CN112645713B - High-strength and high-toughness ceramic composite material and preparation method thereof - Google Patents

High-strength and high-toughness ceramic composite material and preparation method thereof Download PDF

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CN112645713B
CN112645713B CN202011545950.4A CN202011545950A CN112645713B CN 112645713 B CN112645713 B CN 112645713B CN 202011545950 A CN202011545950 A CN 202011545950A CN 112645713 B CN112645713 B CN 112645713B
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powder
composite material
ceramic composite
ceramic
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CN112645713A (en
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戚明杰
邬国平
熊礼俊
程向前
谢方民
洪于喆
郭岱东
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Ningbo Vulcan Technology Co ltd
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Abstract

The application relates to the field of ceramic materials, and particularly discloses a high-toughness ceramic composite material and a preparation method thereof, wherein the preparation method of the ceramic composite material comprises the following steps: weighing ceramic-based powder, elemental Si powder, adhesive, dispersant and deionized water in proportion, mixing and pulping, molding and blank-making to obtain a biscuit, and performing high-temperature nitridation treatment on the biscuit to generate stereo cross-linked beta-Si powder in situ by the elemental Si powder3N4Network of whiskers to obtain porous beta-Si3N4A ceramic composite body; immersing the composite blank body into a coupling agent solution for modification treatment, and filling a liquid organic carbon source into pores in the modified composite blank body by adopting an immersion process after drying; carrying out high-temperature vacuum carbonization on the composite green body; and (3) performing high-temperature vacuum infiltration on the carbonized green body to obtain Si, reacting the melt Si with residual carbon to generate SiC, and filling the residual pores with Si. The preparation method of the ceramic composite material can be used for preparing the compact high-strength and high-toughness ceramic composite material.

Description

High-strength and high-toughness ceramic composite material and preparation method thereof
Technical Field
The application relates to the field of ceramic materials, in particular to a high-toughness ceramic composite material and a preparation method thereof.
Background
The ceramic material has the advantages of high hardness, high strength, high temperature resistance, corrosion resistance and chemical stability, and is widely applied to the fields of aerospace, communication transmission, machining, biomedicine, fine chemical engineering and the like. However, poor toughness is a defect of ceramic material commonality, toughening modification is a difficult problem in the field of engineering ceramics and is also an important research direction, and main toughening means comprise three types of crystal whisker or fiber toughening, microcrack toughening and phase change toughening.
The ceramic whisker is a ceramic small single crystal with a certain length-diameter ratio and few defects, so the ceramic whisker has high strength and is an ideal toughening reinforcement of the ceramic matrix composite. Wherein, beta-Si3N4The whisker has the characteristics of high strength, high toughness, high modulus, high temperature resistance and the like, the diameter of the common whisker is 0.1-10 mu m, the length-diameter ratio can reach 10-1000, and the whisker is a reinforcing and toughening material with excellent performance, and is usually added into ceramic raw material powder, and the ceramic raw material powder is mixed, pressed and sintered to form a ceramic composite material.
With respect to the related art among the above, the inventors consider that the following drawbacks exist: beta-Si3N4The crystal whisker is in a needle shape or a fiber shape, is used as a ceramic additive, is difficult to disperse in the using process, can form fluffy flocculent lumps with large and small sizes, leads to difficult sintering and densification of ceramic materials, and has limited toughening effect on ceramic composite materials.
Disclosure of Invention
To improve beta-Si3N4The application provides a high-toughness ceramic composite material and a preparation method thereof.
In a first aspect, the application provides a preparation method of a high-toughness ceramic composite material, which adopts the following technical scheme:
a preparation method of a high-strength and high-toughness ceramic composite material comprises the following steps:
(1) mixing materials: weighing raw materials according to a ratio, adding deionized water, and mixing to prepare slurry, wherein the raw materials comprise the following components in percentage by weight: the matrix consists of ceramic matrix powder and simple substance Si powder, wherein the ceramic matrix powder accounts for 50-90wt%, and the simple substance Si powder accounts for 10-50 wt%; the addition amount of the adhesive is 0.5-5wt% of the total amount of the matrix, and the addition amount of the dispersant is 0.1-1wt% of the total amount of the matrix; the addition amount of the added deionized water is 50-200 wt% of the total amount of the matrix, the adhesive and the dispersing agent;
(2) molding: forming and blank-making by adopting the slurry obtained in the step (1) to obtain a biscuit;
(3) in-situ nitridation: nitriding the biscuit obtained in the step (2) to obtain porous beta-Si3N4A ceramic composite green body;
(4) modification treatment: the porous beta-Si obtained in the step (3) is treated3N4Soaking the ceramic composite blank body into a coupling agent solution for modification treatment, and drying to obtain a modified porous composite blank body;
(5) carburizing: immersing the modified porous composite blank obtained in the step (4) into a liquid organic carbon source for infiltration to obtain a carburized blank;
(6) high-temperature carbonization: carbonizing the carburized blank body obtained in the step (5) at a high temperature to obtain a porous carbonized blank body;
(7) high-temperature infiltration: and (4) infiltrating Si into the porous carbonized blank obtained in the step (6) at a high temperature, and cooling after complete reaction to obtain the ceramic composite material.
