WO2022088270A1 - Preparation method for ultrahigh-density ceramic body - Google Patents

Preparation method for ultrahigh-density ceramic body Download PDF

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WO2022088270A1
WO2022088270A1 PCT/CN2020/128600 CN2020128600W WO2022088270A1 WO 2022088270 A1 WO2022088270 A1 WO 2022088270A1 CN 2020128600 W CN2020128600 W CN 2020128600W WO 2022088270 A1 WO2022088270 A1 WO 2022088270A1
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ceramic
density
ultra
solvent system
preparing
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PCT/CN2020/128600
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French (fr)
Chinese (zh)
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张乐
邵岑
康健
王忠英
黄国灿
姚庆
李明
费宾
邱凡
赵超
陈浩
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新沂市锡沂高新材料产业技术研究院有限公司
徐州凹凸光电科技有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B3/00—Producing shaped articles from the material by using presses; Presses specially adapted therefor
    • B28B3/003—Pressing by means acting upon the material via flexible mould wall parts, e.g. by means of inflatable cores, isostatic presses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/24—Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
    • B28B11/243—Setting, e.g. drying, dehydrating or firing ceramic articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B13/00—Feeding the unshaped material to moulds or apparatus for producing shaped articles; Discharging shaped articles from such moulds or apparatus
    • B28B13/02—Feeding the unshaped material to moulds or apparatus for producing shaped articles
    • B28B13/021—Feeding the unshaped material to moulds or apparatus for producing shaped articles by fluid pressure acting directly on the material, e.g. using vacuum, air pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28C3/00—Apparatus or methods for mixing clay with other substances
    • 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
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C04B35/505—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds based on yttrium 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
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63416—Polyvinylalcohols [PVA]; Polyvinylacetates
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/6342—Polyvinylacetals, e.g. polyvinylbutyral [PVB]
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63488—Polyethers, e.g. alkylphenol polyglycolether, polyethylene glycol [PEG], polyethylene oxide [PEO]
    • 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
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina

Definitions

  • the invention belongs to the field of advanced ceramic preparation, in particular to a method for preparing an ultra-high-density ceramic china.
  • MLCC multi-layer ceramic capacitors
  • MLCC has become an indispensable component in various electronic devices such as mobile phones and computers.
  • 5G communication the application demand of MLCC in 5G mobile phones is expected to increase by 50-200% compared with 4G mobile phones.
  • Broad market prospects According to data reported by relevant departments, it is expected that the market size of MLCC will exceed 12 billion US dollars in 2021, and the output value of MLCC industry in my country will be as high as 63 billion yuan. It can be seen that vigorously developing MLCC is of great significance in line with my country's strategic development needs.
  • the purpose of the present invention is to provide a method for preparing an ultra-high-density ceramic green body, which can prepare a ceramic green body with no layered structure, no bubbles and high density.
  • the technical scheme adopted in the present invention is as follows: a method for preparing an ultra-high-density ceramic china, comprising the following steps:
  • step (3) Add plasticizer to the ceramic slurry prepared in step (3), the amount of plasticizer added is 3.5-7wt.% of the mass of the ceramic powder, continue planetary stirring for 4-8h, and the rotation speed is 1800- 2600r/min;
  • step (4) Add the binder into the ceramic slurry prepared in step (4), the amount of the binder is 3.5-8wt.% of the mass of the ceramic powder, and continue the planetary vacuum stirring for 30-48h, and the rotation speed is 1800 -2600r/min, adjust the vacuum degree to be below 0.15Mpa, adjust the slurry viscosity to be above 12000cps;
  • step (6) making the ceramic slurry prepared in step (5) into a sheet-like or linear ceramic green body through a wet forming process, and drying it in-situ; and then customizing the cutting and stacking of the ceramic green body according to application requirements;
  • step (6) carrying out warm isostatic pressing of the ceramic body prepared in step (6), the pressure of warm isostatic pressing is 30-80Mpa, the temperature is 60-95 °C, and the holding time is 3-15min;
  • the degreasing heating rate is 0.5-5°C/min, and the temperature is 550-900°C; after degreasing, the cooling rate is 0.5-5°C/min, and the temperature is lowered to 200°C , and then naturally cooled to room temperature to obtain ultra-high-density ceramic china.
  • the dispersant selection is optimized according to the solvent system, and in the water-based solvent system, the dispersant is ammonium citrate, CE-64 (Sima Chemical), etc.; Fish oil, oleic acid, castor oil, polyetherimide PEI, NP-10, etc.
  • the quality of the grinding ball is 1-3 times the quality of the raw material powder
  • the material of the grinding ball is one or more of alumina, zirconia, and agate
  • the diameter of the grinding ball is 2-3 8mm.
  • the mesh number of the sieve is 80-250 mesh, and the sieve is sieved 2-6 times.
  • the selection of the plasticizer is optimized according to the solvent system, and the plasticizer in the water-based solvent system is one or more of polyethylene glycol, acrylic latex, and polyethylene glycol diamine;
  • the plasticizer in the organic solvent system is one or more of butyl benzyl phthalate, dibutyl phthalate, dibutyl phthalate, and propylene carbonate.
  • the binder selection is optimized according to the solvent system, and the binder in the water-based solvent system is one or both of sodium carboxymethyl cellulose and polyvinyl alcohol; in the organic solvent system
  • the binder is one or more of polyvinyl butyral, ethyl methacrylate and polyacrylic acid.
  • the wet molding process is one or more of tape casting, extrusion molding, and injection molding; the method of adding the ceramic slurry to the sample chamber of the molding equipment is gas pumping , the gas pressure is 2-4Mpa.
  • the in-situ drying temperature is above 35-55° C., and the drying time is 30-1200 s to achieve rapid solidification of the ceramic body.
  • the ceramic powder realizes the self-optimization and self-rearrangement of particle positions through the warm isostatic pressing in step (7), and then the preparation of ultra-high-density ceramic green body can be realized by degreasing and debinding in step (8).
  • the relative density of the green body Above 65%, the relative density of ceramic green bodies prepared by common wet and dry forming techniques is about 55%.
