WO2020237980A1 - 一种氮化物陶瓷的制备方法 - Google Patents

一种氮化物陶瓷的制备方法 Download PDF

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WO2020237980A1
WO2020237980A1 PCT/CN2019/111952 CN2019111952W WO2020237980A1 WO 2020237980 A1 WO2020237980 A1 WO 2020237980A1 CN 2019111952 W CN2019111952 W CN 2019111952W WO 2020237980 A1 WO2020237980 A1 WO 2020237980A1
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nitride ceramic
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nitride
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伍尚华
聂光临
黎业华
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Guangdong University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
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    • 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
    • C04B35/581—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 based on aluminium nitride
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
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    • 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
    • C04B35/638—Removal thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
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    • 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
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    • 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

Definitions

  • This application belongs to the technical field of preparation of ceramic materials, and particularly relates to a preparation method of nitride ceramics.
  • Nitride ceramics is an important structural and functional material with good mechanical, chemical, electrical, thermal and high-temperature physical properties. It has a wide range of applications in metallurgy, aerospace, chemical, ceramics, electronics, machinery and semiconductor industries. Silicon nitride and aluminum nitride are the hot spots of research and application. Among them, aluminum nitride ceramics have high thermal conductivity (theoretical thermal conductivity 320W ⁇ m -1 ⁇ K -1 ), excellent electrical insulation properties, and have a thermal expansion coefficient similar to that of silicon and gallium arsenide and other chip materials.
  • the theoretical thermal conductivity of silicon nitride ceramics is as high as 200-320W ⁇ m -1 ⁇ K -1 , and the mechanical properties are excellent.
  • the bending strength can reach 600-900MPa, and the fracture toughness can reach 4-7MPa ⁇ m 1/2 , which is large.
  • the ideal heat dissipation substrate material for power semiconductor devices has broad application prospects in aerospace, electric vehicles, rail transit, photovoltaic inverters, wind power, smart grids, large-scale industrial automation variable frequency servos and other fields.
  • Nitride ceramics are typical covalent bond compounds, and their sintering temperature is usually higher.
  • rare earth metal oxides or alkaline earth metal oxides are usually added as sintering aids.
  • Rare earth metal oxides or alkaline earth metal oxides as sintering aids mainly play two roles: 1form a liquid phase, promote the sintering and densification of nitride ceramics, and reduce the sintering temperature of nitride ceramics; 2with nitride ceramic powder The surface oxide reacts to form a second phase, thereby reducing the oxygen content of the nitride ceramic lattice, which is beneficial to improve the thermal conductivity of the nitride ceramic.
  • rare earth metal oxides or alkaline earth metal oxides sintering aids are mainly introduced through mechanical ball milling and mixing.
  • the method is simple and easy to operate.
  • ball milling mixing can easily lead to uneven dispersion of sintering aids, which is useful for improving the performance of nitride ceramics. Density, thermal conductivity and reliability are unfavorable.
  • the impregnation precipitation technology can realize the uniform distribution of sintering aids in the ceramics at the nanometer level, and can be used in the preparation of alumina and zirconia ceramics, but it is rarely used in the preparation of nitride ceramics.
  • the current impregnation precipitation technology generally prepares the sintering aid component into a water-based infiltration agent, and then introduces the sintering aid component into the ceramic by means of ammonia precipitation. Since nitride ceramics are prone to hydrolysis in a water-containing environment, additional oxygen elements will be introduced, and the thermal conductivity of the nitride ceramics will be drastically reduced during the later sintering process. If the existing infiltration precipitation technology is applied to the preparation of nitride ceramics, more oxygen elements will be introduced into the nitride ceramics, which is not conducive to the improvement of the thermal conductivity of the nitride ceramics.
  • the purpose of this application is to provide a non-water-based infiltration precipitation technology, which aims to improve the dispersion uniformity of sintering aids, and at the same time overcome the easy hydrolysis of nitride ceramic powder in the traditional water-based infiltration precipitation technology And the additional defects introduced by oxygen impurities can improve the thermal conductivity and density of nitride ceramics.
  • This application provides a method for preparing nitride ceramics, including the following steps:
  • Step 1 The nitride ceramic mixture is formed and calcined in sequence to obtain a calcined body;
  • Step 2 Immerse the pre-fired body in a non-aqueous infiltrant solution for impregnation treatment, then remove the residual non-aqueous infiltrant solution on the surface of the pre-fired body, and then immerse it in the precipitating agent Perform in-situ precipitation in the solution to obtain an impregnated body;
  • the non-aqueous infiltrant solution includes solute A and solvent A.
  • the solute A is rare earth nitrate or/and alkaline earth nitrate that is soluble in the solvent A in a non-aqueous environment.
  • the solvent A Is an organic solvent that can dissolve the solute A in a non-aqueous environment;
  • the precipitant solution includes a solute B and a solvent B, and the solute B is an amine organic substance that is soluble in the solvent B in a non-aqueous environment,
  • the solvent B is an organic solvent that can dissolve the solute B in a non-aqueous environment;
  • Step 3 Drying, calcining and sintering the impregnated body in sequence to obtain nitride ceramics.
  • step 1 also includes degreasing treatment; degreasing, pre-sintering, drying, calcination and sintering are conventional methods in the field, and different molding and degreasing are used according to actual product raw materials or product needs. , Pre-sintering, drying, calcining and sintering methods.
  • the nitride ceramic mixture in step 1 may be a nitride ceramic slurry or a nitride ceramic powder mixture.
  • the molding method may be a molding method for 3D printing, a wet molding method, or a dry molding method.
  • the dry molding method may be dry pressing, cold isostatic pressing, etc.
  • the application does not specifically limit the molding method.
  • the nitride of the nitride ceramic mixture is selected from one of aluminum nitride, silicon nitride, boron nitride, gallium nitride, titanium nitride, or transition metal nitride.
  • the nitride of the nitride ceramic mixture is selected from aluminum nitride or silicon nitride.
  • the preparation method of this application can improve the thermal conductivity of aluminum nitride ceramic or silicon nitride ceramic.
  • the porosity of the pre-fired body is 20-50%.
  • the selection of the nitride types of the nitride ceramic mixture is based on: rare earth oxides introduced by rare earth nitrates, and alkaline earth metal oxides introduced by alkaline earth nitrates can be used as sintering aids; rare earth oxide additives The uniform introduction of can improve its thermal conductivity.
  • the nitride of the nitride ceramic mixture is selected from aluminum nitride
  • the nitride ceramic mixture of the present application is a resin-based aluminum nitride ceramic slurry
  • the resin-based aluminum nitride ceramic mixture includes aluminum nitride ceramic powder , Photosensitive resin, dispersant and photoinitiator.