By adopting the technical scheme, the porous biscuit which is pressed and formed is subjected to nitridation treatment, elemental Si in the biscuit reacts with nitrogen at high temperature, and three-dimensional cross-linked beta-Si with needle-shaped, dendritic, feather-shaped and other forms is generated in situ3N4A crystal whisker network can avoid directly mixing beta-Si into the raw material powder3N4Whisker of beta-Si3N4The dispersion of the whiskers is uneven, and the adverse effect is brought. At the same time, porous beta-Si after nitridation3N4The ceramic composite body is carbonized after carburization to form residual carbon, after high-temperature infiltration of Si, the melt Si reacts with the residual carbon to generate SiC, and the residual pores are filled with Si. Obtaining the compact high-strength and high-toughness ceramic composite material. Before carburization, coupling treatment is adopted, so that the wettability of the organic carbon source and the porous inner wall of the blank body is improved, the infiltration of the carbon source is promoted, and measures such as vacuumizing and pressurizing can be adopted to further promote the organic carbon source to infiltrate into pores of the biscuit nitride.
Preferably, the mixed material pulping process in the step (1) adopts ball milling, stirring, sanding or emulsifying processes; the median particle size of the ceramic-based powder is between 2 and 300 mu m; the median particle size of the simple substance Si powder is between 1 and 150 mu m; the adhesive is one or more of dextrin, polyvinyl alcohol and methyl cellulose; the dispersant is one or more of tetramethyl ammonium hydroxide, polyvinyl butyral, ammonia water and n-octyl alcohol.
The powder mixing and pulping equipment adopts an emulsifying machine, a rapid stirrer, a ball mill or a sand mill and the like to mix materials, so that the mixing uniformity of the raw materials and the powder is promoted. The sintering activity and sintering compactness of the powder are maintained by controlling the powder particle size of the ceramic-based powder and the simple substance Si powder. The adhesive has a bonding effect in powder forming, and the dispersing agent promotes the dispersion and uniform mixing of the powder in the mixing process.
Preferably, the ceramic-based powder in step (1) includes SiC and B4C、Si3N4Or Al2O3One or more of powder materials.
By adopting the technical scheme, the ceramic-based powder adopts one or more of conventional engineering ceramic raw materials, and a series of reaction-sintered high-toughness ceramic composite materials are correspondingly obtained.
Preferably, the molding process in step (2) adopts dry pressing, 3D printing, grouting, injection molding or gel injection molding.
By adopting the technical scheme, the forming process also adopts a mature forming technical route, and biscuit blanks can be formed by dry pressing, grouting, injection molding, gel injection molding, 3D printing and the like, so that the process applicability of various ceramic powder bodies is met.
Preferably, in the step (3), the nitridation temperature is 1200 ℃ and 1500 ℃, and the nitridation time is 2-100 hours.
By adopting the technical scheme, the nitridation reaction can be promoted to be complete, and the three-dimensional crosslinked beta-Si can be formed3N4The silicon nitride ceramic with the microstructure can have higher strength and toughness in different directions.
Preferably, the coupling agent solution in the step (4) is an aqueous solution, an ethanol solution or an acetone solution of a coupling agent, and the coupling agent is one or more of a silane coupling agent, an aluminate coupling agent or a titanate coupling agent.
By adopting the technical scheme, the coupling agent solution has good fluidity, can enter the porous blank body to perform surface modification treatment on the hole walls dispersed in the blank body, promotes the infiltration of the organic carbon source and the hole walls to be wetted, and completely fills the porous gaps.
Preferably, the liquid organic carbon source in step (5) comprises liquid phenolic resin, liquid petroleum pitch or ammonium lignosulfonate solution.
By adopting the technical scheme, the material has better fluidity and adsorptivity in the ceramic material, and the carburization efficiency and the dispersion uniformity of carburization in the whole ceramic material are improved.
Preferably, in the step (6), the temperature range of carbonization is 600-.
By adopting the technical scheme, the complete carbonization reaction is promoted, and the reaction is performed on beta-Si3N4The surfaces of the crystal whisker and the ceramic matrix are coated with a layer of residual carbon.
Preferably, in the step (7), Si is infiltrated at high temperature, and one or two of simple substance Si and Si alloy are adopted; the infiltration temperature of the high-temperature siliconizing is 1450 ℃ and 1800 ℃, and the temperature is kept for 1 to 5 hours.
By adopting the technical scheme, the reaction of Si and the carbonized residual carbon is promoted, and the residual porous space is filled to obtain the compact ceramic composite material. The Si or Si alloy for melting and infiltration is a flaky consumable material obtained by mixing single Si and/or Si alloy powder with a small amount of BN powder, a small amount of C powder and a bonding agent and then dry-pressing the mixture, or a mixed powder of the single Si and/or Si alloy powder, the small amount of BN powder and the small amount of C powder is spread on the surface of a ceramic blank. BN and Si are not infiltrated, bonding between the molten silicon and the ceramic product after cooling can be avoided, a small amount of added C powder reacts with simple substance Si and/or Si alloy to generate SiC, a network framework is formed, collapse of sheet-shaped consumable materials due to Si loss can be avoided, and smooth proceeding of the infiltration process is ensured.
In a second aspect, the application provides a high-toughness ceramic composite material, which is prepared by the method and has a high-compact structure and high-toughness comprehensive performance.