  • the present invention has the following beneficial effects:
  • the present invention obtains a supercontinuous ceramic slurry with uniform component distribution and no bubbles by forming a three-dimensional network, and adopts an in-situ solidification method and an air degreasing method to prepare an integrated, non-layered, ultra-high-density ceramic element. blank without additional expensive pretreatment equipment.
  • Fig. 1 is the SEM image of the ceramic sample prepared in Example 2 of the present invention, (a) the SEM image of the section of the ceramic sample after 30Mpa warm isostatic pressing, (b) the ceramic green body after degreasing of the ceramic sample after 30Mpa warm isostatic pressing SEM image.
  • Example 2 is a graph of the measured density of the ceramic samples prepared in Examples 1 and 2 of the present invention under different temperature and isostatic pressures.
  • Figure 3 shows the measured densities of the YAG ceramic samples prepared in the comparative example at different temperatures and isostatic pressures.
  • the ball milling method is planetary ball milling, the rotation speed is 165r/min, and the duration is 15h.
  • the quality of the grinding balls is 3 times that of the raw material powder. times, the material of the grinding ball is alumina, and the diameter of the grinding ball is 3mm.
  • step (4) Add plasticizer dibutyl phthalate to the ceramic slurry prepared in step (4), the amount of plasticizer added is 5 wt.% of the mass of the ceramic powder, continue planetary stirring for 4h, rotating speed is 1800r/min.
  • step (6) adding the binder polyvinyl butyral into the ceramic slurry prepared in step (5), the amount of the binder being 6 wt.% of the mass of the ceramic powder, and continuing the planetary vacuum stirring for 30h, stirring
  • the rotating speed is 2000r/min, the vacuum degree is adjusted to 0.1Mpa, and the slurry viscosity is adjusted to 15000cps.
  • the ceramic slurry prepared in step (6) is prepared into a sheet-shaped ceramic green body through a tape casting process.
  • step (9) Warm isostatic pressing is performed on the ceramic body prepared in step (8) that meets the application requirements.
  • the pressure of the warm isostatic pressing is 30Mpa, the temperature is 85°C, and the pressure holding time is 15min.
  • the ball milling method is planetary ball milling, the rotational speed is 220r/min, and the duration is 15h.
  • the quality of the grinding balls is 3 times that of the raw material powder. times, the material of the grinding ball is agate, and the diameter of the grinding ball is 3mm.
  • step (4) Add plasticizer polyethylene glycol to the ceramic slurry prepared in step (4), the amount of plasticizer added is 8wt.% of the powder mass, and continue planetary stirring for 4h, and the stirring method is planetary , the speed is 2600r/min.
  • step (6) adding the binder polyvinyl alcohol to the ceramic slurry prepared in step (5), the binder addition amount is 6wt.% of the powder mass, and continue to planetary vacuum stirring for 40h, and the stirring speed is 2600r/ min, adjust the vacuum degree to 0.08Mpa, adjust the slurry viscosity to 16000cps.
  • the ceramic slurry prepared in step (6) is prepared into a sheet-shaped ceramic green body through a tape casting process.
  • step (9) carrying out warm isostatic pressing on the ceramic body prepared in step (8) that meets the application requirements, the pressure of warm isostatic pressing is 60Mpa, the temperature is 85°C, and the holding time is 5min.
  • Figure 1(a) SEM image of the section of the ceramic sample after 30Mpa warm isostatic pressing
  • Figure 1(b) SEM image of the ceramic green body after degreasing of the ceramic sample after 30Mpa warm isostatic pressing; it can be seen from Figure 1(b) There is no delamination on the cross section of the sample, and the component distribution is uniform.
  • the ball milling method is planetary ball milling, the rotational speed is 165r/min, and the duration is 20h, wherein the quality of the grinding balls is 4 times that of the raw material powder. times, the material of the grinding ball is alumina, and the diameter of the grinding ball is 3mm.
  • the ceramic density in the present invention refers to the relative density of the ceramic sample after degreasing, that is, the ratio of the actual density to the theoretical density of the ceramic sample.
  • Figure 2 is a graph of the measured density of the ceramic samples prepared in Examples 1 and 2 of the present invention under different temperature and isostatic pressures.
  • Figure 3 shows the measured densities of the YAG ceramic samples prepared in the comparative example at different temperatures and isostatic pressures.
  • the theoretical density of Y 3 Al 5 O 12 is 4.55g/cm 3 and the theoretical density of AlON is 3.69g/cm 3 .
  • relative density measured density/theoretical density, it can be calculated that the YAG ceramic sample prepared in Example 1 is in When the pressing pressure is 30-50MPa, the relative density is about 65-73%; the relative density of the AlON ceramic sample prepared in Example 2 is about 65-73% when the pressing pressure is 30-50MPa; The relative density of the YAG ceramic sample is about 52-55% when the pressing pressure is 200-300MPa.

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  • Ceramic Engineering (AREA)
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  • Structural Engineering (AREA)
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Abstract

Provided is a preparation method for an ultrahigh-density ceramic body, comprising: firstly weighing ceramic raw material powder for ball-milling mixing, and carrying out filtering, drying and sieving after ball-milling; then, mixing sieved ceramic powder with a solvent for planetary stirring, adding a plasticizer after a period of time, continuing to carry out stirring, adding a binder after a period of time, and continuing to carry out planetary vacuum stirring; next, preparing the ceramic body from a ceramic slurry by means of a wet forming process, carrying out in-situ drying, and carrying out custom cutting and stacking on the ceramic body according to application requirements; and finally, successively carrying out hot isostatic pressing and debinding on the ceramic body to obtain the ultrahigh-density ceramic body. The super-continuous ceramic slurry which is uniform in component distribution and free of bubbles is obtained in a mode of forming a three-dimensional network, the integrated and non-layered ceramic body is prepared by using an in-situ curing mode and an air debinding method, the relative density of the prepared ceramic body reaches 65%, and the application prospect is wide.

