[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

CN113233899A - B4B4C-SiC-Si composite material generated by siliconizing reaction of C/graphite preform and preparation method thereof - Google Patents

B4B4C-SiC-Si composite material generated by siliconizing reaction of C/graphite preform and preparation method thereof Download PDF

Info

Publication number
CN113233899A
CN113233899A CN202110640685.6A CN202110640685A CN113233899A CN 113233899 A CN113233899 A CN 113233899A CN 202110640685 A CN202110640685 A CN 202110640685A CN 113233899 A CN113233899 A CN 113233899A
Authority
CN
China
Prior art keywords
graphite
powder
siliconizing
sic
composite material
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.)
Pending
Application number
CN202110640685.6A
Other languages
Chinese (zh)
Inventor
江涛
韩慢慢
付甲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Shiyou University
Original Assignee
Xian Shiyou University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Xian Shiyou University filed Critical Xian Shiyou University
Priority to CN202110640685.6A priority Critical patent/CN113233899A/en
Publication of CN113233899A publication Critical patent/CN113233899A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped 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
    • C04B35/56Shaped 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 carbides or oxycarbides
    • C04B35/563Shaped 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 carbides or oxycarbides based on boron carbide
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64Burning or sintering processes
    • C04B35/65Reaction sintering of free metal- or free silicon-containing compositions
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38Non-oxide ceramic constituents or additives
    • C04B2235/3817Carbides
    • C04B2235/3826Silicon carbides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422Carbon
    • C04B2235/425Graphite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/428Silicon
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658Atmosphere during thermal treatment
    • C04B2235/6581Total pressure below 1 atmosphere, e.g. vacuum
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74Physical characteristics
    • C04B2235/77Density

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Products (AREA)

Abstract

B4Siliconizing reaction of C/graphite preform to generate B4The C-SiC-Si composite material comprises the following components: boron carbide ceramic powder; graphite powder; a phenolic resin binder; silicon powder; the preparation steps are as follows: step 1, mixing boron carbide ceramic powder and graphite powder into a mixed material; step 2, putting the mixed material into a ball milling tank, adding absolute ethyl alcohol and agate milling balls, ball milling into slurry, and drying into B4C/graphite composite powder; step 3, B4Adding phenolic resin binder, absolute ethyl alcohol and agate grinding balls into the C/graphite composite powder, wet ball-milling and mixing in a ball-milling tank to prepare slurry, and drying to prepare B4C/graphite mixed powder; step 4, B of step 34Putting the C/graphite mixed powder into a steel mould, and drying to form a strip-shaped sample prefabricated blank; step 5, putting the strip sample prefabricated blank body into a graphite crucible, and covering the surface of the strip sample prefabricated blank body with a rough layerSilicon powder and siliconizing at high temperature to obtain B4A C-SiC-Si composite material; has the characteristics of high hardness, wear resistance, high-temperature oxidation resistance, simple preparation process and low cost.

