CN116835987A - Preparation method of low-cost boron carbide-nano SiC ceramic composite material - Google Patents
Preparation method of low-cost boron carbide-nano SiC ceramic composite material Download PDFInfo
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- CN116835987A CN116835987A CN202310885252.6A CN202310885252A CN116835987A CN 116835987 A CN116835987 A CN 116835987A CN 202310885252 A CN202310885252 A CN 202310885252A CN 116835987 A CN116835987 A CN 116835987A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 25
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052580 B4C Inorganic materials 0.000 claims abstract description 60
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000006229 carbon black Substances 0.000 claims abstract description 57
- 239000000463 material Substances 0.000 claims abstract description 50
- 239000000843 powder Substances 0.000 claims abstract description 48
- 238000000498 ball milling Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 27
- 235000015895 biscuits Nutrition 0.000 claims abstract description 23
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 230000008595 infiltration Effects 0.000 claims abstract description 12
- 238000001764 infiltration Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000000748 compression moulding Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 30
- 229920002873 Polyethylenimine Polymers 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 229910002804 graphite Inorganic materials 0.000 claims description 15
- 239000010439 graphite Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011268 mixed slurry Substances 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 6
- 239000011856 silicon-based particle Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 9
- 239000011159 matrix material Substances 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 6
- 239000010703 silicon Substances 0.000 abstract description 6
- 238000005475 siliconizing Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract description 2
- 240000007594 Oryza sativa Species 0.000 abstract 1
- 235000007164 Oryza sativa Nutrition 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- -1 polyethylene terephthalate Polymers 0.000 abstract 1
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract 1
- 239000005020 polyethylene terephthalate Substances 0.000 abstract 1
- 235000009566 rice Nutrition 0.000 abstract 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 27
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 26
- 238000005245 sintering Methods 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004063 acid-resistant material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000001272 pressureless sintering Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000002490 spark plasma sintering Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/563—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on boron carbide
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
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Abstract
The invention relates to a preparation method of a low-cost boron carbide-nano SiC ceramic composite material, which comprises the following steps: uniformly dispersing carbon black powder through PEI (polyethylene terephthalate) by ultrasonic, adding boron carbide, performing ball milling to obtain wet materials, adding PVA (polyvinyl alcohol) aqueous solution into the wet materials, and performing ball milling to obtain composite wet materials; drying and grinding the composite wet material to obtain composite powder; compression molding the obtained powder to obtain B 4 C-carbon black biscuit; will B 4 C-carbon black biscuit is used as a matrix, simple substance silicon is used as an infiltration agent, and vacuum infiltration is carried out to obtain the boron carbide ceramic composite material. The invention overcomes the problem that carbon black is easy to agglomerate in boron carbide slurry and blank, realizes that evenly distributed carbon black is introduced into boron carbide ceramic slurry and blank, and forms nanometer in boron carbide ceramic matrix after siliconizing reaction sinteringThe mechanical property of the rice SiC ceramic skeleton is obviously improved, and the process flow is low in cost, easy to operate, pollution-free and suitable for mass industrial production.
Description
Technical Field
The invention relates to the technical field of composite material preparation, in particular to a preparation method of a low-cost boron carbide-nano SiC ceramic composite material.
Background
Boron carbide (B) 4 C) Ceramics play an important role in structural ceramics, and have many excellent properties, the most prominent being low density and high hardness, which is inferior to diamond and cubic boron nitride at normal temperature. Meanwhile, the boron carbide ceramic has the characteristics of high modulus, good wear resistance, excellent neutron absorption performance, high melting point, good conductivity, excellent chemical erosion resistance and the like, and has been widely used as bulletproof armor materials, high-temperature structural materials, atomic reactor control and shielding materials, wear-resistant materials, acid-resistant materials, alkali corrosion materials, cutting grinding and electrothermal materials and the like.
At present, expensive hot press sintering, pressureless sintering and spark plasma sintering are mainly adopted for preparing the boron carbide ceramic, and the boron carbide ceramic with large size and complex shape is difficult to prepare. Therefore, since the 70 th century, a method for preparing a compact boron carbide ceramic material under low cost and sintering the boron carbide ceramic by a siliconizing reaction under vacuum condition has been researched, the sintering process is simplified, the densification temperature of the boron carbide ceramic is reduced, the sintering time is shortened, and the production cost of the boron carbide ceramic is greatly reduced.