  • the photosensitive resin is selected from epoxy acrylate, n-butyl acrylate, isooctyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, vinyl acetate, vinyl pyrrolidone, hexanediol diacrylate, One or more of pentaerythritol tetraacrylate, urethane acrylate, neopentyl glycol diacrylate or dipentaerythritol hexaacrylate; dispersant selected from BYK AT204, BYK 9076, BYK 9077, BYK P104S, BYK 110, BYK Any one or more of W9010, SOLSPERSE 8000, SOLSPERSE 17000, SOLSPERSE 24000, the dispersant content accounts for 1.5% to 2% of the mass of the aluminum nitride ceramic powder; the photoinitiator is selected from Darocur 1173, TPO, Ir
  • the rare earth ions of the rare earth nitrate are selected from Y 3+ , La 3+ , Sm 3+ or Dy 3+, the non-aqueous infiltrant solution; the alkaline earth metal of the alkaline earth nitrate The ion is selected from Mg 2+ or Ca 2+ .
  • the concentration of solute A in the non-aqueous infiltrant solution is 0.1-1.5 mol/L.
  • the solvent A is selected from one or more of ethanol, isopropanol, acetone and ether.
  • the non-aqueous infiltrant solution is selected from the group consisting of yttrium nitrate in ethanol, yttrium nitrate in isopropanol, lanthanum nitrate in ethanol, samarium nitrate in ethanol, samarium nitrate in acetone, and dysprosium nitrate.
  • the amine organics of the solute B are selected from one or more of ethylenediamine, diethylamine, triethylamine, triethylenediamine and monoethanolamine.
  • the solvent B is selected from one or more of ethanol, isopropanol, acetone, diethyl ether, toluene and xylene.
  • the precipitating agent solution is selected from the group consisting of ethylenediamine in ethanol, ethylenediamine in acetone, diethylamine in isopropanol, diethylamine in ethanol, diethylamine in ether, triethylamine Ethanol solution of amine, toluene solution of triethylenediamine, xylene solution of triethylenediamine, ethanol solution of triethylenediamine, acetone solution of triethylenediamine, ethanol solution of monoethanolamine, acetone solution of monoethanolaminekind of.
  • nitride ceramic mixture of this application can also be other nitride ceramic mixture materials, and the components of other nitride ceramic mixtures can be adjusted according to actual needs. This application will not elaborate on other nitride ceramic mixture materials. .
  • this application provides a specific preparation method of nitride ceramics based on light-curing 3D molding technology, including the following steps:
  • Step A forming, degreasing and calcining the nitride ceramic slurry in sequence to obtain a calcined body
  • Step B Immerse the pre-fired body in a non-aqueous infiltrant solution for impregnation treatment, then remove the residual non-aqueous infiltrant solution on the surface of the pre-fired body, and then immerse it in the precipitating agent Perform in-situ precipitation in the solution to obtain an impregnated body;
  • the non-aqueous infiltrant solution includes solute A and solvent A.
  • the solute A is a rare earth nitrate or/and alkaline earth nitrate that is soluble in the solvent A in a non-aqueous environment.
  • the solvent A Is an organic solvent that can dissolve the solute A in a non-aqueous environment;
  • the precipitant solution includes a solute B and a solvent B, and the solute B is an amine organic substance that is soluble in the solvent B in a non-aqueous environment,
  • the solvent B is an organic solvent that can dissolve the solute B in a non-aqueous environment;
  • Step C Drying, calcining and sintering the impregnated body in sequence to obtain nitride ceramics.
  • the solid content of the nitride ceramic slurry is greater than or equal to 40 vol%.
  • the molding technology is a light-curing 3D molding technology.
  • Additive manufacturing technology also known as 3D printing technology
  • DLP digital light processing
  • the light-curing 3D molding technology adopts digital light processing 3D printers, and the light-curing 3D molding technology can prepare nitride ceramic special-shaped parts, and can also prepare nitride ceramic regular parts.
  • the laser wavelength of light curing 3D molding technology is 250-460nm
  • the exposure is 4-100mJ/cm 2
  • the printing layer thickness is 10-50 ⁇ m
  • the single-layer curing time is 1-15s.
  • molding technology of this application can also be other conventional molding technologies, and the operating parameters of other molding technologies can be adjusted according to actual needs. This application will not elaborate on other molding technologies one by one.
  • this application provides a specific preparation method of aluminum nitride ceramics based on light-curing 3D molding technology, including the following steps:
  • Step 1 The aluminum nitride ceramic slurry is formed, degreased and calcined in sequence to obtain a calcined body;
  • Step 2 Immerse the pre-fired body in a non-aqueous infiltrant solution for impregnation treatment, then remove the residual non-aqueous infiltrant solution on the surface of the pre-fired body, and then immerse it in the precipitating agent Perform in-situ precipitation in the solution to obtain an impregnated body;
  • the non-aqueous infiltrant solution includes solute A and solvent A.
  • the solute A is rare earth nitrate and alkaline earth nitrate that are soluble in the solvent A in a non-aqueous environment
  • the solvent A is An organic solvent that can dissolve the solute A in a non-aqueous environment
  • the precipitant solution includes a solute B and a solvent B
  • the solute B is an amine organic substance that is soluble in the solvent B in a non-aqueous environment.
  • Solvent B is an organic solvent that can dissolve the solute B in a non-aqueous environment;
  • Step 3 Drying, calcining and sintering the impregnated body in sequence to obtain aluminum nitride ceramics.
  • the pH value of the precipitation agent solution is 10-12.
  • the time of the impregnation treatment is 1-24 h
  • the temperature of the impregnation treatment is 25-50° C.
  • the time of the in-situ precipitation is 0.2-4 h.
  • the degreasing step includes: vacuum degreasing and air degreasing; vacuum degreasing is to place the green body formed of nitride ceramic slurry in a vacuum furnace and heat it at 0.5-3°C/min The rate is increased to 400 ⁇ 600°C, and every interval of 100°C is kept for 0.5 ⁇ 2h; after vacuum degreasing is completed, the green body is placed in a muffle furnace for further degreasing and carbon removal under air atmosphere at 0.5 ⁇ 3°C/min The heating rate is increased to 400-450°C and kept for 2 to 4 hours, and then cooled to room temperature with the furnace to obtain a nitride ceramic body.
  • the pre-sintering treatment is to place the degreased nitride ceramic body in an atmosphere furnace, and heat it to 1400-1600 at a heating rate of 5-10°C/min under a flowing nitrogen atmosphere. °C, keep for 1 ⁇ 2h, and then cool to room temperature with the furnace to obtain the pre-fired body.
  • the drying temperature is 50-80°C, and the drying time is 2-12h.
  • the calcination treatment process is: heating up to 300-450°C at a heating rate of 2-10°C/min, holding it for 2-6 hours, and then cooling with the furnace.
  • the sintering process is: heating up to 1700-2000°C at a heating rate of 5-10°C/min, holding for 2-8h, and then cooling with the furnace to obtain aluminum nitride ceramics.
  • the traditional infiltrant solution in the prior art is easy to hydrolyze the nitride ceramic powder, thereby introducing more oxygen impurities, which is not conducive to the preparation of high thermal conductivity nitride ceramics; and the oxide sintering aid is introduced through the traditional ball milling process , It is difficult to achieve uniform dispersion of the sintering aid, resulting in uneven microstructure, thermal conductivity and density reduction of the manufactured nitride ceramics. Therefore, this application provides a method for preparing a high thermal conductivity nitride component.
