CN110627504A - Pressureless sintering preparation method of boron carbide composite material - Google Patents
Pressureless sintering preparation method of boron carbide composite material Download PDFInfo
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Abstract
The invention discloses a pressureless sintering preparation method of a boron carbide composite material, which comprises the following raw materials of 83-94.9% of boron carbide, 1-6% of hafnium boride, 1-5% of titanium dioxide, 0.1-6% of carbon, 2-20% of a binder, 0.5-5% of polyimide and 0.5-2% of a dispersant; the materials are subjected to ball milling, spray drying, sieving and drying, mixing, compression molding, biscuit vacuum sintering and other steps to prepare the boron carbide composite material. The boron carbide ceramic composite material has reasonable compatibility, and on the basis of boron carbide powder, a certain amount of hafnium boride and titanium dioxide are added as toughening phases, and optimized preparation process conditions are controlled, so that the prepared boron carbide ceramic composite material has the characteristics of high hardness, small specific gravity, high temperature resistance, good chemical stability, small thermal expansion coefficient, good thermal conductivity and the like, and meanwhile, the toughness is improved.
Description
Technical Field
The invention relates to an inorganic composite material, in particular to a boron carbide composite material and a preparation method thereof.
Background
Boron carbide has a low specific gravity (2.52 g/cm) due to its high hardness (second only to diamond and cubic boron nitride)3) High elastic modulus (450GPa), high temperature resistance, good chemical stability, small thermal expansion coefficient, good thermal conductivity, good neutron absorption capacity and the like, so that the material has the characteristics of mechanical sealing industry, light bulletproof armor, hard abrasive material and the likeThe material, the wear-resistant bearing, the high-grade refractory material, the aerospace, the shielding material of a nuclear reactor and other fields are widely applied. However, since the covalent bond fraction of boron carbide is as high as 93.94%, it is higher than that of other structural ceramics, such as SiC (88%), SiN4(70%), and the like, and therefore, pure boron carbide is difficult to sinter and compact; meanwhile, boron carbide is a brittle material with fracture toughness KIC≤2.2MPa·m1/2There is a need for improved mechanical properties of materials. In order to obtain dense B4C is generally prepared by adopting a hot-pressing sintering method, the preparation is carried out in a vacuum hot-pressing furnace or a common hot-pressing furnace, the hot-pressing temperature is 2100 ℃, the pressure is 80-100MPa, the temperature is kept for a plurality of minutes, and the pressure is required to be kept during the temperature reduction, because B4C has poor thermal shock resistance, so the temperature reduction is slow, the hot pressing temperature is not too high, and B appears at 80-100MPa to 2150 DEG C4C-C eutectic liquid phase, but the temperature is too low, the product density is low, the sintering process has strict control conditions and long preparation time, and the preparation method is not suitable for preparing boron carbide ceramic composite materials with larger size due to the slow cooling. Although boron carbide ceramic products with large size and complex shape can be prepared, the boron carbide ceramic prepared by the conventional pressureless sintering has low density, so that the properties of the ceramic, such as strength, hardness, toughness and the like, are poor, and the boron carbide ceramic becomes a bottleneck for limiting the application of the boron carbide ceramic.
Disclosure of Invention
In order to solve the technical problems, the invention provides a pressureless sintering method capable of preparing boron carbide composite materials with high density and good mechanical properties such as strength, toughness and the like.
The technical scheme is that the pressureless sintering preparation method of the boron carbide composite material is provided, and the preparation raw materials comprise, by weight, 83-94.9% of boron carbide, 1-6% of hafnium boride, 1-5% of titanium dioxide, 0.1-6% of carbon, 2-20% of a binder, 0.5-5% of polyimide and 0.5-2% of a dispersant;
the preparation method comprises the following steps:
(1) weighing the preparation raw materials according to the proportion, and putting the materials except the polyimide into a ball mill for ball milling for 10-60 h; wet grinding is adopted for ball milling, wherein the ball-material ratio is 5:1, and the material-liquid ratio is 1: 1-2.5 g/L;
(2) adding polyimide into the ball-milled material, ageing, performing spray drying granulation, and sieving with a 40-60-mesh sieve, wherein the water content of the powder is controlled to be 0.7-2.5%;
(3) adding a release agent into the sieved powder, and uniformly mixing for later use; the release agent can be selected from paraffin, stearic acid, etc.;
(4) pressing and forming the mixture obtained in the step (3) at a forming pressure of 0.5-4T/cm2；
(5) Trimming and processing the blank obtained in the step (4), and performing vacuum sintering on the processed biscuit, wherein a vacuum hot pressing furnace is generally adopted, the vacuum degree is-0.1 Mpa, the maximum sintering temperature is 2050-2150 ℃, and the heat preservation time at the maximum sintering temperature is 0.5-4 h, and then the biscuit is cooled along with the furnace;
(6) and grinding and polishing the sintered product, and warehousing after the product is qualified through inspection.
Further, the binder is a resin binder.
Further, the carbon is graphite powder or carbon black.
Further, the dispersant is sodium pyrophosphate.
Further, the liquid added in the ball mill in the step (1) comprises water in a volume ratio of: n-butanol: ethanol is 1:1: 1.
Further, in the step (5), the temperature rise rate of sintering is firstly increased to 600 ℃ at the rate of 5-15 ℃/min, heat preservation is carried out for 0.5-2 h, heat preservation and glue removal are carried out, the temperature rise rate of 5-15 ℃/min is suitable for avoiding that the product is prone to cracking due to too fast temperature rise and too late discharge of moisture and gas, then the temperature rise rate of 10 ℃/min is increased to the highest sintering temperature, the stage is a shrinkage stage, the temperature rise rate of 10 ℃/min is suitable, and the product is prone to cracking due to too fast temperature rise.
The invention has the advantages and beneficial effects that:
because the boron carbide ceramic has high brittleness and needs to be reinforced and toughened by adding other substances, the boron carbide composite ceramic material prepared by the method of the invention is sintered, and then the raw materials react to obtain hafnium boride, hafnium carbide, titanium carbide and titanium boride, wherein the hafnium boride, the hafnium carbide and the titanium carbide are mainly utilizedTitanium boride is used as second phase particles to enhance the toughness of the material, the second phase particles and a matrix boron carbide are good in wettability and mixing property, and weak in interfacial reaction and diffusion mutual-solubility effect, so that moderate phase interface bonding strength can be formed, crack deflection toughening, micro-crack toughening and pinning effects can be utilized, the toughness of the material is enhanced, namely the material is broken under the action of a certain external force, the path of a crack deflects and branches in the expansion process, more energy is consumed, the more tortuous and tortuous the more branches, the more energy is consumed, the shorter the length of the crack path is, and the higher the fracture initiativity of the material is predicted; in addition, polyimide, carbon and the like can form CO and CO in the high-temperature sintering process2And the escape, volatilization and reaction of the gas can form fine particles with higher activity, the indirect promotion effect on solid phase sintering at the later stage of the reaction is realized, and the abnormal growth of the particles is inhibited during the sintering of various formed phases, so that the densification of the boron carbide ceramic composite material is facilitated, and the toughness of the boron carbide ceramic composite material is improved. Therefore, the boron carbide ceramic composite material has reasonable compatibility, and a certain amount of hafnium boride and titanium dioxide are added to serve as toughening phases on the basis of boron carbide powder, so that the prepared boron carbide ceramic composite material has the characteristics of high hardness, small specific gravity, high temperature resistance, good chemical stability, small thermal expansion coefficient, good thermal conductivity, good neutron absorption capacity and the like, and meanwhile, the toughness is improved.