In preparing the fused silica reaction sintered boron carbide composite material, an additional carbon source such as carbon black, phenolic resin, and the like is generally required. When the carbon black is used as an external carbon source, the preparation process is free from environmental pollution, and the preparation process of the material is simpler, has lower cost and is more suitable for industrial production. However, when carbon black is used as an external carbon source, the carbon black is usually very small in particle size, carbon black fine powder is extremely easy to agglomerate in the process of mixing materials, and the agglomerated carbon black reacts with silicon in a molten state in the subsequent reaction sintering process to generate a concentrated silicon carbide region; in addition, in the subsequent siliconizing process, the carbon black particles are unevenly dispersed to induce the further dissolution of the boron carbide particles, and new phases nucleate and grow on undissolved boron carbide particles, so that the boron carbide particles grow up, and the mechanical properties of the composite material are not facilitated.
Disclosure of Invention
First, the technical problem to be solved
In view of the above-mentioned shortcomings and disadvantages of the prior art, the invention provides a preparation method of a low-cost boron carbide-nano SiC ceramic composite material, which solves the technical problems that carbon black is difficult to uniformly distribute in boron carbide slurry and blank, a silicon carbide concentrated region is formed in the infiltration process, boron carbide particles grow up, the mechanical properties of the ceramic composite material are poor, and the like.
(II) technical scheme
In order to achieve the above purpose, the main technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a boron carbide-nano SiC ceramic composite material with low cost.
The preparation method of the boron carbide-nano SiC ceramic composite material with low cost provided by the embodiment of the invention comprises the following steps:
s1: completely dissolving polyethyleneimine in deionized water, and adding carbon black powder for ultrasonic dispersion; adding boron carbide powder to obtain mixed slurry; placing the mixed slurry into a ball milling tank for ball milling to obtain ball milling wet materials; adding a polyvinyl alcohol aqueous solution into the ball-milling wet material, and then continuing ball milling to obtain a mixed wet material;
s2: putting the mixed wet material into a baking oven, and drying deionized water to prepare mixed dry material; pulverizing the mixed dry materials into powder, and sieving the powder to obtain fine powder;
s3: compression molding the fine powder to obtain B 4 C-carbon black biscuit;
s4: will B 4 Placing the C-carbon black biscuit in a graphite crucible, and at B 4 Simple substance silicon particles are paved above the C-carbon black biscuit,and carrying out infiltration in a vacuum environment, and cooling to room temperature to obtain the boron carbide ceramic composite material.
According to the invention, in step S1, the molecular weight of the polyethyleneimine is 1800.
According to the present invention, in step S1, the average particle size of the boron carbide powder is 2.1 μm and the particle size range is 1.4 μm to 2.5. Mu.m.
According to the present invention, in step S1, the average particle diameter of the carbon black powder is 22nm.
According to the invention, in the step S1, the mass ratio of the boron carbide powder to the carbon black powder is 9:1, and the addition amount of the polyethyleneimine is 0-1 wt%.
According to the invention, in step S1, the concentration of the aqueous polyvinyl alcohol solution is 5% and the addition amount is 30% by weight.
According to the invention, in the step S1, the ball milling is horizontal ball milling, the ball milling time is 24 hours, ball milling wet materials are obtained, and the mixed wet materials are obtained after adding polyvinyl alcohol aqueous solution into the ball milling wet materials and continuing ball milling for 4 hours.
According to the invention, in step S2, the powder is sieved through a 60 mesh sieve.
According to the invention, in step S4, B 4 Placing the C-carbon black biscuit in a graphite crucible, and at B 4 Paving simple substance silicon particles above the C-carbon black biscuit; the graphite crucible is placed in a graphite vacuum furnace for infiltration, the temperature is 1560-1610 ℃, the heating rate is 5 ℃ or 10 ℃ per minute at 1100-1560-1610 ℃, the vacuum degree is 50 Pa-55 Pa, and the temperature is kept for 30 min-45 min.