  • the traditional infiltration agent solution and precipitant solution are both water-based solutions, and water is used as a solvent to dissolve the infiltration agent and precipitant.
  • This application proposes a non-aqueous infiltration precipitation system (including non-aqueous infiltration Solution and non-aqueous precipitant solution) can avoid the contact and hydrolysis of the nitride ceramic powder with water, avoid the additional introduction of oxygen impurities, and the in-situ precipitation after infiltration realizes the uniform dispersion of the sintering aid. It is beneficial to improve the thermal conductivity of aluminum nitride ceramic products.
  • the nitride ceramic obtained by the preparation method of the present application has the advantages of high density, uniform microstructure, high thermal conductivity, and strong shape and structure design.
  • This application can solve the technical problem that the thermal conductivity of the nitride ceramic powder is reduced due to the hydrolysis of the nitride ceramic powder and the additional introduction of oxygen impurities in the traditional water-based infiltration precipitation technology, and the in-situ precipitation after the infiltration makes the sintering aid
  • the uniformity of dispersion is good, which overcomes the technical defects of the uneven dispersion of the sintering aid in the traditional ball milling and mixing process, which leads to the decrease of its thermal conductivity and density.
  • This application proposes a non-water-based infiltration precipitation technology, which is not only suitable for improving the thermal conductivity of aluminum nitride and silicon nitride ceramics; it is also suitable for the preparation of other hydrolyzed ceramics (nitride or carbide ceramics) to achieve sintering
  • the uniform dispersion of additives then improves the properties of nitride and carbide ceramics (thermal, electrical, magnetic, mechanical properties, etc.). Any changes made based on the design ideas of this application are within the protection scope of this application.
  • Figure 1 is a process flow diagram of the method for preparing nitride ceramics provided by this application;
  • FIG. 2 is a process flow diagram of a method for preparing nitride ceramics based on photocurable 3D printing technology provided by an embodiment of the application;
  • the prepared aluminum nitride ceramic special-shaped infiltration green body is placed in an oven for drying treatment, and then the dried aluminum nitride ceramic special-shaped infiltration green body is placed in a muffle furnace for calcination Processing to obtain aluminum nitride ceramic special-shaped calcined body;
  • This application provides a method for preparing nitride ceramics, which is used to solve the technical defects that the traditional infiltration precipitation technology is easy to cause the nitride ceramic powder to be hydrolyzed and additionally introduce oxygen impurities.
  • the in-situ precipitation after the infiltration is used to achieve sintering
  • the uniform dispersion of additives aims to improve the thermal conductivity and density of nitride ceramics.
  • the raw materials used in the examples of the present application are all commercially available or self-made.
  • the embodiments of the present application provide the first method for preparing nitride ceramics, and the specific steps are as follows:
  • a light-curing 3D printer to perform light-curing 3D printing molding, control the laser wavelength to 250nm, exposure to 100mJ/cm 2 , single-layer curing time to 1s, and printing layer thickness to 50 ⁇ m; 3D according to the preset three-dimensional structure model It is printed and formed to obtain a special-shaped aluminum nitride ceramic green body.
  • the aluminum nitride ceramic component of this embodiment may be a special-shaped ceramic component or a regular ceramic component.
  • the density of the aluminum nitride ceramic parts prepared in this example is 99.8% measured by Archimedes drainage method, and the room temperature thermal conductivity measured by flash method is 205W ⁇ m -1 ⁇ K -1 , that is It shows that the aluminum nitride ceramic part prepared in this embodiment has excellent thermal conductivity and compactness.
  • the embodiment of the application provides a second method for preparing nitride ceramics, and the specific steps are as follows:
  • a light-curing 3D printer to perform light-curing 3D printing and molding, control the laser wavelength to 460nm, exposure to 4mJ/cm 2 , single-layer curing time to 15s, and printing layer thickness to 10 ⁇ m; perform 3D according to the preset three-dimensional structure model It is printed and formed to obtain a special-shaped aluminum nitride ceramic green body.
  • the aluminum nitride ceramic component of this embodiment may be a special-shaped ceramic component or a regular ceramic component.
  • the density of the aluminum nitride ceramic parts prepared in this example is 98.6% measured by Archimedes drainage method, and the room temperature thermal conductivity measured by flash method is 168W ⁇ m -1 ⁇ K -1 , that is It shows that the aluminum nitride ceramic component prepared in this embodiment has excellent thermal conductivity and compactness.
  • the embodiment of the application provides a second method for preparing nitride ceramics, and the specific steps are as follows:
  • a light-curing 3D printer to perform light-curing 3D printing and molding, control the laser wavelength to 460nm, exposure to 15mJ/cm 2 , single-layer curing time to 5s, and printing layer thickness to be 20 ⁇ m; perform 3D according to the preset three-dimensional structure model It is printed and formed to produce a special-shaped aluminum nitride ceramic green body.
  • the aluminum nitride ceramic component of this embodiment may be a special-shaped ceramic component or a regular ceramic component.
  • the density of the aluminum nitride ceramic parts prepared in this example is 99.2% measured by Archimedes drainage method, and the room temperature thermal conductivity measured by flash method is 182W ⁇ m -1 ⁇ K -1 , which means The aluminum nitride ceramic component prepared in this embodiment has excellent thermal conductivity and compactness.
  • This application provides a traditional water-based infiltration precipitation method for preparing nitride ceramics.
  • the specific steps are as follows:
  • Example 1 uses an aqueous solution of Sm(NO 3 ) 6H 2 O as the infiltrant solution, and the aqueous ammonia solution as the precipitant solution.
  • the density of the aluminum nitride ceramic prepared in this comparative example is 98.8% measured by Archimedes drainage method, and the room temperature thermal conductivity measured by flash method is only 68W ⁇ m -1 ⁇ K -1 , indicating The conventional method uses an aqueous infiltrant solution and a precipitant solution to precipitate rare earth nitrates in the pores of the pre-fired body.
  • the pre-fired body is infiltrated and precipitated Hydrolysis is prone to occur in the later drying process, so that additional oxygen is introduced into the aluminum nitride ceramic, resulting in low thermal conductivity of the aluminum nitride ceramic.

