CN110304923A - A kind of preparation method of the boron-carbide-based ceramic composite material based on grain composition - Google Patents

A kind of preparation method of the boron-carbide-based ceramic composite material based on grain composition Download PDF

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CN110304923A
CN110304923A CN201910597379.1A CN201910597379A CN110304923A CN 110304923 A CN110304923 A CN 110304923A CN 201910597379 A CN201910597379 A CN 201910597379A CN 110304923 A CN110304923 A CN 110304923A
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powder
boron
composite material
carbide
grain composition
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张翠萍
茹红强
夏乾
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Northeastern University China
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Abstract

A kind of preparation method of boron-carbide-based ceramic composite material based on grain composition of the invention, step are as follows: by different size B4C powder mixes in proportion, is milled spare；It takes water as a solvent, acrylamide, methylene-bisacrylamide, tetramethylammonium hydroxide are solute, are configured to premixed liquid in proportion, and B is added4Initiator is added after C mixed powder and carries out injection molding solidification, B4C green body is obtained after drying, carbonization；Si is placed in B4On C green body after infiltration in vacuum, boron carbide ceramics composite material is obtained.The method of the present invention is simple, it is high that green body relative density is made；Green body can be machined, and complex-shaped product can be prepared；Sintering temperature is low, and the low-density B that even tissue is controllable, comprehensive mechanical property is excellent can be made at lower cost4C composite；Extrudate density is low, has high specific strength；Sintering front and back product size changes < 1%, belongs to net-shape-sinter.

Description

A kind of preparation method of the boron-carbide-based ceramic composite material based on grain composition
Technical field:
The invention belongs to field of material technology, and in particular to a kind of boron-carbide-based ceramic composite material based on grain composition Preparation method.
Background technique:
Boron carbide (B4C) ceramics occupy an important position in structural ceramics, it has many excellent performances, most outstanding Performance is exactly high rigidity and low-density, its hardness is only second to diamond and cubic boron nitride under room temperature.Meanwhile boron carbide ceramics is also It is invaded with high-modulus, good wearability, excellent neutron-absorbing performance, high-melting-point, good electric conductivity, superior anti-chemistry The features such as erosion ability, is widely used as ballistic armor materials, high-temperature structural material, atomic pile by foreign countries and controls and shield Material, wear-resistant material, acid-alkali-corrosive-resisting material, cutting and grinding tool and thermo electric material etc..But due to boron carbide ceramics atom Between with firm Covalent bonding together, crystal boundary moving resistance is big, sintering activating energy is low, it is extremely tired to obtain high-densit sintered body It is difficult, it usually needs high temperature is sintered, and sintering temperature is usually at 2000 DEG C or so.
Summary of the invention:
The purpose of the present invention is overcoming above-mentioned the shortcomings of the prior art, a kind of boron carbide based on grain composition is provided Based composite ceramic material preparation method.This method can be prepared high relatively close by the method for grain composition attached gel injection molding Degree, the uniform green body of structure, to obtain B4The reaction-sintered boron carbide ceramics composite material of C content height, even tissue, is improved The comprehensive performance of reaction-sintered boron carbide ceramics composite material.
To achieve the above object, the invention adopts the following technical scheme:
A kind of preparation method of the boron-carbide-based ceramic composite material based on grain composition, comprising the following steps:
Step 1: mixed slurry preparation:
(1) varigrained B is taken4C powder, including B4C powder A, B4C powder B, B4C powder C, B4C powder D and B4C powder E, wherein the B4C powder A average particle size is 2 μm, the B4C powder B average particle size is 10 μm, the B4C powder C Average particle size is 20 μm, the B4C powder D average particle size is 40 μm, the B4C powder E average particle size is 120 μm, by matter Ratio is measured, A:B:C:D:E=(0.14~0.3): (0~0.43): (0~0.28): (0~0.29): (0~0.42): (0~ 0.65) it, is mixed to form mixed powder, includes two or three and A in B, C, D or E in the mixed powder；
(2) acrylamide, methylene-bisacrylamide, dispersing agent are mixed with deionized water, in mass ratio, acryloyl Amine: deionized water=0.11~0.25, acrylamide: methylene-bisacrylamide=30~48, dispersing agent: deionized water= 0.027~0.03, stirring forms mixed solution to being completely dissolved；
(3) mixed powder is added into mixed solution, forms water base B4C mixed slurry；Wherein, boron carbide in mixed slurry Content be 60~65vol%；
Step 2: biscuit preparation:
(1) by mixed slurry 3~10min of vacuum degassing, ammonium persulfate, after mixing evenly, injection molding and in a mold is added Solidify, after constant pressure and dry, obtains dry base；Wherein, the ammonium persulfate additional amount is mixed solution quality in mass ratio 0.5~0.7%；
(2) high temperature cabonization is carried out to dry base, grain composition B is made4C biscuit；Wherein, the carburizing temperature is 600 ~900 DEG C, carbonization soaking time is 2~4h；
Step 3: boron-carbide-based ceramic composite material preparation:
(1) in grain composition B4After C biscuit surface uniformly spreads elemental silicon, high temperature infiltration is carried out, sintered body is made, wherein The infiltrating temperature is 1450~1600 DEG C, keeps the temperature 30~60min；
(2) it after being cooled to room temperature sintered body, takes out, removes the extra elemental silicon in surface layer, be made based on grain composition Boron-carbide-based ceramic composite material.
