CN114031376B - 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

Info

Publication number
CN114031376B
CN114031376B CN202111596534.1A CN202111596534A CN114031376B CN 114031376 B CN114031376 B CN 114031376B CN 202111596534 A CN202111596534 A CN 202111596534A CN 114031376 B CN114031376 B CN 114031376B
Authority
CN
China
Prior art keywords
sintering
powder
temperature
stabilized zirconia
yttria
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111596534.1A
Other languages
Chinese (zh)
Other versions
CN114031376A (en
Inventor
李俊国
钟心宇
罗国强
蔡其旺
沈强
涂溶
张联盟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan University of Technology WUT
Original Assignee
Wuhan University of Technology WUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan University of Technology WUT filed Critical Wuhan University of Technology WUT
Priority to CN202111596534.1A priority Critical patent/CN114031376B/en
Publication of CN114031376A publication Critical patent/CN114031376A/en
Application granted granted Critical
Publication of CN114031376B publication Critical patent/CN114031376B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C04B2235/3246—Stabilised zirconias, e.g. YSZ or cerium stabilised zirconia
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/782—Grain size distributions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/785—Submicron sized grains, i.e. from 0,1 to 1 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

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 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 high precision fields such as manufacturing ceramic cleavers.

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 and 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 Al 2 O 3 Adding ZrO into the powder 2 The 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 ZrO 2 Powder of Al 2 O 3 The 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 patent of patent application number 201811435382.5 is that the green body is sintered at the temperature of 1400-1500 ℃ under normal pressure, then hot isostatic pressing sintering is carried out at the temperature of 1300-1400 ℃ in the atmosphere of protective gas to obtain alumina ceramic, a sintering process of two-step sintering is adopted, long-time heat preservation is carried out, and the time required for sintering a sample is increased. The invention patent with the patent application number of 201810622814.7 prepares the ceramic by using a sintering mode of hot isostatic pressing, can achieve certain performance, but has the sintering time as long as several hours, overlong sintering time and larger energy consumption.
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 driedDrying 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: the temperature is raised from room temperature to 600-800 ℃, the heating rate is 50-150 ℃/min, and the sintering pressure is 0MPa;
in the middle stage of sintering: the temperature is continuously increased to 1170-1200 ℃ on the basis of the temperature in the early sintering period, the temperature increasing rate is 100-200 ℃/min, the sintering pressure is gradually increased to 20-40 MPa in the temperature increasing process, the temperature is kept for 3-5 min after the temperature increasing 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, the temperature is heated to 1300-1400 ℃ on the basis of the temperature in the middle sintering stage, the heating rate is 50-100 ℃/min, the heat preservation is carried out for 3-5 min, and in the process, the pressure is continuously kept 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 to 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 leaching, centrifuging 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 of 3-5 times of that of the alumina powder or yttria-stabilized zirconia powder into the alumina powder or yttria-stabilized zirconia powder, and stirring the mixture 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 the centrifugation rate of 5000-7000 r/min for 20-60 min to finish the centrifugation;
and (3) vacuum drying: drying the centrifuged alumina powder or yttria-stabilized zirconia powder for 12-24 hours at the temperature of 100-120 ℃, and finishing vacuum drying to obtain pretreated raw material alumina powder or yttria-stabilized zirconia powder.
According to the scheme, in the step 2), the addition amount of the dispersing agent is 0.01-0.2% of the total mass of the raw materials of the alumina powder and the yttria-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: adopting a 150-mesh sieve, wherein the glue discharging environment is a vacuum environment, the glue discharging temperature is 400-500 ℃, and the glue discharging time is 2-4 h.
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, so that the movement of a grain boundary is hindered, and the purpose of controlling the grain size is achieved; then, heat preservation is carried out, the temperature difference is favorably controlled, the pressure is increased to the required maximum value during heat preservation, 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. Furthermore, chromium oxide is added in the ball milling process, and 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 Cr 2 O 3 With Al 2 O 3 Simultaneously, the corundum structure can form a substitutional solid solution and large-size Cr 3+ Ion substituted Al 3+ 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 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 a sintering process used in examples and comparative examples of the present invention, wherein (a) corresponds to a temperature-pressure curve of sintering process 1, (b) corresponds to a temperature-pressure curve of sintering process 2, and (c) corresponds to a temperature-pressure curve of sintering process 3.
FIG. 3 is an XRD pattern of a product prepared in example 3 of the present invention.
FIG. 4 shows the present inventionCr corresponding to the products prepared in examples 1 to 5 2 O 3 Is in an enlarged view of diffraction peaks corresponding to crystal planes at different concentrations.
FIG. 5 shows Cr values corresponding to products prepared in examples 1 to 5 of the present invention 2 O 3 The 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 was chromium oxide powder, the dispersant was Isobam104 (copolymer of isobutylene and maleic anhydride), and the purity of the aluminum oxide powder was 99.99%, and the particle size was 30 to 80nm; 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 percent, 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 a mass ratio of 4 2 ) Powder, namely respectively performing 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; finishing the treatment of the main raw material, 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 the alumina powder and the yttria-stabilized zirconia powder, and stirring for 60min under the magnetic stirring of 500r/min to complete water leaching; 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 water leaching at a centrifugation speed of 6000r/min for 30min to finish 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 300r/min. Obtaining uniform powder.
3) Drying, sieving, removing glue and shaping
Drying powder: and (3) putting the ball-milled uniform powder 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 the 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 of
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 comprises a sintering early stage, a sintering middle stage and a sintering late stage, and is named as sintering process 3, and the method 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 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 is kept for 3min after the heating is finished, and the pressure is gradually increased while the medium temperature is kept until the sintering pressure reaches 50MPa.
Heating from 700 ℃ to 1170 ℃ and holding at 1170 ℃ for 3min, wherein 3Y-ZrO is present at 1170 ℃ 2 Monoclinic phase (m-ZrO) 2 ) Tetragonal phase (t-ZrO) 2 ) The transformation phase transition temperature, the sintered body generates obvious volume shrinkage at the temperature, the sintering speed is increased to (150 ℃/min) and is heated to 1170 ℃, and then the temperature is kept for 3min so as to control the temperature difference between the inside and the outside of the die, because the temperature of the blank is mainly increased by heating the graphite die when the non-conductive powder is sintered by the discharge plasma, the temperature of the blank is kept uniform because the temperature is quickly increased, and simultaneously, the crystal grains in the blank begin to grow along with the temperature increase, the pressure is increased from 0MPa of 700 ℃ to 37.5MPa (1.2T) at the moment, the pressure is favorable for hindering the movement of the crystal boundary under the pressure so as to achieve the purpose of controlling the size of the crystal grains, and the pressure is increased from 37.5MPa (1.2T) to sintering when the temperature is kept for 3min at 1170 ℃, the pressure is increased from 37.5MPa (1.2T) to sinteringThe pressure is 50MPa (1.6T), and the heat preservation and the pressurization at the moment can ensure that the phase transformation in the zirconia is more sufficient and certain internal stress is kept 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 50MPa.
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 and fine-grain ZTA system complex phase ceramic material is 1.53%, and the sample density is 4.24g/cm 3 The Vickers hardness is 18.27GPa, and the fracture toughness is 5.32MPa 1/2 The 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 X-ray diffraction test, and the XRD diffraction peak shows that the zirconia in the sample is basically 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 are weighed according to the mass ratio of 4.
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 300r/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 1 3 The Vickers hardness is 18.30GPa, and the fracture toughness is 5.64MPa 1/2 The bending strength is 801.01MPa, the average grain size of the alumina is distributed in the range of 0.85 +/-0.1 mu m, the average grain size of the 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, and 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 are weighed according to the mass ratio of 4.
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 300r/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 complex phase ceramic material is cleaned and polished to carry out hardness test, and 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, and table 1 shows that the porosity of the high-hardness and fine-grain ZTA complex phase ceramic material is 0.48%, and the sample density is 4.25g/cm 3 Vickers hardness of 20.18GPa and fracture toughness of 6.37MPa 1/2 The 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 are weighed according to the mass ratio of 4.
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 300r/min. Obtaining uniform powder.
3) Drying, sieving, removing glue and shaping: the procedure was as in example 1.
4) And (3) sintering: the procedure is 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 0.74%, and the sample density is 4.28g/cm as can be seen from Table 1 3 Vickers hardness of 19.02GPa and fracture toughness of 5.54MPa 1/2 The 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 sample of the ZTA complex phase ceramic material is subjected to X-ray diffraction test, and the XRD diffraction peak shows that the zirconia in the sample is basically in a 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 are weighed according to the mass ratio of 4.
2) Mixing and ball milling: adding a dispersing agent and an additive into the pretreated aluminum oxide powder and the yttrium oxide-stabilized zirconia powder in the step 1) to mix into mixed powder, wherein the adding mass of the dispersing agent is 0.2 percent of the total mass of the raw materials of the aluminum oxide powder and the yttrium oxide-stabilized zirconia powder, the adding mass of the additive is 20 percent of the total mass of the aluminum oxide powder and the yttrium oxide-stabilized zirconia powder, then 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 12 hours, and the ball milling speed is 300r/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 complex phase ceramic material is cleaned and polished to carry out hardness test, and is cut to obtain a rectangular sample to carry out bending strength test, XRD phase analysis and field emission scanning electron microscope microstructure analysis on the area, and the table 1 shows that the porosity of the high-hardness and fine-grain ZTA complex phase ceramic material is 0.50%, and the sample density is 4.29g/cm 3 The Vickers hardness is 18.53GPa, and the fracture toughness is 4.79MPa 1/2 The bending strength is 537.69MPa, and the X-ray diffraction test is carried out on the ZTA complex phase ceramic material sample, and the XRD diffraction peak shows that the zirconium oxide in the sample is basically tetragonal.
Comparative example 1
The preparation method of the 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 2 ) 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 aluminum oxide powder and the yttrium oxide-stabilized zirconia powder in the step 1) to mix into mixed powder, wherein the adding mass of the dispersing agent is 0.2 percent of the total mass of the raw materials of the aluminum oxide powder and the yttrium oxide-stabilized zirconia powder, the adding mass of the additive is 5 percent of the total mass of the aluminum oxide powder and the yttrium oxide-stabilized zirconia powder, then 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 12 hours, and the ball milling speed is 300r/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 comprises the following specific 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 3min.
The surface of the high-hardness and fine-grain ZTA 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, and the table 1 shows that the porosity of the high-hardness and fine-grain ZTA complex phase ceramic material is 1.17%, and the sample density is 4.20g/cm 3 The Vickers hardness is 20.04GPa, and the fracture toughness is 5.93MPa 1/2 The bending strength is 473.91MPa, the average grain size of the alumina is distributed in the range of 0.82 +/-0.1 mu m, the average grain size of the 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, and 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 are weighed according to the mass ratio of 4.
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 300r/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 comprises the following specific 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 3min.
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 1 3 The Vickers hardness is 18.32GPa, and the fracture toughness is 4.73MPa 1/2 The bending strength is 542.72MPa, the average grain size of the alumina is distributed in the range of 0.49 +/-0.1 mu m, the average grain size of the zirconia is distributed in the range of 0.23 +/-0.1 mu m, and the zirconia in the sample is basically tetragonal phase according to XRD diffraction peaks when the ZTA complex phase ceramic material sample is subjected to X-ray diffraction test.
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 to 5, it can be seen that the addition of a proper 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 as the chromium oxide continues to increase, the bending strength shows a tendency of first decreasing, then increasing and then decreasing; the hardness, fracture toughness and grain size all show a tendency of increasing first and then decreasing with the increase of chromium oxide. 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 correspondence of products prepared in examples 1 to 5 2 O 3 The diffraction peaks corresponding to the crystal planes when the doping amount of (A) is in different concentrations are shown in FIG. 4, cr 2 O 3 Will be added with Al 2 O 3 Solid solution occurs. Examples 1 to 5Cr 2 O 3 The 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 (8)

1. A preparation method of a high-hardness and fine-grain ZTA complex-phase ceramic material is characterized by comprising the following steps of:
1) Respectively carrying out water leaching, centrifugation and drying on the alumina powder and the yttria-stabilized zirconia powder to complete raw material pretreatment;
2) Adding a dispersing agent and chromium oxide powder into the pretreated aluminum oxide powder and yttrium oxide stabilized zirconia powder in the step 1), ball-milling, vacuum drying, sieving, removing glue, and shaping to obtain a blank; wherein the addition amount of the chromic oxide powder is 1-10% of the total mass of the raw materials of the aluminum oxide powder and the yttrium oxide stabilized zirconia powder, and the grain diameter of the chromic oxide powder is 30-50nm;
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: the temperature is increased from room temperature to 600-800 ℃, the heating rate is 50-150 ℃/min, and the sintering pressure is 0MPa;
in the middle stage of sintering: the temperature is continuously increased to 1170-1200 ℃ on the basis of the temperature at the early stage of sintering, the temperature increase rate is 100-200 ℃/min, the sintering pressure is gradually increased to 20-40 MPa in the temperature increase process, the temperature is kept for 3-5 min after the temperature increase 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, the temperature is heated to 1300-1400 ℃ on the basis of the temperature in the middle sintering stage, the heating rate is 50-100 ℃/min, the heat preservation is carried out for 3-5 min, and in the process, the pressure is continuously maintained 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 to 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 to 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 of 3-5 times that of the alumina powder or yttria-stabilized zirconia powder into the alumina powder or yttria-stabilized zirconia powder, and stirring the mixture for 40-80 min under the magnetic stirring of 300-800 r/min to complete water leaching;
centrifuging: centrifuging the alumina powder or yttria-stabilized zirconia powder subjected to water leaching at the centrifugation rate of 5000-7000 r/min for 20-60 min to finish the centrifugation;
and (3) vacuum drying: 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 the 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 materials of the alumina powder and the yttria-stabilized zirconia powder.
7. The 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: adopting a 150-mesh sieve, wherein the glue discharging environment is a vacuum environment, the glue discharging temperature is 400-500 ℃, and the glue discharging time is 2-4 h.
8. The method according to claim 1, wherein the purity of the chromium oxide powder is 99.99% or more.
CN202111596534.1A 2021-12-24 2021-12-24 Preparation method of high-hardness fine-grain ZTA system complex phase ceramic material Active CN114031376B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111596534.1A CN114031376B (en) 2021-12-24 2021-12-24 Preparation method of high-hardness fine-grain ZTA system complex phase ceramic material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111596534.1A CN114031376B (en) 2021-12-24 2021-12-24 Preparation method of high-hardness fine-grain ZTA system complex phase ceramic material

Publications (2)

Publication Number Publication Date
CN114031376A CN114031376A (en) 2022-02-11
CN114031376B true CN114031376B (en) 2023-03-17

Family

ID=80141076

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111596534.1A Active CN114031376B (en) 2021-12-24 2021-12-24 Preparation method of high-hardness fine-grain ZTA system complex phase ceramic material

Country Status (1)

Country Link
CN (1) CN114031376B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114478010A (en) * 2022-02-18 2022-05-13 佛山市南海宝碳石墨制品有限公司 Hot-pressing rapid forming method for graphite workpiece
CN115872749B (en) * 2022-11-30 2023-12-19 武汉科技大学 High-entropy boride enhancement B 4 C composite ceramic and in-situ synthesis method thereof
CN116003109B (en) * 2022-12-05 2023-10-31 广东工业大学 High-performance alumina ceramic riving knife and preparation method thereof
CN116003125B (en) * 2022-12-06 2023-07-25 重庆文理学院 Preparation method of zirconia ceramic material for automobile exhaust sensor

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101306943A (en) * 2008-06-27 2008-11-19 王昕� Fine-crystal transparent alumina ceramic of high straight-line luminous transmittance and method for preparing same
CN107188543A (en) * 2016-03-15 2017-09-22 中国科学院上海硅酸盐研究所 Cr2O3/ ZTA composite granules and ceramics and preparation method thereof
CN109095916B (en) * 2018-08-14 2021-06-25 徐州凹凸光电科技有限公司 Method for preparing YAG transparent ceramic by SPS sintering
CN110015889B (en) * 2019-04-24 2021-11-02 宁波泰科先进陶瓷有限公司 Preparation method of ZTA ceramic material and material prepared by same
CN111825432A (en) * 2020-07-31 2020-10-27 中南大学湘雅医院 Fine-grain pink ZTA ceramic and preparation method thereof
CN112430114A (en) * 2020-11-04 2021-03-02 湖南精城特种陶瓷有限公司 Zirconium-aluminum composite nano ceramic and preparation method thereof
CN113072368B (en) * 2021-03-15 2022-05-13 杭州电子科技大学 Atmosphere sintering method of high-performance M-type ferrite

Also Published As

Publication number Publication date
CN114031376A (en) 2022-02-11

Similar Documents

Publication Publication Date Title
CN114031376B (en) Preparation method of high-hardness fine-grain ZTA system complex phase ceramic material
WO2017120990A1 (en) Process for preparing net-size, complex-shape transparent ceramic piece
CN109553419B (en) Pneumatic solid-phase sintered boron carbide complex-phase ceramic and preparation method thereof
CN104313380B (en) A kind of step sintering prepares the method for high-compactness Nanograin Cemented Carbide
CN113831144B (en) Method for preparing ceramic material by multi-field coupling ultra-fast sintering
CN109095916B (en) Method for preparing YAG transparent ceramic by SPS sintering
CN108655403B (en) Preparation method of high-purity tantalum target material for electronic material
CN113943162B (en) alpha-SiAlON high-entropy transparent ceramic material and preparation method thereof
CN108794016B (en) Rapid preparation method of AlON transparent ceramic with high infrared transmittance
CN112279650A (en) Preparation method of high-density silicon carbide ceramic composite material
CN114620996A (en) High-efficiency rotary ceramic target for solar cell
CN111116206A (en) Preparation method of compact MoAlB ceramic material, product thereof and preparation method of high-purity MoAlB ceramic powder
NL2030121A (en) Method for preparing large-size high-quality potassium tantalum niobate ceramic target material
CN108465817B (en) Preparation method of high-density pure tungsten product with uniform structure
CN106747433B (en) Zirconia-based nano ceramic tool and die material and preparation method thereof
CN114835473B (en) Alumina ceramic and preparation method thereof
CN114605156B (en) TiB 2 Composite ceramic material for base armor
CN116217239A (en) Preparation method of silicon nitride ceramic with high thermal conductivity and low resistivity
CN114671689A (en) Hot-pressing liquid-phase sintered boron carbide composite ceramic and preparation method thereof
CN108658589A (en) The preparation method of sub-micro crystal alumina ceramic tool matrix material
CN112079645B (en) Textured silicon carbide whisker toughened alumina-based ceramic and preparation method and application thereof
CN113233888A (en) Method for preparing IGZO target material by recycling IGZO waste biscuit
CN114853347A (en) High-thermal-conductivity low-temperature co-fired glass ceramic substrate and preparation method thereof
CN111704445A (en) MgAlON transparent ceramic with high magnesium content and wide optical transmission area and preparation method thereof
CN112521160A (en) B4C/h-BN high-temperature complex-phase ceramic and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant