CN111689778B - High-density SiBCN ceramic material and preparation method thereof - Google Patents
High-density SiBCN ceramic material and preparation method thereof Download PDFInfo
- Publication number
- CN111689778B CN111689778B CN202010611802.1A CN202010611802A CN111689778B CN 111689778 B CN111689778 B CN 111689778B CN 202010611802 A CN202010611802 A CN 202010611802A CN 111689778 B CN111689778 B CN 111689778B
- Authority
- CN
- China
- Prior art keywords
- powder
- density
- ceramic material
- sibcn
- ceramic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
- C04B35/6455—Hot isostatic pressing
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/65—Reaction sintering of free metal- or free silicon-containing compositions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
- C04B2235/386—Boron nitrides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
- C04B2235/425—Graphite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/95—Products characterised by their size, e.g. microceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
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, 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 SiBCN ceramic has low density, excellent tissue structure stability (higher amorphous stability capability, and the capsule structure of the SiBCN ceramic 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 performance (SiBCN fibers can be used in 1500 ℃ air), good thermal shock resistance and ablation resistance, and excellent machining performance, and 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 (microscopic 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. 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 DEG CThe prepared SiBCN ceramic material has low density (only 85 percent of theoretical density), unsatisfactory comprehensive mechanical property and small sample size
And only a single ceramic material can be prepared by single sintering, and the requirement of practical application cannot be met. In 2015 Bin Liang et al (Highly dense amophorus Si) 2 BC 3 N monoliths with excellent mechanical properties prepared by high pressure sintering[J]The Journal of American Ceramic Society,2015,98 (12): 3782-3787) invented a method for preparing SiBCN Ceramic material by high pressure sintering (5 GPa), and the prepared SiBCN Ceramic material is amorphous, has high density, high hardness and excellent oxidation resistance, but has the material size of only being
And only a single block of 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 silicon powder of the cubic system 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 grain diameter of the hexagonal boron nitride powder is 1-10 μm.
A preparation method of a high-density SiBCN ceramic material comprises the following steps:
1. 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 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 size 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. 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;
3. 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;
4. polishing the upper surface and the lower surface of an 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 under 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 after hot isostatic pressing, removing the hot isostatic pressing package, and obtaining the high-density SiBCN ceramic material.
The beneficial effects of the invention are:
1. the high-density SiBCN ceramic material has low raw material cost and is easily and directly available from the market.
2. The hot isostatic pressing technology integrates the advantages of hot pressing and isostatic pressing, and can simultaneously apply high temperature (the highest temperature can be applied in the ceramic sintering process)Up to 2000 ℃ and equally high pressures (up to 200 MPa). 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 Si blocks with high density simultaneously 2 BC 3 When the N ceramic material is used, the density is 2.74g/cm according to analysis and test 3 ～2.83g/cm 3 Hardness of 10.80-11.02 GPa, bending strength of 404.0-471.5 MPa, elastic modulus of 300.2-311.8 GPa, and fracture toughness of 3.52 MPa-m 1/2 ～5.13MPa·m 1/2 Mechanical property far superior to that of Si prepared by mechanical alloying-hot pressing sintering 2 BC 3 N 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, and can be processed by conventional processing means such as turning, milling, grinding and the likeTherefore, the method can be practically applied to high-temperature structural components.
Drawings
FIG. 1 shows encapsulated Si obtained in step four of the example 2 BC 3 A real object diagram of the N ceramic blank;
FIG. 2 shows a hot isostatically pressed can encapsulated Si obtained in step four of the example 2 BC 3 A real object diagram of the N ceramic blank;
FIG. 3 illustrates one embodiment of a one-step post-hipping capsule Si 2 BC 3 Removing the sheath of the N ceramic blank, and then removing five pieces of high-density Si 2 BC 3 N physical diagrams of ceramic material stacks;
FIG. 4 shows flaky amorphous/nanocrystalline Si before and after HIP in example I 2 BC 3 N ceramic green body and high-density Si 2 BC 3 Material object diagram of N ceramic material, 1 is the flake amorphous/nanocrystalline Si prepared in step three 2 BC 3 N ceramic blank, 2 is the high compact Si that step four prepared 2 BC 3 N ceramic material;
FIG. 5 shows the preparation of amorphous/nanocrystalline Si in sheet form in one step three 2 BC 3 N is a topography map of the polished surface of the ceramic blank;
FIG. 6 shows the highly dense Si prepared in example one 2 BC 3 N is a topography map of the polished ceramic material surface;
FIG. 7 shows the preparation of amorphous/nanocrystalline Si flakes in one step three 2 BC 3 N ceramic blank fracture morphology graph;
FIG. 8 shows the highly dense Si prepared in example one 2 BC 3 N is a fracture morphology diagram of the ceramic material;
FIG. 9 shows the highly dense Si prepared in example two 2 BC 3 N physical diagram of 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 embodiment provides a high-density SiBCN ceramic material which is prepared from 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 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 size 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 has low raw material cost and is easy to obtain directly from the market.
2. The hot isostatic pressing technology integrates the advantages of hot pressing and isostatic pressing, and can simultaneously apply high temperature (up to 2000 ℃) and equal high pressure (up to 200 MPa) in the ceramic sintering process. The embodiment 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 five sizes and the same size can be obtained at most by single sintering, the application of the practical SiBCN ceramics engineering can be met, the sintering efficiency of the SiBCN ceramics is obviously improved, the production cost is reduced, the hot isostatic pressing near-net forming technology is adopted, the subsequent machining can be effectively reduced, and the cost is favorably reduced.
When preparing Si blocks with high density simultaneously 2 BC 3 When the N ceramic material is used, the density is 2.74g/cm according to analysis and test 3 ～2.83g/cm 3 Hardness of 1080 GPa-11.02 GPa, bending strength of 404.0 MPa-471.5 MPa, elastic modulus of 300.2 GPa-311.8 GPa, and fracture toughness of 3.52 MPa.m 1/2 ～5.13MPa·m 1/2 Mechanical property far superior to that of Si prepared by mechanical alloying-hot pressing sintering 2 BC 3 N 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:
1. 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 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 size 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 grain diameter of the hexagonal boron nitride powder is 1-10 mu m;
2. 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;
3. 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;
4. polishing the upper surface and the lower surface of an 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 under 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 after hot isostatic pressing, 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 system silicon powder in the step one is 99-99.9%; the purity of the graphite powder in the first step 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 second step is a vibration type ball milling tank or a planetary type ball milling tank. The others are the same as in the second or third embodiment.
The fifth concrete implementation mode is as follows: the second to fourth differences between this embodiment and the specific 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: in the second step, ball milling is carried out for 15 to 35 hours under the conditions of argon atmosphere, the diameter of a grinding ball is 5 to 8mm, and the mass ratio of the ball to the material is (10 to 90): 1. The rest is the same as 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, under the conditions that the sintering temperature is 2000 ℃ and the sintering pressure is 150MPa, carrying out hot isostatic pressing sintering on the ceramic blank packaged by the sheath for 30min. 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 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 the ball material is 50. The others are the same as in the second to tenth embodiments.
The detailed implementation mode is twelve: this embodiment is different from one of the second to eleventh embodiments in that: in the second step, ball milling is carried out for 35 hours under the conditions that the argon atmosphere, the diameter of a grinding ball is 8mm and the mass ratio of the ball material is 10. 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 the ball material is 90. The rest is the same as the second to twelfth embodiments.
The specific implementation mode fourteen are as follows: 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 20min. The others are the same as the embodiments two to fourteen.
The specific implementation modes are 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 20min. 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 30min. The rest is the same as the second to sixteenth embodiments.