In the step 1 (1), B4C mixed powder is by five kinds of specification B4C powder carries out grain composition in proportion, wherein B4The particle size range of C powder A is 1.2~2.8 μm, the B4The particle size range of C powder B is 7~13 μm, the B4C powder The particle size range of C is 15~25 μm, the B4The particle size range of C powder D is 28~52 μm, the B4The granularity of C powder E Range is 80~160 μm.
In the step 1 (2), dispersing agent is tetramethylammonium hydroxide aqueous solution or aq. polyethyleneimine.
In the step 1 (2), the mass concentration of tetramethylammonium hydroxide aqueous solution or aq. polyethyleneimine is 25%.
In the step 2 (1), curing mode are as follows: place 10~20min at room temperature.
In the step 2 (1), constant pressure and dry temperature is 40~60 DEG C, and drying time is 24~48h.
In the step 2 (1), dry base intensity is 40~50MPa.
In the step 2 (2), carbonization heating rate is 1~2 DEG C/min.
In the step 2, grain composition B4Compared with C biscuit is when injection molding, dimensional contraction rate is 1~5%.
In the step 2 (2), grain composition B4C biscuit intensity is 20~30MPa, and density is 1.53~1.74g/cm3。
In the step 3 (1), elemental silicon granularity≤5mm.
In the step 3 (1), the actual interpolation amount of elemental silicon is subject to 2 times or more of theoretical additive amount, to provide Enough elemental silicons realize the abundant infiltration of elemental silicon.
In the step 3 (1), the theoretical addition quality of elemental silicon is, so that B4Gap in C green body fully penetrates into list Matter silicon into sintered body elemental silicon saturation subject to, specific calculating process are as follows: due to reaction seep Si sintering front and back green body size It is basically unchanged.So with vernier caliper measurement B4The size of C green body obtains blank volume V.B4C blank volume removes B4In C green body Volume shared by boron carbide (ignores reacting between boron carbide and silicon), as volume shared by residual pore, i.e. simple substance needed for theory Si volume is multiplied with density 2.3 and adds quality to get to the theoretical of Si.
In the step 3 (1), sintered body and grain composition B4C biscuit is compared, change in size < 1%.
In the step 3 (2), the boron-carbide-based ceramic composite material of preparation is by B4C、Si、B12(B,C,Si)3, SiC tetra- Kind phase composition.
In the step 3 (2), the boron-carbide-based ceramic composite material Vickers hardness of preparation is 26.8~31.2GPa, curved Qu Qiangdu is 195~365MPa, and fracture toughness is 3.6~3.8MPam1/2, bulk density is 2.50~2.51g/cm3, opening Porosity is 0.16~0.25%.
The preparation method of boron-carbide-based ceramic composite material based on grain composition of the invention, passes through the side of grain composition Method can be obviously improved the packed structures of powder granule, effectively improve blank density, to improve main phase in composite material B4The content of C greatly reduces the content of remaining Si, improves the mechanical property of composite material；And pass through gel casting forming, Can to avoid it is dry-pressing formed when arch bridge effect and fine grain reunion, organic matter macromolecular and over cure when carbonization, in green body Sour ammonium etc., is decomposed at high temperature, and the gas evolution of generation only remains a small amount of C simple substance, these C simple substance meeting and Si in infiltration It reacts and generates SiC, prepared blank density is high, even tissue and has some strength, further improves the property of material Energy.