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Abstract

提供一种氮化物陶瓷的制备方法，包括：将氮化物陶瓷混合物依次进行成型和预烧处理；将预烧坯体浸入非水基浸渗剂溶液中进行浸渗处理，然后将其浸入沉淀剂溶液中进行原位沉淀；将浸渗坯体依次进行干燥、煅烧和烧结，得到氮化物陶瓷；其中非水基浸渗剂溶液包括溶质A和溶剂A，溶质A为稀土硝酸盐和碱土硝酸盐，溶剂A为有机溶剂；沉淀剂溶液包括溶质B和溶剂B，溶质B为胺类有机物，溶剂B为有机溶剂。解决了传统浸渗沉淀技术中由于氮化物陶瓷粉体的水解和氧杂质的额外引入而使其热导率降低的技术难题，且浸渗后的原位沉淀使得烧结助剂分散均匀性良好，有利于提升氮化物陶瓷的热导率和可靠性。

Description

一种氮化物陶瓷的制备方法 技术领域
本申请属于陶瓷材料的制备技术领域，尤其涉及一种氮化物陶瓷的制备方法。
背景技术
氮化物陶瓷是一类重要的结构与功能材料，具有良好的力学、化学、电学、热学及高温物理性能，在冶金、航空、化工、陶瓷、电子、机械及半导体等行业具有广泛的应用。氮化硅、氮化铝是研究与应用的热点。其中，氮化铝陶瓷具有高热导率(理论热导率320W·m -1·K -1)，优良的电绝缘性能、与硅和砷化镓等芯片材料的热膨胀系数相近、较低的介电常数和介电损耗，无毒等优异性能，使之成为高能/高频集成电路中陶瓷散热器件的理想候选材料，受到学术界和产业界的广泛关注。随着科技技术的发展革新，对于高导热的异形陶瓷部件的需求日益增长，例如：微电子技术领域中的三维异形陶瓷封装和散热器件(微通道基板)、捷联惯性导航系统用动力调谐陀螺仪的永磁力矩器骨架、大功率LED异型绝缘散热器件等均需要使用高导热的陶瓷异形部件。氮化硅陶瓷的理论热导率高达200-320W·m -1·K -1，且力学性能优良，弯曲强度可达600-900MPa，断裂韧性可达4-7MPa·m 1/2，是大功率半导体器件理想的散热基板材料，在航天航空、电动汽车、轨道交通、光伏逆变、风力发电、智能电网、大型工业自动化变频伺服等领域具有广阔的应用前景。
氮化物陶瓷是典型的共价键化合物，其烧结温度通常较高。为获得完全致密的氮化物陶瓷，通常加入稀土金属氧化物或碱土金属氧化物作为烧结助剂。稀土金属氧化物或碱土金属氧化物作为烧结助剂主要起到两方面的作用：①形成液相，促进氮化物陶瓷的烧结致密化，降低氮化物陶瓷的烧结温度；②与氮化物陶瓷粉体表面氧化物发生反应形成第二相，从而降低氮化物陶瓷晶格氧含量，有利于提升氮化物陶瓷的热导率。目前，稀土金属氧化物或碱土金属氧化物烧结助剂主要是通过机械球磨混合的方式引入，该方法简单，易于操作，但是球磨混合易导致烧结助剂分散不均匀，这对提升氮化物陶瓷的致密度、热导率与可靠性不利。而浸渗沉淀技术可以实现烧结助剂在陶瓷 中的纳米级均匀分布，并在氧化铝、氧化锆陶瓷制备中得以应用，而鲜见其应用于氮化物陶瓷的制备。这是因为目前的浸渗沉淀技术一般是将烧结助剂组元制备成水基浸渗剂，再通过氨水沉淀的方式，将烧结助剂组元引入陶瓷中。由于氮化物陶瓷在含水环境下，易发生水解，继而会额外引入氧元素，在后期烧结过程中会急剧降低氮化物陶瓷的热导率。若将现有的浸渗沉淀技术应用于氮化物陶瓷的制备，会使得氮化物陶瓷中引入较多的氧元素，不利于氮化物陶瓷热导率的提升。因此，亟待开发一种新型的浸渗沉淀技术，使其适用于氮化物陶瓷的制备，既能实现烧结助剂的均匀分散，又可以避免氮化物陶瓷在浸渗沉淀过程中发生水解。
申请内容
有鉴于此，本申请的目的是提供一种非水基浸渗沉淀技术，旨在提高烧结助剂的分散均匀性，且同时克服传统水基浸渗沉淀技术中氮化物陶瓷粉体易发生水解以及氧杂质的额外引入的缺陷，可提高氮化物陶瓷的热导率和致密度。
本申请提供了一种氮化物陶瓷的制备方法，包括以下步骤：
步骤1、将氮化物陶瓷混合物依次进行成型和预烧处理，得到预烧坯体；
步骤2、将所述预烧坯体浸入非水基浸渗剂溶液中进行浸渗处理，然后去除所述预烧坯体表面的残余非水基浸渗剂溶液后，再将其浸入沉淀剂溶液中进行原位沉淀，得到浸渗坯体；
其中，所述非水基浸渗剂溶液包括溶质A和溶剂A，所述溶质A为在非水环境下可溶于所述溶剂A的稀土硝酸盐或/和碱土硝酸盐，所述溶剂A为在非水环境下可溶解所述溶质A的有机溶剂；所述沉淀剂溶液包括溶质B和溶剂B，所述溶质B为在非水环境下可溶于所述溶剂B的胺类有机物，所述溶剂B为在非水环境下可溶解所述溶质B的有机溶剂；
步骤3、将所述浸渗坯体依次进行干燥、煅烧和烧结处理，得到氮化物陶瓷。
需要说明的是，根据不同的成型方法，步骤1还包括脱脂处理；脱脂、预烧、干燥、煅烧和烧结处理为本领域常规的方法，根据实际产品的原料或 者产品需要采用不同的成型、脱脂、预烧、干燥、煅烧和烧结方式。
需要说明的是，根据不同的成型方法，步骤1的氮化物陶瓷混合物可以为氮化物陶瓷浆料，也可以为氮化物陶瓷粉体混合物。
具体的，成型方法可以为用于3D打印的成型方法，也可以为湿法成型方法，也可以为干法成型方法，干法成型方法可以为干压成型、冷等静压成型等方法，本申请不对成型方法做具体限定。
作为优选，步骤1中，所述氮化物陶瓷混合物的氮化物选自氮化铝、氮化硅、氮化硼、氮化镓、氮化钛或过渡金属氮化物中的一种。
更为优选，步骤1中，所述氮化物陶瓷混合物的氮化物选自氮化铝或氮化硅。
需要说明的是，所述氮化物陶瓷混合物的氮化物为氮化铝或氮化硅时，使用本申请的制备方法可以提高氮化铝陶瓷或氮化硅陶瓷的热导率。
作为优选，步骤1中，所述预烧坯体的孔隙率为20-50％。
需要说明的是，氮化物陶瓷混合物的氮化物种类选自的依据为：稀土硝酸盐引入的稀土氧化物，和碱土硝酸盐引入的碱土金属氧化物能够作为其烧结助剂；稀土氧化物助剂的均匀引入能够提升其热导率。