Eighteen specific embodiments: 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, under the conditions that the sintering temperature is 1700 ℃ and the sintering pressure is 190MPa, carrying out hot isostatic pressing sintering on the ceramic blank packaged by the sheath for 60min. 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:
1. 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 2; the molar ratio of Si in the cubic silicon powder to B in the hexagonal boron nitride powder is 2;
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;
2. 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;
3. under the conditions that the sintering temperature is 1700 ℃ and the sintering pressure is 60MPa, the amorphous SiBCN powder is subjected to hot-pressing presintering for 30min to obtain flaky amorphous/nanocrystalline Si 2 BC 3 N ceramic green bodies;
4. flake amorphous/nanocrystalline Si 2 BC 3 Polishing the upper and lower surfaces of the N ceramic blank, cleaning and drying to obtain pretreated Si 2 BC 3 N ceramic blank, in vacuum environment, five pretreated Si pieces 2 BC 3 The N ceramic blanks are stacked and welded and sealed in a hot isostatic pressing sheath to obtain Si packaged by the sheath 2 BC 3 The 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 190MPa 2 BC 3 Carrying out hot isostatic pressing sintering on the N ceramic blank for 30min to obtain the hot isostatic pressed packaged Si 2 BC 3 Removing the hot isostatic pressing sheath from the N ceramic blank to obtain five pieces of high-density Si 2 BC 3 N ceramic material.
Step four, five pretreated Si 2 BC 3 Lamination of N ceramic green bodies, si 2 BC 3 The N ceramic blanks are separated by BN sheets with the thickness of 1mm 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 to prevent bonding between the sheetsDuring the hot isostatic pressing process, the blank and the sheath react or bond.
The purity of the cubic system silicon powder in the first step is 99.5%; the purity of the graphite powder in the step one is 99.9%; the purity of the hexagonal boron nitride powder in the step one 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 materials science and technology ltd, beijing, and has a model number of C-Si-45.
FIG. 1 shows encapsulated Si obtained in step four of the example 2 BC 3 A real object diagram of the N ceramic blank; FIG. 2 shows a hot isostatically pressed capsule encapsulated Si obtained in step four of the example 2 BC 3 A real object diagram of the N ceramic blank; as can be seen from the figure, after the hot isostatic pressing treatment, the size change of the metal sheath is obvious, 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 of the sheath 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 Si 2 BC 3 Removing the sheath of the N ceramic blank, and then removing five pieces of high-density Si 2 BC 3 N physical diagrams of ceramic material stacks; 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 hot isostatic pressing treatment effect 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 removed 2 BC 3 The physical diagram of the N ceramic material stack is different from the shape before the jacket is removed.
FIG. 4 shows a sheet-like amorphous/amorphous alloy before and after HIP treatment in example INanocrystalline Si 2 BC 3 N ceramic green body and highly dense Si 2 BC 3 Material object diagram of N ceramic material, 1 is the flake amorphous/nanocrystalline Si prepared in step three 2 BC 3 N ceramic blank, 2 is the high compact Si that step four prepared 2 BC 3 N 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, as measured for the sample with the largest radial shrinkage, and significant radial shrinkage occurred.
FIG. 5 shows the sheet-like amorphous/nanocrystalline Si prepared in the third step of the example 2 BC 3 N is a topography map of the polished surface of the ceramic blank; FIG. 6 shows the highly dense Si prepared in example one 2 BC 3 N 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 three 2 BC 3 N ceramic blank fracture morphology graph; FIG. 8 shows the highly dense Si prepared in example one 2 BC 3 N 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 equiaxed to lamellar, the size of the grains is increased, and the lamellar is pulled out at the fracture, which is beneficial to improving the fracture toughness of the material.