Boron-carbide-based ceramic composite material based on grain composition preparation of the invention has compared with single particle size powder Greater advantage, the reaction that single particle size powder green compact relative density is low, boron carbide is mutually in sintering are consumed, are caused in composite material The boron content that is carbonized is not high, and remaining Si content is excessive, and the blank structure uniformity as caused by the arch bridge effect between powder is poor, leads Cause product properties unstable and to be improved.
Beneficial effects of the present invention:
(1) B prepared by the present invention4The relative density of C green body can be adjusted according to slurry solid volume fraction, and highest can Reach 70% or more, the 57% of significantly larger than non-particulate gradation green body, and under the premise of grain composition formula is identical, the present invention Gel injection-moulding method made from green body relative density be also higher than the relative density of dry-pressing formed obtained green body.
(2) B prepared by the present invention4C green body, intensity is 30~40MPa before high temperature cabonization, after carbonization intensity be 10~ 20MPa is conducive to carry out the processing to green body, prepares complex-shaped product.
(3) boron carbide ceramics composite material produced by the present invention, microscopic structure are more equal than dry-pressing formed composite material Even, bending strength is improved.
(4) boron carbide ceramics composite material volume density produced by the present invention is only 2.50~2.51g/cm3, have high Specific strength.
(5) the boron-carbide-based ceramic composite material preparation method boron carbide ceramics produced by the present invention based on grain composition is multiple Condensation material, Vickers hardness are 26.8~31.2GPa, and bending strength is 195~365MPa, and fracture toughness is 3.6~3.8MPa m1/2, open porosity is 0.16~0.25%.
Detailed description of the invention:
Fig. 1 is the X-ray of the boron-carbide-based ceramic composite material based on grain composition prepared by the embodiment of the present invention 1~3 Diffraction pattern, (1) is the composite products of embodiment 1 in figure, and (2) are the composite products of embodiment 2, and (3) are embodiment 3 Composite products；
Fig. 2 is the B prepared in the embodiment of the present invention 14The stereoscan photograph of C green body, wherein Fig. 2 (a) is amplification 200 Times, Fig. 2 (b) is 1000 times of amplification；
Fig. 3 is the scanning electricity of the boron-carbide-based ceramic composite material based on grain composition prepared in the embodiment of the present invention 1 Mirror photo and the EDS constituent analysis figure in each region, (a) is the stereoscan photograph of boron carbide ceramics composite material in figure, (b) is The EDS constituent analysis figure in region 1 is (c) the EDS constituent analysis figure in region 2, (d) is the EDS constituent analysis figure in region 3, (e) For the EDS constituent analysis figure in region 4；
Fig. 4 is the scanning electron microscope of the boron-carbide-based ceramic composite material based on grain composition prepared by the embodiment of the present invention 1 Photo, wherein Fig. 4 (a) is 100 times of amplification, and Fig. 4 (b) is 200 times of amplification, and Fig. 4 (c) is 500 times of amplification；
Fig. 5 is the scanning electron microscope of the boron-carbide-based ceramic composite material based on grain composition prepared by the embodiment of the present invention 2 Photo, wherein Fig. 5 (a) is 100 times of amplification, and Fig. 5 (b) is 200 times of amplification, and Fig. 5 (c) is 500 times of amplification；
Fig. 6 is the scanning electron microscope of the boron-carbide-based ceramic composite material based on grain composition prepared by the embodiment of the present invention 3 Photo, wherein Fig. 6 (a) is 100 times of amplification, and Fig. 6 (b) is 200 times of amplification, and Fig. 6 (c) is 500 times of amplification；
Fig. 7 is the scanning electron microscope of the boron-carbide-based ceramic composite material based on grain composition prepared by the embodiment of the present invention 4 Photo, wherein Fig. 7 (a) is 100 times of amplification, and Fig. 7 (b) is 200 times of amplification, and Fig. 7 (c) is 500 times of amplification.
Specific embodiment:
Below with reference to embodiment, the present invention is described in further detail.
Each raw material information used in the embodiment of the present invention is as shown in table 1 below.
Table 1
The B used in the embodiment of the present invention4C powder weight purity > 93%, 2~120 μm of average out to.
The B that average particle size is 2 μm4The particle size range of C powder is 1.2~2.8 μm, the B that average particle size is 10 μm4C powder Particle size range is 7~13 μm, the B that average particle size is 20 μm4The particle size range of C powder is 15~25 μm, and average particle size is 40 μm B4The particle size range of C powder is 28~52 μm, the B that average particle size is 120 μm4The particle size range of C powder is 80~160 μm.
The equipment that compression moulding uses in the embodiment of the present invention is WE-10A type universal hydraulic testing machine.
The equipment that infiltration uses in the embodiment of the present invention is graphite vacuum heating furnace.
The test method of Vickers hardness is Vickers identation hardness method in the embodiment of the present invention, hard using 450SVD Vickers Degree meter.
In the embodiment of the present invention test method of bending strength be three-point bending resistance intensity method, use electronic universal tester for The AG-Xplus100kN electronic universal tester of Amada Co., Ltd.'s manufacture.
The test method of fracture toughness is SENB method in the embodiment of the present invention, uses electronic universal tester for Japanese strain formula The AG-Xplus100kN electronic universal tester of commercial firm's manufacture.
The test method of split shed of the embodiment of the present invention porosity and bulk density uses Archimedes's drainage.
The boron-carbide-based ceramic composite material prepared in the embodiment of the present invention, by B4C、Si、B12(B,C,Si)3, tetra- kinds of SiC Phase composition.
The theoretical addition quality of elemental silicon granularity≤5mm in the embodiment of the present invention, elemental silicon are, so that B4In C green body Gap fully penetrates into elemental silicon into sintered body subject to elemental silicon saturation, specific calculating process are as follows: since Si sintering is seeped in reaction The size of front and back green body is basically unchanged.So with vernier caliper measurement B4The size of C green body obtains blank volume V.B4C green body body Product removal B4Volume shared by boron carbide (ignoring reacting between boron carbide and silicon), as volume shared by residual pore in C green body, That is simple substance Si volume needed for theory is multiplied with density 2.3 and adds quality to get to the theoretical of Si.
Grain composition B before the sintered body obtained after being sintered in the embodiment of the present invention and sintering4C biscuit is compared, and size becomes Change < 1%.
Embodiment 1
Boron-carbide-based ceramic composite material preparation method based on grain composition includes the following steps: average grain diameter point It Wei not 2 μm, 10 μm, 20 μm, 40 μm of B4C powder is uniformly mixed in the ratio of 0.14:0.43:0.14:0.29 with dehydrated alcohol, It sufficiently pulverizes after drying spare.
Acrylamide, methylene-bisacrylamide, tetramethylammonium hydroxide are mixed with deionized water, in mass ratio, third Acrylamide and deionized water quality ratio=0.15, acrylamide and methylene-bisacrylamide mass ratio=48, tetramethyl hydrogen-oxygen Change mass ratio=0.027 of aqueous ammonium and deionized water, stirring forms mixed solution to being completely dissolved, is added in advance by not Same specification B4The mixed powder of C powder preparation, forms water base B4C mixed slurry；Wherein, the content of boron carbide is in mixed slurry 60vol%.
By mixed slurry vacuum degassing 5min, ammonium persulfate solution is added, it is that mixing is molten that quality, which is added, in ammonium persulfate solution Solve the 0.5% of quality.Injection molding and solidify in a mold after mixing evenly, at 40 DEG C of normal pressure after dry 48h, carries out vacuum high-temperature carbon Change, heating rate is 1 DEG C/min, and carburizing temperature is 600 DEG C, keeps the temperature 3h, grain composition B is made4C biscuit, grain composition B4C element Dimensional contraction rate is 3% when base and injection molding.
By grain composition B4C green body is placed in graphite crucible, and elemental silicon block or silicon powder are spread on green body, carries out high temperature Sintered body is made in infiltration；Wherein the dosage of Si is 2 times of theoretical desirable value, and infiltrating temperature is 1500 DEG C, keeps the temperature 30min；
It will be taken out after sintered body furnace cooling, remove the extra elemental silicon in surface layer, the boron carbide based on grain composition is made Based composite ceramic material.
B made from the present embodiment4C blank density is 1.6g/cm3, intensity 20MPa, intensity is 40MPa, base before being carbonized The stereoscan photograph of body is as shown in Figure 2, wherein Fig. 2 (a) is 200 times of amplification, and Fig. 2 (b) is 1000 times of amplification；The present embodiment The Vickers hardness of boron carbide composite material obtained is 26.8GPa, bending strength 365MPa, fracture toughness 3.8MPam1 /2, bulk density 2.50g/cm3, open porosity 0.16%, shown in the X-ray diffractogram of the composite material such as Fig. 1 (1), Stereoscan photograph and the EDS constituent analysis figure in each region are as shown in figure 3, Fig. 3 (a) is the scanning of boron carbide ceramics composite material Electromicroscopic photograph, Fig. 3 (b) are the EDS constituent analysis figure in region 1, and Fig. 3 (c) is the EDS constituent analysis figure in region 2, and Fig. 3 (d) is area The EDS constituent analysis figure in domain 3, Fig. 3 (e) are the EDS constituent analysis figure in region 4；The stereoscan photograph of the composite material such as Fig. 4 It is shown, wherein Fig. 4 (a) is 100 times of amplification, and Fig. 4 (b) is 200 times of amplification, and Fig. 4 (c) is 500 times of amplification；.
Comparative example 1
The dry-pressing formed preparation method of reaction bonded boron carbide ceramics composite material, includes the following steps: average grain diameter Respectively 2 μm, 10 μm, 20 μm, 40 μm of B4C powder is mixed in the ratio of 0.14:0.43:0.14:0.29 with deionized water It is even, be added 5wt% polyvinyl alcohol water solution stir evenly sufficiently drying after pulverize spare, the matter of polyvinyl alcohol water solution Amount is the 15% of powder quality.
Appropriate powder is put into mold, in the forming under the pressure of 200MPa, obtains grain composition B4C green body.
By grain composition B4C green body is placed in graphite crucible, and elemental silicon block or silicon powder are spread on green body, carries out high temperature Sintered body is made in infiltration；Wherein the dosage of Si is 2 times of theoretical desirable value, and infiltrating temperature is 1550 DEG C, keeps the temperature 30min；
It will be taken out after sintered body furnace cooling, remove the extra elemental silicon in surface layer, the boron carbide based on grain composition is made Based composite ceramic material.
Grain composition B made from the present embodiment4C blank density is 1.58g/cm3, boron carbide made from the present embodiment is compound The Vickers hardness of material is 27.9GPa, bending strength 320MPa, fracture toughness 3.4MPam1/2, bulk density is 2.51g/cm3, open porosity 0.23%.
Embodiment 2
Boron-carbide-based ceramic composite material preparation method based on grain composition includes the following steps: average grain diameter point It Wei not 2 μm, 10 μm, 20 μm, 120 μm of B4C powder is mixed in the ratio of 0.19:0.14:0.25:0.42 with dehydrated alcohol It is even, it sufficiently pulverizes after drying spare.
Acrylamide, methylene-bisacrylamide, tetramethylammonium hydroxide are mixed with deionized water, in mass ratio, third Acrylamide and deionized water quality ratio=0.16, acrylamide and methylene-bisacrylamide mass ratio=50, tetramethyl hydrogen-oxygen Change mass ratio=0.029 stirring of aqueous ammonium and deionized water to being completely dissolved, is added in advance by different size B4C powder system Standby mixed powder forms water base B4C mixed slurry；Wherein, the content of boron carbide is 63vol% in mixed slurry.
By mixed slurry vacuum degassing 5min, ammonium persulfate solution is added, it is that mixing is molten that quality, which is added, in ammonium persulfate solution Solve the 0.6% of quality.Injection molding and solidify in a mold after mixing evenly, vacuum high-temperature carbonization carried out after 40 DEG C of normal pressure dry 48h, Heating rate is 1 DEG C/min, and carburizing temperature is 600 DEG C, keeps the temperature 3h, grain composition B is made4C biscuit, grain composition B4C biscuit with Dimensional contraction rate is 2% when injection molding.
By grain composition B4C green body is placed in graphite crucible, and elemental silicon block or silicon powder are spread on green body, carries out high temperature Sintered body is made in infiltration；Wherein the dosage of Si is 2 times of theoretical desirable value, and infiltrating temperature is 1550 DEG C, keeps the temperature 30min；
It will be taken out after sintered body furnace cooling, remove the extra elemental silicon in surface layer, the boron carbide based on grain composition is made Based composite ceramic material.
Grain composition B made from the present embodiment4C blank density is 1.73g/cm3, intensity 15MPa, intensity before being carbonized For 36MPa；The Vickers hardness of boron carbide composite material made from the present embodiment is 28.9GPa, bending strength 211MPa, fracture Toughness is 3.7MPam1/2, bulk density 2.50g/cm3, the X-ray of open porosity 0.25%, the composite material spreads out It penetrates shown in figure such as Fig. 1 (2), the stereoscan photograph of the composite material is as shown in Figure 5, wherein Fig. 5 (a) is 100 times of amplification, Fig. 5 It (b) is 200 times of amplification, Fig. 5 (c) is 500 times of amplification.
Embodiment 3
Boron-carbide-based ceramic composite material preparation method based on grain composition includes the following steps: average grain diameter point It Wei not 2 μm, 10 μm, 120 μm of B4C powder is uniformly mixed in the ratio of 0.2:0.15:0.65 with dehydrated alcohol, sufficiently after drying It pulverizes spare.
Acrylamide, methylene-bisacrylamide, tetramethylammonium hydroxide are mixed with deionized water, in mass ratio, third Acrylamide and deionized water quality ratio=0.16, acrylamide and methylene-bisacrylamide mass ratio=48, tetramethyl hydrogen-oxygen Change mass ratio=0.027 of aqueous ammonium and deionized water, stirring is added in advance to being completely dissolved by different size B4C powder The mixed powder of preparation forms water base B4C mixed slurry；Wherein, the content of boron carbide is 60vol% in mixed slurry.
By mixed slurry vacuum degassing 5min, ammonium persulfate solution is added, it is that mixing is molten that quality, which is added, in ammonium persulfate solution The 0.5% of liquid quality.Injection molding and solidify in a mold after mixing evenly, at 50 DEG C of normal pressure after dry 32h, carries out vacuum high-temperature carbon Change, heating rate is 2 DEG C/min, and carburizing temperature is 600 DEG C, keeps the temperature 4h, grain composition B is made4C biscuit, grain composition B4C element Dimensional contraction rate is 3% when base and injection molding.
By grain composition B4C green body is placed in graphite crucible, and elemental silicon block or silicon powder are spread on green body, carries out high temperature Sintered body is made in infiltration；Wherein the dosage of Si is 2 times of theoretical desirable value, and infiltrating temperature is 1550 DEG C, keeps the temperature 30min；
It will be taken out after sintered body furnace cooling, remove the extra elemental silicon in surface layer, the boron carbide based on grain composition is made Based composite ceramic material.
Grain composition B made from the present embodiment4C blank density is 1.74g/cm3, intensity 10MPa, intensity before being carbonized For 30MPa；The Vickers hardness of boron carbide composite material made from the present embodiment is 31.2GPa, bending strength 195MPa, fracture Toughness is 3.6MPam1/2, bulk density 2.51g/cm3, the X-ray of open porosity 0.22%, the composite material spreads out It penetrates shown in figure such as Fig. 1 (3), the stereoscan photograph of the composite material is as shown in Figure 6, wherein Fig. 6 (a) is 100 times of amplification, Fig. 6 It (b) is 200 times of amplification, Fig. 6 (c) is 500 times of amplification.
Embodiment 4
Boron-carbide-based ceramic composite material preparation method based on grain composition includes the following steps: average grain diameter point It Wei not 2 μm, 20 μm, 120 μm of B4C powder is uniformly mixed in the ratio of 0.3:0.28:0.42 with dehydrated alcohol, sufficiently after drying It pulverizes spare.
Acrylamide, methylene-bisacrylamide, tetramethylammonium hydroxide are mixed with deionized water, in mass ratio, third Acrylamide and deionized water quality ratio=0.18, acrylamide and methylene-bisacrylamide mass ratio=40, tetramethyl hydrogen-oxygen Change mass ratio=0.027 of aqueous ammonium and deionized water, stirring is added in advance to being completely dissolved by different size B4C powder The mixed powder of preparation forms water base B4C mixed slurry；Wherein, the content of boron carbide is 60vol% in mixed slurry.
By mixed slurry vacuum degassing 5min, ammonium persulfate solution is added, it is that mixing is molten that quality, which is added, in ammonium persulfate solution The 0.7% of liquid quality.Injection molding and solidify in a mold after mixing evenly, after 60 DEG C of dryings for 24 hours of normal pressure, carries out vacuum high-temperature carbon Change, heating rate is 2 DEG C/min, and carburizing temperature is 700 DEG C, keeps the temperature 4h, grain composition B is made4C biscuit, grain composition B4C element Dimensional contraction rate is 3% when base and injection molding.
By grain composition B4C green body is placed in graphite crucible, and elemental silicon block or silicon powder are spread on green body, carries out high temperature Sintered body is made in infiltration；Wherein the dosage of Si is 2 times of theoretical desirable value, and infiltrating temperature is 1550 DEG C, keeps the temperature 30min；
It will be taken out after sintered body furnace cooling, remove the extra elemental silicon in surface layer, the boron carbide based on grain composition is made Based composite ceramic material.
Grain composition B made from the present embodiment4C blank density is 1.55g/cm3, intensity 10MPa, intensity before being carbonized For 33MPa；The Vickers hardness of boron carbide composite material made from the present embodiment is 29.5GPa, bending strength 205MPa, fracture Toughness is 3.7MPam1/2, bulk density 2.50g/cm3, open porosity 0.20%, the scanning electron microscope of the composite material Photo is as shown in Figure 7, wherein Fig. 7 (a) is 100 times of amplification, and Fig. 7 (b) is 200 times of amplification, and Fig. 7 (c) is 500 times of amplification.
Embodiment 5
Boron-carbide-based ceramic composite material preparation method based on grain composition includes the following steps: average grain diameter point It Wei not 2 μm, 10 μm, 45 μm of B4C powder is uniformly mixed in the ratio of 0.26:0.32:0.42 with dehydrated alcohol, sufficiently after drying It pulverizes spare.
Acrylamide, methylene-bisacrylamide, tetramethylammonium hydroxide are mixed with deionized water, in mass ratio, third Acrylamide and deionized water quality ratio=0.18, acrylamide and methylene-bisacrylamide mass ratio=45, tetramethyl hydrogen-oxygen Change mass ratio=0.028 of aqueous ammonium and deionized water, stirring is added in advance to being completely dissolved by different size B4C powder The mixed powder of preparation forms water base B4C mixed slurry；Wherein, the content of boron carbide is 60vol% in mixed slurry.
By mixed slurry vacuum degassing 5min, ammonium persulfate solution is added, it is that mixing is molten that quality, which is added, in ammonium persulfate solution The 0.6% of liquid quality.Injection molding and solidify in a mold after mixing evenly, at 60 DEG C of normal pressure it is dry for 24 hours after, carry out vacuum high-temperature carbon Change, heating rate is 1.5 DEG C/min, and carburizing temperature is 700 DEG C, keeps the temperature 4h, grain composition B is made4C biscuit, grain composition B4C Dimensional contraction rate is 3% when biscuit and injection molding.
By grain composition B4C green body is placed in graphite crucible, and elemental silicon block or silicon powder are spread on green body, carries out high temperature Sintered body is made in infiltration；Wherein the dosage of Si is 2 times of theoretical desirable value, and infiltrating temperature is 1480 DEG C, keeps the temperature 30min；
It will be taken out after sintered body furnace cooling, remove the extra elemental silicon in surface layer, the boron carbide based on grain composition is made Based composite ceramic material.
Grain composition B made from the present embodiment4C blank density is 1.53g/cm3, intensity 12MPa, intensity before being carbonized For 35MPa；Boron-carbide-based ceramic composite material preparation method boron carbide composite wood based on grain composition made from the present embodiment The Vickers hardness of material is 26.7GPa, bending strength 310MPa, fracture toughness 3.8MPam1/2, bulk density 2.50g/ cm3, open porosity 0.17%.

Claims (10)

1. a kind of preparation method of the boron-carbide-based ceramic composite material based on grain composition, which is characterized in that including following step It is rapid:
Step 1: mixed slurry preparation:
(1) varigrained B is taken4C powder, including B4C powder A, B4C powder B, B4C powder C, B4C powder D and B4C powder E, In, the B4C powder A average particle size is 2 μm, the B4C powder B average particle size is 10 μm, the B4C powder C is average Granularity is 20 μm, the B4C powder D average particle size is 40 μm, the B4C powder E average particle size is 120 μm, by quality Than A:B:C:D:E=(0.14~0.3): (0~0.43): (0~0.28): (0~0.29): (0~0.42): (0~0.65), It is mixed to form mixed powder, includes two or three and A in B, C, D or E in the mixed powder；
(2) acrylamide, methylene-bisacrylamide, dispersing agent are mixed with deionized water, in mass ratio, acrylamide: is gone Ionized water=0.11~0.25, acrylamide: methylene-bisacrylamide=30~48, dispersing agent: deionized water=0.027~ 0.03, stirring forms mixed solution to being completely dissolved；
(3) mixed powder is added into mixed solution, forms water base B4C mixed slurry；Wherein, boron carbide contains in mixed slurry Amount is 60~65vol%；
Step 2: biscuit preparation:
(1) by mixed slurry 3~10min of vacuum degassing, ammonium persulfate is added, after mixing evenly, injection molding simultaneously solidifies in a mold, After constant pressure and dry, dry base is obtained；Wherein, the ammonium persulfate additional amount be in mass ratio mixed solution quality 0.5~ 0.7%；
(2) high temperature cabonization is carried out to dry base, grain composition B is made4C biscuit；Wherein, the carburizing temperature is 600~900 DEG C, carbonization soaking time is 2~4h；
Step 3: boron-carbide-based ceramic composite material preparation:
(1) in grain composition B4After C billet surface uniformly spreads elemental silicon, high temperature infiltration is carried out, sintered body is made, wherein described Infiltrating temperature is 1450~1600 DEG C, keeps the temperature 30~60min；
(2) it after being cooled to room temperature sintered body, takes out, removes the extra elemental silicon in surface layer, the carbonization based on grain composition is made Boryl ceramic composite.
2. the preparation method of the boron-carbide-based ceramic composite material according to claim 1 based on grain composition, feature It is, in the step 1 (1), B4C mixed powder is by five kinds of specification B4C powder carries out grain composition in proportion, wherein B4C The particle size range of powder A is 1.2~2.8 μm, the B4The particle size range of C powder B is 7~13 μm, the B4C powder C's Particle size range is 15~25 μm, the B4The particle size range of C powder D is 28~52 μm, the B4The particle size range of C powder E It is 80~160 μm.
3. the preparation method of the boron-carbide-based ceramic composite material according to claim 1 based on grain composition, feature It is, in the step 1 (2), dispersing agent is tetramethylammonium hydroxide aqueous solution or aq. polyethyleneimine.
4. the preparation method of the boron-carbide-based ceramic composite material according to claim 3 based on grain composition, feature It is, in the step 1 (2), the mass concentration of tetramethylammonium hydroxide aqueous solution or aq. polyethyleneimine is 25%.
5. the preparation method of the boron-carbide-based ceramic composite material according to claim 3 based on grain composition, feature It is, in the step 2 (1), constant pressure and dry temperature is 40~60 DEG C, and drying time is 24~48h, and dry base intensity is 40 ~50MPa.
6. the preparation method of the boron-carbide-based ceramic composite material according to claim 1 based on grain composition, feature It is, in the step 2 (2), carbonization heating rate is 1~2 DEG C/min.
7. the preparation method of the boron-carbide-based ceramic composite material according to claim 3 based on grain composition, feature It is, in the step 2 (2), grain composition B4C biscuit intensity is 20~30MPa, and density is 1.53~1.74g/cm3。
8. the preparation method of the boron-carbide-based ceramic composite material according to claim 3 based on grain composition, feature Be, in the step 3 (1), elemental silicon granularity≤5mm, the actual interpolation amount of elemental silicon with 2 times of theoretical additive amount and with Subject to upper, to provide enough elemental silicons, the abundant infiltration of elemental silicon is realized, the theoretical addition quality of elemental silicon is, so that B4C base Gap in body fully penetrate into elemental silicon into sintered body elemental silicon saturation subject to.
9. the preparation method of the boron-carbide-based ceramic composite material according to claim 1 based on grain composition, feature It is, in the step 3 (2), the boron-carbide-based ceramic composite material of preparation is by B4C、Si、B12(B,C,Si)3, tetra- kinds of SiC Phase composition.
10. the preparation method of the boron-carbide-based ceramic composite material according to claim 1 based on grain composition, feature It is, in the step 3 (2), the boron-carbide-based ceramic composite material Vickers hardness of preparation is 26.8~31.2GPa, bending Intensity is 195~365MPa, and fracture toughness is 3.6~3.8MPam1/2, bulk density is 2.50~2.51g/cm3, open pore Gap rate is 0.16~0.25%.
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