Description

一种超高密度的陶瓷素坯制备方法A kind of ultra-high density ceramic china preparation method 技术领域technical field
本发明属于先进陶瓷制备领域，具体涉及一种超高密度的陶瓷素坯制备方法。The invention belongs to the field of advanced ceramic preparation, in particular to a method for preparing an ultra-high-density ceramic china.
背景技术Background technique
20世纪60年代，片式多层陶瓷电容器(Multilayer Ceramic Capacitors,MLCC)的出现，标志着电子信息产业迈上了新的台阶。伴随着电子信息产业的技术突破，所有的电子产品都在不断追求“轻、薄、短、小”，MLCC凭借此优势，已经成为目前电容器市场应用最多的产品。In the 1960s, the emergence of multi-layer ceramic capacitors (MLCCs) marked a new step in the electronic information industry. With the technological breakthrough in the electronic information industry, all electronic products are constantly pursuing "light, thin, short and small". With this advantage, MLCC has become the most widely used product in the capacitor market.
目前，在手机、电脑等各类电子设备中，MLCC已经成为不可或缺的组成，围绕着5G通讯的发展前景下，MLCC在5G手机的应用需求量预计比4G手机增长50-200％，具有广阔的市场前景。根据有关部门报道的数据显示，预计2021年MLCC的市场规模将超过120亿美元，MLCC产业在我国的产值将会高达630亿元人民币。可见，大力发展MLCC符合我国战略发展需求，具有重要意义。At present, MLCC has become an indispensable component in various electronic devices such as mobile phones and computers. Under the development prospect of 5G communication, the application demand of MLCC in 5G mobile phones is expected to increase by 50-200% compared with 4G mobile phones. Broad market prospects. According to data reported by relevant departments, it is expected that the market size of MLCC will exceed 12 billion US dollars in 2021, and the output value of MLCC industry in my country will be as high as 63 billion yuan. It can be seen that vigorously developing MLCC is of great significance in line with my country's strategic development needs.
但是，在MLCC实际生产过程中，坯体在烧结阶段会出现形变、翘曲、开裂等缺陷。造成这种现象的根本原因是用于烧结MLCC器件的陶瓷素坯的初始密度偏低致使脱脂后的陶瓷素坯抗弯强度低。因此，制备具有超高密度的陶瓷素坯对MLCC的产业发展具有重要意义。However, in the actual production process of MLCC, defects such as deformation, warpage and cracking of the green body will appear in the sintering stage. The fundamental reason for this phenomenon is that the initial density of the ceramic green body used for sintering MLCC devices is low, resulting in low flexural strength of the ceramic green body after degreasing. Therefore, the preparation of ceramic china with ultra-high density is of great significance to the industrial development of MLCC.
发明内容SUMMARY OF THE INVENTION
本发明的目的是提供一种超高密度的陶瓷素坯制备方法，能够制备出无分层结构、无气泡、高密度的陶瓷素坯。The purpose of the present invention is to provide a method for preparing an ultra-high-density ceramic green body, which can prepare a ceramic green body with no layered structure, no bubbles and high density.
为实现上述目的，本发明采用的技术方案如下：一种超高密度的陶瓷素坯制备方法，包括以下步骤：In order to achieve the above object, the technical scheme adopted in the present invention is as follows: a method for preparing an ultra-high-density ceramic china, comprising the following steps:
(1)按照陶瓷组成化学式中各元素的化学计量比称量陶瓷原料粉体，加入分散剂和溶剂，调节陶瓷浆料的固含量为48-60wt.％，其中分散剂添加量为陶瓷原料粉体质量的0.1-1wt.％；(1) Weigh the ceramic raw material powder according to the stoichiometric ratio of each element in the chemical formula of the ceramic composition, add a dispersant and a solvent, and adjust the solid content of the ceramic slurry to 48-60wt.%, wherein the amount of the dispersant added is the ceramic raw material powder 0.1-1wt.% of body mass;
(2)将配制好的陶瓷浆料与磨球按一定质量比混合后加入球磨罐中进行行星式球磨，转速为120-220r/min，时间为15-35h；球磨结束后过滤、烘干、过 筛；(2) Mix the prepared ceramic slurry and grinding balls according to a certain mass ratio, and then add them to the ball mill tank for planetary ball milling. The rotating speed is 120-220r/min, and the time is 15-35h; sieve;
(3)将过筛后的陶瓷粉体与溶剂按一定质量比混合后进行行星式搅拌，调节陶瓷浆料的固含量为48-60wt％，转速为1800-2600r/min，搅拌4-12h；(3) Mix the sieved ceramic powder and the solvent according to a certain mass ratio, and then perform planetary stirring, adjust the solid content of the ceramic slurry to 48-60wt%, the rotating speed is 1800-2600r/min, and stir for 4-12h;
(4)将增塑剂加入到步骤(3)所制备的陶瓷浆料中，增塑剂加入量为陶瓷粉体质量的3.5-7wt.％，继续行星式搅拌4-8h，转速为1800-2600r/min；(4) Add plasticizer to the ceramic slurry prepared in step (3), the amount of plasticizer added is 3.5-7wt.% of the mass of the ceramic powder, continue planetary stirring for 4-8h, and the rotation speed is 1800- 2600r/min;
(5)将粘结剂加入到步骤(4)所制备的陶瓷浆料中，粘结剂加入量为陶瓷粉体质量的3.5-8wt.％，继续行星式真空搅拌30-48h，转速为1800-2600r/min，调节真空度为0.15Mpa以下，调节浆料粘度为12000cps以上；(5) Add the binder into the ceramic slurry prepared in step (4), the amount of the binder is 3.5-8wt.% of the mass of the ceramic powder, and continue the planetary vacuum stirring for 30-48h, and the rotation speed is 1800 -2600r/min, adjust the vacuum degree to be below 0.15Mpa, adjust the slurry viscosity to be above 12000cps;
(6)将步骤(5)所制备的陶瓷浆料通过湿法成型工艺制成片状或线状的陶瓷素坯，原位干燥；再根据应用需求将陶瓷素坯进行自定义裁剪、堆叠；(6) making the ceramic slurry prepared in step (5) into a sheet-like or linear ceramic green body through a wet forming process, and drying it in-situ; and then customizing the cutting and stacking of the ceramic green body according to application requirements;
(7)将步骤(6)所制备的陶瓷坯体进行温等静压，温等静压的压力为30-80Mpa，温度为60-95℃，保压时间为3-15min；(7) carrying out warm isostatic pressing of the ceramic body prepared in step (6), the pressure of warm isostatic pressing is 30-80Mpa, the temperature is 60-95 ℃, and the holding time is 3-15min;
(8)将步骤(7)得到的陶瓷坯体进行脱脂，脱脂升温速率为0.5-5℃/min，温度为550-900℃；脱脂后降温速率为0.5-5℃/min，降温至200℃，再自然降温至室温，即得到超高密度的陶瓷素坯。(8) degreasing the ceramic body obtained in step (7), the degreasing heating rate is 0.5-5°C/min, and the temperature is 550-900°C; after degreasing, the cooling rate is 0.5-5°C/min, and the temperature is lowered to 200°C , and then naturally cooled to room temperature to obtain ultra-high-density ceramic china.
