CN111689778A - High-density SiBCN ceramic material and preparation method thereof - Google Patents
High-density SiBCN ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-density SiBCN ceramic material and a preparation method thereof, and relates to the SiBCN ceramic material and the preparation method thereof. The invention aims to solve the problems of low density, small size and low production efficiency of the SiBCN ceramic material prepared by the existing mechanical alloying-hot pressing sintering method. A high-density SiBCN ceramic material is prepared from silicon powder of cubic crystal system, graphite powder and hexagonal boron nitride powder. The method comprises the following steps: weighing cubic silicon powder, graphite powder and hexagonal boron nitride powder, putting the cubic silicon powder, graphite powder and hexagonal boron nitride powder into a ball milling tank for ball milling, then performing hot pressing and presintering, and finally sealing in a sheath for hot isostatic pressing to complete the preparation of the high-density SiBCN ceramic material. The invention is used for preparing the high-density SiBCN ceramic material and the preparation thereof.
Description
Technical Field
The invention relates to a SiBCN ceramic material and a preparation method thereof.
Background
The silicon-boron-carbon-nitrogen ceramic material is a novel high-temperature heat-proof structural ceramic material which has just been developed in about 20 years, and SiBCN ceramic has the advantages of low density, excellent structural stability (higher amorphous stability, and the capsule structure after crystallization can effectively inhibit the growth of crystal grains), excellent comprehensive mechanical properties (high strength, high hardness, high toughness and the like), good oxidation resistance, good high-temperature creep property, excellent comprehensive high-temperature property (SiBCN fibers can be used in 1500 ℃ air), good thermal shock resistance and ablation resistance, and excellent machining property, so that the SiBCN ceramic material attracts extensive attention of researchers in the field of materials. At present, the main preparation methods of the silicon-boron-carbon-nitrogen ceramic bulk material comprise an organic precursor conversion method and a mechanical alloying-hot pressing sintering method (an inorganic method).
In the previous research on preparing silicon-boron-carbon-nitrogen ceramic by a precursor conversion method, the focus is on firstly synthesizing an organic precursor by using an organic monomer as a raw material, then cracking the precursor at high temperature to obtain inorganic powder, and finally sintering the ceramic powder to obtain the ceramic material. The silicon-boron-carbon-nitrogen ceramic material prepared by the organic precursor conversion method has excellent performance, but has a plurality of problems: 1. the steps of preparing the amorphous silicon boron carbon nitrogen ceramic composite material by using the organic precursor are complex, the process is difficult to control, the synthesis environment requirement is strict, all the steps of raw material storage, the synthesis process and the synthesis of the organic precursor are required to be operated in a highly anhydrous and oxygen-free environment, and the synthesis process is slow; 2. the amorphous silicon boron carbon nitrogen ceramic composite material prepared by using the organic precursor has low yield and small single synthesis amount, and solid byproducts generated in part of organic synthesis processes are not easy to remove; 3. the cracking speed is required to be only 1 ℃/minute in the process of preparing the silicon-boron-carbon-nitrogen ceramic by the cracking method, the cracking temperature is required to be about 1400 ℃ when being high, the cracking amount of each time is small, the operation is required to be carried out under the protection of high-purity inert gas, and the control is difficult; 4. the silicon-boron-carbon-nitrogen ceramic obtained by the cracking method can not realize complete densification, is a porous material and can not meet the actual use requirement; 5. the raw materials for organic synthesis are high in price and poor in environmental friendliness. These disadvantages greatly limit the large-scale application of the silicon-boron-carbon-nitrogen ceramic composite material in the aspect of engineering.
Zhuihua Yang et al (microstuctural features and properties of the nano-crystalline SiC/BN (C) composite ceramic prepared from the mechanical alloyed SiBCN powder [ J ] 2012]Journal of Alloys and Compounds,2012,537: 346-. Firstly, mixing and ball-milling raw materials to obtain amorphous SiBCN powder, and then sintering by adopting a hot-pressing sintering process to prepare the SiBCN ceramic material. The process for preparing the SiBCN ceramic material by an inorganic method is simple, but the sintering temperature is up to 2000 ℃, the prepared SiBCN ceramic material has low density (only 85 percent of theoretical density), the comprehensive mechanical property is not ideal, and the sample size is small
And only a single ceramic material can be prepared by single sintering, and the requirement of practical application cannot be met. Bin Liang et al (Highly denseammophorus Si) 20152BC3N monoliths with excellent mechanical properties prepared byhigh pressure sintering[J]Journal of American Ceramic Society,2015,98(12):3782-
And only a single material can be obtained by single sintering, and the production efficiency and the material size cannot meet the requirements of practical application. The SiBCN ceramic material prepared by an inorganic method has low production efficiency, and the comprehensive indexes such as the size, the density and the like of the material can not meet the requirements of practical application, so that the application of the SiBCN ceramic material in the aspect of engineering is greatly limited.
Disclosure of Invention
The invention provides a high-density SiBCN ceramic material and a preparation method thereof, aiming at solving the problems of low density, small size and low production efficiency of the SiBCN ceramic material prepared by the existing mechanical alloying-hot pressing sintering method.
A high-density SiBCN ceramic material is prepared from silicon powder of cubic system, graphite powder and hexagonal boron nitride powder;
the molar ratio of Si in the cubic silicon powder to C in the graphite powder is 1 (0.05-2); the molar ratio of Si in the cubic silicon powder to B in the hexagonal boron nitride powder is 1 (0.5-2);
the grain diameter of the silicon powder of the cubic system is 1-50 mu m; the particle size of the graphite powder is 1-10 mu m; the particle size of the hexagonal boron nitride powder is 1-10 mu m.
A preparation method of a high-density SiBCN ceramic material comprises the following steps:
firstly, weighing cubic silicon powder, graphite powder and hexagonal boron nitride powder;
the molar ratio of Si in the cubic silicon powder to C in the graphite powder is 1 (0.05-2); the molar ratio of Si in the cubic silicon powder to B in the hexagonal boron nitride powder is 1 (0.5-2);
the grain diameter of the silicon powder of the cubic system is 1-50 mu m; the particle size of the graphite powder is 1-10 mu m; the particle size of the hexagonal boron nitride powder is 1-10 mu m;
secondly, putting the weighed cubic silicon powder, graphite powder and hexagonal boron nitride powder into a ball milling tank, and carrying out ball milling for 1-50 h under the conditions of argon atmosphere, the diameter of a milling ball of 3-10 mm and the mass ratio of ball materials of (5-100): 1 to obtain amorphous SiBCN powder;
thirdly, under the conditions that the sintering temperature is 1500-1700 ℃ and the sintering pressure is 20-80 MPa, carrying out hot-pressing pre-sintering on the amorphous SiBCN powder for 10-60 min to obtain an amorphous/nanocrystalline silicon boron carbon nitrogen ceramic blank;
and fourthly, polishing the upper surface and the lower surface of the amorphous/nanocrystalline silicon boron carbon nitrogen ceramic blank, cleaning and drying to obtain a pretreated silicon boron carbon nitrogen ceramic blank, welding and sealing one or more pretreated silicon boron carbon nitrogen ceramic blanks into a hot isostatic pressing package in a vacuum environment to obtain a packaged ceramic blank, carrying out hot isostatic pressing sintering on the packaged ceramic blank for 10-60 min under the conditions that the sintering temperature is 1700-2000 ℃ and the sintering pressure is 150-190 MPa to obtain a packaged ceramic blank, removing the hot isostatic pressing package, and obtaining the high-density SiBCN ceramic material.
The invention has the beneficial effects that:
1. the high-density SiBCN ceramic material has low raw material cost and is easily and directly available from the market.
2. Hot isostatic pressing technology integrates the advantages of hot pressing and isostatic pressing technology, and can simultaneously apply high temperature (up to 2000 ℃) and high pressure (up to 200MPa) which are equal in all directions during the sintering process of ceramics. The invention adopts the combination of the hot isostatic pressing sintering technology and the mechanical alloying technology to prepare the high-density SiBCN ceramic material, and solves the problems that the prior mechanical alloying-hot pressing sintering method for preparing the SiBCN ceramic material has low relative density (85 percent) and small size
The production efficiency is low. The density of the SiBCN ceramic material sintered by the hot isostatic pressing technology can reach more than 96 percent of the theoretical density, and the maximum size reaches
At present, the SiBCN ceramics with the same size of five blocks can be obtained at most by single sintering, the application of the practical engineering of the SiBCN ceramics can be met, the sintering efficiency of the SiBCN ceramics is obviously improved, the production cost is reduced, the subsequent machining can be effectively reduced by adopting the hot isostatic pressing near-net forming technology, and the cost is favorably reduced.
When preparing high-density multi-Si blocks simultaneously2BC3When the N ceramic material is used, the density is 2.74g/cm according to analysis and test3～2.83g/cm3The hardness is 10.80 GPa-11.02 GPa, the bending strength is 404.0 MPa-471.5 MPa, the elastic modulus is 300.2 GPa-311.8 GPa, and the fracture toughness is 3.52 MPa.m1/2～5.13MPa·m1/2Mechanical property far superior to that of Si prepared by mechanical alloying-hot pressing sintering2BC3N ceramic material.
3. The high-density SiBCN ceramic material has large size and the maximum size reaches
And the SiBCN ceramic material with five block sizes can be prepared at the same time by one-time sintering at present, which cannot be obtained by the prior preparation method and can meet the application requirements of certain special parts in aviation and aerospace. The high-density SiBCN ceramic material obtained by the invention not only has good mechanical property, but also has good processability, can be processed by conventional processing means such as turning, milling, grinding and the like, and can be practically applied to high-temperature structural components.
Drawings
FIG. 1 shows encapsulated Si obtained in a fourth step of the example2BC3A real object diagram of the N ceramic blank;
FIG. 2 shows a hot isostatically pressed capsule encapsulated Si obtained in step four of the example2BC3A real object diagram of the N ceramic blank;
FIG. 3 illustrates one embodiment of a one step post-four hot isostatic pressing capsule packaging Si2BC3Removing the sheath of the N ceramic blank, and then removing five pieces of high-density Si2BC3N physical diagram of ceramic material stack;
FIG. 4 shows flaky amorphous/nanocrystalline Si before and after HIP in example I2BC3N ceramic green body and high-density Si2BC3Material object diagram of N ceramic material, 1 is the flake amorphous/nanocrystalline Si prepared in step three2BC3N ceramic blank, 2 is the high compact Si that step four prepared2BC3N ceramic material;
FIG. 5 shows the preparation of amorphous/nanocrystalline Si in sheet form in one step three2BC3N is a topography map of the polished surface of the ceramic blank;
FIG. 6 shows the highly dense Si prepared in example one2BC3N is a topography map of the polished ceramic material surface;
FIG. 7 shows the preparation of amorphous/nanocrystalline Si flakes in one step three2BC3N ceramic blank fracture morphology graph;
FIG. 8 shows the highly dense Si prepared in example one2BC3N is a fracture morphology diagram of the ceramic material;
FIG. 9 shows the highly dense Si prepared in example two2BC3And N is a physical diagram of the ceramic material.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
The first embodiment is as follows: the high-density SiBCN ceramic material is prepared from silicon powder of a cubic crystal system, graphite powder and hexagonal boron nitride powder;
the molar ratio of Si in the cubic silicon powder to C in the graphite powder is 1 (0.05-2); the molar ratio of Si in the cubic silicon powder to B in the hexagonal boron nitride powder is 1 (0.5-2);
the grain diameter of the silicon powder of the cubic system is 1-50 mu m; the particle size of the graphite powder is 1-10 mu m; the particle size of the hexagonal boron nitride powder is 1-10 mu m.
The beneficial effects of the embodiment are as follows:
1. the high-density SiBCN ceramic material of the embodiment has low raw material cost and is easy to directly obtain from the market.
2. Hot isostatic pressing technology integrates the advantages of hot pressing and isostatic pressing technology, and can simultaneously apply high temperature (up to 2000 ℃) and high pressure (up to 200MPa) which are equal in all directions during the sintering process of ceramics. The embodiment adopts a hot isostatic pressing sintering technology and a machineThe alloying technology is combined to prepare the high-density SiBCN ceramic material, and the problems of low relative density (85%) and small size of the SiBCN ceramic material prepared by the existing mechanical alloying-hot pressing sintering method are solved
The production efficiency is low. The density of the SiBCN ceramic material sintered by the hot isostatic pressing technology can reach more than 96 percent of the theoretical density, and the maximum size reaches
At present, the SiBCN ceramics with the same size of five blocks can be obtained at most by single sintering, the application of the practical engineering of the SiBCN ceramics can be met, the sintering efficiency of the SiBCN ceramics is obviously improved, the production cost is reduced, the subsequent machining can be effectively reduced by adopting the hot isostatic pressing near-net forming technology, and the cost is favorably reduced.
When preparing high-density multi-Si blocks simultaneously2BC3When the N ceramic material is used, the density is 2.74g/cm according to analysis and test3～2.83g/cm3The hardness is 10.80 GPa-11.02 GPa, the bending strength is 404.0 MPa-471.5 MPa, the elastic modulus is 300.2 GPa-311.8 GPa, and the fracture toughness is 3.52 MPa.m1/2～5.13MPa·m1/2Mechanical property far superior to that of Si prepared by mechanical alloying-hot pressing sintering2BC3N ceramic material.
3. The high-density SiBCN ceramic material has large size and the maximum size reaches
And the SiBCN ceramic material with five block sizes can be prepared at the same time by one-time sintering at present, which cannot be obtained by the prior preparation method and can meet the application requirements of certain special parts in aviation and aerospace. The high-density SiBCN ceramic material obtained by the embodiment has good mechanical property and good machinability, can be machined by conventional machining means such as turning, milling and grinding, and can be practically applied to high-temperature structural components.
The second embodiment is as follows: the embodiment provides a preparation method of a high-density SiBCN ceramic material, which is completed by the following steps:
firstly, weighing cubic silicon powder, graphite powder and hexagonal boron nitride powder;
the molar ratio of Si in the cubic silicon powder to C in the graphite powder is 1 (0.05-2); the molar ratio of Si in the cubic silicon powder to B in the hexagonal boron nitride powder is 1 (0.5-2);
the grain diameter of the silicon powder of the cubic system is 1-50 mu m; the particle size of the graphite powder is 1-10 mu m; the particle size of the hexagonal boron nitride powder is 1-10 mu m;
secondly, putting the weighed cubic silicon powder, graphite powder and hexagonal boron nitride powder into a ball milling tank, and carrying out ball milling for 1-50 h under the conditions of argon atmosphere, the diameter of a milling ball of 3-10 mm and the mass ratio of ball materials of (5-100): 1 to obtain amorphous SiBCN powder;
thirdly, under the conditions that the sintering temperature is 1500-1700 ℃ and the sintering pressure is 20-80 MPa, carrying out hot-pressing pre-sintering on the amorphous SiBCN powder for 10-60 min to obtain an amorphous/nanocrystalline silicon boron carbon nitrogen ceramic blank;
and fourthly, polishing the upper surface and the lower surface of the amorphous/nanocrystalline silicon boron carbon nitrogen ceramic blank, cleaning and drying to obtain a pretreated silicon boron carbon nitrogen ceramic blank, welding and sealing one or more pretreated silicon boron carbon nitrogen ceramic blanks into a hot isostatic pressing package in a vacuum environment to obtain a packaged ceramic blank, carrying out hot isostatic pressing sintering on the packaged ceramic blank for 10-60 min under the conditions that the sintering temperature is 1700-2000 ℃ and the sintering pressure is 150-190 MPa to obtain a packaged ceramic blank, removing the hot isostatic pressing package, and obtaining the high-density SiBCN ceramic material.
The third concrete implementation mode: the second embodiment is different from the first embodiment in that: the purity of the cubic crystal system silicon powder in the step one is 99-99.9%; the purity of the graphite powder in the step one is 99-99.9%; the purity of the hexagonal boron nitride powder in the step one is 98-99.9%. The rest is the same as the second embodiment.
The fourth concrete implementation mode: this embodiment is different from the second or third embodiment in that: and the ball milling tank in the step two is a vibration type ball milling tank or a planetary ball milling tank. The other is the same as the second or third embodiment.
The fifth concrete implementation mode: the second to fourth differences from the embodiments are: and the hot isostatic pressing sheath in the fourth step is a carbon film sheath, a glass sheath or a metal sheath. The other points are the same as those in the second to fourth embodiments.
The sixth specific implementation mode: the present embodiment is different from one of the second to fifth embodiments in that: and in the second step, ball milling is carried out for 15-35 h under the conditions of argon atmosphere, the diameter of a grinding ball is 5-8 mm, and the mass ratio of the ball material to the grinding ball is (10-90): 1. The other points are the same as those in the second to fifth embodiments.
The seventh embodiment: the present embodiment is different from one of the second to sixth embodiments in that: and in the fourth step, carrying out hot isostatic pressing sintering on the ceramic blank packaged by the sheath for 30min under the conditions that the sintering temperature is 2000 ℃ and the sintering pressure is 150 MPa. The other points are the same as those in the second to sixth embodiments.
The specific implementation mode is eight: the present embodiment is different from one of the second to seventh embodiments in that: and in the fourth step, carrying out hot isostatic pressing sintering on the ceramic blank packaged by the sheath for 30min under the conditions that the sintering temperature is 1900 ℃ and the sintering pressure is 190 MPa. The other points are the same as those in the second to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the second to eighth embodiments in that: and in the fourth step, under a vacuum environment, laminating, welding and sealing five pretreated silicon-boron-carbon-nitrogen ceramic blanks into a hot isostatic pressing sheath to obtain the ceramic blanks packaged by the sheath. The other points are the same as those in the second to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the second to ninth embodiments in that: when the five pretreated silicon-boron-carbon-nitrogen ceramic blanks are stacked, the silicon-boron-carbon-nitrogen ceramic blanks are separated by a BN sheet with the thickness of 1mm, and after the blanks are stacked, a BN isolating layer with the thickness of 1.5mm is arranged between the blanks and the hot isostatic pressing sheath. The other points are the same as those in the second to ninth embodiments.
The concrete implementation mode eleven: this embodiment is different from one of the second to tenth embodiments in that: and in the second step, ball milling is carried out for 20 hours under the conditions of argon atmosphere, the diameter of a grinding ball is 6mm and the mass ratio of ball materials is 50: 1. The others are the same as in the second to tenth embodiments.
The specific implementation mode twelve: this embodiment is different from one of the second to eleventh embodiments in that: and in the second step, ball milling is carried out for 35 hours under the conditions of argon atmosphere, the diameter of a grinding ball is 8mm and the mass ratio of ball materials is 10: 1. The other is the same as in embodiments two to eleven.
The specific implementation mode is thirteen: this embodiment is different from one of the second to twelfth embodiments in that: and in the second step, ball milling is carried out for 15 hours under the conditions of argon atmosphere, the diameter of a grinding ball is 5mm and the mass ratio of ball materials is 90: 1. The rest is the same as the second to twelfth embodiments.
The specific implementation mode is fourteen: this embodiment is different from one of the second to thirteenth embodiments in that: in the third step, the amorphous SiBCN powder is hot-pressed and presintered for 30min under the conditions that the sintering temperature is 1800 ℃ and the sintering pressure is 30 MPa. The others are the same as in embodiments two to thirteen.
The concrete implementation mode is fifteen: this embodiment is different from the embodiment in one of two to fourteen: in the third step, under the conditions that the sintering temperature is 1700 ℃ and the sintering pressure is 20MPa, the amorphous SiBCN powder is subjected to hot-pressing pre-sintering for 20 min. The others are the same as the embodiments from twenty to fourteen.
The specific implementation mode is sixteen: the present embodiment differs from one of the second to fifteenth embodiments in that: in the third step, under the conditions that the sintering temperature is 1500 ℃ and the sintering pressure is 80MPa, the amorphous SiBCN powder is subjected to hot-pressing pre-sintering for 20 min. The others are the same as in embodiments two to fifteen.
Seventeenth embodiment: this embodiment differs from the second to sixteenth embodiment in that: in the third step, under the conditions that the sintering temperature is 1700 ℃ and the sintering pressure is 60MPa, the amorphous SiBCN powder is subjected to hot-pressing pre-sintering for 30 min. The rest is the same as the second to sixteenth embodiments.
The specific implementation mode is eighteen: this embodiment is different from one of the second to seventeenth embodiments in that: and in the fourth step, carrying out hot isostatic pressing sintering on the ceramic blank packaged by the sheath for 45min under the conditions that the sintering temperature is 1800 ℃ and the sintering pressure is 190 MPa. The other is the same as in the second to seventeenth embodiments.
The detailed embodiment is nineteen: this embodiment differs from one of the second to eighteen embodiments in that: and in the fourth step, carrying out hot isostatic pressing sintering on the ceramic blank packaged by the sheath for 60min under the conditions that the sintering temperature is 1700 ℃ and the sintering pressure is 190 MPa. The others are the same as the embodiments twenty to eighteen.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
a preparation method of a high-density SiBCN ceramic material comprises the following steps:
firstly, weighing cubic silicon powder, graphite powder and hexagonal boron nitride powder;
the molar ratio of Si in the silicon powder of the cubic system to C in the graphite powder is 2: 3; the molar ratio of Si in the cubic silicon powder to B in the hexagonal boron nitride powder is 2: 1;
the grain diameter (D90) of the silicon powder of the cubic system is 45 mu m; the median particle size of the graphite powder is 2.0 mu m; the average grain diameter of the hexagonal boron nitride powder is 5.1 mu m;
secondly, putting the weighed cubic silicon powder, graphite powder and hexagonal boron nitride powder into a ball milling tank, and carrying out ball milling for 40h under the conditions of argon atmosphere, grinding ball diameter of 5mm and ball material mass ratio of 20:1 to obtain amorphous SiBCN powder;
thirdly, under the conditions that the sintering temperature is 1700 ℃ and the sintering pressure is 60MPa, the amorphous SiBCN powder is subjected to hot-pressing pre-sintering for 30min to obtain flaky amorphous/nanocrystalline Si2BC3An N ceramic green body;
fourthly,Flake amorphous/nanocrystalline Si2BC3Polishing the upper and lower surfaces of the N ceramic blank body, cleaning and drying to obtain pretreated Si2BC3N ceramic blank, in vacuum environment, five pretreated Si pieces2BC3The N ceramic blanks are stacked and welded and sealed in a hot isostatic pressing sheath to obtain Si packaged by the sheath2BC3The N ceramic blank is prepared by wrapping and packaging the encapsulated Si under the conditions that the sintering temperature is 1900 ℃ and the sintering pressure is 190MPa2BC3Carrying out hot isostatic pressing sintering on the N ceramic blank for 30min to obtain the hot isostatic pressed packaged Si2BC3Removing the hot isostatic pressing sheath from the N ceramic blank to obtain five pieces of high-density Si2BC3N ceramic material.
Step four, five pretreated Si2BC3Lamination of N ceramic green bodies, Si2BC3The N ceramic blanks are separated by BN sheets with the thickness of 1mm so as to prevent bonding between the sheets in the hot isostatic pressing process, and meanwhile, after the blanks are stacked, a BN isolating layer with the thickness of 1.5mm is arranged between the blanks and the hot isostatic pressing sheath so as to prevent reaction or bonding between the blanks and the sheath in the hot isostatic pressing process.
The purity of the cubic system silicon powder in the first step is 99.5 percent; the purity of the graphite powder in the step one is 99.9%; the purity of the hexagonal boron nitride powder in the first step is 98%.
And the ball milling tank in the step two is a planetary ball milling tank.
And the hot isostatic pressing sheath in the fourth step is a metal molybdenum sheath.
The silicon powder of cubic system described in the first step of this embodiment is purchased from jin research new materials science and technology ltd, beijing, and has a model number of C-Si-45.
FIG. 1 shows encapsulated Si obtained in a fourth step of the example2BC3A real object diagram of the N ceramic blank; FIG. 2 shows a hot isostatically pressed capsule encapsulated Si obtained in step four of the example2BC3A real object diagram of the N ceramic blank; as can be seen, after the hot isostatic pressing treatment, a significant dimension appeared in the metal capsuleThe change is that the radial shrinkage of the middle part of the sheath is obvious, the radial shrinkage of the upper end part and the lower end part is small, and the height of the sheath is also obviously reduced.
FIG. 3 illustrates one embodiment of a one step post-four hot isostatic pressing capsule packaging Si2BC3Removing the sheath of the N ceramic blank, and then removing five pieces of high-density Si2BC3N physical diagram of ceramic material stack; it can be seen from the figure that after the hot isostatic pressing treatment, the sizes of the ceramic blanks are changed and slightly different, which is determined by the distribution of the pressure field inside the capsule during the hot isostatic pressing treatment, and the more the size of the ceramic blanks is shrunk, the more the effect of the hot isostatic pressing treatment is obvious, and the higher the density of the ceramic is. Because a BN isolation layer is arranged between the sheath and the SiBCN ceramic blank, after hot isostatic pressing treatment, the shrinkage conditions of the blank materials are slightly different; due to the existence of BN layer, five pieces of high-density Si appear after the sheath is removed2BC3The physical diagram of the N ceramic material stack is different from the shape before the jacket is removed.
FIG. 4 shows flaky amorphous/nanocrystalline Si before and after HIP in example I2BC3N ceramic green body and high-density Si2BC3Material object diagram of N ceramic material, 1 is the flake amorphous/nanocrystalline Si prepared in step three2BC3N ceramic blank, 2 is the high compact Si that step four prepared2BC3N ceramic material; it can be seen that after the hot isostatic pressing treatment, the ceramic sheet was reduced from 32mm to 29.4mm in diameter, and the radial shrinkage was significant, when measured on the sample with the largest radial shrinkage.
FIG. 5 shows the preparation of amorphous/nanocrystalline Si in sheet form in one step three2BC3N is a topography map of the polished surface of the ceramic blank; FIG. 6 shows the highly dense Si prepared in example one2BC3N is a topography map of the polished ceramic material surface; it can be seen that the surface of the SiBCN ceramic material becomes significantly dense after the hot isostatic pressing treatment.
FIG. 7 shows the preparation of amorphous/nanocrystalline Si flakes in one step three2BC3N ceramic blank fracture morphology graph; FIG. 8Highly dense Si prepared for example one2BC3N is a fracture morphology diagram of the ceramic material; as can be seen from the figure, after the hot isostatic pressing treatment, the grains at the port are changed from equiaxial to lamellar, the size of the grains is increased, and the phenomenon of lamellar extraction at the fracture is generated, which is beneficial to improving the fracture toughness of the material.
The high-density Si prepared in this example was tested2BC3The density of the N ceramic material is 2.83g/cm at most399.6% of theoretical density, 11.02GPa of hardness, 471.5MPa of bending strength, 311.8GPa of elastic modulus, and 5.13 MPa-m of fracture toughness1/2。
Example two:
a preparation method of a high-density SiBCN ceramic material comprises the following steps:
firstly, weighing cubic silicon powder, graphite powder and hexagonal boron nitride powder;
the molar ratio of Si in the silicon powder of the cubic system to C in the graphite powder is 2: 3; the molar ratio of Si in the cubic silicon powder to B in the hexagonal boron nitride powder is 2: 1;
the grain diameter (D90) of the silicon powder of the cubic system is 45 mu m; the median particle size of the graphite powder is 2.0 mu m; the average grain diameter of the hexagonal boron nitride powder is 5.1 mu m;
secondly, putting the weighed cubic silicon powder, graphite powder and hexagonal boron nitride powder into a ball milling tank, and carrying out ball milling for 40h under the conditions of argon atmosphere, grinding ball diameter of 5mm and ball material mass ratio of 20:1 to obtain amorphous SiBCN powder;
thirdly, under the conditions that the sintering temperature is 1700 ℃ and the sintering pressure is 60MPa, the amorphous SiBCN powder is subjected to hot-pressing pre-sintering for 30min to obtain amorphous/nano-crystalline Si2BC3An N ceramic green body;
fourthly, mixing amorphous/nanocrystalline Si2BC3Polishing the upper and lower surfaces of the N ceramic blank body, cleaning and drying to obtain pretreated Si2BC3N ceramic blank, in vacuum environment, five pretreated Si pieces2BC3The N ceramic green bodies are laminated and welded and sealed to heat or the likeStatically pressing the inner part of the sheath to obtain the Si encapsulated by the sheath2BC3The N ceramic blank is prepared by wrapping and packaging the packaged Si under the conditions that the sintering temperature is 1700 ℃ and the sintering pressure is 190MPa2BC3Carrying out hot isostatic pressing sintering on the N ceramic blank for 30min to obtain the hot isostatic pressed packaged Si2BC3Removing the hot isostatic pressing sheath from the N ceramic blank to obtain five pieces of high-density Si2BC3N ceramic material.
Step four, five pretreated Si2BC3Lamination of N ceramic green bodies, Si2BC3The N ceramic blanks are separated by BN sheets with the thickness of 1mm so as to prevent bonding between the sheets in the hot isostatic pressing process, and meanwhile, after the blanks are stacked, a BN isolating layer with the thickness of 1.5mm is arranged between the blanks and the hot isostatic pressing sheath so as to prevent reaction or bonding between the blanks and the sheath in the hot isostatic pressing process.
The purity of the cubic system silicon powder in the first step is 99.5 percent; the purity of the graphite powder in the step one is 99.9%; the purity of the hexagonal boron nitride powder in the first step is 98%.
And in the second step, the ball milling tank is a planetary ball milling tank.
And the hot isostatic pressing sheath in the fourth step is a metal molybdenum sheath.
The silicon powder of cubic system described in the first step of this embodiment is purchased from jin research new materials science and technology ltd, beijing, and has a model number of C-Si-45.
FIG. 9 shows the highly dense Si prepared in example two2BC3N physical diagram of ceramic material; as can be seen from the figure, the highly dense Si prepared in this example2BC3The size of the N ceramic material can reach
The high-density Si prepared in this example was tested2BC3The density of the N ceramic material is 2.82g/cm at most399.3% of theoretical density, 10.80GPa of hardness, 404.0MPa of bending strength, 300.2GPa of elastic modulus and 3.52 MPa.m of fracture toughness1/2。
Claims (10)
1. A high-density SiBCN ceramic material is characterized in that the ceramic material is prepared from silicon powder of cubic system, graphite powder and hexagonal boron nitride powder;
the molar ratio of Si in the cubic silicon powder to C in the graphite powder is 1 (0.05-2); the molar ratio of Si in the cubic silicon powder to B in the hexagonal boron nitride powder is 1 (0.5-2);
the grain diameter of the silicon powder of the cubic system is 1-50 mu m; the particle size of the graphite powder is 1-10 mu m; the particle size of the hexagonal boron nitride powder is 1-10 mu m.
2. The process for preparing a highly dense SiBCN ceramic material according to claim 1, wherein said process comprises the steps of:
firstly, weighing cubic silicon powder, graphite powder and hexagonal boron nitride powder;
the molar ratio of Si in the cubic silicon powder to C in the graphite powder is 1 (0.05-2); the molar ratio of Si in the cubic silicon powder to B in the hexagonal boron nitride powder is 1 (0.5-2);
the grain diameter of the silicon powder of the cubic system is 1-50 mu m; the particle size of the graphite powder is 1-10 mu m; the particle size of the hexagonal boron nitride powder is 1-10 mu m;
secondly, putting the weighed cubic silicon powder, graphite powder and hexagonal boron nitride powder into a ball milling tank, and carrying out ball milling for 1-50 h under the conditions of argon atmosphere, the diameter of a milling ball of 3-10 mm and the mass ratio of ball materials of (5-100): 1 to obtain amorphous SiBCN powder;
thirdly, under the conditions that the sintering temperature is 1500-1700 ℃ and the sintering pressure is 20-80 MPa, carrying out hot-pressing pre-sintering on the amorphous SiBCN powder for 10-60 min to obtain an amorphous/nanocrystalline silicon boron carbon nitrogen ceramic blank;
and fourthly, polishing the upper surface and the lower surface of the amorphous/nanocrystalline silicon boron carbon nitrogen ceramic blank, cleaning and drying to obtain a pretreated silicon boron carbon nitrogen ceramic blank, welding and sealing one or more pretreated silicon boron carbon nitrogen ceramic blanks into a hot isostatic pressing package in a vacuum environment to obtain a packaged ceramic blank, carrying out hot isostatic pressing sintering on the packaged ceramic blank for 10-60 min under the conditions that the sintering temperature is 1700-2000 ℃ and the sintering pressure is 150-190 MPa to obtain a packaged ceramic blank, removing the hot isostatic pressing package, and obtaining the high-density SiBCN ceramic material.
3. The method for preparing high-density SiBCN ceramic material according to claim 2, wherein: the purity of the cubic crystal system silicon powder in the step one is 99-99.9%; the purity of the graphite powder in the step one is 99-99.9%; the purity of the hexagonal boron nitride powder in the step one is 98-99.9%.
4. The method for preparing high-density SiBCN ceramic material according to claim 2, wherein: and the ball milling tank in the step two is a vibration type ball milling tank or a planetary ball milling tank.
5. The method for preparing high-density SiBCN ceramic material according to claim 2, wherein: and the hot isostatic pressing sheath in the fourth step is a carbon film sheath, a glass sheath or a metal sheath.
6. The method for preparing high-density SiBCN ceramic material according to claim 2, wherein: and in the second step, ball milling is carried out for 15-35 h under the conditions of argon atmosphere, the diameter of a grinding ball is 5-8 mm, and the mass ratio of the ball material to the grinding ball is (10-90): 1.
7. The method for preparing high-density SiBCN ceramic material according to claim 2, wherein: and in the fourth step, carrying out hot isostatic pressing sintering on the ceramic blank packaged by the sheath for 30min under the conditions that the sintering temperature is 2000 ℃ and the sintering pressure is 150 MPa.
8. The method for preparing high-density SiBCN ceramic material according to claim 2, wherein: and in the fourth step, carrying out hot isostatic pressing sintering on the ceramic blank packaged by the sheath for 30min under the conditions that the sintering temperature is 1900 ℃ and the sintering pressure is 190 MPa.
9. The method for preparing high-density SiBCN ceramic material according to claim 2, wherein: and in the fourth step, under a vacuum environment, laminating, welding and sealing five pretreated silicon-boron-carbon-nitrogen ceramic blanks into a hot isostatic pressing sheath to obtain the ceramic blanks packaged by the sheath.
10. The method for preparing a highly dense SiBCN ceramic material according to claim 9, wherein: when the five pretreated silicon-boron-carbon-nitrogen ceramic blanks are stacked, the silicon-boron-carbon-nitrogen ceramic blanks are separated by a BN sheet with the thickness of 1mm, and after the blanks are stacked, a BN isolating layer with the thickness of 1.5mm is arranged between the blanks and the hot isostatic pressing sheath.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116477952A (en) * | 2023-05-09 | 2023-07-25 | 哈尔滨工业大学 | Preparation method of tantalum hafnium carbide-silicon boron carbon nitrogen ceramic diffusion couple |
| CN116693297A (en) * | 2023-06-20 | 2023-09-05 | 哈尔滨工业大学 | Preparation method of metastable SiBCN ceramic with PDCs-SiBCN three-dimensional network cladding structure |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4495123A (en) * | 1982-01-20 | 1985-01-22 | Elektroschmelzwerk Kempten Gmbh | Dense shaped articles consisting of polycrystalline hexagonal boron nitride and process for their manufacture by isostatic hot pressing |
| CN103588483A (en) * | 2013-11-28 | 2014-02-19 | 哈尔滨工业大学 | Silicon boron zirconium carbonitride ceramic composite material and preparation methods thereof |
| CN103613385A (en) * | 2013-11-28 | 2014-03-05 | 哈尔滨工业大学 | Amorphous high-hardness silicon-boron-carbon-nitrogen ceramic material and preparation method thereof |
| WO2016023200A1 (en) * | 2014-08-11 | 2016-02-18 | 河海大学 | Preparation method for high-density hexagonal boron nitride ceramic material |
| CN111196726A (en) * | 2020-01-06 | 2020-05-26 | 哈尔滨工业大学 | SiBCN-Ta4HfC5Complex phase ceramic and preparation method thereof |
-
2020
- 2020-06-30 CN CN202010611802.1A patent/CN111689778B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4495123A (en) * | 1982-01-20 | 1985-01-22 | Elektroschmelzwerk Kempten Gmbh | Dense shaped articles consisting of polycrystalline hexagonal boron nitride and process for their manufacture by isostatic hot pressing |
| CN103588483A (en) * | 2013-11-28 | 2014-02-19 | 哈尔滨工业大学 | Silicon boron zirconium carbonitride ceramic composite material and preparation methods thereof |
| CN103613385A (en) * | 2013-11-28 | 2014-03-05 | 哈尔滨工业大学 | Amorphous high-hardness silicon-boron-carbon-nitrogen ceramic material and preparation method thereof |
| WO2016023200A1 (en) * | 2014-08-11 | 2016-02-18 | 河海大学 | Preparation method for high-density hexagonal boron nitride ceramic material |
| CN111196726A (en) * | 2020-01-06 | 2020-05-26 | 哈尔滨工业大学 | SiBCN-Ta4HfC5Complex phase ceramic and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 杨丛松等: "高强度氧化钪陶瓷的制备技术研究", 《稀有金属》 * |
| 杨丛松等: "高强度氧化钪陶瓷的制备技术研究", 《稀有金属》, no. 02, 28 February 2017 (2017-02-28), pages 2 * |
| 杨勋烈 等编: "《粉末冶金：热等静压》", 31 May 1983, 冶金工业出版社, pages: 116 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116477952A (en) * | 2023-05-09 | 2023-07-25 | 哈尔滨工业大学 | Preparation method of tantalum hafnium carbide-silicon boron carbon nitrogen ceramic diffusion couple |
| CN116477952B (en) * | 2023-05-09 | 2024-05-17 | 哈尔滨工业大学 | Preparation method of tantalum hafnium carbide-silicon boron carbon nitrogen ceramic diffusion couple |
| CN116693297A (en) * | 2023-06-20 | 2023-09-05 | 哈尔滨工业大学 | Preparation method of metastable SiBCN ceramic with PDCs-SiBCN three-dimensional network cladding structure |
| CN116693297B (en) * | 2023-06-20 | 2024-08-23 | 哈尔滨工业大学 | Preparation method of metastable SiBCN ceramic with PDCs-SiBCN three-dimensional network cladding structure |
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