. Obtaining uniform powder.
3) Drying, sieving, removing glue and shaping: the procedure was as in example 1.
4) And (3) sintering: and (3) placing the green body obtained in the step 3) into a discharge plasma sintering furnace, sealing the discharge plasma sintering furnace and vacuumizing, wherein the temperature in the discharge plasma sintering furnace is room temperature, the environment is vacuum, and sintering is started, and the sintering process is named as sintering process 1.
The method specifically comprises the following steps: heating the discharge plasma sintering furnace, heating the discharge plasma sintering furnace from room temperature to 700 ℃, wherein the heating rate is 100 ℃/min, then heating to 1350 ℃, the heating rate is 130 ℃/min, the pressure is linearly increased along with the heating process, the sintering pressure is increased to 30MPa when the temperature is increased to 1350 ℃, and finally, the temperature is preserved and the pressure is maintained for 3 min.
Cleaning and polishing the surface of the high-hardness and fine-grain ZTA complex phase ceramic material to perform hardness test, cutting the surface to obtain a rectangular sample, performing bending strength test, XRD phase analysis, and performing field emission scanning electron microscope microstructure analysis on the region, and the high-hardness and fine-grain ZTA complex phase ceramic material obtained in the table 1 can be knownThe porosity of the phase ceramic material is 1.17%, and the sample density is 4.20g/cm3The Vickers hardness is 20.04GPa, and the fracture toughness is 5.93MPa1/2The bending strength is 473.91MPa, the average grain size of alumina is distributed in the range of 0.82 +/-0.1 mu m, the average grain size of zirconia is distributed in the range of 0.37 +/-0.1 mu m, and the ZTA complex phase ceramic material sample is subjected to X-ray diffraction test, wherein the XRD diffraction peak shows that the zirconia in the sample is basically tetragonal phase.
Comparative example 2
Provides a preparation method of a ZTA complex phase ceramic material, which comprises the following steps:
1) pretreatment of raw materials: the alumina powder and the yttria-stabilized zirconia powder were weighed in a mass ratio of 4:1, and the specific pretreatment operation was the same as in example 1.
2) Mixing and ball milling: adding a dispersing agent and an additive into the pretreated alumina powder and yttria-stabilized zirconia powder in the step 1) to form mixed powder, wherein the adding mass of the dispersing agent is 0.2% of the total mass of the raw material alumina powder and yttria-stabilized zirconia powder, the adding mass of the additive is 5% of the total mass of the alumina powder and yttria-stabilized zirconia powder, putting the mixed powder into a ball milling tank, adding zirconia ball milling balls with the mass being 3 times that of the mixed powder, and carrying out ball milling, wherein the ball milling time is 12h, and the ball milling speed is 300 r/min. Obtaining uniform powder.
3) Drying, sieving, removing glue and shaping: the procedure was as in example 1.
4) And (3) sintering: and (3) placing the green body obtained in the step 3) into a discharge plasma sintering furnace, sealing the discharge plasma sintering furnace and vacuumizing, wherein the temperature in the discharge plasma sintering furnace is room temperature, the environment is vacuum, and sintering is started, and the sintering process is named as sintering process 2.
The method specifically comprises the following steps: heating the discharge plasma sintering furnace, heating the discharge plasma sintering furnace from room temperature to 700 ℃, wherein the heating rate is 100 ℃/min, then heating to 1350 ℃, the heating rate is 130 ℃/min, the pressure is linearly increased along with the heating process, the sintering pressure is increased to 50MPa when the temperature is increased to 1350 ℃, and finally, the temperature is preserved and the pressure is maintained for 3 min.
The surface of the high-hardness and fine-grain ZTA system complex phase ceramic material is cleaned and polished to carry out hardness test, the surface is cut to obtain a rectangular sample to carry out bending strength test, XRD phase analysis and field emission scanning electron microscope microstructure analysis are carried out on the area, the porosity of the high-hardness and fine-grain ZTA system complex phase ceramic material is 1.07 percent, and the sample density is 4.25g/cm from the table 13The Vickers hardness is 18.32GPa, and the fracture toughness is 4.73MPa1/2The bending strength is 542.72MPa, the average grain size of alumina is distributed in the range of 0.49 +/-0.1 mu m, the average grain size of zirconia is distributed in the range of 0.23 +/-0.1 mu m, and the ZTA complex phase ceramic material sample is subjected to X-ray diffraction test, and the XRD diffraction peak shows that the zirconia in the sample is basically tetragonal phase.
TABLE 1 Performance test data for examples 1-5 and comparative examples 1-2
Figure BDA0003431403260000111
The design of the sintering rate and the sintering pressure in the early stage of sintering is the key for improving the compactness of the complex phase ceramic, and as can be clearly compared in figure 1, the microstructure of the sintering process 2 and the sintering process 3 under the component ZTA-5Cr can obviously show that the surface pores of the complex phase ceramic sintered by the sintering process 3 are obviously reduced. As can be seen from fig. 2, the temperature and pressure curves of the sintering process 1, the sintering process 2 and the sintering process 3 are changed. The pores in the sintered body are obviously reduced after the sintering process is optimized, the grain size of the complex phase ceramic is reduced through the reasonable sintering process, the sintered sample particles are tightly arranged, the bending strength and the fracture toughness of the sample are improved, and meanwhile, the sample also has higher hardness.
From examples 1-5, it can be seen that adding a suitable amount of chromium oxide is beneficial to refining the grain size and improving the hardness, fracture toughness and bending strength, wherein a small amount of chromium oxide (1%) can significantly improve the bending strength, but with the continued increase of chromium oxide, the bending strength shows a tendency of first decreasing, then increasing, and then decreasing; hardness and fracture toughnessThe properties and the grain size both tend to increase and then decrease as the chromium oxide increases. From the comparison of the data in table 1, it is apparent that the grain size of the sample is somewhat reduced as the sintering pressure is increased. Cr corresponding to the products prepared in examples 1 to 52O3The diffraction peaks corresponding to the crystal planes when the doping amount of (A) is in different concentrations are shown in FIG. 4, Cr2O3Will be added with Al2O3Solid solution occurs. Examples 1 to 5Cr2O3The microstructure diagram of the doping amount at different concentrations is shown in fig. 5.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

Claims (10)

1. A preparation method of a high-hardness and fine-grain ZTA complex-phase ceramic material is characterized by comprising the following steps:
1) respectively carrying out water leaching, centrifugation and drying on the alumina powder and the yttria-stabilized zirconia powder to finish the pretreatment of the raw materials;
2) adding a dispersing agent into the alumina powder and the yttria-stabilized zirconia powder pretreated in the step 1), ball-milling, vacuum drying, sieving, removing glue, and shaping to obtain a blank;
3) placing the green body obtained in the step 2) into a spark plasma sintering furnace for sintering, wherein the sintering comprises a sintering early stage, a sintering middle stage and a sintering late stage, and the specific sintering process comprises the following steps:
and (3) sintering earlier stage: raising the temperature from room temperature to 600-800 ℃, wherein the temperature raising rate is 50-150 ℃/min, and the sintering pressure is 0 MPa;
in the middle stage of sintering: continuously heating to 1170-1200 ℃ on the basis of the temperature at the early stage of sintering, wherein the heating rate is 100-200 ℃/min, the sintering pressure gradually rises to 20-40 MPa in the heating process, the temperature is kept for 3-5 min after the heating is finished, and the pressure is gradually increased while the temperature is kept until the sintering pressure reaches 45-60 MPa;
and (3) at the later stage of sintering: after the heat preservation in the middle sintering stage is finished, heating the temperature to 1300-1400 ℃ on the basis of the temperature in the middle sintering stage, wherein the heating rate is 50-100 ℃/min, and preserving the heat for 3-5 min, and in the process, continuously maintaining the pressure to be consistent with the pressure in the middle sintering stage;
and after the heat preservation in the later sintering stage is finished, stopping heating and pressurizing, and cooling to room temperature along with the furnace to obtain the high-hardness fine-grain ZTA system complex-phase ceramic material.
2. The preparation method according to claim 1, wherein in the step 1), the mass ratio of the alumina powder to the yttria-stabilized zirconia powder is (60-90): (10-40).
3. The preparation method according to claim 1, wherein in the step 1), the purity of the alumina powder is more than 99.99%, and the particle size is 30-80 nm; the purity of the yttria-stabilized zirconia powder is more than 99.99 percent, and the particle size is 30-80 nm.
4. The preparation method according to claim 1, wherein in the step 1), the three steps of water immersion, centrifugation and vacuum drying pretreatment are sequentially repeated for 2-3 times.
5. The preparation method according to claim 1, wherein in the step 1), the pretreatment process is:
water leaching: adding deionized water with the mass being 3-5 times that of the alumina powder or yttria-stabilized zirconia powder into the alumina powder or yttria-stabilized zirconia powder, and stirring for 40-80 min under the magnetic stirring of 300-800 r/min to finish water leaching;
centrifuging: centrifuging the alumina powder or yttria-stabilized zirconia powder subjected to water leaching at a centrifugation rate of 5000-7000 r/min for 20-60 min to finish centrifuging;
and (3) vacuum drying: and drying the centrifuged alumina powder or yttria-stabilized zirconia powder at the temperature of 100-120 ℃ for 12-24 hours to complete vacuum drying, thereby obtaining pretreated raw material alumina powder or yttria-stabilized zirconia powder.
6. The preparation method according to claim 1, wherein in the step 2), the amount of the dispersant added is 0.01 to 0.2% of the total mass of the raw material alumina powder and yttria-stabilized zirconia powder.
7. The production method according to claim 1, wherein in the step 2),
ball milling: the ball milling time is 12-24 h, the ball milling speed is 150-300 r/min, and uniform powder is obtained;
and (3) vacuum drying: the drying time is 12-24 h, and the drying temperature is 60-100 ℃;
sieving and removing glue: and a 150-mesh sieve is adopted, the glue discharging environment is a vacuum environment, the glue discharging temperature is 400-500 ℃, and the glue discharging time is 2-4 hours.
8. The preparation method according to claim 1, wherein the step 2) further comprises adding chromium oxide powder during ball milling.
9. The method according to claim 8, wherein the purity of the chromium oxide powder is 99.99% or more, and the particle diameter is 30 to 50 nm.
10. The preparation method according to claim 8, wherein the addition amount of the chromium oxide powder is 1-20% of the total mass of the raw material alumina powder and the yttria-stabilized zirconia powder.
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