CN107698263A - A kind of preparation method of ceramic material - Google Patents

A kind of preparation method of ceramic material Download PDF

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CN107698263A
CN107698263A CN201710614861.2A CN201710614861A CN107698263A CN 107698263 A CN107698263 A CN 107698263A CN 201710614861 A CN201710614861 A CN 201710614861A CN 107698263 A CN107698263 A CN 107698263A
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ceramic
slurry
ceramic slurry
freezing
preparation
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余娟丽
张天翔
赵英民
裴雨辰
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Aerospace Research Institute of Materials and Processing Technology
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Aerospace Research Institute of Materials and Processing Technology
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B35/16Shaped 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 silicates other than clay
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped 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
    • C04B35/58Shaped 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
    • C04B35/584Shaped 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 silicon nitride
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/624Sol-gel processing
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    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing 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
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    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215Barium oxides or oxide-forming salts thereof
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    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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  • Organic Chemistry (AREA)
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Abstract

The present invention proposes a kind of preparation method of ceramic material, with microcosmic layer structure, it is rod shaped ceramic crystal layer between layer and layer micro interface, described ceramic material is formed by being sintered after the chilled shaping of ceramic slurry, drying, described ceramic slurry adds ceramic powder and small molecule multi-hydroxy alcohol type organic using Ludox as liquid phase.The present invention is using successively freezing and the growth morphology of ice crystal in alcohol type organic control freezing solidification process, because water crystallization forms zigzag micro ice crystal structure between the frozen coating and frozen coating micro interface that make to be formed in successively refrigerating process in microstructure, base substrate interlayer is promoted to combine closely, it is ensured that ceramic layered good agglutinating property.

Description

A kind of preparation method of ceramic material
Technical field
The present invention relates to a kind of preparation method of ceramic material, belong to field of ceramic preparation technology.
Background technology
Ceramic material has high temperature resistant, wear-resistant, corrosion resistant feature, and intensity is high, the coefficient of expansion is low, thermal conductivity It is good, more potential and advantage is used at high temperature.But its shortcoming is also it will be apparent that the fragility of ceramic material is larger, tough Property it is relatively low, further development of these shortcomings for ceramic material and the large-scale application in engineering are a very big bottles Neck.The fragility of ceramic material intuitively shows as absence of aura, the explosion type fracture under applied load, indirectly shows as resisting Mechanical impact property's difference and thermal shocking are poor.Therefore, the toughness of ceramic material is increased, improving the use reliability of ceramic material is The wide variety of key of structural ceramics.
At present, mutually mainly there is following four method to improve the toughness of ceramic material and intensity by adding toughness reinforcing:(1) Grain dis-persion toughening;(2) transformation toughening;(3) long fibre toughness reinforcing;(4) it is crystal whisker toughened.Research shows that these methods have certain increasing Tough effect, but still can not solve the fatal defects i.e. fracture suddenly of ceramic material.Importantly, the preparation technology of these methods It is stricter with the requirement to experiment and use condition, therefore certain difficulty be present in terms of the engineer applied of reality.
Layered composite ceramic material makes ceramic material overcome non-layer compared to other toughness reinforcing modes, its unique structure The defects of shape brittleness of ceramics is big, while the comprehensive mechanical performance of composition phase material is kept, increase substantially the fracture of material Toughness, the higher field of safety coefficient is can apply to, the application field of ceramic material is expanded, layered composite ceramic is not The shortcomings that fracture toughness being present in conventional ceramic is relatively low is only effectively improved, moreover, ceramic layered in preparation technology Advantage is also obvious.Its production cycle is shorter, easy to spread and simple to operate.So it is designed with larger The free degree, design and interlayer design in layer can be considered, by material selection and the aspect of structure design two come to material Performance optimizes.
At present, the molding mode of laminated ceramic composite includes:(1) blank is laid compressing;(2) preformed layer stacks Shaping;(3) again by laminated into type after slurry of the base layer by coating sandwich material;(4) phase between the slurry between raw material Mutually deposition aftershaping.Wherein preformed layer stacks shaping and mainly includes two kinds of rolling formation and flow casting molding.Existing stratiform pottery Macroscopical layer structure is presented in the ceramic material that porcelain production method makes, and improvement of this macroscopical layer structure to material property has Certain limitation, while easily there is sintering delamination, and cause laminated structure ceramics to prepare failure.
The content of the invention
It is an object of the invention to overcome prior art insufficient, there is provided one kind has global formation and controllability is good, work Skill is simple, Coating combination is good, the preparation method of the delamination free laminate ceramic of sintering.
The technical solution of the present invention:A kind of preparation method of ceramic material, is realized by following steps:
The first step, ceramic slurry is prepared,
Described ceramic slurry adds ceramic powder and small molecule multi-hydroxy alcohol type organic using Ludox as liquid phase;
Described small molecule multi-hydroxy alcohol type organic addition be ceramic slurry in liquid phase water quality 0.5~ 5%, molecular weight is less than 10000;
Ceramic slurry carries out ball milling mixing, obtains well mixed ceramic slurry.
The present invention is by adding small molecule multi-hydroxy alcohol type organic to the ice crystal during ceramic slurry freezing gel Crystal size and form optimize control, and it is in microcrystalline form to make ice crystal, it is possible to reduce moisture removes the hole left to final pottery The influence of ceramic material mechanical property and reliability.
The present invention is not particularly limited to the species of small molecule multi-hydroxy alcohol type organic, such as common glycerine, second Glycol etc..The addition of small molecule multi-hydroxy alcohol type organic can not be too many, otherwise can be to the consistency of final ceramic material Impact;Otherwise addition can not can not play very little and suppress freezing and expansion effect in follow-up freezing gel technique, with Freezing gel technique does not have the synergy of control ice-crystal growth.The present invention gives small molecule multi-hydroxy alcohol type organic Preferred addition, make its neither influence consistency and can play synergy;Under the same terms, small molecule multi-hydroxy alcohols When the addition of organic matter changes within the above range, the combination property of final ceramic is slightly influenceed, during beginning with Small molecule multi-hydroxy alcohol type organic addition increase, combination property slightly improve, addition reach 1% or so (1 ± 0.2%) when, combination property is optimal, and then, as addition increases, combination property is declined slightly.
The ceramic powder of the present invention can be conventional use of ceramic powder, such as silicon nitride powder, carborundum powder, aluminum oxide Powder, silicon dioxide powder etc..It is preferred that following ceramic powder, may eventually form Si in sintering3N4/ BAS complex phase ceramics.
Silicon nitride powder, barium monoxide powder and alumina powder, wherein barium monoxide, the addition of aluminum oxide are with alkaline silica sol two On the basis of the quality of silica, according to stoichiometric proportion BaO-A12O3-2SiO2Addition, silicon nitride powder quality are accounted in mixed slurry (silicon nitride powder and BAS mass ratio are 55 for the 55~90% of solid phase gross mass:45~90:10), solid phase gross mass refers to silicon nitride The silica containing quality sum of institute in powder, barium monoxide powder, alumina powder and Ludox;BAS mass refers to barium monoxide powder, oxidation The silica containing quality sum of institute in aluminium powder and Ludox.
BAS compositions can not very little, on the one hand because BAS final content is by Ludox (contained titanium dioxide in mixed slurry Silicon) determine, Ludox very little, is unfavorable for follow-up ceramic slurry freezing solidification, and BAS content can not be less than in mixed slurry The 10% of solid phase gross mass;On the other hand, silicon nitride powder mass content can not be too low in mixed slurry, otherwise in blank sintering mistake Cheng Zhong, a large amount of liquid phases can be formed due to the high sintering fusing of BAS contents, cause base substrate scorification, therefore, silicon nitride powder quality can not be lacked The 55% of solid phase gross mass in slurry.When silicon nitride powder quality accounts for 55~90% of solid phase gross mass in mixed slurry, ability Give full play to BAS and Si3N4Between mutual promoting action when sintering, and meet low temperature gel solidification, form Si3N4/ BAS is multiple Phase ceramics.
Ludox can be generally 15~30% by commercially available acquisition, solid content in the present invention.Beta-silicon nitride powder, aluminum oxide The requirement such as the particle diameter of the ceramic powders such as powder, barium monoxide powder and purity is known in the art technology, and those skilled in the art can be with Selected according to specific requirement.
A small amount of dispersant can be added in described ceramic slurry according to needs of production, dispersant makes powder more preferable Be dispersed in colloidal sol, ammonium polyacrylate or TMAH can be used, also can use to end article without unfavorable shadow Other loud species dispersants, addition are 0.5~3% of solid powder gross mass in ceramic slurry.
Second step, ceramic slurry freezing gel shaping, obtains ceramic body;
Under the auxiliary of moulds of industrial equipment, the moulds of industrial equipment for being filled with ceramic slurry are successively freezed since one end, Refrigerating process employing mode one or mode two,
Mode one, the moulds of industrial equipment for being filled with ceramic slurry are placed in refrigerated container, are slowly noted from refrigerated container bottom Enter≤- 80 DEG C of refrigerant, ceramic slurry is successively freezed since bottom, every layer of freezing thickness≤1 μm is that is, each Height≤1 μm of the refrigerant of secondary injection, freezing soaking time are no less than 0.5 minute;
Mode two, according to freezing direction, the ceramic slurry being filled in moulds of industrial equipment persistently slowly enters≤- 80 DEG C In refrigerant, admission velocity is no more than 1 μm/3min.
Using successively slowly control freezing, in conjunction with small molecule multi-hydroxy alcohol type organic to ceramic slurry freezing gel During ice crystal crystal habit be controlled, microcosmic layer structure can be formed in microstructure, while freeze successively During between the frozen coating and frozen coating micro interface that are formed because water crystallization process forms zigzag micro ice crystal structure, rear In continuous sintering, the ceramic bar-shaped crystalline substance of formation can grow in the micropore that micro ice crystal structure leaves, and be formed in interlayer micro interface The interlayer structure that the bar-shaped crystalline phase of ceramics mutually interweaves, so as to promote base substrate interlayer is microcosmic to combine closely and burning that stratified material is good Tie performance.In this step, under the auxiliary of moulds of industrial equipment, the mould of ceramic slurry will be filled with cryogenic temperature and freezing rate Under conditions of control, into frozen matter, successively freezing control is realized, realizes the curing molding of ceramic slurry, being formed has one Determine the ceramic body of intensity.
This step make use of Ludox at low temperature can be with the characteristic of gel solidification, the ceramic slurry to needing freeze forming From bottom slowly progressively freeze, and carry out the control of cryogenic temperature and freezing rate, make ceramic slurry freeze forming process In gradually form thin layer (≤1 μm) integrated molding microcosmic layer structure;The alcohol type organic control of addition is utilized simultaneously The growth morphology of ice crystal in solidification process is freezed, is made between layer and layer micro interface because water crystallization forms zigzag micro ice crystal knot Structure, base substrate interlayer is promoted to combine closely, it is ensured that ceramic layered good agglutinating property, high-performance laminated structure ceramics material to be finally made Material.
3rd step, ceramic blank drying sintering, obtains ceramic material.
This step is dried and is known in the art technology, and ceramic body can be dried at ambient pressure, and drying temperature does not have strict Limitation, can be dried at normal temperatures, can also the optional temperature below 200 DEG C as needed, drying time is 2~48 hours, Selected according to the degree of drying of drying temperature and ceramic body, ensure that base substrate is thoroughly dried.
Base substrate is sintered to techniques well known, can use pressureless sintering, gas pressure sintering or hot pressed sintering, sintering Atmosphere is nitrogen.
The beneficial effect of the present invention compared with prior art:
(1) present invention is using successively freezing and the growth morphology of ice crystal in alcohol type organic control freezing solidification process, system Standby high performance ceramic material, make in microstructure between the frozen coating and frozen coating micro interface that are formed in successively refrigerating process Because water crystallization forms zigzag micro ice crystal structure, base substrate interlayer is promoted to combine closely, it is ensured that ceramic layered good agglutinating property;
(2) present invention energy global formation, technique is simple, controllability is good, Coating combination is good, sintering is without delamination.
Brief description of the drawings
Fig. 1 is the microcosmic stratiform structural representation of the present invention;
Fig. 2 is preparation flow figure of the present invention;
Fig. 3 a, b are the ceramic material microstructure that the embodiment of the present invention 1 is prepared.
Embodiment
With reference to instantiation and accompanying drawing, the present invention is described in detail.
The present invention is bar-shaped crystal structure layer between layer and layer micro interface as shown in figure 1, have microcosmic layer structure, Ceramic material is sintered after successively freeze forming, drying by ceramic slurry and formed, and ceramic slurry adds using alkaline silica sol as liquid phase Add ceramic powder and small molecule multi-hydroxy alcohol type organic, control every a layer thickness≤1 μm successively freezed.
Embodiment 1
Prepare Si3N4/ BAS diphase ceramic materials
Preparation process by following steps as shown in Fig. 2 realized:
1st, prepared by ceramic slurry
Slurry is formed by Ludox, silicon nitride powder, barium monoxide powder and alumina powder, and adds 1% tetramethyl hydroxide Ammonium adds 1% (on the basis of the quality of liquid phase water in ceramic slurry) glycerine, wherein barium monoxide, aluminum oxide as dispersant Addition on the basis of the quality of silica in Ludox, according to BaO-A12O3-2SiO2Stoichiometric proportion adds, nitridation Silica flour and BAS mass ratio are 70:30;Ball mill mixing 5h in high speed ball mill.
2nd, successively freeze
Mould is injected after slurry degassing, under the auxiliary of moulds of industrial equipment, controls cryogenic temperature and freezing rate to lift Mode is progressively slowly pushed into -80 DEG C of refrigerated container according to freezing direction, and fltting speed is 1 μm/3min, and realization successively freezes Control, the integral solidifying of printout is realized, form the ceramic body with some strength, the demoulding, obtain base substrate.
3rd, drying and sintering
Base substrate is dried, dried sample (normal pressure) in nitrogen atmosphere is warming up to 5 DEG C/min speed 1780 DEG C are sintered, and are incubated 3h, finally give microcosmic stratiform Si3N4/ BAS diphase ceramic materials.Sintered body bending strength and disconnected It is respectively 430MPa and 350J/m to split work(2
Microstructure such as Fig. 3 a, b can be seen that the material is comparatively dense, and Coating combination is good, have more in material Obvious laminate structure, the bar-shaped crystalline substance of ceramics grow between adjacent layer and layer micro interface, and it is bar-shaped to form ceramics in microcosmic interlayer Crystal structure layer, so as to promote the microcosmic interlayer of base substrate to combine closely.
Embodiment 2,3
Prepare Si3N4/ BAS complex phase ceramics, it is total to account for solid phase in mixed slurry respectively for silicon nitride powder quality during ceramic slurry matches Quality is 55% and 90%, and ceramic slurry adds 1% (on the basis of the quality of liquid phase water in ceramic slurry) ethylene glycol, and slurry takes off Mould is injected after gas, under the auxiliary of moulds of industrial equipment, is put into refrigerated container, refrigerant injects from refrigerated container bottom, often Secondary injection rate ensures that ceramic slurry freezing thickness is 1 μm, freezes 1min, remaining step such as embodiment 1.Obtained Si3N4/ BAS is multiple Phase ceramics are similar with Fig. 3 a, b in microstructure, and sintered body bending strength and fracture achievement are similar to Example 1.
Embodiment 4,5
Prepare Si3N4/ BAS complex phase ceramics, 0.5% and 5% is added respectively (using the quality of liquid phase water in ceramic slurry as base It is accurate) glycerine, remaining step such as embodiment 1.Obtained Si3N4/ BAS complex phase ceramics are similar with Fig. 3 a, b in microstructure, burn Knot body bending strength and work to break are slightly below embodiment 1.
Unspecified part of the present invention is known to the skilled person technology.

Claims (7)

1. a kind of preparation method of ceramic material, it is characterised in that realized by following steps:
The first step, ceramic slurry is prepared,
Described ceramic slurry adds ceramic powder and small molecule multi-hydroxy alcohol type organic using Ludox as liquid phase;
Second step, ceramic slurry freezing gel shaping, obtains ceramic body,
Under the auxiliary of moulds of industrial equipment, the moulds of industrial equipment for being filled with ceramic slurry are successively freezed since one end, successively Every a layer thickness≤1 μm of freezing;
3rd step, ceramic blank drying sintering, obtains ceramic material.
A kind of 2. preparation method of ceramic material according to claim 1, it is characterised in that:It is successively cold in the second step Freeze employing mode one or mode two,
Mode one, the moulds of industrial equipment for being filled with ceramic slurry are placed in refrigerated container, be slowly injected into from refrigerated container bottom≤- 80 DEG C of refrigerant, ceramic slurry is successively freezed since bottom, every layer of freezing thickness≤1 μm, i.e., noted each time Height≤1 μm of the refrigerant entered, freezing soaking time are no less than 0.5 minute;
Mode two, according to freezing direction, the ceramic slurry being filled in moulds of industrial equipment persistently slowly enters≤- 80 DEG C of freezing In medium, admission velocity is no more than 1 μm/3min.
A kind of 3. preparation method of ceramic material according to claim 1, it is characterised in that:The first step small molecular Multi-hydroxy alcohol type organic addition is 0.5~5% of the quality of liquid phase water in ceramic slurry.
A kind of 4. preparation method of ceramic material according to claim 1, it is characterised in that:Ceramic powder in the first step Body is silicon nitride powder, barium monoxide powder and alumina powder, and wherein the addition of barium monoxide, aluminum oxide is with titanium dioxide in alkaline silica sol On the basis of the quality of silicon, according to stoichiometric proportion BaO-A12O3-2SiO2Addition, silicon nitride powder quality account for solid in mixed slurry The 55~90% of gross mass.
A kind of 5. preparation method of ceramic material according to claim 1, it is characterised in that:Ceramic slurry in the first step A small amount of dispersant is added in material, addition is 0.5~3% of solid gross mass in ceramic slurry.
A kind of 6. preparation method of ceramic material according to claim 1, it is characterised in that:The first step small molecular Multi-hydroxy alcohol type organic addition is 1 ± 0.2% of the quality of liquid phase water in ceramic slurry.
A kind of 7. preparation method of ceramic material according to claim 1, it is characterised in that:The first step small molecular Multi-hydroxy alcohol type organic molecular weight is less than 10000.
CN201710614861.2A 2017-07-26 2017-07-26 A kind of preparation method of ceramic material Pending CN107698263A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4919852A (en) * 1988-06-30 1990-04-24 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Lightweight ceramic insulation and method
CN103896561A (en) * 2014-03-06 2014-07-02 大连理工大学 Preparation method of silicon dioxide thermal insulation material with regular layered structure
CN104496484A (en) * 2014-12-02 2015-04-08 航天特种材料及工艺技术研究所 Method for preparing Si3N4/BAS composite ceramic material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4919852A (en) * 1988-06-30 1990-04-24 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Lightweight ceramic insulation and method
CN103896561A (en) * 2014-03-06 2014-07-02 大连理工大学 Preparation method of silicon dioxide thermal insulation material with regular layered structure
CN104496484A (en) * 2014-12-02 2015-04-08 航天特种材料及工艺技术研究所 Method for preparing Si3N4/BAS composite ceramic material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
孙孟勇: ""冷冻干燥法制备多孔Si3N4陶瓷及性能研究"", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 *

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