In summary, the present application has the following beneficial effects:
1. ceramic-based powder and simple substance Si powder are formed into a mixed biscuit, and the simple substance Si powder is subjected to high-temperature nitridation treatment to gradually generate acicular, dendritic or feather-like beta-Si in situ3N4The whiskers gradually spread and grow among the ceramic-based powder particles to form a three-dimensional staggered and mutually cross-linked whisker network, and are mutually consolidated with the ceramic-based powder particles to form high-strength and high-toughness porous beta-Si3N4A ceramic composite green body; and after the composite blank is modified, carburized and carbonized, infiltrating Si in vacuum, reacting the melt Si with the carbonized residual carbon to generate SiC, and filling the residual pores with Si to prepare a compact ceramic composite material, so that the strength and the toughness of the ceramic material are further improved.
2. The method adopts a nitriding treatment process to generate beta-Si in situ in the ceramic body3N4Network of whiskers, relative to outsourced Si3N4The crystal whisker not only can greatly reduce the cost, but also has no crystal whisker dust in the production process and the use process, avoids causing personal injury to operators, and thoroughly solves the problem of beta-Si3N4The use safety of the crystal whisker is difficult.
3. In situ generated stereo cross-linked beta-Si3N4The network has the outstanding advantages of uniform distribution, isotropy, adjustable content, firm cross-linking and the like, and the reinforcing and toughening effect of the network is far superior to that of the crystal whisker.
4. The preparation method has wide application range, and the ceramic-based powder comprises SiC and B4C、Si3N4Or Al2O3And one or more of other engineering ceramic raw materials known in the industry, and accordingly a series of high-strength and high-toughness ceramic composite materials are obtained.
5. The application is based on the stereo-crosslinking of beta-Si3N4The forming process of the crystal whisker network and the blank has wide application range, including dry pressing, grouting, injection molding, injection, gel injection molding, 3D printing and the like.
6. Developed based on stereo-crosslinking of beta-Si3N4The high-strength and high-toughness ceramic composite material of the whisker network overcomes the defects of poor toughness and insufficient strength of the traditional silicon carbide ceramic, has excellent comprehensive properties of high toughness, high strength, light weight, high thermal conductivity, high temperature resistance, low expansion, thermal shock resistance and the like, is suitable for preparing large and complex structural parts, and has wide application prospects in the application fields of aerospace, war industry, electronics and traditional engineering ceramics.
Detailed Description
The present application will be described in further detail with reference to examples.
Examples
Embodiment 1 a method for preparing a high-toughness ceramic composite material, comprising the following steps:
1) mixing materials: weighing 500g of SiC powder with the median particle size of 2 microns, 500g of Si powder with the median particle size of 1 micron, 5g of dextrin, 5g of tetramethylammonium hydroxide and 2020 g of deionized water, putting the above raw materials into a ball mill, and ball-milling for 5 hours to obtain mixed slurry, wherein the ball-material ratio is 5:1 and the rotating speed is 30 r/min.
2) Molding: and (3) carrying out spray drying granulation on the obtained slurry, drying to obtain granules with the average particle size of 150 mu m, obtaining a biscuit by adopting a dry method mould pressing method, and limiting the pressing height by a limiter so as to control the volume of the biscuit and control the overall porosity of the biscuit to be 25%.
3) In-situ nitridation: and putting the biscuit into a nitriding furnace, vacuumizing to 20Pa, and then filling nitrogen with 0.2MPa, wherein the nitriding temperature is 1200 ℃ and the nitriding time is 100 hours. Cooling to obtain the porous beta-Si3N4a/SiC composite green body.
4) Modification treatment: and (3) immersing the composite blank body into a silane coupling agent ethanol solution, performing modification treatment after 1 hour of immersion, wherein the concentration of the silane coupling agent is 2 wt%, and then drying for 1 hour at 70 ℃.
5) Carburizing: immersing the modified composite blank in liquid phenolic resin, carrying out vacuum pressure impregnation, wherein the viscosity of the liquid phenolic resin is 120 poise/25 ℃, pumping air until the vacuum pressure is 20Pa, carrying out pressure impregnation, wherein the impregnation pressure is 0.4MPa, taking out after 2 hours, drying, and cleaning the residual resin on the surface to obtain the carburized blank.
6) High-temperature carbonization: and putting the carburized blank body into a degreasing furnace, and carbonizing the carburized blank body in a vacuum environment (the vacuum pressure is 20Pa) at the temperature of 600 ℃ for 10 hours to obtain a porous carbonized blank body.
7) High-temperature infiltration: uniformly mixing elemental silicon powder with the median particle size of 200 microns with hexagonal boron nitride, C powder and phenolic resin (model 2123) with the median particle size of 10 microns to obtain mixed powder, wherein the weight ratio of the elemental silicon powder to the hexagonal boron nitride, the C powder and the phenolic resin is 90:5:3:2, the mass ratio of the added amount of the mixed powder to a carbonized green body is 2:1, performing dry pressing on the mixed powder to obtain infiltration pieces (the prepressing pressure is 50MPa), vertically stacking the infiltration pieces and the porous carbonized green body at intervals repeatedly, placing the infiltration pieces in a vacuum sintering furnace for infiltration treatment, vacuumizing to 20Pa, heating to 1450 ℃, and keeping the temperature for 5 hours. And cooling along with the furnace, and taking out to obtain the ceramic composite material.
Example 2
A preparation method of a high-strength and high-toughness ceramic composite material comprises the following steps:
1) mixing materials: weighing the following raw materials by weight, wherein the median particle size is 50 mu m B4500g of C powder and Si with 50 mu m median particle size3N4400g of powder, 100 g of Si powder with the median particle size of 30 mu m, 20 g of polyvinyl alcohol, 10g of dextrin, 10g of polyvinyl butyral and 1500 g of deionized water, and the raw materials are put into a stirrer, the rotating speed is 60r/min, and the stirring is carried out for 5 hours to obtain mixed slurry.
2) Molding: and (3) carrying out spray drying granulation on the obtained slurry, wherein the average particle size of the granules is 300 mu m, obtaining a biscuit by adopting a dry method mould pressing method, and limiting the pressing height by a limiter, so that the volume of the biscuit is controlled, and the overall porosity of the biscuit is controlled at 30%.
3) In-situ nitridation: and putting the biscuit into a nitriding furnace, vacuumizing to 20Pa, and then filling nitrogen with 0.4MPa, wherein the nitriding temperature is 1500 ℃, and the nitriding time is 50 hours. Cooling to obtain porous beta-Si3N4/B4C/Si3N4And (4) compounding the green body.
4) Modification treatment: and immersing the composite blank body into a titanate coupling agent aqueous solution for 1 hour for modification treatment, wherein the concentration of the titanate coupling agent is 1wt%, and then drying for 1 hour at 100 ℃.
5) Carburizing: immersing the modified composite blank body in liquid petroleum asphalt, wherein the viscosity of the liquid petroleum asphalt is 100 poise/25 ℃, pumping air until the vacuum pressure is 20Pa, pressurizing and impregnating, the impregnation pressure is 0.4MPa, taking out and drying after impregnating for 3 hours, and cleaning residual asphalt on the surface to obtain the carburized blank body.
6) High-temperature carbonization: and putting the carburized blank body into a degreasing furnace, vacuumizing to 20Pa, heating to 1000 ℃, and carrying out carbonization treatment for 1 hour to obtain the porous carbonized blank body.
7) High-temperature infiltration: uniformly mixing elemental silicon powder with the particle size of 2mm with hexagonal boron nitride and C powder with the median particle size of 10 mu m to obtain mixed powder, wherein the weight ratio of the elemental silicon powder to the hexagonal boron nitride to the C powder is 92:5:3, the mass ratio of the addition amount of the mixed powder to the mass ratio of the mixed powder to the carbonized green body is 2:1, putting the porous carbonized green body into a graphite crucible, keeping the upper surface of the porous carbonized green body horizontal, spreading a layer of elemental silicon powder mixed powder on the upper surface of the porous carbonized green body, putting the graphite crucible into a vacuum sintering furnace for infiltration treatment, vacuumizing to 20Pa, heating to 1450 ℃, and keeping the temperature for 5 hours. And cooling along with the furnace, and taking out to obtain the ceramic composite material.
Example 3
A preparation method of a high-strength and high-toughness ceramic composite material comprises the following steps:
1) mixing materials: weighing 750 g of SiC powder with the median particle size of 150 mu m, 250 g of Si powder with the median particle size of 100 mu m, 50g of methyl cellulose, 1 g of n-octanol and 525 g of deionized water according to the weight, putting the raw materials into a sand mill, grinding at the grinding ratio of 6:1 and the rotation speed of 20r/min, and sanding for 5 hours to obtain the mixed slurry.
2) Molding: and (3) carrying out spray drying granulation on the obtained slurry, enabling the average particle size of the granules to be 300 mu m, obtaining a pressed blank by adopting a dry method die pressing method, and limiting the pressing height by a limiter so as to control the volume of the pressed blank and control the overall porosity of the pressed blank to be about 35%.
3) In-situ nitridation: the biscuit is put into a nitriding furnace, firstly vacuumized to 20Pa, and then filled with nitrogen of 0.3MPa, wherein the nitriding temperature is 1200 ℃, and the nitriding time is 80 hours. Cooling to obtain porous beta-Si3N4/And (3) preparing a SiC composite blank.
4) Modification treatment: and (3) immersing the composite blank body into an aluminate coupling agent acetone solution, wherein the concentration of the titanate coupling agent is 1wt%, impregnating for 2 hours for modification treatment, and then drying for 1 hour at 70 ℃.
5) Carburizing treatment: immersing the modified composite pressed compact into an ammonium lignosulfonate aqueous solution, wherein the concentration of ammonium lignosulfonate is 75 wt%, taking out and drying after immersing for 12 hours, and cleaning residual ammonium lignosulfonate on the surface to obtain a carburized blank body.
6) High-temperature carbonization: the carburized body was placed in a degreasing furnace, and the green compact was carbonized for 5 hours in a vacuum atmosphere (vacuum pressure 20Pa) at 800 ℃.
7) High-temperature infiltration: uniformly mixing elemental silicon powder with the median particle size of 300 microns with hexagonal boron nitride, C powder and polyvinyl alcohol (model 1788) with the median particle size of 10 microns to obtain mixed powder, wherein the weight ratio of the elemental silicon powder to the hexagonal boron nitride, the C powder and the polyvinyl alcohol is 90:3:5:2, the mass ratio of the added amount of the mixed powder to a carbonized blank body is 1:1, performing dry pressing on the mixed powder to obtain infiltration pieces (the prepressing pressure is 50MPa), vertically stacking the infiltration pieces and the porous carbonized blank body at intervals repeatedly, placing the infiltration pieces in a vacuum sintering furnace for infiltration treatment, vacuumizing to 20Pa, heating to 1700 ℃, and keeping the temperature for 3 hours. And cooling the ceramic composite material along with the furnace, and taking out the ceramic composite material to obtain the ceramic composite material.
Example 4
A preparation method of a high-strength and high-toughness ceramic composite material comprises the following steps:
1) mixing materials: weighing the following raw materials by weight, wherein the median particle size is 100 mu m Al2O3600 g of powder, 400g of Si powder with the median particle size of 70 mu m, 25 g of methylcellulose, 5g of polyvinyl butyral, 5g of ammonia water and 1300 g of deionized water, and the raw materials are put into a ball mill with the ball-material ratio of 6:1 and the rotating speed of 30r/min, and are ball-milled for 5 hours to obtain mixed slurry.
2) Molding: and (3) carrying out spray drying granulation on the obtained slurry, wherein the average particle size of granules is 350 mu m, obtaining a pressed blank by adopting a dry method die pressing method, and limiting the pressing height by a limiter, so that the volume of the pressed blank is controlled, and the overall porosity of the pressed blank is controlled to be about 30%.
3) In-situ nitridation: and putting the biscuit into a nitriding furnace, vacuumizing to 20Pa, and then filling nitrogen with 0.2MPa, wherein the nitriding temperature is 1300 ℃ and the nitriding time is 60 hours. Cooling to obtain the porous beta-Si3N4/Al2O3And (4) compounding the green body.
4) Modification treatment: and (3) immersing the composite blank body into silane and aluminate coupling agent acetone solution for 2 hours for modification treatment, wherein the concentration of the silane coupling agent is 1wt%, the concentration of the aluminate coupling agent is 2%, and then drying for 1 hour at 70 ℃.
5) Carburizing: immersing the modified composite pressed compact in ammonium lignosulfonate aqueous solution (with the concentration of 70 wt%) for 15 hours, taking out and drying, and cleaning residual ammonium lignosulfonate on the surface to obtain a carburized blank body.
6) High-temperature carbonization: and putting the carburized blank body into a degreasing furnace, and carbonizing the pressed blank body in a vacuum environment at 1000 ℃ for 2 hours.
7) Uniformly mixing elemental silicon powder with the particle size of 2mm and hexagonal boron nitride and C powder with the median particle size of 50 mu m to obtain mixed powder, wherein the weight ratio of the elemental silicon powder to the hexagonal boron nitride to the C powder is 92:5:3, the mass ratio of the added amount of the mixed powder to a carbonized green body is 1:1, putting a porous carbonized green body into a graphite crucible, keeping the upper surface of the porous carbonized green body horizontal, spreading a layer of elemental silicon powder mixed powder on the upper surface of the porous carbonized green body, putting the graphite crucible into a vacuum sintering furnace for infiltration treatment, vacuumizing to 20Pa, heating to 1600 ℃, and keeping the temperature for 4 h. And cooling the ceramic composite material along with the furnace, and taking out the ceramic composite material to obtain the ceramic composite material.
Example 5
The difference between the embodiment and the embodiment 1 is that aluminum-silicon alloy powder (silicon content is 18 wt%) with a median particle size of 200 μm and elemental silicon powder are uniformly mixed with hexagonal boron nitride, C powder and phenolic resin (model 2123) with a median particle size of 10 μm to obtain mixed powder, the weight ratio of the aluminum-silicon alloy powder, the elemental silicon powder, the hexagonal boron nitride, the C powder and the phenolic resin is 18:72:5:3:2, the mass ratio of the added amount of the mixed powder to a carbonized green body is 2:1, the mixed powder is subjected to dry pressing to obtain infiltration pieces (prepressing pressure is 50MPa), the infiltration pieces and a porous carbonized green body are vertically stacked repeatedly at intervals, the infiltration pieces are placed in a vacuum sintering furnace for infiltration treatment, the vacuum is pumped to 20Pa, the temperature is raised to 1450 ℃, and the heat preservation time is 5 hours. And cooling along with the furnace, and taking out to obtain the ceramic composite material.
Example 6
The difference between the embodiment and the embodiment 1 is that, in the embodiment and the embodiment 1, aluminum silicon alloy powder (silicon content is 18 wt%) and simple substance silicon powder with a median particle size of 200 μm are uniformly mixed with hexagonal boron nitride, C powder and phenolic resin (model 2123) with a median particle size of 10 μm to obtain mixed powder, the weight ratio of the aluminum silicon alloy powder, the simple substance silicon powder, the hexagonal boron nitride, the C powder and the phenolic resin is 30:60:5:3:2, the mass ratio of the added amount of the mixed powder to a carbonized green body is 2:1, the mixed powder is subjected to dry pressing to obtain infiltration pieces (prepressing pressure is 50MPa), the infiltration pieces and a porous carbonized green body are vertically and repeatedly stacked at intervals, the infiltration pieces and the porous carbonized green body are placed in a vacuum sintering furnace for infiltration treatment, the vacuum is pumped to 20Pa, the temperature is raised to 1450 ℃, and the heat preservation time is 5 h. And cooling along with the furnace, and taking out to obtain the ceramic composite material.
Example 7
A preparation method of a high-strength and high-toughness ceramic composite material comprises the following steps:
1) mixing materials: weighing 700 g of SiC powder with the median particle size of 200 mu m, 300 g of Si powder with the median particle size of 50 mu m, 15g of polyvinyl alcohol, 5g of tetramethylammonium hydroxide and 1800 g of deionized water according to the proportion, putting the raw materials into a sand mill, and sanding for 4 hours at the ball-to-material ratio of 4:1 and the rotating speed of 30r/min to obtain the mixed slurry.
2) Molding: the resulting slurry was spray-dried for granulation, and the average particle size of the resulting granules was about 600 μm after drying. A biscuit is obtained by adopting a 3DP glue spraying printing process, the 3DP glue spraying printing process is adopted, a porous structure is modeled by 3D, the porosity is 30%, the adhesive is silica gel, and the powder spreading thickness is 0.1 mm.
3) In-situ nitridation: will elementThe blank is put into a nitriding furnace, firstly the vacuum pumping is carried out until the pressure is 20Pa, then nitrogen with the pressure of 0.4MPa is filled, the nitriding temperature is 1400 ℃, and the nitriding time is 25 hours. Cooling to obtain the porous beta-Si3N4a/SiC composite green body.
4) Modification treatment: and (3) immersing the composite blank body into a silane coupling agent ethanol solution, performing modification treatment after 1 hour of immersion, wherein the concentration of the silane coupling agent is 2 wt%, and then drying for 1 hour at 70 ℃.
5) Carburizing: immersing the modified composite blank in liquid phenolic resin, carrying out vacuum pressure impregnation, wherein the viscosity of the liquid phenolic resin is 120 poise/25 ℃, pumping air until the vacuum pressure is 20Pa, carrying out pressure impregnation, wherein the impregnation pressure is 0.4MPa, taking out after 2 hours, drying, and cleaning the residual resin on the surface to obtain the carburized blank.
6) High-temperature carbonization: and putting the carburized blank body into a degreasing furnace, and carbonizing the carburized blank body in a vacuum environment (the vacuum pressure is 20Pa) at the temperature of 600 ℃ for 10 hours to obtain a porous carbonized blank body.
7) High-temperature infiltration: uniformly mixing elemental silicon powder with the particle size of 3mm with hexagonal boron nitride with the median particle size of 100 mu m, C powder and polyvinyl alcohol (model 1788) to obtain mixed powder, wherein the weight ratio of the elemental silicon powder to the hexagonal boron nitride to the C powder to the polyvinyl alcohol is 90:3:5:2, the mass ratio of the added amount of the mixed powder to a carbonized blank body is 1.2:1, performing dry pressing on the mixed powder to obtain infiltration pieces (the prepressing pressure is 50MPa), repeatedly stacking the infiltration pieces and the porous carbonized blank body vertically at intervals, vacuumizing to 20Pa, heating to 1600 ℃, and keeping the temperature for 4 h. And cooling along with the furnace, and taking out to obtain the ceramic composite material.
Example 8
A preparation method of a high-strength and high-toughness ceramic composite material comprises the following steps:
1) mixing materials: weighing the following raw materials by weight, 500g of SiC powder with the median particle size of 300 mu m and 150 mu m of B4100 g of C powder, 400g of 75-micron Si powder, 15g of polyvinyl alcohol, 2 g of methyl cellulose, 8 g of tetramethylammonium hydroxide and 500g of deionized water, and the raw materials are put into a ball mill for ball milling with the ball-material ratio of 4:1 and the rotating speed of 40r/min for 6 hours to obtain mixed slurry.
2) Molding: and adding the mixed slurry into a grouting mold, and drying at 85 ℃ for 1h to prepare a biscuit.
3) In-situ nitridation: putting the biscuit into a nitriding furnace, firstly vacuumizing to 20Pa, then filling nitrogen with 0.4MPa, nitriding at the high temperature of 1500 ℃ for 35 hours, and cooling to obtain the porous beta-Si3N4/SiC/B4C, compounding the green body.
4) Modification treatment: and (3) immersing the composite blank body into an aluminate coupling agent aqueous solution, performing modification treatment after 1 hour of immersion, wherein the concentration of the aluminate coupling agent is 2 wt%, and then drying for 1 hour at 100 ℃.
5) Carburizing treatment: immersing the modified composite pressed compact in liquid petroleum asphalt, carrying out vacuum pressure impregnation, wherein the viscosity of the liquid petroleum asphalt is 100 poise/25 ℃, pumping air until the vacuum pressure is 20Pa, carrying out pressure impregnation, wherein the impregnation pressure is 0.4MPa, taking out after 2 hours, drying, and cleaning residual asphalt on the surface to obtain a carburized blank body.
6) High-temperature carbonization: and putting the carburized blank body into a degreasing furnace, and carbonizing the carburized blank body in a vacuum environment (the vacuum pressure is 20Pa) at 800 ℃ for 8 hours to obtain a porous carbonized blank body.
7) Uniformly mixing elemental silicon powder with the particle size of 3mm and hexagonal boron nitride and C powder with the median particle size of 100 mu m to obtain mixed powder, wherein the weight ratio of the elemental silicon powder to the hexagonal boron nitride and the C powder is 90:5:5, the mass ratio of the addition amount of the mixed powder to the carbonized green body is 1.8:1, placing the porous carbonized green body into a graphite crucible, keeping the upper surface of the porous carbonized green body horizontal, spreading a layer of elemental silicon powder mixed powder on the upper surface of the porous carbonized green body, placing the graphite crucible into a vacuum sintering furnace for infiltration treatment, vacuumizing to 20Pa, heating to 1700 ℃, and keeping the temperature for 2 h. And cooling along with the furnace, and taking out to obtain the ceramic composite material.
Example 9
A preparation method of a high-strength and high-toughness ceramic composite material comprises the following steps:
1) mixing materials: weighing the following raw materials by weight, and weighing Al with the median particle size of 2 mu m2O3650g of Si powder with the median particle size of 1 mu m, 50g of polyvinyl alcohol, 5g of n-octanol, 10g of stearic acid and 500g of deionized water, putting the raw materials into a ball mill, mixing and ball-milling for 4 hours to obtain slurry, and freeze-drying the slurry at-40 ℃ for 6 hours to obtain mixed powder.
2) Molding: and mixing the obtained mixed powder at the mixing temperature of 120 ℃ for 1.5h to obtain a mixture, cooling the mixture, crushing the mixture to be less than 2mm, putting the mixture into a hopper of an injection molding machine, and performing injection molding through an injection molding machine to obtain a biscuit, wherein the injection molding temperature is 250 ℃ and the injection molding pressure is 80 MPa.
3) In-situ nitridation: and putting the biscuit into a nitriding furnace, vacuumizing, filling nitrogen, performing nitriding treatment at high temperature, vacuumizing to 20Pa, filling 1MPa of nitrogen, and nitriding at 1500 ℃ for 2 hours. Cooling to obtain the porous beta-Si3N4/Al2O3And (4) compounding the green body.
4) Modification treatment: and (3) immersing the composite blank body into an aluminate coupling agent aqueous solution for 1 hour for modification treatment, wherein the concentration of the aluminate coupling agent is 2 wt%, and then drying for 1 hour at 100 ℃.
5) Carburizing: and immersing the modified composite blank body in an ammonium lignosulphonate aqueous solution, wherein the concentration of ammonium lignosulphonate is 80 wt%, immersing for 24 hours, taking out and drying to obtain the carburized blank body.
6) High-temperature carbonization: and putting the carburized blank body into a degreasing furnace, and carbonizing the carburized blank body in a vacuum environment (the vacuum pressure is 20Pa) at the temperature of 600 ℃ for 10 hours to obtain a porous carbonized blank body.
7) High-temperature infiltration: uniformly mixing elemental silicon powder with the particle size of 2mm and hexagonal boron nitride and C powder with the median particle size of 30 mu m to obtain mixed powder, wherein the weight ratio of the elemental silicon powder to the hexagonal boron nitride to the C powder is 90:5:5, the mass ratio of the addition amount of the mixed powder to the mass ratio of the mixed powder to the carbonized green body is 2:1, putting the porous carbonized green body into a graphite crucible, keeping the upper surface of the porous carbonized green body horizontal, spreading a layer of elemental silicon powder mixed powder on the upper surface of the porous carbonized green body, putting the graphite crucible into a vacuum sintering furnace for infiltration treatment, vacuumizing to 20Pa, heating to 1450 ℃, and keeping the temperature for 5 hours. And cooling along with the furnace, and taking out to obtain the ceramic composite material.
Comparative example
Comparative example 1
Unlike example 1, the preparation method of the ceramic composite material of comparative example 1 includes only steps 1) -2) to prepare porous beta-Si3N4a/SiC composite green body.
Comparative example 2
Unlike example 1, the overall porosity of the biscuit in step 2) of comparative example 2 was controlled at 20%.
Comparative example 3
Unlike example 1, the overall porosity of the biscuit in step 2) of comparative example 3 was controlled at 40%.
Comparative example 4
Unlike example 1, comparative example 4 did not include step 3) coupling modification treatment.
Comparative example 5
Different from the embodiment 5, the weight ratio of the aluminum-silicon alloy powder, the elemental silicon powder, the hexagonal boron nitride, the C powder and the phenolic resin is 10:80:5:3: 2.
Comparative example 6
Different from the embodiment 5, the weight ratio of the aluminum-silicon alloy powder, the elemental silicon powder, the hexagonal boron nitride, the C powder and the phenolic resin is 35:55:5:3: 2.
Performance test
Detection method/test method
The bending strength and the fracture toughness are tested according to the national standard GB/T6569-2006 fine ceramic bending strength test method and the GB/T23806-2009 fine ceramic fracture toughness test method unilateral and crack Beam (SEPB) method respectively.
The test results of examples 1 to 9 and comparative examples 1 to 6 are shown in Table 1
TABLE 1
Figure BDA0002856216360000101
Figure BDA0002856216360000111
In combination with examples 1-9 and Table 1, it can be seen that the high toughness ceramic composite materials prepared in examples 1-9 have fracture toughness of 11 Pa.m1/2The bending strength is 490MPa or more. The ceramic composite material has high density which can reach more than 98.5 percent. In the embodiments 5 and 6, the silicon-aluminum alloy and the elemental silicon powder are adopted to infiltrate and fill the porous gaps, so that the ceramic material can be further reinforced and toughened, presumably because the alloy can reduce the melting point of Si and promote the wettability of Si; the interface strength of the generated silicon carbide and the original silicon carbide is improved, and the toughness is further improved.
By combining the analysis of example 1 and comparative example 1, it can be seen that porous beta-Si3N4The fracture strength and the bending strength of the ceramic composite material prepared by the SiC composite blank without modification treatment, carburization treatment, carbonization treatment and high-temperature infiltration are obviously reduced, presumably because of porous beta-Si3N4the/SiC composite blank also has porous gaps which are not dense.
It is found by combining the analysis of example 1 and comparative examples 2 and 3 that the overall porosity of the biscuit is too low or too high, which is not good for the reinforcement and toughening of the ceramic material, presumably because the porosity is too low, the pore diameter is reduced, the pores may become closed after the nitriding treatment, resulting in insufficient carburization, and because of the Si3N4The composite material is not infiltrated to nonferrous metals, and Si is difficult to infiltrate in a region without carbon, so that the composite material is finally reserved with a large number of small-size pores, and the material performance is difficult to improve; excessive porosity, sintering of ceramic matrix and beta-Si in the matrix3N4The content of the silicon is low, the content of the simple substance silicon is high, so that the strength and the toughness of the composite material are reduced, and the temperature resistance is reduced.
The analysis of the combination of example 1 and comparative example 4 shows that the performance of the ceramic composite material is reduced without the coupling treatment, and the possible reason is that the pore walls and the organic carbon source can not be effectively wetted, so that the organic carbon source can not completely fill the pores, and therefore, the beta-Si can not be completely filled in the pores3N4Is not completely coated by residual carbon due to Si3N4The non-ferrous metal is not infiltrated, and finally Si is difficult to infiltrate into pores.
The analysis of combining the example 5 with the comparative example 5 and the comparative example 6 shows that when the adding proportion of the aluminum-silicon powder is too small, the pores of the composite material are not easy to be completely filled; when the addition amount is too large, aluminum reacts with carbon due to high aluminum content to generate low-strength Al4C3This will cause the strength of the composite to decrease.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (7)

1. A preparation method of a high-strength and high-toughness ceramic composite material comprises the following steps:
(1) mixing materials: weighing raw materials according to a ratio, adding deionized water, and mixing to prepare slurry, wherein the raw materials comprise the following components in percentage by weight:
the matrix consists of ceramic-based powder and elemental Si powder, wherein the ceramic-based powder accounts for 50-90wt%, and the elemental Si powder accounts for 10-50 wt%;
the addition amount of the adhesive is 0.5-5wt% of the total amount of the matrix,
the addition amount of the dispersant is 0.1-1wt% of the total amount of the matrix;
the addition amount of the added deionized water is 50-200 wt% of the total amount of the matrix, the adhesive and the dispersant;
the ceramic-based powder comprises B4C、Si3N4Or Al2O3One or more of powder materials;
(2) molding: forming and blank-making by adopting the slurry obtained in the step (1) to obtain a biscuit;
(3) in-situ nitridation: nitriding the biscuit obtained in the step (2) to obtain porous beta-Si3N4A ceramic composite green body;
the nitriding temperature is 1200-1500 ℃, and the nitriding time is 2-100 hours;
(4) modification treatment: the porous beta-Si obtained in the step (3) is treated3N4Soaking the ceramic composite blank body into a coupling agent solution for modification treatment, and drying to obtain a modified porous composite blank body;
(5) carburizing: immersing the modified porous composite blank obtained in the step (4) into a liquid organic carbon source for impregnation to obtain a carburized blank;
the liquid organic carbon source comprises phenolic resin, asphalt or ammonium lignosulfonate solution;
(6) high-temperature carbonization: carbonizing the carburized blank body obtained in the step (5) at a high temperature to obtain a porous carbonized blank body;
(7) high-temperature infiltration: infiltrating Si into the porous carbonized green body obtained in the step (6) at high temperature, and cooling after complete reaction to obtain a ceramic composite material;
the high-temperature infiltration Si adopts one or two of simple substance Si and Si alloy;
the simple substance Si or Si alloy is a sheet-shaped consumable material obtained by mixing single substance Si and/or Si alloy powder with a small amount of BN powder, a small amount of C powder and an adhesive and performing dry pressing;
or the mixed powder of single Si and/or Si alloy powder, a small amount of BN powder and a small amount of C powder is spread on the surface of the ceramic blank.
2. The preparation method of the high-strength and high-toughness ceramic composite material as claimed in claim 1, wherein the method comprises the following steps:
the mixed material pulping process in the step (1) adopts ball milling, stirring, sanding or emulsifying process;
the median particle size of the ceramic-based powder is between 2 and 300 mu m;
the median particle size of the simple substance Si powder is between 1 and 150 mu m;
the adhesive is more than one of dextrin, polyvinyl alcohol and methyl cellulose;
the dispersing agent is more than one of tetramethyl ammonium hydroxide, polyvinyl butyral, ammonia water and n-octanol.
3. The method for preparing a ceramic composite material according to claim 1, wherein: and (3) the forming process in the step (2) adopts dry pressing, 3D printing, grouting, injection molding or gel injection molding.
4. The preparation method of the high-strength and high-toughness ceramic composite material as claimed in claim 1, wherein the method comprises the following steps: the coupling agent solution in the step (4) is water solution, ethanol solution or acetone solution of the coupling agent, and the coupling agent is more than one of silane coupling agent, aluminate coupling agent or titanate coupling agent.
5. The preparation method of the high-strength and high-toughness ceramic composite material as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (6), the temperature range of carbonization is 600-1000 ℃, and the carbonization heat preservation time is 1-10 hours.
6. The preparation method of the high-strength and high-toughness ceramic composite material as claimed in claim 1, wherein the method comprises the following steps: in the step (7), the infiltration temperature of the high-temperature infiltration Si is 1450-.
7. A high-toughness ceramic composite material, which is prepared by the preparation method of the high-toughness ceramic composite material as claimed in any one of claims 1 to 6.
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