The high-density Si prepared in this example was tested 2 BC 3 The density of the N ceramic material is up to 2.83g/cm 3 99.6% of theoretical density, 11.02GPa of hardness, 471.5MPa of bending strength, 311.8GPa of elastic modulus and 5.13 MPa.m of fracture toughness 1/2 。
Example two:
a preparation method of a high-density SiBCN ceramic material comprises the following steps:
1. 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; the molar ratio of Si in the cubic silicon powder to B in the hexagonal boron nitride powder is 2;
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;
2. 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;
3. under the conditions that the sintering temperature is 1700 ℃ and the sintering pressure is 60MPa, the amorphous SiBCN powder is subjected to hot-pressing presintering for 30min to obtain amorphous/nanocrystalline Si 2 BC 3 N ceramic green bodies;
4. amorphous/nanocrystalline Si 2 BC 3 Polishing the upper and lower surfaces of the N ceramic blank, cleaning and drying to obtain pretreated Si 2 BC 3 N ceramic blank, in vacuum environment, five pretreated Si pieces 2 BC 3 The N ceramic blanks are stacked and welded and sealed in a hot isostatic pressing sheath to obtain Si packaged by the sheath 2 BC 3 The 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 190MPa 2 BC 3 Carrying out hot isostatic pressing sintering on the N ceramic blank for 30min to obtain the hot isostatic pressed packaged Si 2 BC 3 Removing the hot isostatic pressing sheath from the N ceramic blank to obtain five pieces of high-density Si 2 BC 3 N ceramic material.
Step four, five pretreated Si 2 BC 3 Lamination of N ceramic green bodies, si 2 BC 3 The 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 two 2 BC 3 N physical representation of the ceramic material; as can be seen from the figure, the highly dense Si prepared in this example 2 BC 3 The size of the N ceramic material can reach
The high-density Si prepared in this example was tested 2 BC 3 The density of the N ceramic material is 2.82g/cm at most 3 99.3% of theoretical density, 10.80GPa of hardness, 404.0MPa of bending strength, 300.2GPa of elastic modulus and 3.52 MPa.m of fracture toughness 1/2 。
Claims (6)
1. The preparation method of the high-density SiBCN ceramic material is characterized by comprising the following steps:
1. 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; the molar ratio of Si in the cubic silicon powder to B in the hexagonal boron nitride powder is 2;
the grain diameter D90 of the silicon powder of the cubic system is 45 mu m; the median particle diameter of the graphite powder is 2.0 mu m; the average grain diameter of the hexagonal boron nitride powder is 5.1 mu m;
2. putting the weighed silicon powder, graphite powder and hexagonal boron nitride powder of the cubic system 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;
3. 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;
4. polishing the upper surface and the lower surface of an amorphous/nanocrystalline silicon boron carbon nitrogen ceramic blank, cleaning and drying to obtain a pretreated silicon boron carbon nitrogen ceramic blank, laminating, welding and sealing five pretreated silicon boron carbon nitrogen ceramic blanks into a hot isostatic pressing package in a vacuum environment to obtain a packaged ceramic blank, performing 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 hot isostatic pressing packaged ceramic blank, removing the hot isostatic pressing package, and obtaining a high-density SiBCN ceramic material;
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 isolation layer with the thickness of 1.5mm is arranged between the blanks and the hot isostatic pressing sheath.
2. The method for preparing high-density SiBCN ceramic material according to claim 1, wherein: the purity of the cubic 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%.
3. The method for preparing high-density SiBCN ceramic material according to claim 1, wherein: and the ball milling tank in the second step is a vibration type ball milling tank or a planetary type ball milling tank.
4. The method for preparing high-density SiBCN ceramic material according to claim 1, wherein: and the hot isostatic pressing sheath in the fourth step is a carbon film sheath, a glass sheath or a metal sheath.
5. The method for preparing high-density SiBCN ceramic material according to claim 1, 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.