Description

B4Siliconizing reaction of C/graphite preform to generate B4C-SiC-Si composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a composite material B4Siliconizing reaction of C/graphite preform to generate B4C-SiC-Si composite material anda preparation method thereof.
Background
Boron carbide ceramic materials have high strength, high toughness, high melting point, high hardness, good wear resistance, corrosion resistance and high temperature oxidation resistance, and are widely used in the engineering field. Boron carbide ceramic materials are widely used in the engineering field due to their high strength and hardness, good wear resistance and good high temperature oxidation resistance. The silicon carbide ceramic has high strength, high toughness, high hardness, good wear resistance, high temperature oxidation resistance and the like. Therefore, the boron carbide ceramic material and the silicon carbide material can be compounded to prepare the boron carbide/silicon carbide composite material. The boron carbide/silicon carbide composite material has higher strength and toughness, higher hardness and wear resistance, good high-temperature oxidation resistance and the like. The performance of the boron carbide/silicon carbide composite material is obviously superior to that of boron carbide ceramic materials and silicon carbide materials. Therefore, the preparation of boron carbide/silicon carbide composite materials becomes the main direction of research and development. At present, the boron carbide/silicon carbide composite material can be prepared by adopting a hot-pressing sintering process, but the preparation cost is higher by adopting the hot-pressing sintering process, the preparation process is more complex, and the shape and the size of the prepared product are limited, so that the industrial production and the large-scale production are difficult to realize.
Disclosure of Invention
To overcome the above-mentioned deficiencies of the prior art, it is an object of the present invention to provide B4Siliconizing reaction of C/graphite preform to generate B4The invention discloses a C-SiC-Si composite material and a preparation method thereof, and provides a method for preparing B by adopting a high-temperature liquid siliconizing process4The C-SiC-Si composite material is prepared by mixing boron carbide ceramic and graphite powder to prepare B4C/graphite composite powder, and preparing into strip-shaped green body sample by pressure molding process, B4The relative density of the prefabricated blank body of the C/graphite composite powder strip sample is about 60-70%, the porosity is about 30-40%, and liquid silicon is infiltrated into B by a siliconizing reaction process4Preparing the interior of the C/graphite composite powder strip sample prefabricated blank body to ensure that liquid silicon and B4C/The boron carbide ceramic material and the graphite material in the graphite composite powder strip sample prefabricated blank react to generate the silicon carbide material, the graphite and the liquid silicon completely react to generate the silicon carbide, the boron carbide ceramic material also exists in the composite material sample matrix, and the residual silicon also exists in the composite material matrix, so that B is generated through the siliconizing reaction4A C-SiC-Si composite block; the reaction of liquid silicon with boron carbide to produce silicon carbide is shown by the following formula: 3B4C+5Si=3SiC+2SiB6Or B4C+2Si=SiC+SiB4The reaction of liquid silicon and graphite to form silicon carbide is shown by the following formula: si + C = SiC. The siliconizing reaction process has the advantages of low preparation cost and simple preparation process, can be used for preparing parts with complex shapes, can realize industrial production, and is beneficial to realizing large-scale production; b prepared by siliconizing reaction method4The C-SiC-Si composite material has extremely high relative density, uniform and compact microstructure, extremely low porosity and B prepared by a siliconizing reaction method4The C-SiC-Si composite material has high mechanical property, high hardness, good wear resistance and high-temperature oxidation resistance; the invention adopts a siliconizing reaction method to prepare B4The C-SiC-Si composite material has important research significance and practical value.
In order to achieve the purpose, the invention adopts the technical scheme that:
B4siliconizing reaction of C/graphite preform to generate B4The C-SiC-Si composite material comprises the following components in parts by weight:
90-60 parts of boron carbide ceramic powder; 10-40 parts of graphite powder; 7-10 parts of phenolic resin binder; 110 to 150 parts of silicon powder.
The boron carbide ceramic powder is micron-sized, and the particle size of the powder is 3-5 mu m.
The graphite powder is micron-sized, and the particle size of the graphite powder is 10-15 mu m.
B4Siliconizing reaction of C/graphite preform to generate B4The preparation method of the C-SiC-Si composite material is characterized by comprising the following steps:
step 1, mixing 90-60 parts of micron-sized boron carbide ceramic powder with the powder granularity of 3-5 microns and 10-40 parts of micron-sized graphite powder with the powder granularity of 10-15 microns to obtain a mixed material, wherein the graphite powder accounts for 10-40 wt% of the mixed material;
step 2, putting the mixed material obtained in the step 1 into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls, mechanically milling for 24 hours to prepare slurry, and drying the slurry to obtain B4C/graphite composite powder;
step 3, obtaining B4Adding 10 parts of phenolic resin binder into the C/graphite composite powder, filling the mixture into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls, mixing the mixture by wet ball milling for 24 hours to prepare slurry, and drying the slurry to prepare B containing the phenolic resin binder4C/graphite mixed powder;
step 4, adding B containing phenolic resin binder4C/graphite mixed powder is filled into a steel mould, is molded on a molding press under the pressure of 200MPa to prepare a strip-shaped sample prefabricated blank body, and is dried in a drying oven at the temperature of 150 ℃ for 24 hours to obtain a hardened and cured strip-shaped sample prefabricated blank body;
and 5, placing the hardened and solidified strip-shaped sample prefabricated blank into a graphite crucible, covering the surface of the strip-shaped sample prefabricated blank with coarse silicon powder, and placing the graphite crucible into a high-temperature siliconizing furnace for siliconizing.
The size of the strip-shaped sample prefabricated blank is 50mm multiplied by 5mm multiplied by 6 mm.
The siliconizing process comprises the steps of siliconizing at 1600 ℃, keeping the temperature for 2 hours, and carrying out the siliconizing reaction process under the vacuum condition, wherein the vacuum degree is 1 multiplied by 10-2Pa, decomposing the phenolic resin into gas substances at high temperature, pumping away the gas substances by a vacuum pump of the vacuum siliconizing furnace, and finally, remaining carbon in the matrix, wherein the remaining carbon reacts with liquid silicon in the siliconizing process to form a small amount of silicon carbide. So B is prepared by a siliconizing reaction process4A C-SiC-Si composite material block.
The invention has the beneficial effects that:
the invention adopts the high-temperature liquid siliconizing process to ensure that B4The C/graphite composite powder prefabricated blank is subjected to siliconizing reaction to generate B4C-SiC-Si composite material.
The invention adopts a siliconizing reaction method to prepare B4A C-SiC-Si composite material block. Can adopt a hot-pressing sintering process to prepare B4The C-SiC-Si composite material is high in preparation cost and complex in preparation process by adopting a hot-pressing sintering process, and the shape and the size of a prepared product are limited, so that industrial production and large-scale production are difficult to realize. The invention provides a method for preparing B by adopting a high-temperature siliconizing process4The C-SiC-Si composite material is prepared by mixing boron carbide ceramic powder and graphite powder, and preparing a strip-shaped sample prefabricated blank body through pressure molding, wherein the B is prepared through a pressure molding process4The C/graphite composite powder prefabricated blank is a porous material, B4The relative density of the C/graphite composite powder strip-shaped sample prefabricated blank body is about 60-70%, the porosity is about 30-40%, liquid silicon permeates into the strip-shaped sample prefabricated blank body through a siliconizing reaction process, the liquid silicon reacts with boron carbide ceramic materials and graphite materials in the strip-shaped sample prefabricated blank body to generate silicon carbide materials, graphite and the liquid silicon completely react to generate silicon carbide, the boron carbide ceramic materials exist in a siliconizing sample matrix, residual silicon also exists in the composite material matrix, and the generated silicon carbide and the residual silicon fill up pores in the sample, so that dense and hard B is generated through the siliconizing reaction4A C-SiC-Si composite material block. The reaction of liquid silicon with boron carbide to produce silicon carbide is shown by the following formula: 3B4C+5Si=3SiC+2SiB6Or B4C+2Si=SiC+SiB4The reaction of liquid silicon and graphite to form silicon carbide is shown by the following formula: si + C = SiC. The siliconizing reaction process has the advantages of low preparation cost, simple preparation process, capability of preparing parts with complex shapes, realization of industrial production and contribution to large-scale production. B prepared by siliconizing reaction method4The C-SiC-Si composite material has extremely high relative density, uniform and compact microstructure, extremely low porosity andand B prepared by siliconizing reaction4The C-SiC-Si composite material has high mechanical property, high hardness, good wear resistance, high-temperature oxidation resistance and the like. So the invention adopts the siliconizing reaction method to prepare B4The C-SiC-Si composite material has important research significance and practical value.
B obtained by siliconizing reaction4The C-SiC-Si composite material has a uniform and compact microstructure, higher relative density, higher mechanical property, higher hardness, good wear resistance and good high-temperature oxidation resistance.
B prepared by siliconizing reaction method4The C-SiC-Si composite material has extremely high density and relative density. And B prepared by siliconizing process4The density and relative density of the C-SiC-Si composite material is dependent on B4The content of graphite in the C/graphite composite powder prefabricated blank is increased gradually, because the content of graphite is increased, graphite and liquid silicon completely react to generate silicon carbide, more silicon carbide is generated through siliconizing reaction, and the density of boron carbide is 2.52g/cm3The density of the silicon carbide is 3.21g/cm3The density of silicon is 2.32g/cm3And the resulting silicon carbide and residual silicon fill the pores in the siliconized sample, resulting in B4The density and relative density of the C-SiC-Si composite material is dependent on B4The content of graphite in the C/graphite composite powder preform body is gradually increased. B prepared by siliconizing reaction method4The C-SiC-Si composite material has extremely high bending strength and fracture toughness. And B prepared by siliconizing process4The bending strength and fracture toughness of the C-SiC-Si composite material follow B4The content of graphite in the C/graphite composite powder prefabricated blank is increased gradually, because the content of graphite is increased, graphite and liquid silicon are completely reacted to generate silicon carbide, more silicon carbide is generated through siliconizing reaction, the bending strength and the fracture toughness of the silicon carbide are extremely high, and the generated silicon carbide and residual silicon fill up pores in a siliconizing sample, so that B is caused4The relative density of the C-SiC-Si composite material is increased, thereby leading to B4C-SiThe bending strength and fracture toughness of the C-Si composite material follow that of B4The content of graphite in the C/graphite composite powder preform body is gradually increased. B prepared by siliconizing reaction method4The C-SiC-Si composite material has extremely high Vickers hardness and elastic modulus. And B prepared by siliconizing process4Vickers hardness and elastic modulus of C-SiC-Si composite with B4The content of graphite in the C/graphite composite powder prefabricated blank is increased gradually, because the content of graphite is increased, graphite and liquid silicon completely react to generate silicon carbide, more silicon carbide is generated through a siliconizing reaction, the Vickers hardness and the elastic modulus of the silicon carbide are extremely high, and the generated silicon carbide and residual silicon fill up pores in a siliconizing sample, so that the B/graphite composite powder prefabricated blank is subjected to B/graphite composite powder prefabricated blank4The relative density of the C-SiC-Si composite material is increased, thereby leading to B4Vickers hardness and elastic modulus of C-SiC-Si composite with B4The content of graphite in the C/graphite composite powder preform body is gradually increased. B prepared by siliconizing reaction4The C-SiC-Si composite material has extremely high Vickers hardness and can greatly improve B4The wear resistance of the surface of the C-SiC-Si composite material. So B4The C-SiC-Si composite material has excellent wear resistance. Due to siliconizing product B4The surface of the C-SiC-Si composite material is mainly provided with silicon carbide and a small amount of residual silicon, the content of boron carbide is very low, and the silicon carbide and the silicon have excellent high-temperature oxidation resistance, so the siliconized product B4The C-SiC-Si composite material also has excellent high-temperature oxidation resistance. So B4The C-SiC-Si composite material has high mechanical property, good wear resistance and good high-temperature oxidation resistance.
By using B4The C/graphite composite prefabricated blank body can be used for preparing B by a siliconizing reaction method4C-SiC-Si composite material block and can prepare B with complex shape4The C-SiC-Si composite material block can realize large-scale industrial production and has great development prospect in the engineering field.
Drawings
FIG. 1 shows a process B prepared by a high-temperature liquid siliconizing process according to the method provided by the invention4And the X-ray diffraction pattern of the surface of the C-SiC-Si composite material.
FIG. 2 shows a process B prepared by a high-temperature liquid siliconizing process according to the method provided by the invention4And scanning electron microscope photographs of the interior of the C-SiC-Si composite material.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments and the accompanying drawings.
Example 1
B4Siliconizing reaction of C/graphite preform to generate B4The C-SiC-Si composite material comprises the following components in parts by weight:
90 parts of boron carbide ceramic powder; 10 parts of graphite powder; 7 parts of phenolic resin binder; 110 parts of silicon powder.
The boron carbide ceramic powder is micron-sized, and the particle size of the powder is 3 mu m;
the graphite powder is micron-sized, and the particle size of the graphite powder is 10 mu m;
example 2
B4Siliconizing reaction of C/graphite preform to generate B4The C-SiC-Si composite material comprises the following components:
60 parts of boron carbide ceramic powder; 40 parts of graphite powder; 10 parts of phenolic resin binder; 150 parts of silicon powder.
The boron carbide ceramic powder is micron-sized, and the particle size of the powder is 5 mu m;
the graphite powder is micron-sized, and the particle size of the powder is 15 mu m.
Example 3
B4Siliconizing reaction of C/graphite preform to generate B4The C-SiC-Si composite material is characterized by comprising the following components:
70 parts of boron carbide ceramic powder; 30 parts of graphite powder; 8 parts of phenolic resin binder; 130 parts of silicon powder.
The boron carbide ceramic powder is micron-sized, and the particle size of the powder is 4 mu m;
the graphite powder is micron-sized, and the particle size of the powder is 13 mu m.
Example 4
B4Siliconizing reaction of C/graphite preform to generate B4The C-SiC-Si composite material comprises the following components:
80 parts of boron carbide ceramic powder; 20 parts of graphite powder; 9 parts of phenolic resin binder; 120 parts of silicon powder.
The boron carbide ceramic powder is micron-sized, and the particle size of the powder is 5 mu m;
the graphite powder is micron-sized, and the particle size of the powder is 12 mu m.
Example 5
B4Siliconizing reaction of C/graphite preform to generate B4The preparation method of the C-SiC-Si composite material comprises the following steps:
step 1, mixing 90 parts of micron-sized boron carbide ceramic powder with the powder granularity of 3 microns with 10 parts of micron-sized graphite powder with the powder granularity of 10 microns to obtain a mixed material, wherein the graphite powder accounts for 10wt% of the mixed material;
step 2, putting the mixed material obtained in the step 1 into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls, mechanically milling for 24 hours to prepare slurry, and drying the slurry to obtain B4C/graphite composite powder;
step 3, obtaining B4Adding 7 parts of phenolic resin binder into the C/graphite composite powder, putting the C/graphite composite powder into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls, mixing the materials through wet ball milling for 24 hours to prepare slurry, and drying the slurry to prepare B containing the phenolic resin binder4C/graphite mixed powder;
step 4, adding B containing phenolic resin binder4C/graphite mixed powder is filled into a steel mould, is molded on a molding press under the pressure of 200MPa to prepare a strip-shaped sample prefabricated blank body, and is dried in a drying oven at the temperature of 150 ℃ for 24 hours to obtain a hardened and cured strip-shaped sample prefabricated blank body;
and 5, placing the hardened and solidified strip-shaped sample prefabricated blank into a graphite crucible, covering the surface of the strip-shaped sample prefabricated blank with 110 parts of crude silicon powder, and placing the graphite crucible into a high-temperature siliconizing furnace for siliconizing.
The size of the strip-shaped sample prefabricated blank is 50mm multiplied by 5mm multiplied by 6 mm.
The siliconizing process comprises the steps of siliconizing at 1600 ℃, keeping the temperature for 2 hours, and carrying out the siliconizing reaction process under the vacuum condition, wherein the vacuum degree is 1 multiplied by 10-2Pa, decomposing the phenolic resin into gas substances at high temperature, pumping away the gas substances by a vacuum pump of the vacuum siliconizing furnace, and finally, remaining carbon in the matrix, wherein the remaining carbon reacts with liquid silicon in the siliconizing process to form a small amount of silicon carbide. So B is prepared by a siliconizing reaction process4A C-SiC-Si composite material block.
Example 6
B4Siliconizing reaction of C/graphite preform to generate B4The preparation method of the C-SiC-Si composite material comprises the following steps:
step 1, mixing 60 parts of micron-sized boron carbide ceramic powder with the powder granularity of 5 microns with 40 parts of micron-sized graphite powder with the powder granularity of 15 microns to obtain a mixed material, wherein the graphite powder accounts for 40wt% of the mixed material;
step 2, putting the mixed material obtained in the step 1 into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls, mechanically milling for 24 hours to prepare slurry, and drying the slurry to obtain B4C/graphite composite powder;
step 3, obtaining B4Adding 10 parts of phenolic resin binder into the C/graphite composite powder, filling the mixture into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls, mixing the mixture by wet ball milling for 24 hours to prepare slurry, and drying the slurry to prepare B containing the phenolic resin binder4C/graphite mixed powder;
step 4, adding B containing phenolic resin binder4C/graphite mixed powder is filled into a steel mould, is molded on a molding press under the pressure of 200MPa to prepare a strip-shaped sample prefabricated blank body, and is dried in a drying oven at the temperature of 150 ℃ for 24 hours to obtain a hardened and cured strip-shaped sample prefabricated blank body;
and 5, placing the hardened and solidified strip-shaped sample prefabricated blank into a graphite crucible, covering the surface of the strip-shaped sample prefabricated blank with 150 parts of coarse silicon powder, and placing the graphite crucible into a high-temperature siliconizing furnace for siliconizing.
The size of the strip-shaped sample prefabricated blank is 50mm multiplied by 5mm multiplied by 6 mm.
The siliconizing process comprises the steps of siliconizing at 1600 ℃, keeping the temperature for 2 hours, and carrying out the siliconizing reaction process under the vacuum condition, wherein the vacuum degree is 1 multiplied by 10-2Pa, wherein the phenolic resin is decomposed into gas substances at high temperature and is pumped away by a vacuum pump of a vacuum siliconizing furnace, residual carbon is finally remained in the matrix, the residual carbon reacts with liquid silicon in the siliconizing process to form a small amount of silicon carbide, and B is prepared by the siliconizing reaction process4A C-SiC-Si composite material block.
Example 7
B4Siliconizing reaction of C/graphite preform to generate B4The preparation method of the C-SiC-Si composite material comprises the following steps:
step 1, mixing 70 parts of micron-sized boron carbide ceramic powder with the powder granularity of 4 microns with 30 parts of micron-sized graphite powder with the powder granularity of 13 microns to obtain a mixed material, wherein the graphite powder accounts for 30wt% of the mixed material;
step 2, putting the mixed material obtained in the step 1 into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls, mechanically milling for 24 hours to prepare slurry, and drying the slurry to obtain B4C/graphite composite powder;
step 3, obtaining B4Adding 8 parts of phenolic resin binder into the C/graphite composite powder, filling the C/graphite composite powder into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls, mixing the materials through wet ball milling for 24 hours to prepare slurry, and drying the slurry to prepare B containing the phenolic resin binder4C/graphite mixed powder;
step 4, adding B containing phenolic resin binder4C/graphite mixed powder is filled into a steel mould, is molded on a molding press under the pressure of 200MPa to prepare a strip-shaped sample prefabricated blank body, and is dried in a drying oven at the temperature of 150 ℃ for 24 hours to obtain a hardened and cured strip-shaped sample prefabricated blank body;
and 5, placing the hardened and solidified strip-shaped sample prefabricated blank into a graphite crucible, covering the surface of the strip-shaped sample prefabricated blank with 130 parts of coarse silicon powder, and placing the graphite crucible into a high-temperature siliconizing furnace for siliconizing.
The size of the strip-shaped sample prefabricated blank is 50mm multiplied by 5mm multiplied by 6 mm.
The siliconizing process comprises the steps of siliconizing at 1600 ℃, keeping the temperature for 2 hours, and carrying out the siliconizing reaction process under the vacuum condition, wherein the vacuum degree is 1 multiplied by 10-2Pa, decomposing the phenolic resin into gas substances at high temperature, pumping away the gas substances by a vacuum pump of the vacuum siliconizing furnace, and finally, remaining carbon in the matrix, wherein the remaining carbon reacts with liquid silicon in the siliconizing process to form a small amount of silicon carbide. So B is prepared by a siliconizing reaction process4A C-SiC-Si composite material block.
Example 8
B4Siliconizing reaction of C/graphite preform to generate B4The preparation method of the C-SiC-Si composite material comprises the following steps:
step 1, mixing 80 parts of micron-sized boron carbide ceramic powder with the powder granularity of 5 microns with 20 parts of micron-sized graphite powder with the powder granularity of 12 microns to obtain a mixed material, wherein the graphite powder accounts for 20wt% of the mixed material;
step 2, putting the mixed material obtained in the step 1 into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls, mechanically milling for 24 hours to prepare slurry, and drying the slurry to obtain B4C/graphite composite powder;
step 3, obtaining B4Adding 9 parts of phenolic resin binder into the C/graphite composite powder, putting the C/graphite composite powder into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls, mixing the materials through wet ball milling for 24 hours to prepare slurry, and drying the slurry to prepare B containing the phenolic resin binder4C/graphite mixed powder;
step 4, adding B containing phenolic resin binder4C/graphite mixed powder is filled into a steel mould, is molded on a molding press under the pressure of 200MPa to prepare a strip-shaped sample prefabricated blank body, and is dried in a drying oven at the temperature of 150 ℃ for 24 hours to obtain a hardened and cured strip-shaped sample prefabricated blank body;
and 5, placing the hardened and solidified strip-shaped sample prefabricated blank into a graphite crucible, covering the surface of the strip-shaped sample prefabricated blank with 120 parts of coarse silicon powder, and placing the graphite crucible into a high-temperature siliconizing furnace for siliconizing.
The size of the strip-shaped sample prefabricated blank is 50mm multiplied by 5mm multiplied by 6 mm.
The siliconizing process comprises the steps of siliconizing at 1600 ℃, keeping the temperature for 2 hours, and carrying out the siliconizing reaction process under the vacuum condition, wherein the vacuum degree is 1 multiplied by 10-2Pa, decomposing the phenolic resin into gas substances at high temperature, pumping away the gas substances by a vacuum pump of the vacuum siliconizing furnace, and finally, remaining carbon in the matrix, wherein the remaining carbon reacts with liquid silicon in the siliconizing process to form a small amount of silicon carbide. So B is prepared by a siliconizing reaction process4A C-SiC-Si composite material block.
Example 9
Step 1, adopting 90 parts of micron-sized boron carbide ceramic powder as a raw material, wherein the particle size of the powder is about 4-5 mu m; 10 parts of micron-sized graphite powder is used as a raw material, and the particle size of the powder is about 14-15 mu m; mixing boron carbide ceramic powder and graphite powder according to a certain proportion, wherein the graphite powder is prepared B4The mass fraction of the C/graphite composite powder is 10 parts;
step 2, putting the mixed raw materials obtained in the step 1 into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls for mixing, mechanically milling for 24 hours to prepare slurry, and drying the slurry to obtain B4C/graphite composite powder;
step 3, in B4Adding 10 parts by mass of phenolic resin binder into the C/graphite composite powder, and adding B4Putting the C/graphite composite powder and 10 parts of phenolic resin binder into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls, mixing by wet ball milling for 24 hours to prepare slurry, and drying the slurry to prepare B containing the phenolic resin binder4C/graphite mixed powder;
step 4, adding B containing phenolic resin binder4The C/graphite mixed powder is filled into a steel mould and pressed on a forming press under 200MPaAnd (3) preparing a strip-shaped sample prefabricated blank body by force forming, wherein the dimension of the strip-shaped sample prefabricated blank body is 50mm multiplied by 5mm multiplied by 6mm, drying the strip-shaped sample prefabricated blank body in a drying oven at 150 ℃ for 24h to obtain a hardened and cured strip-shaped sample prefabricated blank body, and the phenolic resin binder plays a role in curing and hardening the strip-shaped sample prefabricated blank body. Wherein graphite powder is B prepared410 parts of C/graphite composite powder prefabricated blank;
and 5, putting the strip sample prefabricated blank into a graphite crucible, covering the surface of the strip sample prefabricated blank with 110 parts of crude silicon powder, and putting the graphite crucible into a high-temperature siliconizing furnace for siliconizing.
B is to be4Preparing the C/graphite composite powder into a strip-shaped sample prefabricated blank body by a pressure forming process, wherein the size of the strip-shaped sample prefabricated blank body is 50mm multiplied by 5mm multiplied by 6mm, and carrying out siliconizing treatment on the strip-shaped sample prefabricated blank body. And putting the strip sample prefabricated blank into a graphite crucible, covering coarse silicon powder on the surface of the strip sample prefabricated blank, and putting the graphite crucible into a high-temperature siliconizing furnace for siliconizing treatment. The phenolic resin is decomposed into gas substances under the high-temperature condition, the gas substances are pumped away by a vacuum pump of the vacuum siliconizing furnace, residual carbon is finally remained in the matrix, and the residual carbon just reacts with liquid silicon in the siliconizing process to form a small amount of silicon carbide. The siliconizing process comprises siliconizing at 1600 deg.C for 2 hr under vacuum degree of 1 × 10-2Pa, obtaining a siliconizing sample after siliconizing treatment. Because the melting point of silicon is 1410 ℃, at the temperature of 1600 ℃, the solid silicon powder can be completely melted to form liquid silicon, and the liquid silicon can be infiltrated into B4The C/graphite composite powder is prefabricated in the blank body, and the liquid silicon and the B4Reacting boron carbide ceramic material on the surface and inside of the C/graphite composite powder prefabricated blank with graphite material to generate silicon carbide, reacting liquid silicon with the boron carbide ceramic material to generate silicon carbide, reacting the liquid silicon with graphite to generate silicon carbide, completely reacting the graphite with the liquid silicon to generate silicon carbide, filling the pores inside the sample with the generated silicon carbide and residual silicon, and enabling the boron carbide ceramic material still to exist in the composite material sampleInternally, residual silicon is also present within the composite matrix. So B is prepared by a siliconizing reaction process4A C-SiC-Si composite material block. B prepared by siliconizing reaction4The C-SiC-Si composite material has a uniform and compact microstructure, higher relative density, higher mechanical property, higher hardness, good wear resistance, higher high-temperature oxidation resistance and the like.
Example 10
Step 1, 80 parts of micron-sized boron carbide ceramic powder is used as a raw material, and the particle size of the powder is about 3-5 microns; 20 parts of micron-sized graphite powder is used as a raw material, and the particle size of the powder is about 10-15 mu m; mixing boron carbide ceramic powder and graphite powder according to a certain proportion, wherein the graphite powder is prepared B4The mass fraction of the C/graphite composite powder is 20 parts;
step 2, putting the raw materials mixed in the step 1 into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls for mixing, mechanically milling for 24 hours to prepare slurry, and drying the slurry to obtain B4C/graphite composite powder;
step 3, in B4Adding 10 parts by mass of phenolic resin binder into the C/graphite composite powder, and adding B4Putting the C/graphite composite powder and 10 parts of phenolic resin binder into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls, mixing by wet ball milling for 24 hours to prepare slurry, and drying the slurry to prepare B containing the phenolic resin binder4C/graphite mixed powder;
step 4, adding B containing phenolic resin binder4And (3) filling the C/graphite mixed powder into a steel mould, forming the mixture on a forming press machine by 200MPa pressure to prepare a strip sample prefabricated blank body, wherein the size of the strip sample prefabricated blank body is 50mm multiplied by 5mm multiplied by 6mm, and drying the strip sample prefabricated blank body in a drying box at 150 ℃ for 24h to obtain a hardened and cured strip sample prefabricated blank body. The phenolic resin binder has the functions of solidifying and hardening the strip-shaped sample prefabricated blank, wherein the graphite powder is prepared B4The mass fraction of the C/graphite composite powder prefabricated blank is 20 parts;
and 5, putting the strip sample prefabricated blank into a graphite crucible, covering the surface of the strip sample prefabricated blank with 120 parts of coarse silicon powder, and putting the graphite crucible into a high-temperature siliconizing furnace for siliconizing.
B is to be4Preparing the C/graphite composite powder into a strip-shaped sample prefabricated blank body by a pressure forming process, wherein the size of the strip-shaped sample prefabricated blank body is 50mm multiplied by 5mm multiplied by 6mm, and carrying out siliconizing treatment on the strip-shaped sample prefabricated blank body. And putting the strip sample prefabricated blank into a graphite crucible, covering coarse silicon powder on the surface of the strip sample prefabricated blank, and putting the graphite crucible into a high-temperature siliconizing furnace for siliconizing treatment. The phenolic resin is decomposed into gas substances under the high-temperature condition, the gas substances are pumped away by a vacuum pump of the vacuum siliconizing furnace, residual carbon is finally remained in the matrix, and the residual carbon just reacts with liquid silicon in the siliconizing process to form a small amount of silicon carbide. The siliconizing process comprises siliconizing at 1600 deg.C for 2 hr under vacuum degree of 1 × 10-2Pa, obtaining a siliconizing sample after siliconizing treatment. Because the melting point of silicon is 1410 ℃, at the temperature of 1600 ℃, the solid silicon powder can be completely melted to form liquid silicon, and the liquid silicon can be infiltrated into B4The C/graphite composite powder is prefabricated in the blank body, and the liquid silicon and the B4The boron carbide ceramic material on the surface and inside of the C/graphite composite powder preform body reacts with the graphite material to generate silicon carbide, the liquid silicon reacts with the boron carbide ceramic material to generate silicon carbide, the liquid silicon also reacts with the graphite to generate silicon carbide, the graphite and the liquid silicon completely react to generate silicon carbide, the generated silicon carbide and residual silicon fill the pores inside the sample, the boron carbide ceramic material still exists inside the composite material sample, and the residual silicon also exists inside the composite material matrix. So B is prepared by a siliconizing reaction process4A C-SiC-Si composite material block. B prepared by siliconizing reaction4The C-SiC-Si composite material has a uniform and compact microstructure, higher relative density, higher mechanical property, higher hardness, good wear resistance and higher high-temperature oxidation resistancePerformance, etc.
Example 11
Step 1, adopting 70 parts of micron-sized boron carbide ceramic powder as a raw material, wherein the granularity of the powder is about 3-4 mu m; 30 parts of micron-sized graphite powder is used as a raw material, and the particle size of the powder is about 13-14 mu m; mixing boron carbide ceramic powder and graphite powder according to a certain proportion, wherein the graphite powder is prepared B4The mass fraction of the C/graphite composite powder is 30 parts;
step 2, putting the mixed raw materials obtained in the step 1 into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls for mixing, mechanically milling for 24 hours to prepare slurry, and drying the slurry to obtain B4C/graphite composite powder;
step 3, in B4Adding 10 parts by mass of phenolic resin binder into the C/graphite composite powder, and adding B4Putting the C/graphite composite powder and 10 parts of phenolic resin binder into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls, mixing by wet ball milling for 24 hours to prepare slurry, and drying the slurry to prepare B containing the phenolic resin binder4C/graphite mixed powder;
step 4, adding B containing phenolic resin binder4And (3) filling the C/graphite mixed powder into a steel mould, forming the mixture on a forming press machine by 200MPa pressure to prepare a strip sample prefabricated blank body, wherein the size of the strip sample prefabricated blank body is 50mm multiplied by 5mm multiplied by 6mm, and drying the strip sample prefabricated blank body in a drying box at 150 ℃ for 24h to obtain a hardened and cured strip sample prefabricated blank body. The phenolic resin binder has the functions of curing and hardening the strip-shaped sample preform. Wherein graphite powder is B prepared4The mass fraction of the C/graphite composite powder prefabricated blank is 30 parts;
and 5, putting the strip-shaped sample prefabricated blank into a graphite crucible, covering the surface of the sample with 130 parts of coarse silicon powder, and putting the graphite crucible into a high-temperature siliconizing furnace for siliconizing.
B is to be4Preparing the C/graphite composite powder into a strip sample prefabricated blank body by a pressure forming process, wherein the size of the strip sample prefabricated blank body is 50mm multiplied by 5mm multiplied by 6mm, and processing the strip sampleAnd carrying out siliconizing treatment on the prefabricated blank body. And putting the strip sample prefabricated blank into a graphite crucible, covering coarse silicon powder on the surface of the strip sample prefabricated blank, and putting the graphite crucible into a high-temperature siliconizing furnace for siliconizing treatment. The phenolic resin is decomposed into gas substances under the high-temperature condition, the gas substances are pumped away by a vacuum pump of the vacuum siliconizing furnace, residual carbon is finally remained in the matrix, and the residual carbon just reacts with liquid silicon in the siliconizing process to form a small amount of silicon carbide. The siliconizing process comprises siliconizing at 1600 deg.C for 2 hr under vacuum degree of 1 × 10-2Pa, obtaining a siliconizing sample after siliconizing treatment. Because the melting point of silicon is 1410 ℃, at the temperature of 1600 ℃, the solid silicon powder can be completely melted to form liquid silicon, and the liquid silicon can be infiltrated into B4The C/graphite composite powder is prefabricated in the blank body, and the liquid silicon and the B4The boron carbide ceramic material on the surface and inside of the C/graphite composite powder preform body reacts with the graphite material to generate silicon carbide, the liquid silicon reacts with the boron carbide ceramic material to generate silicon carbide, the liquid silicon also reacts with the graphite to generate silicon carbide, the graphite and the liquid silicon completely react to generate silicon carbide, the generated silicon carbide and residual silicon fill the pores inside the sample, the boron carbide ceramic material still exists inside the composite material sample, and the residual silicon also exists inside the composite material matrix. So B is prepared by a siliconizing reaction process4A C-SiC-Si composite material block. B prepared by siliconizing reaction4The C-SiC-Si composite material has a uniform and compact microstructure, higher relative density, higher mechanical property, higher hardness, good wear resistance, higher high-temperature oxidation resistance and the like.
Example 12
Step 1, 60 parts of micron-sized boron carbide ceramic powder is used as a raw material, and the particle size of the powder is about 3-4 mu m; 40 parts of micron-sized graphite powder with the particle size of about 10-12 mu m is used as a raw material, and boron carbide ceramic powder and graphite powder are mixed according to the proportion, wherein the graphite powder is prepared B4The mass fraction of the C/graphite composite powder is40 parts of a mixture;
step 2, putting the mixed raw materials obtained in the step 1 into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls for mixing, mechanically milling for 24 hours to prepare slurry, and drying the slurry to obtain B4C/graphite composite powder;
step 3, in B4Adding 10 parts of phenolic resin binder into the C/graphite composite powder, and adding B4Putting the C/graphite composite powder and 10 parts of phenolic resin binder into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls, mixing for 24 hours by wet ball milling to prepare slurry, and drying the slurry to prepare B containing the phenolic resin binder4C/graphite mixed powder;
step 4, adding B containing phenolic resin binder4Filling the C/graphite mixed powder into a steel mould, forming the C/graphite mixed powder into a strip sample prefabricated blank body on a forming press through 200MPa pressure, wherein the size of the strip sample prefabricated blank body is 50mm multiplied by 5mm multiplied by 6mm, drying the strip sample prefabricated blank body in a drying box at 150 ℃ for 24h to obtain a hardened and cured strip sample prefabricated blank body, and a phenolic resin binder plays roles in curing and hardening the strip sample prefabricated blank body, wherein the graphite powder is prepared in the step B 440 parts of C/graphite composite powder prefabricated blank;
and 5, placing the hardened and solidified strip-shaped sample prefabricated blank into a graphite crucible, covering the surface of the strip-shaped sample prefabricated blank with 150 parts of coarse silicon powder, and placing the graphite crucible into a high-temperature siliconizing furnace for siliconizing.
B is to be4Preparing the C/graphite composite powder into a strip-shaped sample prefabricated blank body by a pressure forming process, wherein the size of the strip-shaped sample prefabricated blank body is 50mm multiplied by 5mm multiplied by 6mm, and carrying out siliconizing treatment on the strip-shaped sample prefabricated blank body. And putting the strip sample prefabricated blank into a graphite crucible, covering coarse silicon powder on the surface of the strip sample prefabricated blank, and putting the graphite crucible into a high-temperature siliconizing furnace for siliconizing treatment. The phenolic resin is decomposed into gas substances under the high-temperature condition, the gas substances are pumped away by a vacuum pump of the vacuum siliconizing furnace, residual carbon is finally remained in the matrix, and the residual carbon just reacts with liquid silicon in the siliconizing process to form a small amount of silicon carbide.The siliconizing process comprises siliconizing at 1600 deg.C for 2 hr under vacuum degree of 1 × 10-2Pa, obtaining a siliconizing sample after siliconizing treatment. Because the melting point of silicon is 1410 ℃, at the temperature of 1600 ℃, the solid silicon powder can be completely melted to form liquid silicon, and the liquid silicon can be infiltrated into B4The C/graphite composite powder is prefabricated in the blank body, and the liquid silicon and the B4The boron carbide ceramic material on the surface and inside of the C/graphite composite powder preform body reacts with the graphite material to generate silicon carbide, the liquid silicon reacts with the boron carbide ceramic material to generate silicon carbide, the liquid silicon also reacts with the graphite to generate silicon carbide, the graphite and the liquid silicon completely react to generate silicon carbide, the generated silicon carbide and residual silicon fill the pores inside the sample, the boron carbide ceramic material still exists inside the composite material sample, and the residual silicon also exists inside the composite material matrix. So B is prepared by a siliconizing reaction process4A C-SiC-Si composite material block. B prepared by siliconizing reaction4The C-SiC-Si composite material has a uniform and compact microstructure, higher relative density, higher mechanical property, higher hardness, good wear resistance, higher high-temperature oxidation resistance and the like.
As can be seen from examples 9-12, in examples 9-12 micron-sized boron carbide ceramic powder and micron-sized graphite powder were mixed and a small amount of phenolic binder was added to form B containing phenolic binder4C/graphite composite powder, wherein the graphite powder is in B4The mass fractions of the C/graphite composite powder are respectively 10wt%, 20wt%, 30wt% and 40 wt%. B prepared4C/graphite composite powder is put into a steel mould to be pressed and formed into a strip-shaped sample prefabricated blank body, B4The relative density of the prefabricated blank body of the C/graphite composite powder strip sample is about 60-70%, the porosity is about 30-40%, the prefabricated blank body of the strip sample is placed into a graphite crucible, the surface of the prefabricated blank body of the strip sample is covered with coarse silicon powder, and the graphite crucible is placed into a high-temperature siliconizing furnace to carry out a high-temperature liquid siliconizing process, wherein the siliconizing process is that the siliconizing process is carried outThe silicon temperature is 1600 ℃, the siliconizing time is 2 hours, the siliconizing reaction process is carried out under the vacuum condition, and the siliconizing sample is obtained after siliconizing treatment. The liquid silicon permeates into the sample blank body through the siliconizing process, the liquid silicon can react with the boron carbide ceramic material and the graphite material to generate silicon carbide, the graphite material completely reacts with the liquid silicon to generate silicon carbide, and the boron carbide ceramic material is also present in the formed composite material, so that the boron carbide ceramic material, the generated silicon carbide and the residual silicon form B4C-SiC-Si composite material. B prepared by siliconizing reaction4The C-SiC-Si composite material has higher relative density, uniform and compact microstructure, higher mechanical property, higher hardness, good wear resistance, higher high-temperature oxidation resistance and the like. The main advantages of the present invention over the existing technology are therefore:
1) the invention adopts a siliconizing reaction method to prepare B4A C-SiC-Si composite material block. Can adopt a hot-pressing sintering process to prepare B4The C-SiC-Si composite material is high in preparation cost and complex in preparation process by adopting a hot-pressing sintering process, and the shape and the size of a prepared product are limited, so that industrial production and large-scale production are difficult to realize. The invention provides a method for preparing B by adopting a high-temperature liquid siliconizing process4The C-SiC-Si composite material is prepared by mixing boron carbide ceramic powder and graphite powder to prepare B4C/graphite composite powder and press forming to obtain B4C/graphite composite powder strip specimen preform, B4The relative density of the prefabricated blank body of the C/graphite composite powder strip sample is about 60-70%, the porosity is about 30-40%, and liquid silicon is infiltrated into B by a siliconizing reaction process4Inside the prefabricated blank of the C/graphite composite powder strip sample, liquid silicon reacts with boron carbide ceramic material and graphite material inside the sample to generate silicon carbide material, graphite completely reacts with the liquid silicon to generate silicon carbide, the boron carbide ceramic material also exists inside the sample matrix, and residual silicon also exists in the composite material matrix, so that B is generated through siliconizing reaction4A C-SiC-Si composite material block.The siliconizing reaction process has the advantages of low preparation cost, simple preparation process, capability of preparing parts with complex shapes, realization of industrial production and contribution to large-scale production.
2) B prepared by siliconizing reaction method4The C-SiC-Si composite material has extremely high relative density, uniform and compact microstructure, extremely low porosity and B prepared by a siliconizing reaction method4The C-SiC-Si composite material has high mechanical property, high hardness, good wear resistance, high-temperature oxidation resistance and the like. B prepared by siliconizing reaction4The C-SiC-Si composite material has high mechanical property, high hardness, good wear resistance and high-temperature oxidation resistance, so that the C-SiC-Si composite material can be applied to the field of wear-resistant engineering or the field of high-temperature-resistant engineering. So the invention adopts the siliconizing reaction method to prepare B4The C-SiC-Si composite material has important research significance and practical value. Therefore, the invention greatly expands B4The application range of the C-SiC-Si composite material in the engineering field. Therefore, the invention has important research significance and practical value. The invention aims to promote and promote B4The C-SiC-Si composite material lays a foundation for wide application in the engineering field.
Because the melting point of silicon is 1410 ℃, at the temperature of 1600 ℃, the solid silicon powder can be completely melted to form liquid silicon, and the liquid silicon can be infiltrated into B4The C/graphite composite powder is prefabricated in the blank body, and the liquid silicon and the B4The boron carbide ceramic material on the surface and inside of the C/graphite composite powder preform body reacts with the graphite material to generate silicon carbide, the liquid silicon reacts with the boron carbide ceramic material to generate silicon carbide, the liquid silicon also reacts with the graphite to generate silicon carbide, the graphite completely reacts with the liquid silicon to generate silicon carbide, the generated silicon carbide and residual silicon fill the pores inside the sample, the boron carbide ceramic material still exists inside the siliconized sample, and the residual silicon also exists inside the siliconized sample. So B is prepared by a siliconizing reaction process4A C-SiC-Si composite material block. B is4C/graphite composite powder prefabricated blankSiliconizing the mixture to obtain B4C-SiC-Si composite material samples.
The phenolic resin binder has the functions of curing and hardening the strip-shaped sample prefabricated blank.
FIG. 1 shows a process B prepared by a high-temperature liquid siliconizing process according to the method provided by the invention4X-ray diffraction pattern of the surface of the C-SiC-Si composite material. FIG. 1 shows a process B prepared by a high-temperature liquid siliconizing process4XRD pattern of C-SiC-Si composite material. As can be seen from FIG. 1, a diffraction peak of boron carbide ceramic phase, a diffraction peak of silicon carbide phase, and a diffraction peak of silicon phase appear in the XRD pattern, which indicates that liquid silicon and B are present during high-temperature liquid siliconizing4Reacting boron carbide ceramic phase in the C/graphite composite powder prefabricated blank to generate silicon carbide, and reacting liquid silicon with B4The graphite in the C/graphite composite powder prefabricated blank also reacts to generate silicon carbide, the graphite and the liquid silicon completely react to generate the silicon carbide, the boron carbide ceramic phase does not completely react, and the rest boron carbide ceramic phase exists, so that the boron carbide ceramic phase also exists in the composite material matrix, and the liquid silicon has a certain residual amount after reacting with the boron carbide ceramic phase and the graphite material to generate the silicon carbide, and the formed residual silicon exists in the composite material matrix, so that the composite material mainly comprises the boron carbide ceramic phase, the silicon carbide and the residual silicon. Diffraction peaks of the boron carbide ceramic phase, silicon carbide, and residual silicon appear in the XRD pattern.
FIG. 2 shows a process B prepared by a high-temperature liquid siliconizing process according to the method provided by the invention4And scanning electron microscope photographs of the interior of the C-SiC-Si composite material. FIG. 2 shows a process B prepared by a high-temperature liquid siliconizing process4Scanning electron microscope photographs of the C-SiC-Si composite material. As can be seen from the scanning electron micrograph, the siliconizing sample obtained by the siliconizing reaction, namely B4The C-SiC-Si composite material sample shows a uniform and compact microstructure, B4The C-SiC-Si composite material sample has no pores inside and very dense tissue, which shows that the siliconized sample has higher relative density which can reach more than 98 percent. Thus B4The C-SiC-Si composite material has higher relative densityBut can improve the bending strength and fracture toughness of the sample, and improve the hardness, wear resistance and the like.

Claims (4)

1.B4Siliconizing reaction of C/graphite preform to generate B4The C-SiC-Si composite material is characterized by comprising the following components:
60-90 parts of boron carbide ceramic powder; 10-40 parts of graphite powder; 7-10 parts of phenolic resin binder; 110 to 150 parts of silicon powder.
2. B according to claim 14Siliconizing reaction of C/graphite preform to generate B4The C-SiC-Si composite material is characterized in that the boron carbide ceramic powder is micron-sized, and the particle size of the boron carbide ceramic powder is 3-5 mu m.
3. B according to claim 14Siliconizing C/graphite powder preform to generate B4The C-SiC-Si composite material is characterized in that the graphite is micron-sized, and the powder granularity is 10-15 mu m.
4.B4Siliconizing reaction of C/graphite preform to generate B4The preparation method of the C-SiC-Si composite material is characterized by comprising the following steps:
step 1, mixing 90-60 parts of micron-sized boron carbide ceramic powder with the powder granularity of 3-5 microns and 10-40 parts of micron-sized graphite powder with the powder granularity of 10-15 microns to obtain a mixed material, wherein the graphite powder accounts for 10-40 wt% of the mixed material;
step 2, putting the mixed material obtained in the step 1 into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls, mechanically milling for 24 hours to prepare slurry, and drying the slurry to obtain B4C/graphite composite powder;
step 3, obtaining B4Adding 10 parts of phenolic resin binder into the C/graphite composite powder, filling the mixture into a ball milling tank, adding 300 ml of absolute ethyl alcohol and agate milling balls, mixing the mixture by wet ball milling for 24 hours to prepare slurry, and drying the slurryDrying to form B containing phenolic resin binder4C/graphite mixed powder;
step 4, adding B containing phenolic resin binder4C/graphite mixed powder is filled into a steel mould, is molded on a molding press under the pressure of 200MPa to prepare a strip-shaped sample prefabricated blank body, and is dried in a drying oven at the temperature of 150 ℃ for 24 hours to obtain a hardened and cured strip-shaped sample prefabricated blank body;
step 5, placing the hardened and solidified strip-shaped sample prefabricated blank body into a graphite crucible, covering the surface of the strip-shaped sample prefabricated blank body with coarse silicon powder, and placing the graphite crucible into a high-temperature siliconizing furnace for siliconizing;
the size of the strip-shaped sample prefabricated blank body is 50mm multiplied by 5mm multiplied by 6 mm;
the siliconizing process comprises the steps of siliconizing at 1600 ℃, keeping the temperature for 2 hours, carrying out the siliconizing reaction process under the vacuum condition, wherein the vacuum degree is 1 multiplied by 10-2Pa, wherein the phenolic resin is decomposed into gas substances at high temperature and is pumped away by a vacuum pump of a vacuum siliconizing furnace, residual carbon is finally remained in the matrix, the residual carbon reacts with liquid silicon in the siliconizing process to form a small amount of silicon carbide, and B is prepared by the siliconizing reaction process4A C-SiC-Si composite material block.
CN202110640685.6A 2021-06-09 2021-06-09 B4B4C-SiC-Si composite material generated by siliconizing reaction of C/graphite preform and preparation method thereof Pending CN113233899A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110640685.6A CN113233899A (en) 2021-06-09 2021-06-09 B4B4C-SiC-Si composite material generated by siliconizing reaction of C/graphite preform and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110640685.6A CN113233899A (en) 2021-06-09 2021-06-09 B4B4C-SiC-Si composite material generated by siliconizing reaction of C/graphite preform and preparation method thereof

Publications (1)

Publication Number Publication Date
CN113233899A true CN113233899A (en) 2021-08-10

Family

ID=77137307

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110640685.6A Pending CN113233899A (en) 2021-06-09 2021-06-09 B4B4C-SiC-Si composite material generated by siliconizing reaction of C/graphite preform and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113233899A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116041065A (en) * 2022-11-28 2023-05-02 中南大学 Preparation method of 3D printing B4C-based composite ceramic
CN116102354A (en) * 2022-11-07 2023-05-12 江苏核电有限公司 Composition for main pump bearing bush and preparation method thereof
CN116496089A (en) * 2022-01-19 2023-07-28 中国科学院上海硅酸盐研究所 A preparation method of reaction sintered boron carbide-silicon carbide composite ceramic material for deep sea

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005079207A2 (en) * 2003-11-25 2005-09-01 M Cubed Technologies, Inc. Boron carbide composite bodies, and methods for making same
CN101456737A (en) * 2009-01-05 2009-06-17 西安交通大学 Boron carbide base composite ceramic and preparation method thereof
US20110009255A1 (en) * 2005-12-22 2011-01-13 Coorstek, Inc. Boron-silicon-carbon ceramic materials and method of making
CN101967059A (en) * 2010-09-17 2011-02-09 西安交通大学 Method for preparing silicon carbide bullet-proof ceramics
CN102219518A (en) * 2011-03-31 2011-10-19 浙江立泰复合材料有限公司 Boron carbide-silicon carbide complex ceramic and preparation method thereof
CN102464490A (en) * 2010-11-17 2012-05-23 东北大学 Method for preparing boron-carbide-based ceramic composite material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005079207A2 (en) * 2003-11-25 2005-09-01 M Cubed Technologies, Inc. Boron carbide composite bodies, and methods for making same
US20110009255A1 (en) * 2005-12-22 2011-01-13 Coorstek, Inc. Boron-silicon-carbon ceramic materials and method of making
CN101456737A (en) * 2009-01-05 2009-06-17 西安交通大学 Boron carbide base composite ceramic and preparation method thereof
CN101967059A (en) * 2010-09-17 2011-02-09 西安交通大学 Method for preparing silicon carbide bullet-proof ceramics
CN102464490A (en) * 2010-11-17 2012-05-23 东北大学 Method for preparing boron-carbide-based ceramic composite material
CN102219518A (en) * 2011-03-31 2011-10-19 浙江立泰复合材料有限公司 Boron carbide-silicon carbide complex ceramic and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116496089A (en) * 2022-01-19 2023-07-28 中国科学院上海硅酸盐研究所 A preparation method of reaction sintered boron carbide-silicon carbide composite ceramic material for deep sea
CN116102354A (en) * 2022-11-07 2023-05-12 江苏核电有限公司 Composition for main pump bearing bush and preparation method thereof
CN116102354B (en) * 2022-11-07 2024-04-09 江苏核电有限公司 Composition for main pump bearing bush and preparation method thereof
CN116041065A (en) * 2022-11-28 2023-05-02 中南大学 Preparation method of 3D printing B4C-based composite ceramic
CN116041065B (en) * 2022-11-28 2024-04-12 中南大学 Preparation method of 3D printing B4C-based composite ceramic

Similar Documents

Publication Publication Date Title
CN113233899A (en) B4B4C-SiC-Si composite material generated by siliconizing reaction of C/graphite preform and preparation method thereof
CN109053206B (en) A kind of short fiber reinforced oriented MAX phase ceramic matrix composite material and preparation method
KR101367347B1 (en) Biphasic nanoporous vitreous carbon material and method of making the same
CN102464490B (en) Method for preparing boron-carbide-based ceramic composite material
CN101555137B (en) (TiB2+TiC)/Ti3SiC2Complex phase ceramic material and preparation method thereof
CN102219536B (en) B4C/SiC whisker/SiC multiphase ceramic matrix composite and preparation method thereof
CN113292318A (en) Preparation method of ZTA/high-chromium cast iron composite wear-resistant material
CN110028322A (en) A kind of preparation method of multiphase composite sealing ring
CN1600743A (en) A high-strength dense silicon carbide ceramic ball and its preparation method
CN105084902B (en) A kind of preparation method of titanium diboride based composite ceramic material
CN110304923B (en) Preparation method of boron carbide-based ceramic composite material based on particle grading
CN110282977A (en) A kind of B4C/TiB2The preparation method of layered composite ceramic material
CN106800420A (en) A kind of silicon carbide whisker in-situ composite corindon high-temperature ceramic materials and preparation method thereof
CN113582700B (en) Preparation method of low-cost titanium boride ceramic composite material
CN110256093A (en) A kind of reduction infiltration process preparation SiCfThe method of remaining silicone content in/SiC ceramic matrix composite material
CN105601282A (en) Preparation method of silicon nitride-based ceramic composite material
WO2011011606A2 (en) Methods of forming sintered boron carbide
CN109231990A (en) A kind of preparation method of tungsten carbide-diamond composite
CN108439990B (en) A kind of titanium diboride-based ceramic composite material and preparation method thereof
CN101555136B (en) Titanium silicon carbide/titanium diboride-titanium carbide composite material and preparation method thereof
CN111747748B (en) Ultrahigh-temperature heat-proof/insulation integrated ZrC/Zr 2 C complex phase material and preparation method thereof
JPH0822782B2 (en) Method for producing fiber-reinforced ceramics
EP0257134A1 (en) A method for producing high-density sintered silicon carbide articles
KR100299099B1 (en) Manufacturing Method of Silicon Carbide Ceramic Seals by Liquid Phase Reaction Sintering
AU689270B2 (en) Preparation of high density zirconium carbide ceramics with preceramic polymer binders

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