优选地，步骤(2)中，分散剂选择根据溶剂体系进行优化，水基溶剂体系中分散剂为柠檬酸铵、CE-64(司马化工产)等；有机溶剂体系中分散剂为鲱鱼油、鱼油、油酸、蓖麻油、聚醚酰亚胺PEI、NP-10等。Preferably, in step (2), the dispersant selection is optimized according to the solvent system, and in the water-based solvent system, the dispersant is ammonium citrate, CE-64 (Sima Chemical), etc.; Fish oil, oleic acid, castor oil, polyetherimide PEI, NP-10, etc.
优选地，步骤(2)中，所述磨球质量为原料粉体质量的1-3倍，磨球材质为氧化铝、氧化锆、玛瑙中的一种或多种，磨球直径为2-8mm。Preferably, in step (2), the quality of the grinding ball is 1-3 times the quality of the raw material powder, the material of the grinding ball is one or more of alumina, zirconia, and agate, and the diameter of the grinding ball is 2-3 8mm.
优选地，步骤(2)中，筛网目数为80-250目，过筛2-6次。Preferably, in step (2), the mesh number of the sieve is 80-250 mesh, and the sieve is sieved 2-6 times.
优选地，步骤(4)中，增塑剂选择根据溶剂体系进行优化，水基溶剂体系中增塑剂为聚乙二醇、丙烯酸乳胶、聚乙二醇二胺中的一种或多种；有机溶剂体系中增塑剂为邻苯二甲酸丁基苄酯、邻苯二甲酸二丁酯、酞酸二丁酯、碳酸丙烯脂中的一种或多种。Preferably, in step (4), the selection of the plasticizer is optimized according to the solvent system, and the plasticizer in the water-based solvent system is one or more of polyethylene glycol, acrylic latex, and polyethylene glycol diamine; The plasticizer in the organic solvent system is one or more of butyl benzyl phthalate, dibutyl phthalate, dibutyl phthalate, and propylene carbonate.
优选地，步骤(5)中，粘结剂选择根据溶剂体系进行优化，水基溶剂体系中粘结剂为羧甲基纤维素钠、聚乙烯醇中的一种或两种；有机溶剂体系中粘结剂为聚乙烯醇缩丁醛，甲基丙烯酸乙酯、聚丙烯酸中的一种或多种。Preferably, in step (5), the binder selection is optimized according to the solvent system, and the binder in the water-based solvent system is one or both of sodium carboxymethyl cellulose and polyvinyl alcohol; in the organic solvent system The binder is one or more of polyvinyl butyral, ethyl methacrylate and polyacrylic acid.
优选地，步骤(6)中，所述湿法成型工艺为流延成型、挤出成型、注射成 型工艺中的一种或几种；陶瓷浆料加入至成型设备样品仓的方式为气体泵送，气体压强为2-4Mpa。Preferably, in step (6), the wet molding process is one or more of tape casting, extrusion molding, and injection molding; the method of adding the ceramic slurry to the sample chamber of the molding equipment is gas pumping , the gas pressure is 2-4Mpa.
优选地，步骤(6)中，原位干燥温度为35-55℃以上，干燥时长30-1200s即可实现陶瓷坯体的快速固化。Preferably, in step (6), the in-situ drying temperature is above 35-55° C., and the drying time is 30-1200 s to achieve rapid solidification of the ceramic body.
陶瓷粉体通过步骤(7)的温等静压实现颗粒位置自优化与自重排，然后通过步骤(8)的脱脂排胶即可实现超高密度陶瓷素坯的制备，素坯的相对密度在65％以上，采用普通湿法、干法成型技术制备的陶瓷素坯相对密度约为55％。The ceramic powder realizes the self-optimization and self-rearrangement of particle positions through the warm isostatic pressing in step (7), and then the preparation of ultra-high-density ceramic green body can be realized by degreasing and debinding in step (8). The relative density of the green body Above 65%, the relative density of ceramic green bodies prepared by common wet and dry forming techniques is about 55%.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1.本发明以形成三维网络的方式得到组分分布均匀、无气泡的超连续陶瓷浆料，采用原位固化的方式与空气脱脂法制备出一体化、无分层、超高密度的陶瓷素坯，无需额外昂贵的预处理设备。1. The present invention obtains a supercontinuous ceramic slurry with uniform component distribution and no bubbles by forming a three-dimensional network, and adopts an in-situ solidification method and an air degreasing method to prepare an integrated, non-layered, ultra-high-density ceramic element. blank without additional expensive pretreatment equipment.
2.本发明所制备出的陶瓷素坯相对密度(相对密度＝实测密度/理论密度)达到65％，远高于现有的干法成型工艺、普通湿法成型。2. The relative density (relative density=measured density/theoretical density) of the ceramic green body prepared by the present invention reaches 65%, which is much higher than the existing dry molding process and ordinary wet molding.