更优选的，所述氮化物陶瓷混合物的氮化物选自氮化铝，本申请的氮化物陶瓷混合物为树脂基氮化铝陶瓷浆料，树脂基氮化铝陶瓷混合物包括氮化铝陶瓷粉体、光敏树脂、分散剂和光引发剂。其中，光敏树脂选自环氧丙烯酸酯、丙烯酸正丁酯、丙烯酸异辛酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、醋酸乙烯酯、乙烯基吡咯烷酮、己二醇二丙烯酸酯、季戊四醇四丙烯酸酯、聚氨酯丙烯酸酯、新戊二醇二丙烯酸酯或二季戊四醇六丙烯酸酯中的一种或几种；分散剂选自BYK AT204、BYK 9076、BYK 9077、BYK P104S、BYK 110、BYK W9010、SOLSPERSE 8000、SOLSPERSE 17000、SOLSPERSE 24000中的任一种或多种，分散剂掺量占氮化铝陶瓷粉体质量的1.5％～2％；光引发剂选自Darocur 1173、TPO、Irgacure 819、Irgacure 184、Irgacure 127、Irgacure 369、Irgacure 907中的任一种或多种，光引发剂掺量占光敏树脂质量的0.1％～3％。
作为优选，步骤2中，所述稀土硝酸盐的稀土离子选自Y 3+、La 3+、Sm 3+或 Dy 3+所述非水基浸渗剂溶液；所述碱土硝酸盐的碱土金属离子选自Mg 2+或Ca 2+。
作为优选，步骤2中，所述非水基浸渗剂溶液的溶质A的浓度为0.1-1.5mol/L。
作为优选，步骤2中，所述溶剂A选自乙醇、异丙醇、丙酮和乙醚中的一种或多种。
更为优选，所述非水基浸渗剂溶液选自硝酸钇的乙醇溶液、硝酸钇的异丙醇溶液、硝酸镧的乙醇溶液、硝酸钐的乙醇溶液、硝酸钐的丙酮溶液、硝酸镝的乙醇溶液、硝酸镝的乙醚溶液、硝酸镁的乙醇溶液、硝酸钙的乙醇溶液或硝酸钙的丙酮溶液中的一种。
作为优选，步骤2中，所述溶质B的胺类有机物选自乙二胺、二乙胺、三乙胺、三乙烯二胺和一乙醇胺中的一种或多种。
作为优选，步骤2中，所述溶剂B选自乙醇、异丙醇、丙酮、乙醚、甲苯和二甲苯中的一种或多种。
更为优选，所述沉淀剂溶液选自乙二胺的乙醇溶液、乙二胺的丙酮溶液、二乙胺的异丙醇溶液、二乙胺的乙醇溶液、二乙胺的乙醚溶液、三乙胺的乙醇溶液、三乙烯二胺的甲苯溶液、三乙烯二胺的二甲苯溶液、三乙烯二胺的乙醇溶液、三乙烯二胺的丙酮溶液、一乙醇胺的乙醇溶液、一乙醇胺的丙酮溶液中的一种。
需要说明的是，本申请的氮化物陶瓷混合物也可以为其他氮化物陶瓷混合物料，其他氮化物陶瓷混合物的组分可以根据实际需要进行调整，本申请不对其他氮化物陶混合物料作一一赘述。
需要说明的是，如需要使用二元或三元复合烧结助剂，可以配制所需要的单元非水基浸渗剂溶液，进行二次或三次浸渗沉淀，将烧结助剂组元依次引入；也可配制二元或三元非水基浸渗剂溶液，进行一次浸渗沉淀，同时将二元或三元烧结助剂引入。
具体的，本申请提供了一种基于光固化3D成型技术的氮化物陶瓷的具体的制备方法，包括以下步骤：
步骤A、将氮化物陶瓷浆料依次进行成型、脱脂和预烧处理，得到预烧坯体；
步骤B、将所述预烧坯体浸入非水基浸渗剂溶液中进行浸渗处理，然后去除所述预烧坯体表面的残余非水基浸渗剂溶液后，再将其浸入沉淀剂溶液中进行原位沉淀，得到浸渗坯体；
其中，所述非水基浸渗剂溶液包括溶质A和溶剂A，所述溶质A为在非水环境下可溶于所述溶剂A的稀土硝酸盐或/和碱土硝酸盐，所述溶剂A为在非水环境下可溶解所述溶质A的有机溶剂；所述沉淀剂溶液包括溶质B和溶剂B，所述溶质B为在非水环境下可溶于所述溶剂B的胺类有机物，所述溶剂B为在非水环境下可溶解所述溶质B的有机溶剂；
步骤C、将所述浸渗坯体依次进行干燥、煅烧和烧结处理，得到氮化物陶瓷。
其中，所述氮化物陶瓷浆料的固含量大于等于40vol％。
具体的，步骤A中，所述成型技术为光固化3D成型技术。增材制造技术(也称为3D打印技术)作为一种新兴的成型制造技术，基于数字光处理(DLP)的3D打印技术，具有单层固化速度快、成型精度高、对陶瓷浆料粘度要求低、系统结构简单且易于实现等优点，在陶瓷异形部件制备领域中具有非常好的应用前景。光固化3D成型技术采用数字光处理3D打印机，采用光固化3D成型技术可以制备氮化物陶瓷异形部件，也可以制备氮化物陶瓷规则部件。光固化3D成型技术的光固化成型的激光波长为250～460nm，曝光量为4～100mJ/cm 2，打印层厚为10～50μm，单层固化时间为1～15s。
需要说明的是，本申请的成型技术也可以为其他常规成型技术，其他成型技术的操作参数可以根据实际需要进行调整，本申请不对其他成型技术作一一赘述。
更具体的，本申请提供了一种基于光固化3D成型技术的氮化铝陶瓷的具体的制备方法，包括以下步骤：
步骤一、将氮化铝陶瓷浆料依次进行成型、脱脂和预烧处理，得到预烧坯体；
步骤二、将所述预烧坯体浸入非水基浸渗剂溶液中进行浸渗处理，然后去除所述预烧坯体表面的残余非水基浸渗剂溶液后，再将其浸入沉淀剂溶液中进行原位沉淀，得到浸渗坯体；
其中，所述非水基浸渗剂溶液包括溶质A和溶剂A，所述溶质A为在非水环境下可溶于所述溶剂A的稀土硝酸盐和碱土硝酸盐，所述溶剂A为在非水环境下可溶解所述溶质A的有机溶剂；所述沉淀剂溶液包括溶质B和溶剂B，所述溶质B为在非水环境下可溶于所述溶剂B的胺类有机物，所述溶剂B为在非水环境下可溶解所述溶质B的有机溶剂；
步骤三、将所述浸渗坯体依次进行干燥、煅烧和烧结处理，得到氮化铝陶瓷。
更为优选，所述沉淀剂溶液的pH值为10～12。
作为优选，步骤二中，所述浸渗处理的时间为1-24h，所述浸渗处理的温度为25-50℃，所述原位沉淀的时间为0.2-4h。
更为优选，步骤一中，所述脱脂的步骤依次包括：真空脱脂与空气脱脂；真空脱脂是将氮化物陶瓷浆料成型的生坯置于真空炉内，以0.5～3℃/min的加热速率升温至400～600℃，其中每间隔100℃保温0.5～2h；真空脱脂完成后，将坯体置于马弗炉内，在空气气氛下进行进一步脱脂除碳，以0.5～3℃/min的加热速率升温至400～450℃，并保温2～4h，然后随炉冷却至室温，得到氮化物陶瓷坯体。
更为优选，步骤一中，所述预烧处理是将脱脂后的氮化物陶瓷坯体置于气氛炉内，在流动氮气气氛下，以5～10℃/min的加热速率升温至1400～1600℃，并保温1～2h，然后随炉冷却至室温，得到预烧坯体。
更为优选，步骤三中，所述干燥温度为50～80℃，干燥时间为2～12h。
更为优选，步骤三中，所述煅烧处理工艺为：以2～10℃/min的加热速率升温至300～450℃，并保温2～6h，然后随炉冷却。
更为优选，步骤三中，所述烧结工艺为：以5～10℃/min的加热速率升温至1700～2000℃，保温2～8h，然后随炉冷却，得到氮化铝陶瓷。
现有技术中传统的浸渗剂溶液易使得氮化物陶瓷粉体水解，从而额外引入了较多的氧杂质，不利于高导热氮化物陶瓷的制备；且通过传统球磨工艺引入氧化物烧结助剂，难以实现烧结助剂的均匀分散，从而导致制得的氮化物陶瓷微观结构不均匀、热导率和致密度降低。因此，本申请提供了一种高导热氮化物部件的制备方法。传统的浸渗剂溶液和沉淀剂溶液均为水基溶液， 采用水作为溶剂对浸渗剂和沉淀剂进行溶解，本申请提出了一种非水基浸渗沉淀体系(包括非水基浸渗剂溶液和非水基沉淀剂溶液)，可避免氮化物陶瓷粉体与水的接触和水解，避免了氧杂质的额外引入，且浸渗后的原位沉淀实现了烧结助剂的均匀分散，有利于提升氮化铝陶瓷制品的热导率，本申请的制备方法得到的氮化物陶瓷具有致密度高、微观结构均匀、热导率高、且形状结构可设计性强的优点。
本申请能解决传统的水基浸渗沉淀技术中由于氮化物陶瓷粉体的水解和氧杂质的额外引入而使其热导率降低的技术难题，且浸渗后的原位沉淀使得烧结助剂分散均匀性良好，克服了传统球磨混料工艺中烧结助剂不均匀分散导致其热导率和致密度降低的技术缺陷。
本申请提出了非水基浸渗沉淀技术，不仅适用于提升氮化铝、氮化硅陶瓷的热导率；也适用于其它易发生水解陶瓷(氮化物或碳化物陶瓷)的制备，实现烧结助剂的均匀分散继而改善氮化物、碳化物陶瓷的性能(热学、电学、磁学、力学性能等)。凡依据本申请设计思想所作的任何改变都在本申请的保护范围之内。
附图说明
为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍。
图1为本申请提供的氮化物陶瓷的制备方法的工艺流程图；
图2为本申请实施例提供的基于光固化3D打印技术的氮化物陶瓷的制备方法的工艺流程图；
具体为：
(1)异形生坯成型：将AIN粉体、光敏树脂、分散剂和光引发剂球磨混合，配制得到树脂基陶瓷浆料，利用基于光固化3D打印技术进行光固化成型，制得氮化铝陶瓷异形生坯；
(2)脱脂、预烧：对所制得的氮化铝陶瓷异形生坯进行脱脂，制得氮化铝陶瓷异形坯体；然后置于气氛炉进行预烧处理，制得氮化铝陶瓷异形预烧坯体；
(3)浸渗、原位沉淀：将制得的氮化铝陶瓷异形预烧坯体置于配制的非水基浸渗剂溶液内，浸渗处理1～24h后，取出擦净预烧坯体表面的浸渗剂溶液，然后置于所配置的沉淀剂溶液内进行原位沉淀0.2～2h，制得氮化铝陶瓷异形浸渗坯体；
(4)干燥、煅烧：将制得的氮化铝陶瓷异形浸渗坯体置于烘箱中进行干燥处理，然后将干燥后的氮化铝陶瓷异形浸渗坯体置于马弗炉内进行煅烧处理，制得氮化铝陶瓷异形煅烧坯体；
(5)烧结：将制得的氮化铝陶瓷异形煅烧坯体置于气氛炉内进行烧结致密化，制得氮化铝陶瓷异形部件。
具体实施方式
本申请提供了一种氮化物陶瓷的制备方法，用于解决传统的浸渗沉淀技术易使得氮化物陶瓷粉体发生水解和额外引入氧杂质的技术缺陷，利用浸渗后的原位沉淀实现烧结助剂的均匀分散，旨在提高氮化物陶瓷的热导率和致密度。
下面将对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
其中，本申请的实施例所用原料均为市售或自制。
实施例1
本申请实施例提供了第一种氮化物陶瓷的制备方法，具体步骤如下：
1、称取68重量份氮化铝陶瓷粉体、32重量份己二醇二丙烯酸酯、1重量份BYK 9076分散剂，球磨10h后加入0.068份Darocur 1173光引发剂，继续球磨5min，制得固含量为40vol％的氮化铝陶瓷浆料。
2、利用光固化3D打印机进行光固化3D打印成型，控制激光波长为250nm，曝光量为100mJ/cm 2，单层固化时间为1s，打印层厚为50μm；按照预设的三维结构模型进行3D打印成型，制得异形的氮化铝陶瓷生坯。
3、将氮化铝陶瓷生坯置于真空炉内进行脱脂处理，以0.5℃/min的加热速率升至400℃，其中每间隔100℃保温2h；随炉冷却至室温后，将真空脱脂处理后的生坯取出并置于马弗炉内，以3℃/min的加热速率升至450℃，并保温2h，随炉冷却至室温，制得氮化铝坯体。
4、将氮化铝坯体置于气氛炉内进行预烧处理，在流动氮气气氛下，以10℃/min的加热速率升至1600℃，并保温1h，然后，随炉冷却至室温，得预烧坯体。
5、利用42重量份的Y(NO 3)·6H 2O与58重量份的无水乙醇配制Y 3+浓度为1.5mol/L的非水基浸渗剂溶液，将预烧坯体置于非水基浸渗剂溶液内，于50℃浸渗温度下处理1h，取出并擦净预烧坯体表面的非水基浸渗剂溶液。
6、通过向乙二胺中滴加无水乙醇的方法配制pH值为12的乙二胺乙醇溶液，即制得沉淀剂溶液，然后将浸渗处理后的坯体置于该沉淀剂溶液中，原位沉淀2h后取出，即得浸渗坯体。
7、将制得的浸渗坯体置于烘箱内进行干燥处理，以80℃热处理2h，以去除浸渗坯体内残留的乙醇溶剂。
8、将干燥后的氮化铝陶瓷浸渗坯体置于马弗炉内进行煅烧处理，在空气气氛下，以2℃/min的加热速率升至450℃，保温2h后，随炉冷却，制得氮化铝陶瓷煅烧坯体。
9、将氮化铝陶瓷煅烧坯体置于气氛炉内进行烧结处理，在流动氮气气氛下，以10℃/min的加热速率升至2000℃，保温2h，然后随炉冷却即得氮化铝陶瓷部件。
本实施例的氮化铝陶瓷部件可以为异形的陶瓷部件，也可以为规则的陶瓷部件。利用阿基米德排水法测得本实施例制得的氮化铝陶瓷部件的致密度为99.8％，利用闪光法测得的室温热导率为205W·m -1·K -1，即说明本实施例的制得的氮化铝陶瓷部件具有优良的导热性能和致密性能。
实施例2
本申请实施例提供了第二种氮化物陶瓷的制备方法，具体步骤如下：
1、称取72重量份氮化铝陶瓷粉体、12重量份聚氨酯丙烯酸酯、14.6重量份丙烯酸正丁酯、1.4重量份SOLSPERSE 8000分散剂，球磨24h后加入0.8份Irgacure 184光引发剂，继续球磨10min，制得固含量为44vol％的氮化铝陶瓷浆料。
2、利用光固化3D打印机进行光固化3D打印成型，控制激光波长为460nm，曝光量为4mJ/cm 2，单层固化时间为15s，打印层厚为10μm；按照预设的三维结构模型进行3D打印成型，制得异形的氮化铝陶瓷生坯。
3、将氮化铝陶瓷生坯置于真空炉内进行脱脂处理，以3℃/min的加热速率升至600℃，其中每间隔100℃保温0.5h；随炉冷却至室温后，将真空脱脂处理后的生坯取出并置于马弗炉内，以0.5℃/min的加热速率升至400℃，并保温4h，随炉冷却至室温，制得氮化铝坯体。
4、将氮化铝坯体置于气氛炉内进行预烧处理，在流动氮气气氛下，以5℃/min的加热速率升至1400℃，并保温2h，然后，随炉冷却至室温，得预烧坯体。