In the preparation process, firstly, ball milling is carried out on the materials according to a certain ball-to-material ratio and a certain liquid-to-material ratio, so that the materials are further refined and uniformly mixed to form a complete solid solution; recovering liquid medium (sieving with 120 mesh sieve) after wet grinding, drying powder, adding release agent, sieving with 40-60 mesh sieve, and press molding in a mold to obtain biscuit with certain shape, density and density distribution. In the process, the particle size and the pressing pressure of the powder have influence on the performance of the final composite material, the screened powder particles of 40-60 meshes have less agglomeration and good dispersion, the press forming is convenient, more fine and uniform internal structures can be formed, and the ceramic composite material with better performances such as hardness, toughness and the like is obtained. At the same time, the pressing pressure is applied to the green compact pressing density and the green compact deformation after sinteringCracking is greatly influenced, and the cracking rate is 0.5-4T/cm2Under the pressing pressure, the density distribution of the biscuit is relatively uniform, and the phenomena of deformation and cracking can not occur in the sintering process. After the pressing and forming, the invention adopts the vacuum sintering process to prepare the boron carbide ceramic composite material, and controls the sintering temperature and the heat preservation time within the range of the invention, so as to avoid the problems that the crystal grains obviously grow up and the compactness is deteriorated due to overhigh temperature or overlong heat preservation time, thereby reducing the material performance.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Example 1
The invention provides a pressureless sintering preparation method of a boron carbide composite material, which comprises the following steps of: 83% of boron carbide, 1% of hafnium boride, 4% of titanium dioxide, 1% of graphite powder, 9% of polyvinyl alcohol resin binder, 1.5% of polyimide and 0.5% of sodium pyrophosphate dispersant;
putting the materials except the polyimide in the raw materials into a ball mill for ball milling for 10 hours, wherein the ball-to-material ratio is 5:1, and adding a mixture of water: n-butanol: the ball-milling liquid consists of ethanol in a volume ratio of 1:1:1, and the material-liquid ratio is 1: 1;
adding polyimide into the ball-milled material, ageing, performing spray drying granulation, and sieving with a 40-mesh sieve, wherein the water content of the powder is controlled to be 0.7-1.0%; adding a release agent into the sieved powder, uniformly mixing, and performing compression molding under the molding pressure of 0.5T/cm2；
Trimming and processing the blank obtained by pressing, and carrying out vacuum sintering on the processed biscuit, wherein the heating rate is firstly increased to 600 ℃ at the rate of 10 ℃/min, the temperature is kept for 1h, then increased to the highest sintering temperature at the rate of 10 ℃/min, the highest sintering temperature is 2050 ℃, the temperature is kept for 0.5h at the highest sintering temperature, and then the biscuit is cooled along with a furnace;
and grinding and polishing the sintered product, and warehousing after the product is qualified through inspection.
Example 2
The invention provides a pressureless sintering preparation method of a boron carbide composite material, which comprises the following steps of: 94.9 percent of boron carbide, 1 percent of hafnium boride, 1 percent of titanium dioxide, 0.1 percent of graphite powder, 2 percent of polyvinyl alcohol resin binder, 0.5 percent of polyimide and 0.5 percent of sodium pyrophosphate dispersant;
putting the materials except the polyimide in the raw materials into a ball mill for ball milling for 60 hours, wherein the ball-to-material ratio is 5:1, and adding a mixture of water: n-butanol: the ball-milling liquid consists of ethanol in a volume ratio of 1:1:1, and the material-liquid ratio is 1: 2.5;
adding polyimide into the ball-milled material, ageing, performing spray drying granulation, and then sieving by using a 60-mesh sieve, wherein the water content of the powder is controlled to be 1.5-2.5%; adding a release agent into the sieved powder, uniformly mixing, and performing compression molding at the molding pressure of 4T/cm2；
Trimming and processing the blank obtained by pressing, and carrying out vacuum sintering on the processed biscuit, wherein the heating rate is firstly 5 ℃/min to 600 ℃, the temperature is kept for 2h, then the heating rate is 10 ℃/min to the highest sintering temperature, the highest sintering temperature is 2150 ℃, the temperature is kept for 4h at the highest sintering temperature, and then the blank is cooled along with a furnace;
and grinding and polishing the sintered product, and warehousing after the product is qualified through inspection.
Example 3
The invention provides a pressureless sintering preparation method of a boron carbide composite material, which comprises the following steps of: 90% of boron carbide, 3% of hafnium boride, 2% of titanium dioxide, 0.5% of graphite powder, 2% of polyvinyl alcohol resin binder, 1.5% of polyimide and 1% of sodium pyrophosphate dispersant;
putting the materials except the polyimide in the raw materials into a ball mill for ball milling for 30h, wherein the ball-material ratio is 5:1, and adding a mixture of water: n-butanol: the ball-milling liquid consists of ethanol in a volume ratio of 1:1:1, and the material-liquid ratio is 1: 1.5;
adding polyimide into the ball-milled material, ageing, performing spray drying granulation, and then sieving with a 50-mesh sieve, wherein the water content of the powder is controlled to be 0.7-1.0%; adding a release agent into the sieved powder, uniformly mixing, and performing compression molding at the molding pressure of 2T/cm2；
Trimming and processing the blank obtained by pressing, and carrying out vacuum sintering on the processed biscuit, wherein the heating rate is that the temperature is increased to 600 ℃ at the first speed of 15 ℃/min, the temperature is kept for 0.5h, then the temperature is increased to the highest sintering temperature at the second speed of 10 ℃/min, the highest sintering temperature is 2100 ℃, the temperature is kept for 4h at the highest sintering temperature, and then the blank is cooled along with a furnace;
and grinding and polishing the sintered product, and warehousing after the product is qualified through inspection.
Comparative example 1
This comparative example differs from example 1 only in that no hafnium boride is contained in the preparation raw material, and the rest is the same as example 1.
Comparative example 2
This comparative example differs from example 1 only in that no titanium dioxide was contained in the starting material for the preparation, and the remainder is the same as example 1.
Comparative examples 3 to 4
Comparative example 3 differs from example 1 only in that the ball milling time in the preparation process is 5h, and the rest is the same as example 1; comparative example 4 differs from example 1 only in that the preparation process has a ball milling time of 65h, as in example 1.
Comparative examples 5 to 6
Comparative example 5 differs from example 1 only in that the preparation process was carried out with a mesh number of 30 mesh, as in example 1; comparative example 6 differs from example 1 only in that the preparation process has a mesh number of 65 mesh, and is otherwise the same as example 1.
Comparative examples 7 to 8
Comparative example 7 differs from example 1 only in that the green compact pressing pressure during the preparation process was 0.3T/cm2Otherwise, the same as in example 1; comparative example 8 differs from example 1 only in that the blank pressing pressure during the preparation process was 5T/cm2Otherwise, the same procedure as in example 1 was repeated.
Comparative example 9
This comparative example differs from example 1 only in that the ball milling liquid was water during the preparation, and the remainder is the same as example 1.
Comparative examples 10 to 11
Comparative example 10 is different from example 1 only in that the sintering temperature is uniformly raised to the maximum sintering temperature at 4 ℃/min in the preparation process, and the rest is the same as example 1; comparative example 11 is different from example 1 only in that the preparation process sintering temperature is uniformly raised to the maximum sintering temperature at 20 c/min, and the rest is the same as example 1.
The boron carbide composite materials obtained in examples 1 to 3 and comparative examples 1 to 10 were tested for their properties, and the results were as follows:
in the preparation process, firstly, ball milling is carried out on the materials according to a certain ball-to-material ratio and a certain liquid-to-material ratio, so that the materials are further refined and uniformly mixed to form a complete solid solution; recovering liquid medium and drying powder after wet grinding, adding a release agent, sieving by a 40-60 mesh sieve, and putting into a mould for compression molding to obtain a biscuit with a certain shape, density and density distribution. The powder particles of 40-60 meshes obtained by screening have less agglomeration and good dispersion, and can form more fine and uniform internal structures inside the blank. Meanwhile, the invention is 0.5-4T/cm2Under the pressing pressure, the density distribution of the biscuit is relatively uniform, and the phenomena of deformation and cracking can not occur in the sintering process. After compression molding, the boron carbide ceramic composite material is prepared by adopting a vacuum sintering process, the sintering temperature is controlled to be 2050-2150 ℃, and the heat preservation time is 0.5-4 hours at the highest sintering temperature, so that crystal grains grown in the sintering process are uniform and fine, the internal structure of the formed ceramic composite material is uniform, stable and compact, and the material performance is ensured. From the test results, the composite material prepared by the invention has the advantages that the sintering density can reach 97.8 percent, the hardness can reach 35.1GPa, the bending strength can reach 555MPa, and the fracture toughness can reach 5.0 MPa.m by controlling the preparation raw materials and the preparation conditions1/2The elastic modulus can reach 380.5GPa, and the obtained ceramic composite material is obviously superior to the comparative example in the comprehensive properties such as mechanical property, sintering density and the like.
