CN110723973A - Preparation method of SiBCN composite ceramic with high temperature stability - Google Patents
Preparation method of SiBCN composite ceramic with high temperature stability Download PDFInfo
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Abstract
The invention relates to a preparation method of SiBCN composite ceramic with high temperature stability, which is characterized by comprising the following steps: step A: preparing a polysilazane precursor, mixing an initial reactant and a solvent to prepare a solution, wherein the mass ratio of the solvent to the initial reactant is (4-10): 1, stirring at the temperature of 20-80 ℃, introducing ammonia gas for 3-6 h, recovering the solvent after the reaction is finished, and drying the product to obtain the polysilazane precursor. The invention provides a brand new preparation method of SiBCN ceramic powder with good stability and corrosion resistance by adopting a method of combining a precursor conversion method and mechanical alloying and taking acrylonitrile trichlorosilane as an initiator.
Description
Technical Field
The invention relates to the field of composite ceramic synthesis, in particular to a preparation method of SiBCN composite ceramic with high temperature stability.
Background
The ceramic material has excellent properties of structural stability, oxidation resistance, creep resistance, high-temperature stability, high strength, corrosion resistance, low density and the like, and can be widely applied to the fields of transportation, aerospace, energy, information, microelectronics and the like. Compared with binary and ternary system ceramics, the SiBCN multi-element system ceramics has more excellent high temperature resistance and oxidation resistance, and is a novel ceramic material which is widely concerned. However, when the existing multi-component system ceramic is used for preparing an ultra-high temperature part structure of a hypersonic aircraft, the mechanical property of the ceramic still cannot meet the requirement. Based on the special structure and excellent properties of SiBCN ceramics, a great deal of research has been conducted in recent years to explore the synthesis raw materials and methods, structural features, and high temperature stability thereof.
The current synthesis methods are mainly divided into the following methods: precursor conversion methods, mechanical alloying methods, and reactive magnetron sputtering methods. The three have own advantages and disadvantages: the precursor conversion method is the most common and well-developed preparation method at present, the process starts from simple molecular monomers, and can obtain a desired structure by designing a synthesis route so as to achieve ideal performance, but the process route is long, expensive or toxic raw materials and organic solvents can harm operators or pollute the environment, the pyrolysis process is accompanied by large thermal weight loss, and meanwhile, the obtained ceramic product also has a large number of pores or certain defects, and the ceramic product is generally difficult to be made into a target product with a large size. The raw materials required by the mechanical alloy method are cheap and easy to obtain, and the method is also suitable for preparing large-size block ceramics, but high-energy ball milling is required, then hot-pressing sintering is carried out at high temperature and high pressure, the required equipment is expensive, large-scale development and use are not easy to realize, the microstructure mechanism of the prepared block ceramics is not as uniform as that of the precursor method, and crystallization is easy to occur at high temperature. The magnetron sputtering method is to sputter and deposit compounds containing elements of Si, B, C and N through inert gas, then to sinter, and can prepare ceramic films with uniform texture at a lower temperature, but the cost is high, certain pollution is generated to the environment, certain harm is caused to human bodies, the size of the prepared ceramic product is single, and large-scale production is not easy, so the research is not extensive. Therefore, a preparation method of a novel composite ceramic is urgently needed at present.
Disclosure of Invention
The invention aims to solve the problems of high production cost, single structure and pollution in the production process of ceramic materials in the prior art, and further provides a preparation method of the SiBCN composite ceramic with good stability and corrosion resistance and high temperature stability.
The technical scheme of the invention is as follows: a preparation method of SiBCN composite ceramic with high temperature stability comprises the following steps:
step A: preparation of polysilazane precursor
Mixing an initial reactant and a solvent to prepare a solution, wherein the mass ratio of the solvent to the initial reactant is (4-10): stirring at the temperature of 20-80 ℃, introducing ammonia gas for 3-6 h, recovering the solvent after the reaction is finished, and drying the product to obtain a polysilazane precursor;
and B: preparation of SiBCN ceramic powder
Adding silicon powder, carbon powder and boride powder according to different molar ratios, ball-milling the mixed powder in the atmosphere of inert gas, preparing mechanical alloying powder by ball-milling, and sintering under the protection of inert gas to obtain the SiBCN composite ceramic.
The reaction starting material is acrylonitrile trichlorosilane, hexamethyldisilazane, bis (trimethylsilyl) carbodiimide, methylvinylsilazane, a vinylated polysiloxane-based diimide, or disilylcarbodiimide.