5、利用5.5重量份的Dy(NO 3)·6H 2O与94.5重量份的无水乙醇配制Dy 3+浓度为0.1mol/L的非水基浸渗剂溶液，将预烧坯体置于非水基浸渗剂溶液内，于25℃浸渗温度下处理24h，取出并擦净预烧坯体表面的非水基浸渗剂溶液。
6、通过向二乙胺中滴加无水乙醇的方法配制pH值为10的乙二胺乙醇溶液，即制得沉淀剂溶液，然后将浸渗处理后的坯体置于该沉淀剂溶液中，原位沉淀0.2h后取出，即得浸渗坯体。
7、将制得的浸渗坯体置于烘箱内进行干燥处理，以50℃热处理12h，以去除浸渗坯体内残留的乙醇溶剂。
8、将干燥后的氮化铝陶瓷浸渗坯体置于马弗炉内进行煅烧处理，在空气气氛下，以10℃/min的加热速率升至300℃，保温6h后，随炉冷却，制得氮化铝陶瓷煅烧坯体。
9、将氮化铝陶瓷煅烧坯体置于气氛炉内进行烧结处理，在流动氮气气氛 下，以5℃/min的加热速率升至600℃，保温0.5h后，以5℃/min的加热速率升至1700℃，保温8h，然后随炉冷却即得氮化铝陶瓷部件。
本实施例的氮化铝陶瓷部件可以为异形的陶瓷部件，也可以为规则的陶瓷部件。利用阿基米德排水法测得本实施例制得的氮化铝陶瓷部件的致密度为98.6％，利用闪光法测得的室温热导率为168W·m -1·K -1，即说明本实施例制得的氮化铝陶瓷部件具有优良的导热性能和致密性能。
实施例3
本申请实施例提供了第二种氮化物陶瓷的制备方法，具体步骤如下：
1、称取70重量份氮化铝陶瓷粉体、14重量份季戊四醇四丙烯酸酯、14.9重量份甲基丙烯酸羟乙酯、1.1重量份BYK W9010分散剂，球磨12h后加入0.3份TPO光引发剂，继续球磨8min，制得固含量为42vol％的氮化铝陶瓷浆料。
2、利用光固化3D打印机进行光固化3D打印成型，控制激光波长为460nm，曝光量为15mJ/cm 2，单层固化时间为5s，打印层厚为20μm；按照预设的三维结构模型进行3D打印成型，制得异形的氮化铝陶瓷生坯。
3、将氮化铝陶瓷生坯置于真空炉内进行脱脂处理，以2℃/min的加热速率升至500℃，其中每间隔100℃保温1h；随炉冷却至室温后，将真空脱脂处理后的生坯取出并置于马弗炉内，以1℃/min的加热速率升至420℃，并保温3h，随炉冷却至室温，制得氮化铝坯体。
4、将氮化铝坯体置于气氛炉内进行预烧处理，在流动氮气气氛下，以8℃/min的加热速率升至1500℃，并保温1.5h，然后，随炉冷却至室温，得预烧坯体。
5、利用36重量份的Sm(NO 3)·6H 2O与64重量份的无水乙醇配制Sm 3+浓度为1mol/L的非水基浸渗剂溶液，将预烧坯体置于非水基浸渗剂溶液内，于40℃浸渗温度下处理12h，取出并擦净预烧坯体表面的非水基浸渗剂溶液。
6、通过向二乙胺中滴加异丙醇的方法配制pH值为11的乙二胺异丙醇溶液，即制得沉淀剂溶液，然后将浸渗处理后的坯体置于该沉淀剂溶液中，原位沉淀1h后取出，即得浸渗坯体。
7、将制得的浸渗坯体置于烘箱内进行干燥处理，以60℃热处理10h，以去除浸渗坯体内残留的乙醇和异丙醇溶剂。
8、将干燥后的氮化铝陶瓷浸渗坯体置于马弗炉内进行煅烧处理，在空气气氛下，以5℃/min的加热速率升至400℃，保温4h后，随炉冷却，制得氮化铝陶瓷煅烧坯体。
9、将氮化铝陶瓷煅烧坯体置于气氛炉内进行烧结处理，在流动氮气气氛下，以2℃/min的加热速率升至500℃，保温1h后，以8℃/min的加热速率升至1800℃，保温4h，然后随炉冷却即得氮化铝陶瓷部件。
本实施例的氮化铝陶瓷部件可以为异形的陶瓷部件，也可以为规则的陶瓷部件。利用阿基米德排水法测得本实施例制得的氮化铝陶瓷部件的致密度99.2％，利用闪光法测得的室温热导率为182W·m -1·K -1，即说明本实施例制得的氮化铝陶瓷部件具有优良的导热性能和致密性能。
对比例1
本申请提供了一种传统的水基浸渗沉淀技术制备氮化物陶瓷的方法，具体步骤如下：
1、称取70重量份氮化铝陶瓷粉体、14重量份季戊四醇四丙烯酸酯、14.9重量份甲基丙烯酸羟乙酯、1.1重量份BYK W9010分散剂，球磨12h后加入0.3份TPO光引发剂，继续球磨8min制得固含量为42vol％的氮化铝陶瓷浆料。
2、利用光固化3D打印机进行固化成型，控制激光波长为460nm，曝光量为15mJ/cm 2，单层固化时间为5s，打印层厚为20μm；按照预设的三维结构模型进行3D打印成型，制得异形的氮化铝陶瓷生坯。
3、将氮化铝陶瓷生坯置于真空炉内进行脱脂处理，以2℃/min的加热速率升至500℃，其中每间隔100℃保温1h；随炉冷却至室温后，将真空脱脂处理后的生坯取出并置于马弗炉内，以1℃/min的加热速率升至420℃，并保温3h，随炉冷却至室温即制得氮化铝坯体。
4、将氮化铝坯体置于气氛炉内进行预烧处理，在流动氮气气氛下，以8℃/min的加热速率升至1500℃，并保温1.5h，然后随炉冷却至室温即可 得氮化铝陶瓷预烧坯体。
5、利用36重量份的Sm(NO 3)·6H 2O与80重量份的去离子水配制Sm 3+浓度为1mol/L的浸渗剂溶液，将氮化铝预烧坯体置于浸渗剂溶液内，于40℃浸渗温度下处理12h，取出并擦净预烧坯体表面的浸渗剂溶液。
6、配制pH值为11的氨水溶液，然后将浸渗处理后的坯体置于氨水溶液中，原位沉淀1h后取出，即得氮化铝浸渗坯体。
7、将制得的氮化铝浸渗坯体置于烘箱内，以60℃热处理10h，以去除浸渗坯体内残留的水分。
8、将干燥后的氮化铝陶瓷浸渗坯体置于马弗炉内，在空气气氛下，以5℃/min的加热速率升至400℃，保温4h后，随炉冷却，制得氮化铝陶瓷煅烧坯体。
9、将氮化铝陶瓷煅烧坯体置于气氛炉内，在流动氮气气氛下，以2℃/min的加热速率升至500℃，保温1h后，以8℃/min的加热速率升至1800℃，保温4h，然后随炉冷却即得氮化铝陶瓷部件。
本对比例与实施例1的区别在于，本对比例采用Sm(NO 3)·6H 2O的水溶液为浸渗剂溶液，氨水溶液为沉淀剂溶液。利用阿基米德排水法测得本对比例制得的氮化铝陶瓷的致密度为98.8％，利用闪光法测得的室温热导率仅为68W·m -1·K -1，说明常规方法采用含水的浸渗剂溶液和沉淀剂溶液，将稀土硝酸盐沉淀在预烧坯体的孔隙中，由于浸渗剂溶液和沉淀剂溶液含有水分，使得预烧坯体在浸渗沉淀以及后期的干燥过程中易发生水解，从而在氮化铝陶瓷内引入额外的氧，导致制得的氮化铝陶瓷的热导率较低。