(III) beneficial effects
The beneficial effects of the invention are as follows: according to the preparation method of the boron carbide-nano SiC ceramic composite material with low cost, the boron carbide and the economic and practical carbon black are used as main raw materials, the Polyethyleneimine (PEI) is introduced as the dispersing agent, the carbon black powder which is easy to agglomerate can be uniformly dispersed into a boron carbide matrix, and the carbon black does not have the problem of environmental pollution when being used as an external carbon source instead of organic matters such as phenolic resin; the dissolution and growth of boron carbide crystal grains are inhibited by combining infiltration reaction sintering, and the boron carbide ceramic composite material with the reinforced nano SiC ceramic skeleton is prepared, so that the bending strength, the fracture toughness and the like are improved to a certain extent. Based on the method, carbon black which is uniformly distributed is introduced into the boron carbide ceramic body, a nano SiC ceramic skeleton is formed in the boron carbide ceramic matrix after sintering, and the growth of boron carbide particles in the siliconizing process is avoided, so that the mechanical properties of the material are obviously improved, the production cost of the boron carbide ceramic is further reduced, and the method is easy to operate and pollution-free and is suitable for mass industrial production.
(1) B prepared by the invention 4 The agglomeration condition of carbon black powder is obviously improved after the C-carbon black mixed slurry is dispersed by PEI.
(2) B prepared by the invention 4 The relative density of the C-carbon black blank is improved compared with that of the blank without PEI, and the porosity of the blank is reduced.
(3) In the invention, the boron carbide ceramic composite material prepared by adopting PEI dispersed carbon black is prepared by reacting uniformly dispersed carbon black with Si to generate nano SiC, B 4 C particles are surrounded by nano SiC to inhibit B 4 The particles C grow up and bond with each other to form a ceramic skeleton, so that the bending strength and fracture toughness of the material are improved to 470MPa and 4.5 MPa-m respectively 1/2 。
(4) The boron carbide ceramic composite material prepared by dispersing PEI has higher volume density, lower Si content and lower open porosity, so the PEI has higher Vickers hardness and reaches 22GPa.
(5) The invention has the advantages of cheap and easily obtained raw materials, simple and feasible process flow, no pollution, low equipment requirement and low production cost, and is suitable for mass production.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of the low-cost boron carbide-nano SiC ceramic composite material;
FIG. 2 is an X-ray diffraction pattern of a method for preparing a boron carbide-nano SiC ceramic composite material with low cost in an embodiment of the invention.
Fig. 3 is an SEM secondary electron photograph of a method for preparing a boron carbide-nano SiC ceramic composite material with low cost according to an embodiment of the present invention.
Fig. 4 is an SEM back-scattered electron image of a method for preparing a low cost boron carbide-nano SiC ceramic composite in an embodiment of the present invention.
Fig. 5 is a TEM photograph of nano SiC particles in the preparation method of the low cost boron carbide-nano SiC ceramic composite material of example 1 of the present invention.
Detailed Description
The invention will be better explained by the following detailed description of the embodiments with reference to the drawings.
The raw material information used in the examples of the present invention is shown in table 1 below.
TABLE 1 raw material information
Boron carbide (B) used in the examples of the present invention 4 C) The average particle size of the powder is 2.1 mu m, the particle size range is 1.4-2.5 mu m, and the weight purity is 95%.
The average particle diameter of the carbon black powder used was 22nm.
The equipment used for molding in the embodiment of the invention is a WE-10A hydraulic universal tester.
The equipment adopted by the infiltration reaction sintering in the embodiment of the invention is a vacuum graphite reaction sintering furnace.
In the embodiment of the invention, the Archimedes drainage method is adopted to measure the volume density and the open porosity of the green body and the sintered body.
In the embodiment of the invention, the bending strength and the fracture toughness of the material are respectively measured by adopting a three-point bending method and a single-side notched beam method, and an AG-Xplus100kN electronic universal tester manufactured by Japanese Co., ltd is used as an instrument.
In the embodiment of the invention, vickers indentation hardness method is adopted to measure the Vickers hardness of the material, and an instrument is an HVS-50Z Vickers hardness meter.
In the embodiment of the invention, smartlab (9) X-ray diffractometer is adopted to analyze the phase composition of the ceramic composite materialThe prepared boron carbide ceramic composite material is prepared from B12 (C, si, B) 3 SiC and free Si.
In the embodiment of the invention, a scanning electron microscope (JSM-7001F) provided with an EDS spectrometer is adopted to observe the microstructure of the composite material.
Example 1 and comparative example 1 were boron carbide ceramic composites prepared by siliconizing reaction sintering with carbon black as an additional carbon source when the added amounts of Polyethylenimine (PEI) were 1wt% and 0wt%, respectively
Example 1: a preparation method of a low-cost boron carbide-nano SiC ceramic composite material comprises the following steps:
s1: completely dissolving polyethyleneimine in deionized water, and adding carbon black powder for ultrasonic dispersion; adding boron carbide powder to obtain mixed slurry; putting the mixed slurry into a ball milling tank for ball milling to obtain ball milling wet materials; adding a polyvinyl alcohol aqueous solution into the ball-milling wet material, and then continuing ball milling to obtain a mixed wet material; the molecular weight of the polyethyleneimine is 1800; the average granularity of the boron carbide powder is 2.1 mu m, and the granularity range is 1.4 mu m-2.5 mu m; the average particle diameter of the carbon black powder is 22nm; the mass ratio of the boron carbide powder to the carbon black powder is 9:1, and the addition amount of the polyethyleneimine is 0-1 wt%; the concentration of the polyvinyl alcohol aqueous solution is 5%, and the addition amount is 30% by weight; the ball milling is horizontal ball milling, the ball milling time is 24 hours, ball milling wet materials are obtained, and the ball milling wet materials are added with polyvinyl alcohol aqueous solution and then are continuously ball milled for 4 hours, so that mixed wet materials are obtained;
s2: putting the mixed wet material into a baking oven, and drying deionized water to prepare a mixed dry material; pulverizing the mixed dry material into powder, and sieving the powder to obtain fine powder; sieving the powder with a 60-mesh sieve;
s3: compression molding the fine powder to obtain a B4C-carbon black biscuit;
s4: the B is carried out 4 Placing the C-carbon black biscuit in a graphite crucible, and at the position B 4 And paving simple substance silicon particles above the C-carbon black biscuit, carrying out infiltration in a vacuum environment, and cooling to room temperature to obtain the boron carbide ceramic composite material. Will be spentThe B is 4 Placing the C-carbon black biscuit in a graphite crucible, and at the position B 4 Paving simple substance silicon particles above the C-carbon black biscuit; the graphite crucible is placed in a graphite vacuum furnace for infiltration, the temperature is 1560-1610 ℃, the heating rate is 5 ℃ or 10 ℃ per minute when the temperature is 1100 ℃ to 1560-1610 ℃, the vacuum degree is 50 Pa-55 Pa, and the temperature is kept for 30 min-45 min.
From the foregoing, the preparation method of the boron carbide-nano SiC ceramic composite material with low cost comprises the following steps: firstly, boron carbide powder and carbon black powder are 9:1 weighing powder, 1wt% of polyethyleneimine and 30wt% of polyvinyl alcohol aqueous solution, adding deionized water into a beaker, completely dissolving the polyethyleneimine into the deionized water, adding carbon black powder for ultrasonic dispersion, adding boron carbide powder, uniformly mixing through mechanical stirring, ball milling for 24 hours, adding polyvinyl alcohol (PVA) aqueous solution into wet materials after ball milling, continuing ball milling for 4 hours, drying, granulating and sieving with a 60-mesh sieve for later use.
Filling the fine powder into a mold, maintaining the unidirectional pressure at 200MPa and the pressure for more than 10s to obtain B 4 C-carbon black biscuit.
Will B 4 Placing the C-carbon black biscuit into a graphite crucible, uniformly paving simple substance silicon blocks on the upper layer of the biscuit, and performing high-temperature infiltration sintering in a graphite reaction furnace to obtain a sintered body; the sintering parameters are as follows: heating to 10 ℃ per minute from 1100 ℃ to 1570 ℃, preserving heat for 45min, and then cooling along with the furnace.
And taking out the cooled sintered body, and polishing off residual elemental silicon on the surface of the sintered body to obtain the boron carbide ceramic composite material for testing.
In this example, B is prepared 4 The density of the C-carbon black biscuit is 1.49g/cm 3 The open porosity is 41.7%; the volume density of the prepared boron carbide ceramic composite material is 2.63g/cm 3 The open porosity was 0.27%, the residual silicon content was 29.7% by weight, the flexural strength was 470MPa, and the fracture toughness was 4.5 MPa.m 1/2 The vickers hardness was 22GPa. The X-ray diffraction pattern of the composite material is shown in fig. 2 (a); the SEM secondary electron photograph is shown in fig. 3 (a), (b) and (c), wherein (a) is 100 times magnified, (b) is 300 times magnified, and (c) is 1000 times magnified; SEM back-scattered electron images such asFig. 4 (a), (b), and (c), wherein (a) is a magnification of 2000 times, (b) is a magnification of 3000 times, and (c) is a magnification of 5000 times; TEM photograph of nano SiC particles as in FIG. 5, showing B 4 Bright field image of C-SiC framework.
Comparative example 1:
the preparation method of the boron carbide ceramic composite material is the same as in example 1, except that the addition of Polyethyleneimine (PEI) is omitted after the addition of deionized water, ultrasonic dispersion is directly performed, and then boron carbide (B) is added 4 C) The powder is evenly mixed by mechanical stirring, ball milling is carried out for 24 hours, then, polyvinyl alcohol (PVA) aqueous solution is added into wet materials, ball milling is continued for 4 hours, and granulation and 60-mesh sieving are carried out for standby.
The subsequent process of example 1 was then continued to produce a boron carbide ceramic composite.
In this comparative example, B was prepared 4 The density of the C-carbon black biscuit is 1.33g/cm 3 The open porosity is 45.3%; the volume density of the prepared boron carbide ceramic composite material is 2.59g/cm 3 The open porosity was 0.53%, the residual silicon content was 34.9% by weight, the flexural strength was 330MPa, and the fracture toughness was 4.0 MPa.m 1/2 The vickers hardness was 20GPa. The X-ray diffraction pattern of the composite material is shown in fig. 2 (b); the SEM secondary electron photographs are shown in fig. 3 (d), (e) and (f), wherein (d) is 100 times magnified, (e) is 300 times magnified, and (f) is 1000 times magnified; the SEM backscattered electron image is shown in fig. 4 (d), (e) and (f), where (d) is at 2000 x magnification, (e) is at 3000 x magnification, and (f) is at 5000 x magnification.
As can be seen from a comparison of FIGS. 3 (a) and (d), without the addition of Polyethyleneimine (PEI), a number of isolated SiC-rich regions appear in the material, which indicates that the carbon black is already present in B prior to reaction sintering 4 Agglomeration occurs in the C-carbon black biscuit, and the material structure in FIG. 3 (a) is uniform, which shows that the carbon black is uniformly distributed in the boron carbide matrix after being dispersed by Polyethyleneimine (PEI); as apparent from the comparison of FIGS. 3 (c) and (f), the SiC particles in FIG. 3 (f) are isolated from each other and do not form a junction structure, so that the reinforcing effect on the boron carbide matrix is limited, and as can be seen from FIG. 5, a nano SiC network structure is formed in FIG. 3 (c), which has a strong resistance to crack initiation and propagationAnd the mechanical property of the composite material is improved.
As is apparent from comparison of fig. 4 (c) and (f), the composite material obtained in comparative example 1 has a much larger particle size of the boron carbide particles than that of example 1, which shows that the carbon concentration distribution around the boron carbide particles is uneven when no Polyethyleneimine (PEI) is added, and a concentration gradient of carbon is formed around the boron carbide particles during reaction sintering, resulting in dissolution of part of the boron carbide particles and growth of part of the boron carbide particles; after PEI is added, nano silicon carbide is uniformly formed around the boron carbide particles, the particle growth tendency is small, and the tissue is uniform.
In the present invention, unless expressly stated or limited otherwise, a first feature is "on" or "under" a second feature, which may be in direct contact with the first and second features, or in indirect contact with the first and second features via an intervening medium. Moreover, a first feature "above," "over" and "on" a second feature may be a first feature directly above or obliquely above the second feature, or simply indicate that the first feature is higher in level than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is level lower than the second feature.
In the description of the present specification, the terms "one embodiment," "some embodiments," "examples," "particular examples," or "some examples," etc., refer to particular features, structures, materials, or characteristics described in connection with the embodiment or example as being included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that alterations, modifications, substitutions and variations may be made in the above embodiments by those skilled in the art within the scope of the invention.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (9)
1. The preparation method of the boron carbide-nano SiC ceramic composite material with low cost is characterized by comprising the following steps:
s1: completely dissolving polyethyleneimine in deionized water, and adding carbon black powder for ultrasonic dispersion;
adding boron carbide powder to obtain mixed slurry;
placing the mixed slurry into a ball milling tank for ball milling to obtain ball milling wet materials;
adding a polyvinyl alcohol aqueous solution into the ball-milling wet material, and then continuing ball milling to obtain a mixed wet material;
s2: putting the mixed wet material into a baking oven, and drying deionized water to prepare a mixed dry material;
pulverizing the mixed dry material into powder, and sieving the powder to obtain fine powder;
s3: compression molding the fine powder to obtain B 4 C-carbon black biscuit;
s4: the B is carried out 4 Placing the C-carbon black biscuit in a graphite crucible, and at the position B 4 And paving simple substance silicon particles above the C-carbon black biscuit, carrying out infiltration in a vacuum environment, and cooling to room temperature to obtain the boron carbide ceramic composite material.
2. The method for preparing the low-cost boron carbide-nano SiC ceramic composite material according to claim 1, which is characterized in that:
in step S1, the molecular weight of the polyethyleneimine is 1800.
3. The method for preparing the low-cost boron carbide-nano SiC ceramic composite material according to claim 1, which is characterized in that:
in step S1, the average particle size of the boron carbide powder is 2.1 μm, and the particle size range is 1.4 μm to 2.5 μm.
4. The method for preparing the boron carbide-nano SiC ceramic composite material with low cost according to claim 1, which is characterized in that:
in step S1, the carbon black powder has an average particle diameter of 22nm.
5. The method for preparing the low-cost boron carbide-nano SiC ceramic composite material according to claim 1, which is characterized in that:
in the step S1, the mass ratio of the boron carbide powder to the carbon black powder is 9:1, and the addition amount of the polyethyleneimine is 0-1 wt%.
6. The method for preparing the low-cost boron carbide-nano SiC ceramic composite material according to claim 1, which is characterized in that:
in step S1, the concentration of the aqueous solution of polyvinyl alcohol was 5% and the addition amount was 30% by weight.
7. The method for preparing the low-cost boron carbide-nano SiC ceramic composite material according to claim 1, which is characterized in that:
in the step S1, the ball milling is horizontal ball milling, the ball milling time is 24 hours, ball milling wet materials are obtained, and the ball milling wet materials are continuously ball milled for 4 hours after polyvinyl alcohol aqueous solution is added into the ball milling wet materials, so that mixed wet materials are obtained.
8. The method for preparing the low-cost boron carbide-nano SiC ceramic composite material according to claim 1, which is characterized in that:
in step S2, the powder is sieved through a 60 mesh sieve.
9. The method for preparing the low-cost boron carbide-nano SiC ceramic composite material according to claim 1, which is characterized in that:
in step S4, the B is performed 4 Placing the C-carbon black biscuit in a graphite crucible, and at the position B 4 Paving simple substance silicon particles above the C-carbon black biscuit;
the graphite crucible is placed in a graphite vacuum furnace for infiltration, the temperature is 1560-1610 ℃, the heating rate is 5 ℃ or 10 ℃ per minute when the temperature is 1100 ℃ to 1560-1610 ℃, the vacuum degree is 50 Pa-55 Pa, and the temperature is kept for 30 min-45 min.
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