The solvent is toluene, acetonitrile, glyme, hexane, xylene, acetone, dimethyl sulfoxide, diethyl ether or triethylamine.
The boride is BN, B4C or B2O3。
The temperature gradient of the sintering is set as follows: the temperature is increased to 300 ℃ at the room temperature by 5 ℃/min and is kept at the temperature for 2h, then is increased to 800 ℃ at the same speed, is kept at the temperature for 2h, is increased to 1400 ℃ at the same temperature increasing speed, is kept at the temperature for 6h and is naturally cooled, and the SiBCN composite ceramic is taken out at the room temperature.
The temperature gradient of the sintering is set as follows: raising the temperature to 200 ℃ at the room temperature at the speed of 5 ℃/min, preserving the heat for 2h at the temperature, then raising the temperature to 600 ℃ at the same speed, preserving the heat for 2h at the temperature, finally raising the temperature to 1400 ℃ at the same temperature raising speed, preserving the heat for 6h at the temperature, naturally cooling, and taking out the SiBCN composite ceramic at the room temperature.
The temperature gradient of the sintering is set as follows: raising the temperature to 400 ℃ at the room temperature at the speed of 5 ℃/min, preserving the heat for 2h at the temperature, then raising the temperature to 1000 ℃ at the same speed, preserving the heat for 2h at the temperature, finally raising the temperature to 1400 ℃ at the same temperature raising speed, preserving the heat for 6h at the temperature, naturally cooling, and taking out the SiBCN composite ceramic at the room temperature.
The invention also relates to the SiBCN composite ceramic prepared by the method.
The invention has the following beneficial effects: the invention provides a brand new preparation method of SiBCN ceramic powder with good stability and corrosion resistance by adopting a method of combining a precursor conversion method and mechanical alloying and taking acrylonitrile trichlorosilane as an initiator.
Ball milled Si2BC2.5The N powder has good compressibility and can be used for preparing block ceramic, and the SiBCN ceramic powder also has good acid-base corrosion resistance.
Description of the drawings:
FIG. 1 is a schematic diagram showing the effect of temperature on polysilazane yield in the present invention.
FIG. 2 is a schematic diagram showing the effect of solvent ratio on polysilazane yield in the present invention.
FIG. 3 is a schematic diagram showing the effect of ammonolysis time on polysilazane yield in the present invention.
FIG. 4 is a schematic diagram showing the influence (b) of the content of element C on the ceramization yield (a) and thermal stability of the powder according to the present invention.
FIG. 5 is a schematic diagram showing the influence of Si content on the powder ceramization yield (a) and the thermal stability of the ceramic powder (b) in the present invention.
FIG. 6 is a schematic diagram showing the influence of the content of element B on the powder ceramization yield (a) and the thermal stability of the ceramic powder (B) in the present invention.
FIG. 7 is a schematic diagram showing the influence of the ball-to-powder ratio on the ceramization yield (a) and the thermal stability of the ceramic powder (b) in the present invention.
FIG. 8 is a schematic diagram showing the influence of the ball time on the powder ceramization yield (a) and the thermal stability of the ceramic powder (b) in the present invention.
FIG. 9 is a schematic diagram showing the influence of the rotation speed on the powder ceramization yield (a) and the thermal stability of the ceramic powder (b) in the present invention.
Detailed Description
The technical scheme of the invention is as follows: a preparation method of SiBCN composite ceramic with high temperature stability comprises the following steps:
step A: preparation of polysilazane precursor
Mixing an initial reactant and a solvent to prepare a solution, wherein the mass ratio of the solvent to the initial reactant is (4-10): stirring at the temperature of 20-80 ℃, introducing ammonia gas for 3-6 h, recovering the solvent after the reaction is finished, and drying the product to obtain a polysilazane precursor;
and B: preparation of SiBCN ceramic powder
Adding silicon powder, carbon powder and boride powder according to different molar proportions, ball-milling the mixed powder in the atmosphere of inert gas, preparing mechanical alloying powder by ball milling, and sintering under the protection of inert gas to obtain the SiBCN composite ceramic.
The reaction starting material is acrylonitrile trichlorosilane, hexamethyldisilazane, bis (trimethylsilyl) carbodiimide, methylvinylsilazane, a vinylated polysiloxane-based diimide, or disilylcarbodiimide.
The solvent is toluene, acetonitrile, glyme, hexane, xylene, acetone, dimethyl sulfoxide, diethyl ether or triethylamine.
The boride is BN, B4C or B2O3。
The temperature gradient of the sintering is set as follows: the temperature is increased to 300 ℃ at the room temperature by 5 ℃/min and is kept at the temperature for 2h, then is increased to 800 ℃ at the same speed, is kept at the temperature for 2h, is increased to 1400 ℃ at the same temperature increasing speed, is kept at the temperature for 6h and is naturally cooled, and the SiBCN composite ceramic is taken out at the room temperature.
The temperature gradient of the sintering is set as follows: raising the temperature to 200 ℃ at the room temperature at the speed of 5 ℃/min, preserving the heat for 2h at the temperature, then raising the temperature to 600 ℃ at the same speed, preserving the heat for 2h at the temperature, finally raising the temperature to 1400 ℃ at the same temperature raising speed, preserving the heat for 6h at the temperature, naturally cooling, and taking out the SiBCN composite ceramic at the room temperature.
The temperature gradient of the sintering is set as follows: raising the temperature to 400 ℃ at the room temperature at the speed of 5 ℃/min, preserving the heat for 2h at the temperature, then raising the temperature to 1000 ℃ at the same speed, preserving the heat for 2h at the temperature, finally raising the temperature to 1400 ℃ at the same temperature raising speed, preserving the heat for 6h at the temperature, naturally cooling, and taking out the SiBCN composite ceramic at the room temperature.
TABLE 1 design of parameters for molar ratios of elements
Table 2-4 ball milling process parameter design
Detailed description of the invention
Mixing acrylonitrile trichlorosilane and an acetonitrile solvent, wherein the solvent ratio (the mass of the solvent/the mass of the acrylonitrile trichlorosilane) is 4:1, sequentially adding the acetonitrile and the acrylonitrile trichlorosilane into a three-neck flask to prepare a solution, introducing ammonia gas under the stirring conditions of different temperatures (20 ℃, 40 ℃, 60 ℃ and 80 ℃) for 6 hours of ammonolysis, recovering the solvent after the reaction is finished, and putting the product into an oven for drying overnight to obtain a white powdery polysilazane precursor.
By using BC4Selecting a boron source with the molar ratio of Si to B to C to N being 2 to 1 to 2.5 to 1, and introducing Si powder, C powder and B powder4C, ball milling the mixed powder, wherein in the whole ball milling process, the mixed powder needs to be ensured to be under argon, the rotating speed is 1200rpm, the ball-to-material ratio is 40, the ball milling time is 30 hours, and the diameter of a milling ball is 3 x 6 x 9mm3Preparing mechanical alloy by ball millingAfter the powder is changed, the powder needs to be sintered under the condition of protective atmosphere nitrogen to complete ceramic conversion, and the temperature gradient is as follows: raising the temperature to 300 ℃ at the room temperature by 5 ℃/min, preserving the heat for 2h at the temperature, then raising the temperature to 800 ℃ at the same speed, preserving the heat for 2h at the temperature, finally raising the temperature to 1400 ℃ at the same temperature raising speed, preserving the heat for 6h at the temperature, naturally cooling, and taking out the ceramic powder at the room temperature. FIG. 1 is a graph showing the effect of temperature on polysilazane yield.
Detailed description of the invention
Mixing hexamethyldisilazane and an acetone solvent, adding acetonitrile and acrylonitrile trichlorosilane into a three-neck flask in sequence according to the mass ratio of the solvent to the acrylonitrile trichlorosilane (4: 1, 6:1, 8:1 and 10:1 respectively) to prepare a solution, introducing ammonia gas under the stirring condition of 60 ℃, carrying out ammonolysis for 6 hours, recovering the solvent after the reaction is finished, and putting the product into an oven to dry overnight to obtain a white powdery polysilazane precursor.
BN is used as a boron source, the molar ratio of Si to B to C to N is 2 to 1 to 2.5 to 1, and Si powder, C powder and B powder are introduced4C, ball milling the mixed powder, wherein in the whole ball milling process, the mixed powder needs to be ensured to be under argon, the rotating speed is 1200rpm, the ball-to-material ratio is 40, the ball milling time is 30 hours, and the diameter of a milling ball is 3 x 6 x 9mm3After mechanical alloying powder is prepared by ball milling, the powder needs to be sintered under the condition of protective atmosphere nitrogen to complete ceramic conversion, and the temperature gradient is as follows: raising the temperature to 300 ℃ at the room temperature by 5 ℃/min, preserving the heat for 2h at the temperature, then raising the temperature to 800 ℃ at the same speed, preserving the heat for 2h at the temperature, finally raising the temperature to 1400 ℃ at the same temperature raising speed, preserving the heat for 6h at the temperature, naturally cooling, and taking out the ceramic powder at the room temperature. Figure 2 is a schematic representation of the effect of solvent ratio on polysilazane yield.
Detailed description of the invention
Mixing bis (trimethylsilyl) carbodiimide and a xylene solvent, selecting a solvent ratio (solvent mass/acrylonitrile trichlorosilane mass) of 4:1, sequentially adding the solvent and an initial reactant into a three-neck flask to prepare a solution, introducing ammonia gas (3h, 4h, 5h and 6h) for different times under the stirring condition of 60 ℃, recovering the solvent after the reaction is finished, and putting a product into an oven to dry overnight to obtain a white powdery polysilazane precursor.
By using B2O3Selecting a source B, introducing Si powder, C powder and B powder according to the molar ratio of Si to B to C to N being 2:1 to 2.5:14C, ball milling the mixed powder, wherein in the whole ball milling process, the mixed powder needs to be ensured to be under argon, the rotating speed is 1200rpm, the ball-to-material ratio is 40, the ball milling time is 30 hours, and the diameter of a milling ball is 3 x 6 x 9mm3After mechanical alloying powder is prepared by ball milling, the powder needs to be sintered under the condition of protective atmosphere nitrogen to complete ceramic conversion, and the temperature gradient is as follows: raising the temperature to 300 ℃ at the room temperature by 5 ℃/min, preserving the heat for 2h at the temperature, then raising the temperature to 800 ℃ at the same speed, preserving the heat for 2h at the temperature, finally raising the temperature to 1400 ℃ at the same temperature raising speed, preserving the heat for 6h at the temperature, naturally cooling, and taking out the ceramic powder at the room temperature. FIG. 3 is a graph showing the effect of ammonolysis time on polysilazane yield.
Detailed description of the invention
Mixing methylvinyl silazane and a hexane solvent, selecting a solvent ratio (solvent mass/acrylonitrile trichlorosilane mass) of 4:1, sequentially adding the solvent and an initial reactant into a three-neck flask to prepare a solution, introducing ammonia gas under the stirring condition of 60 ℃, carrying out ammonolysis for 6 hours, recovering the solvent after the reaction is finished, and putting a product into an oven to be dried overnight to obtain a white powdery polysilazane precursor.
By using BC4Selecting different element molar ratios (as shown in Table 3) for the source B, and introducing Si powder, C powder and B powder4C, ball milling the mixed powder, wherein in the whole ball milling process, the mixed powder needs to be ensured to be under argon, the rotating speed is 1200rpm, the ball-to-material ratio is 40, the ball milling time is 30 hours, and the diameter of a milling ball is 3 x 6 x 9mm3After mechanical alloying powder is prepared by ball milling, the powder needs to be sintered under the condition of protective atmosphere nitrogen to complete ceramic conversion, and the temperature gradient is as follows: increasing the temperature to 300 ℃ at room temperature at 5 ℃/min and keeping the temperature for 2h, and thenRaising the temperature to 800 ℃ at the same speed, preserving the heat for 2h at the temperature, finally raising the temperature to 1400 ℃ at the same speed, preserving the heat for 6h at the temperature, naturally cooling, and taking out the ceramic powder at room temperature. FIG. 4 is a diagram showing the influence (b) of the content of element C on the ceramization yield (a) and thermal stability of the powder. FIG. 5 is a schematic diagram showing the influence (b) of Si content on the powder ceramization yield (a) and the thermal stability of the ceramic powder. FIG. 6 is a diagram showing the influence of the content of element B on the ceramization yield (a) of the powder and the thermal stability of the ceramic powder (B).
TABLE 3 atomic ratio settings of the elements
Detailed description of the invention
Mixing vinyl polysiloxane diimide and glyme, selecting a solvent ratio (mass of the solvent/mass of acrylonitrile trichlorosilane) to be 4:1, sequentially adding the solvent and an initial reactant into a three-neck flask to prepare a solution, introducing ammonia gas under the stirring condition of 60 ℃, carrying out ammonolysis for 6 hours, recovering the solvent after the reaction is finished, and putting a product into an oven to be dried overnight to obtain a white powdery polysilazane precursor.
BN is used as a B source, the molar ratio of Si to B to C to N is 2 to 1 to 2.5 to 1, and Si powder, C powder and B powder are introduced4And C, performing ball milling on the mixed powder, wherein in the whole ball milling process, different ball milling parameters (shown in table 4) are designed under the condition that the mixed powder is required to be ensured to be under argon, after mechanical alloying powder is prepared by ball milling, the powder is required to be sintered under the condition of nitrogen in protective atmosphere to complete ceramic conversion, and the temperature gradient is as follows specifically: raising the temperature to 300 ℃ at the room temperature by 5 ℃/min, preserving the heat for 2h at the temperature, then raising the temperature to 800 ℃ at the same speed, preserving the heat for 2h at the temperature, finally raising the temperature to 1400 ℃ at the same temperature raising speed, preserving the heat for 6h at the temperature, naturally cooling, and taking out the ceramic powder at the room temperature. Fig. 7 is a schematic diagram showing the influence of the ball to powder ceramization yield (a) and the thermal stability of the ceramic powder (b). FIG. 8 is a graph of ball time versus powder ceramming yield (a) and ceramic powderInfluence of thermal stability (b) schematic. Fig. 9 is a schematic diagram showing the influence of the rotation speed on the powder ceramization yield (a) and the thermal stability of the ceramic powder (b).
TABLE 4 ball milling Process parameter design
The above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the embodiments of the present invention, and those skilled in the art can easily make various changes and modifications according to the main concept and spirit of the present invention, so the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A preparation method of SiBCN composite ceramic with high temperature stability is characterized by comprising the following steps:
step A: preparation of polysilazane precursor
Mixing an initial reactant and a solvent to prepare a solution, wherein the mass ratio of the solvent to the initial reactant is (4-10): stirring at the temperature of 20-80 ℃, introducing ammonia gas for 3-6 h, recovering the solvent after the reaction is finished, and drying the product to obtain a polysilazane precursor;
and B: preparation of SiBCN ceramic powder
Adding silicon powder, carbon powder and boride powder according to different molar proportions, ball-milling the mixed powder in the atmosphere of inert gas, preparing mechanical alloying powder by ball milling, and sintering under the protection of inert gas to obtain the SiBCN composite ceramic.
2. The method of high temperature stabilization of SiBCN composite ceramic according to claim 1, wherein the reaction starting material is acrylonitrile trichlorosilane, hexamethyldisilazane, bis (trimethylsilyl) carbodiimide, methylvinylsilazane, a vinylated polysiloxane-based diimide, or disilylcarbodiimide.
3. The method of high temperature stabilization of SiBCN composite ceramic according to claim 1, wherein the solvent is toluene, acetonitrile, glyme, hexane, xylene, acetone, dimethyl sulfoxide, diethyl ether, or triethylamine.
4. The method of claim 1, wherein the boride is BN, B4C or B2O3。
5. The method of high temperature stabilization of SiBCN composite ceramic according to claim 1, wherein said sintering temperature gradient is set as follows: the temperature is increased to 300 ℃ at the room temperature by 5 ℃/min and is kept at the temperature for 2h, then is increased to 800 ℃ at the same speed, is kept at the temperature for 2h, is increased to 1400 ℃ at the same temperature increasing speed, is kept at the temperature for 6h and is naturally cooled, and the SiBCN composite ceramic is taken out at the room temperature.
6. The method of high temperature stabilization of SiBCN composite ceramic according to claim 1, wherein said sintering temperature gradient is set as follows: raising the temperature to 200 ℃ at the room temperature at the speed of 5 ℃/min, preserving the heat for 2h at the temperature, then raising the temperature to 600 ℃ at the same speed, preserving the heat for 2h at the temperature, finally raising the temperature to 1400 ℃ at the same temperature raising speed, preserving the heat for 6h at the temperature, naturally cooling, and taking out the SiBCN composite ceramic at the room temperature.
7. The method of high temperature stabilization of SiBCN composite ceramic according to claim 1, wherein said sintering temperature gradient is set as follows: raising the temperature to 400 ℃ at the room temperature at the speed of 5 ℃/min, preserving the heat for 2h at the temperature, then raising the temperature to 1000 ℃ at the same speed, preserving the heat for 2h at the temperature, finally raising the temperature to 1400 ℃ at the same temperature raising speed, preserving the heat for 6h at the temperature, naturally cooling, and taking out the SiBCN composite ceramic at the room temperature.
8. A high temperature stable SiBCN composite ceramic prepared by the method of any of the above claims 1 to 7.
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