以上所述仅是本申请的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本申请原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本申请的保护范围。

Claims (10)

  1. 一种氮化物陶瓷的制备方法，其特征在于，包括以下步骤：
    步骤1、将氮化物陶瓷混合物依次进行成型和预烧处理，得到预烧坯体；
    步骤2、将所述预烧坯体浸入非水基浸渗剂溶液中进行浸渗处理，然后去除所述预烧坯体表面的残余非水基浸渗剂溶液后，再将其浸入沉淀剂溶液中进行原位沉淀，得到浸渗坯体；
    其中，所述非水基浸渗剂溶液包括溶质A和溶剂A，所述溶质A为在非水环境下可溶于所述溶剂A的稀土硝酸盐或/和碱土硝酸盐，所述溶剂A为在非水环境下可溶解所述溶质A的有机溶剂；所述沉淀剂溶液包括溶质B和溶剂B，所述溶质B为在非水环境下可溶于所述溶剂B的胺类有机物，所述溶剂B为在非水环境下可溶解所述溶质B的有机溶剂；
    步骤3、将所述浸渗坯体依次进行干燥、煅烧和烧结处理，得到氮化物陶瓷。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤1中，所述氮化物陶瓷混合物的氮化物选自氮化铝、氮化硅、氮化硼、碳氮化钛或过渡金属氮化物中的一种。
  3. 根据权利要求1所述的制备方法，其特征在于，步骤1中，所述预烧坯体的孔隙率为20-50％。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤1中，所述成型技术为光固化3D成型技术。
  5. 根据权利要求4所述的制备方法，其特征在于，步骤2中，所述非水基浸渗剂溶液的溶质A的浓度为0.1-1.5mol/L。
  6. 根据权利要求1所述的制备方法，其特征在于，步骤2中，所述稀土硝酸盐的稀土离子选自Y 3+、La 3+、Sm 3+或Dy 3+，所述碱土硝酸盐的碱土金属离子选自Mg 2+或Ca 2+。
  7. 根据权利要求1所述的制备方法，其特征在于，步骤2中，所述溶剂A选自乙醇、异丙醇、丙酮和乙醚中的一种或多种。
  8. 根据权利要求1所述的制备方法，其特征在于，步骤2中，所述溶质B的胺类有机物选自乙二胺、二乙胺、三乙胺、三乙烯二胺和一乙醇胺中的一种或多种。
  9. 根据权利要求1所述的制备方法，其特征在于，步骤2中，所述溶剂B选自乙醇、异丙醇、丙酮、乙醚、甲苯和二甲苯中的一种或多种。
  10. 根据权利要求1所述的制备方法，其特征在于，步骤2中，所述浸渗处理的时间为1-24h，所述浸渗处理的温度为25-50℃，所述原位沉淀的时间为0.2-4h。
PCT/CN2019/111952 2019-05-29 2019-10-18 一种氮化物陶瓷的制备方法 Ceased WO2020237980A1 (zh)

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CN110028324B (zh) * 2019-05-29 2021-01-26 广东工业大学 一种氮化物陶瓷的制备方法
CN110395994A (zh) * 2019-08-30 2019-11-01 广东工业大学 一种覆膜氮化物陶瓷复合粉体及其制备方法、氮化物陶瓷部件及其制备方法
CN110451936B (zh) * 2019-09-04 2022-06-24 广东工业大学 一种复相陶瓷及其制备方法和应用
CN111732434A (zh) * 2020-07-07 2020-10-02 韶关学院 一种利用原位生成的氧化物作为烧结助剂的陶瓷制备方法
CN112430119A (zh) * 2020-11-16 2021-03-02 广东省科学院材料与加工研究所 基于光固化成型技术制备高孔隙率h-BN基陶瓷材料的方法
CN113200749B (zh) * 2021-04-21 2022-05-10 中材高新氮化物陶瓷有限公司 一种高压绝缘材料及其制备方法和应用
CN116986910B (zh) * 2023-08-11 2025-04-15 广东工业大学 一种粘接剂喷射成型技术制备氮化铝陶瓷的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003002752A (ja) * 2001-06-25 2003-01-08 Isuzu Motors Ltd セラミックスの開発方法
CN102674819A (zh) * 2012-05-16 2012-09-19 台州学院 一种高韧性氧化铝陶瓷及其制备方法与应用
CN106914620A (zh) * 2017-01-19 2017-07-04 昆明理工大学 一种陶瓷/金属复合材料耐磨磨球的制备方法
CN110028324A (zh) * 2019-05-29 2019-07-19 广东工业大学 一种氮化物陶瓷的制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106699137A (zh) * 2017-01-20 2017-05-24 广东工业大学 一种基于光固化成型的3d打印制备zta复相陶瓷的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003002752A (ja) * 2001-06-25 2003-01-08 Isuzu Motors Ltd セラミックスの開発方法
CN102674819A (zh) * 2012-05-16 2012-09-19 台州学院 一种高韧性氧化铝陶瓷及其制备方法与应用
CN106914620A (zh) * 2017-01-19 2017-07-04 昆明理工大学 一种陶瓷/金属复合材料耐磨磨球的制备方法
CN110028324A (zh) * 2019-05-29 2019-07-19 广东工业大学 一种氮化物陶瓷的制备方法

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