The results show that the boron carbide ceramic composite material has reasonable compatibility, the toughness of the boron carbide matrix is enhanced by using hafnium boride, hafnium carbide, titanium carbide and titanium boride as second-phase particles, and the boron carbide ceramic composite material with good toughness and high strength is finally prepared by optimizing the process conditions of ball milling, drying, sieving, drying, pressing, vacuum sintering and the like.
Materials, reagents and experimental equipment related to the embodiment of the invention are all commercial products conforming to the field of inorganic materials unless otherwise specified.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, modifications and decorations can be made without departing from the core technology of the present invention, and these modifications and decorations shall also fall within the protection scope of the present invention. Any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (6)
1. The pressureless sintering preparation method of the boron carbide composite material is characterized by comprising the following preparation steps:
(1) weighing preparation raw materials according to the proportion, wherein the preparation raw materials comprise, by weight, 83-94.9% of boron carbide, 1-6% of hafnium boride, 1-5% of titanium dioxide, 0.1-6% of carbon, 2-20% of binder, 0.5-5% of polyimide and 0.5-2% of dispersant; putting the materials except the polyimide into a ball mill for ball milling for 10-60 h; in the ball milling process, the ball-to-material ratio is 5:1, and the material-to-liquid ratio is 1: 1-2.5 g/L;
(2) adding polyimide into the ball-milled material, ageing, performing spray drying granulation, and sieving with a 40-60-mesh sieve, wherein the water content of the powder is controlled to be 0.7-2.5%;
(3) adding a release agent into the sieved powder, and uniformly mixing for later use;
(4) pressing and forming the mixture obtained in the step (3) at a forming pressure of 0.5-4T/cm2；
(5) And (4) trimming and processing the blank obtained in the step (4), sintering the processed biscuit in vacuum, keeping the temperature at the highest sintering temperature of 2050-2150 ℃ for 0.5-4 h, and cooling along with a furnace.
2. The pressureless sintering production method of a boron carbide composite material according to claim 1, wherein the binder is a resin binder.
3. The pressureless sintering production method of a boron carbide composite material according to claim 1, wherein the carbon is graphite powder or carbon black.
4. The pressureless sintering production method of a boron carbide composite material according to claim 1, wherein the dispersant is sodium pyrophosphate.
5. The pressureless sintering preparation method of boron carbide composite material according to claim 1, wherein the liquid added by ball milling in the step (1) is composed of water in volume ratio: n-butanol: ethanol is 1:1: 1.
6. The pressureless sintering preparation method of the boron carbide composite material according to claim 1, wherein in the step (5), the sintering temperature rise rate is firstly 5-15 ℃/min to 600 ℃, the temperature is kept for 0.5-2 h, and then 10 ℃/min is increased to the maximum sintering temperature.
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| CN111825458A (en) * | 2020-07-31 | 2020-10-27 | 中南大学 | High-density boron carbide ceramic material and pressureless sintering preparation method thereof |
| CN113345615A (en) * | 2021-05-31 | 2021-09-03 | 中国工程物理研究院材料研究所 | Paraffin/boron carbide neutron protection composite material and preparation method thereof |
| CN117430424A (en) * | 2023-12-20 | 2024-01-23 | 山东金鸿新材料股份有限公司 | Preparation method of composite boron carbide ceramic and application of composite boron carbide ceramic in bulletproof ceramic plugboard |
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| CN113345615B (en) * | 2021-05-31 | 2022-12-27 | 中国工程物理研究院材料研究所 | Paraffin/boron carbide neutron protection composite material and preparation method thereof |
| CN117430424A (en) * | 2023-12-20 | 2024-01-23 | 山东金鸿新材料股份有限公司 | Preparation method of composite boron carbide ceramic and application of composite boron carbide ceramic in bulletproof ceramic plugboard |
| CN117430424B (en) * | 2023-12-20 | 2024-03-19 | 山东金鸿新材料股份有限公司 | Preparation method of composite boron carbide ceramic and application of composite boron carbide ceramic in bulletproof ceramic plugboard |
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