附图说明Description of drawings
图1是本发明实施例2制备的陶瓷样品的SEM图，(a)30Mpa温等静压后的陶瓷样品断面的SEM图，(b)30Mpa温等静压后的陶瓷样品脱脂后陶瓷素坯的SEM图。Fig. 1 is the SEM image of the ceramic sample prepared in Example 2 of the present invention, (a) the SEM image of the section of the ceramic sample after 30Mpa warm isostatic pressing, (b) the ceramic green body after degreasing of the ceramic sample after 30Mpa warm isostatic pressing SEM image.
图2为本发明实施例1、2所制备的陶瓷样品在不同温等静压压力下的实测密度图。2 is a graph of the measured density of the ceramic samples prepared in Examples 1 and 2 of the present invention under different temperature and isostatic pressures.
图3是对比例制备的YAG陶瓷样品在不同温等静压压力下的实测密度。Figure 3 shows the measured densities of the YAG ceramic samples prepared in the comparative example at different temperatures and isostatic pressures.
具体实施方式Detailed ways
下面结合附图和具体实施例对本发明作进一步详细说明。The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
实施例1Example 1
(1)按照陶瓷Y 3Al 5O 12中各元素的化学计量比分别称量陶瓷原料粉体氧化铝、氧化钇，加入陶瓷原料粉体质量0.5wt.％的分散剂PEI，加入无水乙醇，调节陶瓷浆料的固含量为50wt.％。 (1) According to the stoichiometric ratio of each element in the ceramic Y 3 Al 5 O 12 , respectively weigh the ceramic raw material powder alumina and yttrium oxide, add the dispersant PEI with a mass of 0.5 wt.% of the ceramic raw material powder, and add anhydrous ethanol , adjust the solid content of the ceramic slurry to 50wt.%.
(2)将配制好的陶瓷浆料与磨球一起加入刚玉球磨罐中进行球磨，球磨方式为行星式球磨，转速为165r/min，时长为15h，其中磨球质量为原料粉体质量的3倍，磨球材质为氧化铝，磨球直径为3mm。(2) Add the prepared ceramic slurry together with the grinding balls into the corundum ball milling tank for ball milling. The ball milling method is planetary ball milling, the rotation speed is 165r/min, and the duration is 15h. The quality of the grinding balls is 3 times that of the raw material powder. times, the material of the grinding ball is alumina, and the diameter of the grinding ball is 3mm.
(3)将球磨后陶瓷浆料中的球磨介质滤出，烘干，过100目筛，过筛3次。(3) The ball-milling medium in the ceramic slurry after ball-milling is filtered out, dried, passed through a 100-mesh sieve, and sieved three times.
(4)将过筛后的陶瓷粉体加入溶剂无水乙醇进行行星式搅拌，调节陶瓷浆料固含量为60wt.％，搅拌4h，搅拌转速1800r/min。(4) Add the sieved ceramic powder into the solvent absolute ethanol for planetary stirring, adjust the solid content of the ceramic slurry to 60wt.%, stir for 4h, and stir at a speed of 1800r/min.
(5)将增塑剂邻苯二甲酸二丁酯加入到步骤(4)所制备的陶瓷浆料中，增塑剂加入量为陶瓷粉体质量的5wt.％，继续行星式搅拌4h，转速为1800r/min。(5) Add plasticizer dibutyl phthalate to the ceramic slurry prepared in step (4), the amount of plasticizer added is 5 wt.% of the mass of the ceramic powder, continue planetary stirring for 4h, rotating speed is 1800r/min.
(6)将粘结剂聚乙烯醇缩丁醛加入至步骤(5)所制备的陶瓷浆料中，粘结剂加入量为陶瓷粉体质量的6wt.％，继续行星式真空搅拌30h，搅拌转速为2000r/min，调节真空度为0.1Mpa，调节浆料粘度为15000cps。(6) adding the binder polyvinyl butyral into the ceramic slurry prepared in step (5), the amount of the binder being 6 wt.% of the mass of the ceramic powder, and continuing the planetary vacuum stirring for 30h, stirring The rotating speed is 2000r/min, the vacuum degree is adjusted to 0.1Mpa, and the slurry viscosity is adjusted to 15000cps.
(7)将步骤(6)所制备的陶瓷浆料通过流延成型工艺制备成片状陶瓷素坯。(7) The ceramic slurry prepared in step (6) is prepared into a sheet-shaped ceramic green body through a tape casting process.
(8)将步骤(7)所制备的陶瓷素坯根据应用需求进行自定义裁剪、堆叠。(8) Customizing and stacking the ceramic green body prepared in step (7) according to application requirements.
(9)将步骤(8)所制备的满足应用需求的陶瓷坯体进行温等静压，温等静压的压力为30Mpa，温度为85℃，保压时间为15min。(9) Warm isostatic pressing is performed on the ceramic body prepared in step (8) that meets the application requirements. The pressure of the warm isostatic pressing is 30Mpa, the temperature is 85°C, and the pressure holding time is 15min.
(10)将步骤(9)得到的陶瓷坯体进行脱脂，脱脂升温速率为0.5℃/min，温度为600℃；脱脂后降温速率为0.5℃/min，降温至200℃，再自然降温至室温，即得到超高密度的陶瓷素坯。(10) degreasing the ceramic body obtained in step (9), the degreasing heating rate is 0.5 ℃/min, and the temperature is 600 ℃; after degreasing, the cooling rate is 0.5 ℃/min, cooling to 200 ℃, and then naturally cooling to room temperature , that is, to obtain ultra-high-density ceramic china.
实施例2Example 2
(1)按照陶瓷AlON中各元素的化学计量比分别称量原料粉体氮化铝和氧化铝，加入陶瓷原料粉体质量1wt.％的分散剂柠檬酸铵，加入超纯水，调节陶瓷浆料的固含量为48wt.％。(1) According to the stoichiometric ratio of each element in the ceramic AlON, weigh the raw material powders of aluminum nitride and aluminum oxide respectively, add the dispersant ammonium citrate with a mass of 1 wt.% of the ceramic raw material powder, add ultrapure water, and adjust the ceramic slurry The solids content of the feed was 48 wt.%.
(2)将配制好的陶瓷浆料与磨球一起加入尼龙球磨罐中进行球磨，球磨方式为行星式球磨，转速为220r/min，时长为15h，其中磨球质量为原料粉体质量的3倍，磨球材质为玛瑙，磨球直径为3mm。(2) Add the prepared ceramic slurry together with the grinding balls into the nylon ball milling tank for ball milling. The ball milling method is planetary ball milling, the rotational speed is 220r/min, and the duration is 15h. The quality of the grinding balls is 3 times that of the raw material powder. times, the material of the grinding ball is agate, and the diameter of the grinding ball is 3mm.
(3)将球磨后陶瓷浆料中的球磨介质滤出，烘干，过200目筛，过筛2次。(3) Filter out the ball-milling medium in the ceramic slurry after ball-milling, dry it, pass through a 200-mesh sieve, and sieve twice.
(4)将过筛后的陶瓷粉体加入溶剂超纯水进行行星式搅拌，调节陶瓷浆料固含量为60wt.％，搅拌8h，搅拌转速2600r/min。(4) Add the sieved ceramic powder into solvent ultrapure water for planetary stirring, adjust the solid content of the ceramic slurry to 60wt.%, stir for 8h, and stir at a speed of 2600r/min.
(5)将增塑剂聚乙二醇加入到步骤(4)所制备的陶瓷浆料中，增塑剂加入量为粉体质量的8wt.％，继续行星式搅拌4h，搅拌方式为行星式，转速为2600r/min。(5) Add plasticizer polyethylene glycol to the ceramic slurry prepared in step (4), the amount of plasticizer added is 8wt.% of the powder mass, and continue planetary stirring for 4h, and the stirring method is planetary , the speed is 2600r/min.
(6)将粘结剂聚乙烯醇加入至步骤(5)所制备的陶瓷浆料中，粘结剂加入 量为粉体质量的6wt.％，继续行星式真空搅拌40h，搅拌转速为2600r/min，调节真空度为0.08Mpa，调节浆料粘度为16000cps。(6) adding the binder polyvinyl alcohol to the ceramic slurry prepared in step (5), the binder addition amount is 6wt.% of the powder mass, and continue to planetary vacuum stirring for 40h, and the stirring speed is 2600r/ min, adjust the vacuum degree to 0.08Mpa, adjust the slurry viscosity to 16000cps.
(7)将步骤(6)所制备的陶瓷浆料通过流延成型工艺制备成片状陶瓷素坯。(7) The ceramic slurry prepared in step (6) is prepared into a sheet-shaped ceramic green body through a tape casting process.
(8)将步骤(7)所制备的陶瓷素坯根据应用需求进行自定义裁剪、堆叠。(8) Customizing and stacking the ceramic green body prepared in step (7) according to application requirements.
(9)将步骤(8)所制备的满足应用需求的陶瓷坯体进行温等静压，温等静压的压力为60Mpa，温度为85℃，保压时间为5min。(9) carrying out warm isostatic pressing on the ceramic body prepared in step (8) that meets the application requirements, the pressure of warm isostatic pressing is 60Mpa, the temperature is 85°C, and the holding time is 5min.
(10)将步骤(9)得到的陶瓷坯体进行脱脂，脱脂升温速率为3℃/min，温度为900℃；脱脂后降温速率为3℃/min，降温至200℃；再自然降温至室温，即得到超高密度的陶瓷素坯。(10) degreasing the ceramic body obtained in step (9), the degreasing heating rate is 3 ℃/min, and the temperature is 900 ℃; after degreasing, the cooling rate is 3 ℃/min, and the temperature is cooled to 200 ℃; and then the temperature is naturally cooled to room temperature , that is, to obtain ultra-high-density ceramic china.
图1(a)30Mpa温等静压后的陶瓷样品断面的SEM图，图1(b)30Mpa温等静压后的陶瓷样品脱脂后陶瓷素坯的SEM图；从图1(b)可以看出，样品断面无分层，组分分布均匀。Figure 1(a) SEM image of the section of the ceramic sample after 30Mpa warm isostatic pressing, Figure 1(b) SEM image of the ceramic green body after degreasing of the ceramic sample after 30Mpa warm isostatic pressing; it can be seen from Figure 1(b) There is no delamination on the cross section of the sample, and the component distribution is uniform.
对比例Comparative ratio
(1)按照Y 3Al 5O 12陶瓷中各元素的化学计量比分别称量陶瓷原料粉体Y 3O 2、Al 2O 3，加入陶瓷原料粉体质量0.5wt.％的PEI作为分散剂，加入无水乙醇作为溶剂，调节陶瓷浆料的质量固含量为50wt.％。 (1) According to the stoichiometric ratio of each element in the Y 3 Al 5 O 12 ceramics, respectively weigh the ceramic raw material powders Y 3 O 2 and Al 2 O 3 , and add 0.5 wt.% PEI as a dispersant. , adding absolute ethanol as a solvent, and adjusting the mass solid content of the ceramic slurry to 50wt.%.
(2)将配制好的陶瓷浆料与磨球一起加入刚玉球磨罐中进行球磨，球磨方式为行星式球磨，转速为165r/min，时长为20h，其中磨球质量为原料粉体质量的4倍，磨球材质为氧化铝，磨球直径为3mm。(2) Add the prepared ceramic slurry together with the grinding balls into the corundum ball milling tank for ball milling. The ball milling method is planetary ball milling, the rotational speed is 165r/min, and the duration is 20h, wherein the quality of the grinding balls is 4 times that of the raw material powder. times, the material of the grinding ball is alumina, and the diameter of the grinding ball is 3mm.
(3)将球磨后陶瓷浆料中的球磨介质滤出，烘干，过100目筛，过筛3次。(3) The ball-milling medium in the ceramic slurry after ball-milling is filtered out, dried, passed through a 100-mesh sieve, and sieved three times.
(4)将过筛后的陶瓷粉体加入弹性模具中，然后使用真塑封机进行塑封，将塑封后的陶瓷样品放入冷等静压机中加压，调节冷等静压机的加压压力为10、200、250Mpa，保压时间为10min，待冷等静压机泄压后，即可得到可用于密度测试的陶瓷样品。(4) Add the sieved ceramic powder into the elastic mold, then use a real plastic sealing machine for plastic sealing, put the plastic-sealed ceramic sample into a cold isostatic press for pressure, and adjust the pressure of the cold isostatic press The pressure is 10, 200, 250Mpa, and the pressure holding time is 10min. After the pressure of the cold isostatic press is released, the ceramic sample that can be used for density testing can be obtained.
本发明所述的陶瓷密度是指陶瓷样品脱脂后的相对密度，即陶瓷样品的实际密度与理论密度的比值。The ceramic density in the present invention refers to the relative density of the ceramic sample after degreasing, that is, the ratio of the actual density to the theoretical density of the ceramic sample.
本发明所述实施例的实际密度测试方法为：将采用本发明制备的陶瓷素坯采用激光切割的方式制成25*25mm的陶瓷样品10只，采用万分表测试64次样品边长(单边测试16次)取平均值测得单边变成；采用万分表测试样品厚度的30 次；使用高精度天平(天平有效数字小数点后4位，天平单位：g)。根据密度计算公式(密度＝质量/体积)，即可得到陶瓷样品的实测密度。将计算的10只陶瓷样品的实测密度取平均值，得到陶瓷样品的实测密度。The actual density test method of the embodiment of the present invention is as follows: the ceramic green body prepared by the present invention is laser-cut to make 10 ceramic samples of 25*25mm, and the sample side length (unilateral side length) is tested 64 times by a multimeter. Test 16 times) take the average value to measure the unilateral change; use a multimeter to test the thickness of the sample 30 times; use a high-precision balance (the effective number of the balance is 4 decimal places, the balance unit: g). According to the density calculation formula (density=mass/volume), the measured density of the ceramic sample can be obtained. The measured density of the calculated 10 ceramic samples was averaged to obtain the measured density of the ceramic sample.
图2为本发明实施例1、2所制备的陶瓷样品在不同温等静压压力下的实测密度图。图3是对比例制备的YAG陶瓷样品在不同温等静压压力下的实测密度。Figure 2 is a graph of the measured density of the ceramic samples prepared in Examples 1 and 2 of the present invention under different temperature and isostatic pressures. Figure 3 shows the measured densities of the YAG ceramic samples prepared in the comparative example at different temperatures and isostatic pressures.
Y 3Al 5O 12的理论密度为4.55g/cm 3，AlON的理论密度为3.69g/cm 3，根据相对密度＝实测密度/理论密度，可以计算得到实施例1制得的YAG陶瓷样品在加压压力为30～50MPa时的相对密度约为65～73％；实施例2制得的AlON陶瓷样品在加压压力为30～50MPa时的相对密度约为65～73％；对比例制得的YAG陶瓷样品在加压压力为200～300MPa时的相对密度约为52～55％。 The theoretical density of Y 3 Al 5 O 12 is 4.55g/cm 3 and the theoretical density of AlON is 3.69g/cm 3 . According to relative density=measured density/theoretical density, it can be calculated that the YAG ceramic sample prepared in Example 1 is in When the pressing pressure is 30-50MPa, the relative density is about 65-73%; the relative density of the AlON ceramic sample prepared in Example 2 is about 65-73% when the pressing pressure is 30-50MPa; The relative density of the YAG ceramic sample is about 52-55% when the pressing pressure is 200-300MPa.

Claims (8)

  1. 一种超高密度的陶瓷素坯制备方法，其特征在于，包括以下步骤：A method for preparing an ultra-high-density ceramic green body, comprising the following steps:
    (1)按照陶瓷组成化学式中各元素的化学计量比称量陶瓷原料粉体，加入分散剂和溶剂，调节陶瓷浆料的固含量为48-60wt.％，其中分散剂添加量为陶瓷原料粉体质量的0.1-1wt.％；(1) Weigh the ceramic raw material powder according to the stoichiometric ratio of each element in the chemical formula of the ceramic composition, add a dispersant and a solvent, and adjust the solid content of the ceramic slurry to 48-60wt.%, wherein the amount of the dispersant added is the ceramic raw material powder 0.1-1wt.% of body mass;
    (2)将配制好的陶瓷浆料与磨球按一定质量比混合后加入球磨罐中进行行星式球磨，转速为120-220r/min，时间为15-35h；球磨结束后过滤、烘干、过筛；(2) Mix the prepared ceramic slurry and grinding balls according to a certain mass ratio, and then add them to the ball mill tank for planetary ball milling. The rotating speed is 120-220r/min, and the time is 15-35h; sieve;
    (3)将过筛后的陶瓷粉体与溶剂按一定质量比混合后进行行星式搅拌，调节陶瓷浆料的固含量为48-60wt％，转速为1800-2600r/min，时间为4-12h；(3) Mix the sieved ceramic powder and the solvent according to a certain mass ratio, and then perform planetary stirring, adjust the solid content of the ceramic slurry to 48-60wt%, the rotating speed is 1800-2600r/min, and the time is 4-12h ;
    (4)将增塑剂加入到步骤(3)所制备的陶瓷浆料中，增塑剂加入量为陶瓷粉体质量的3.5-7wt.％，继续行星式搅拌4-8h，转速为1800-2600r/min；(4) Add plasticizer to the ceramic slurry prepared in step (3), the amount of plasticizer added is 3.5-7wt.% of the mass of the ceramic powder, continue planetary stirring for 4-8h, and the rotation speed is 1800- 2600r/min;
    (5)将粘结剂加入到步骤(4)所制备的陶瓷浆料中，粘结剂加入量为陶瓷粉体质量的3.5-8wt.％，继续行星式真空搅拌30-48h，转速为1800-2600r/min，调节真空度为0.15Mpa以下，调节浆料粘度为12000cps以上；(5) Add the binder into the ceramic slurry prepared in step (4), the amount of the binder is 3.5-8wt.% of the mass of the ceramic powder, and continue the planetary vacuum stirring for 30-48h, and the rotation speed is 1800 -2600r/min, adjust the vacuum degree to be below 0.15Mpa, adjust the slurry viscosity to be above 12000cps;
    (6)将步骤(5)所制备的陶瓷浆料通过湿法成型工艺制成片状或线状的陶瓷素坯，原位干燥；再根据应用需求将陶瓷素坯进行自定义裁剪、堆叠；(6) making the ceramic slurry prepared in step (5) into a sheet-like or linear ceramic green body through a wet forming process, and drying it in-situ; and then customizing the cutting and stacking of the ceramic green body according to application requirements;
    (7)将步骤(6)所制备的陶瓷坯体进行温等静压，温等静压的压力为30-80Mpa，温度为60-95℃，保压时间为3-15min；(7) carrying out warm isostatic pressing of the ceramic body prepared in step (6), the pressure of warm isostatic pressing is 30-80Mpa, the temperature is 60-95 ℃, and the holding time is 3-15min;
    (8)将步骤(7)得到的陶瓷坯体进行脱脂，脱脂升温速率为0.5-5℃/min，温度为550-900℃；脱脂后降温速率为0.5-5℃/min，降温至200℃，再自然降温至室温，即得到超高密度的陶瓷素坯。(8) degreasing the ceramic body obtained in step (7), the degreasing heating rate is 0.5-5°C/min, and the temperature is 550-900°C; after degreasing, the cooling rate is 0.5-5°C/min, and the temperature is lowered to 200°C , and then naturally cooled to room temperature to obtain ultra-high-density ceramic china.
  2. 根据权利要求1所述的一种超高密度的陶瓷素坯制备方法，其特征在于，步骤(1)中，分散剂选择根据溶剂体系进行优化，水基溶剂体系中分散剂为柠檬酸铵、CE-64中的一种或多种；有机溶剂体系中分散剂为鲱鱼油、鱼油、油酸、蓖麻油、聚醚酰亚胺、NP-10中的一种或多种。A method for preparing an ultra-high-density ceramic china according to claim 1, characterized in that, in step (1), the dispersant selection is optimized according to the solvent system, and the dispersant in the water-based solvent system is ammonium citrate, One or more of CE-64; the dispersant in the organic solvent system is one or more of herring oil, fish oil, oleic acid, castor oil, polyetherimide, and NP-10.
  3. 根据权利要求1所述的一种超高密度的陶瓷素坯制备方法，其特征在于，步骤(2)中，所述磨球质量为原料粉体质量的1-3倍，磨球材质为氧化铝、氧化锆、玛瑙中的一种或多种，磨球直径为2-8mm。The method for preparing an ultra-high-density ceramic china according to claim 1, wherein in step (2), the quality of the grinding ball is 1-3 times the quality of the raw material powder, and the material of the grinding ball is oxidized One or more of aluminum, zirconia and agate, and the diameter of the grinding ball is 2-8mm.
  4. 根据权利要求1所述的一种超高密度的陶瓷素坯制备方法，其特征在于， 步骤(2)中，筛网目数为80-250目，过筛2-6次。The method for preparing an ultra-high-density ceramic china according to claim 1, characterized in that, in step (2), the mesh number of the sieve is 80-250 mesh, and the sieve is sieved 2-6 times.
  5. 根据权利要求1所述的一种超高密度的陶瓷素坯制备方法，其特征在于，步骤(4)中，增塑剂选择根据溶剂体系进行优化，水基溶剂体系中增塑剂为聚乙二醇、丙烯酸乳胶、聚乙二醇二胺中的一种或多种；有机溶剂体系中增塑剂为邻苯二甲酸丁基苄酯、邻苯二甲酸二丁酯、酞酸二丁酯、碳酸丙烯脂中的一种或多种。The method for preparing an ultra-high-density ceramic china according to claim 1, characterized in that, in step (4), the selection of the plasticizer is optimized according to the solvent system, and the plasticizer in the water-based solvent system is polyethylene One or more of glycol, acrylic latex, polyethylene glycol diamine; the plasticizer in the organic solvent system is butyl benzyl phthalate, dibutyl phthalate, dibutyl phthalate , one or more of propylene carbonate.
  6. 根据权利要求1所述的一种超高密度的陶瓷素坯制备方法，其特征在于，步骤(5)中，粘结剂选择根据溶剂体系进行优化，水基溶剂体系中粘结剂为羧甲基纤维素钠、聚乙烯醇中的一种或两种；有机溶剂体系中粘结剂为聚乙烯醇缩丁醛，甲基丙烯酸乙酯、聚丙烯酸中的一种或多种。The method for preparing an ultra-high-density ceramic china according to claim 1, characterized in that, in step (5), the binder selection is optimized according to a solvent system, and the binder in the water-based solvent system is carboxymethyl One or both of sodium cellulose and polyvinyl alcohol; the binder in the organic solvent system is one or more of polyvinyl butyral, ethyl methacrylate and polyacrylic acid.
  7. 根据权利要求1所述的一种超高密度的陶瓷素坯制备方法，其特征在于，步骤(6)中，所述湿法成型工艺为流延成型、挤出成型、注射成型工艺中的一种或几种，陶瓷浆料加入至成型设备样品仓的方式为气体泵送，气体压强为2-4Mpa。The method for preparing an ultra-high-density ceramic green body according to claim 1, wherein in step (6), the wet molding process is one of tape casting, extrusion molding, and injection molding. One or more, the ceramic slurry is added to the sample chamber of the molding equipment by gas pumping, and the gas pressure is 2-4Mpa.
  8. 根据权利要求1所述的一种超高密度的陶瓷素坯制备方法，其特征在于，步骤(6)中，原位干燥温度为35-55℃以上，干燥时间为30-1200s。The method for preparing an ultra-high-density ceramic china according to claim 1, characterized in that, in step (6), the in-situ drying temperature is above 35-55°C, and the drying time is 30-1200s.
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