6. The method for preparing high-density SiBCN ceramic material according to claim 1, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010611802.1A CN111689778B (en) | 2020-06-30 | 2020-06-30 | High-density SiBCN ceramic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010611802.1A CN111689778B (en) | 2020-06-30 | 2020-06-30 | High-density SiBCN ceramic material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111689778A CN111689778A (en) | 2020-09-22 |
| CN111689778B true CN111689778B (en) | 2023-01-17 |
Family
ID=72484590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010611802.1A Active CN111689778B (en) | 2020-06-30 | 2020-06-30 | High-density SiBCN ceramic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111689778B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3201563A1 (en) * | 1982-01-20 | 1983-07-28 | Elektroschmelzwerk Kempten GmbH, 8000 München | Dense molded body made of polycrystalline, hexagonal boron nitride and process for its production by hot isostatic pressing |
| CN103588483B (en) * | 2013-11-28 | 2015-02-11 | 哈尔滨工业大学 | Silicon boron zirconium carbonitride ceramic composite material and preparation methods thereof |
| CN103613385B (en) * | 2013-11-28 | 2015-01-07 | 哈尔滨工业大学 | Amorphous high-hardness silicon-boron-carbon-nitrogen ceramic material and preparation method thereof |
| CN104177091B (en) * | 2014-08-11 | 2015-11-18 | 河海大学 | A kind of preparation method of high-compactness hexagonal boron nitride stupalith |
| CN111196726B (en) * | 2020-01-06 | 2022-07-08 | 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
Also Published As
| Publication number | Publication date |
|---|---|
| CN111689778A (en) | 2020-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109553419B (en) | Pneumatic solid-phase sintered boron carbide complex-phase ceramic and preparation method thereof | |
| CN110735076B (en) | High-entropy metal ceramic and preparation method and application thereof | |
| CN101870586A (en) | Amorphous and nanocrystalline Si-B-C-N ceramic composite material and preparation method thereof | |
| CN110627508A (en) | High-entropy boride-based ceramic and preparation method and application thereof | |
| CN103626496B (en) | Non-stoichiometric ratio TiC, AlN and TiN composite material | |
| CN110484796B (en) | Transition metal carbide high-entropy ceramic particles and preparation method thereof | |
| CN114315359B (en) | Method for preparing high-strength and high-toughness complex-phase high-entropy ceramic by using solid solution coupling method and application | |
| CN110903091B (en) | SiC-Ti3SiC2Composite material and preparation method thereof | |
| CN103588483B (en) | Silicon boron zirconium carbonitride ceramic composite material and preparation methods thereof | |
| CN110436928B (en) | High-performance nano twin crystal boron carbide ceramic block material and preparation method thereof | |
| CN110342943B (en) | Method for synthesizing binderless polycrystalline boron nitride block under industrial pressure and application thereof | |
| CN111825458A (en) | High-density boron carbide ceramic material and pressureless sintering preparation method thereof | |
| CN111848170A (en) | Boron carbide-based composite ceramic material and preparation method thereof | |
| CN107937792B (en) | Gradient composite ceramic cutter material and preparation method thereof | |
| CN113716580A (en) | High-entropy boride micro-nano ceramic particle and preparation method thereof | |
| CN101824576B (en) | Zirconium-aluminum-silicon-carbon-silicon carbide composite material and preparation method thereof | |
| CN112500167A (en) | Preparation method of densified titanium carbide composite ceramic | |
| CN113773090B (en) | ZrB2Preparation method of-ZrC-SiC nano composite ceramic material | |
| CN111689778B (en) | High-density SiBCN ceramic material and preparation method thereof | |
| CN113416077A (en) | High-temperature ceramic cutter material with double composite structures and preparation method and application thereof | |
| CN113416078B (en) | Non-stoichiometric titanium boride and high-entropy boride ceramic prepared from same | |
| CN102557644B (en) | Method for preparing titanium diboride ceramic with titanium aluminum carbon as sintering aid | |
| CN109734452B (en) | Pressureless sintering preparation of high-density Ti2Method for preparing AlN ceramic | |
| CN115073186B (en) | Silicon nitride ceramic sintered body and preparation method thereof | |
| CN108975339B (en) | Preparation process of transition metal carbide powder and transition metal carbide-nitride composite powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Li Daxin Inventor after: Zhu Qishuai Inventor after: Liang Bin Inventor after: Jia Dechang Inventor after: Yang Zhihua Inventor after: Cai Delong Inventor after: Duan Xiaoming Inventor after: He Peigang Inventor after: Zhou Yu Inventor before: Yang Zhihua Inventor before: Zhu Qishuai Inventor before: Liang Bin Inventor before: Jia Dechang Inventor before: Li Daxin Inventor before: Cai Delong Inventor before: Duan Xiaoming Inventor before: He Peigang Inventor before: Zhou Yu |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |