CN110304923B - Preparation method of boron carbide-based ceramic composite material based on particle grading - Google Patents

Preparation method of boron carbide-based ceramic composite material based on particle grading Download PDF

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CN110304923B
CN110304923B CN201910597379.1A CN201910597379A CN110304923B CN 110304923 B CN110304923 B CN 110304923B CN 201910597379 A CN201910597379 A CN 201910597379A CN 110304923 B CN110304923 B CN 110304923B
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boron carbide
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张翠萍
茹红强
夏乾
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Northeastern University China
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Abstract

The invention relates to a preparation method of a boron carbide-based ceramic composite material based on particle gradation, which comprises the following steps: different specifications B4Mixing the powder C uniformly according to a proportion, and grinding the mixture into powder for later use; preparing a premixed solution by using water as a solvent and acrylamide, methylene bisacrylamide and tetramethylammonium hydroxide as solutes according to a proportion, adding B4C, mixing the powder, adding an initiator, carrying out injection molding curing, drying and carbonizing to obtain a B4C green body; placing Si in B4And C, performing vacuum infiltration on the green body to obtain the boron carbide ceramic composite material. The method is simple, and the prepared green body has high relative density; the blank can be machined to prepare a product with a complex shape; the sintering temperature is low, and the low-density B with uniform and controllable structure and excellent comprehensive mechanical property can be prepared at lower cost4C, a composite material; the product has low density and high specific strength; the size change of the product before and after sintering is less than 1 percent, belonging to net size sintering.

Description

Preparation method of boron carbide-based ceramic composite material based on particle grading
The technical field is as follows:
the invention belongs to the technical field of materials, and particularly relates to a preparation method of a boron carbide-based ceramic composite material based on particle grading.
Background art:
boron carbide (B)4C) Ceramics play an important role in structural ceramics, and have many excellent properties, the most prominent of which are high hardness and low density, and the hardness at normal temperature is inferior to that of diamond and cubic boron nitride. Meanwhile, the boron carbide ceramic also has the characteristics of high modulus, good wear resistance, excellent neutron absorption performance, high melting point, good conductivity, excellent chemical corrosion resistance and the like, and is widely used as bulletproof armor materials, high-temperature structural materials, atomic reactor control and shielding materials, wear-resistant materials, acid and alkali corrosion resistant materials, cutting and grinding tools, electric heating materials and the like. However, boron carbide ceramic atoms are bonded by strong covalent bonds, and therefore, the resistance to grain boundary movement is large, and the activation energy for sintering is low, so that it is extremely difficult to obtain a highly dense sintered body, and it is usually necessary to sinter at an extremely high temperature, and the sintering temperature is usually about 2000 ℃.
The invention content is as follows:
the invention aims to overcome the defects in the prior art and provide a preparation method of a boron carbide-based ceramic composite material based on particle grading. The method can prepare a blank with high relative density and uniform structure by combining grain composition with gel casting, thereby obtaining B4The reaction sintering boron carbide ceramic composite material with high C content and uniform structure improves the comprehensive performance of the reaction sintering boron carbide ceramic composite material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a boron carbide-based ceramic composite material based on particle grading comprises the following steps:
step 1: preparing mixed slurry:
(1) taking B with different particle sizes4C powder comprising B4C powder A, B4C powder B, B4C powder C, B4C powders D and B4C powder E, wherein B4The average particle size of the powder A is 2 mu m, and the average particle size of the powder B is4The average particle size of the C powder B is 10 mu m, and the B4The average particle size of C powder is 20 μm, and B powder4The average particle size of the C powder D is 40 mu m, and the B powder D4The average particle size of the powder C E is 120 mu m, and the mass ratio of A: b: c: d: e ═ 0.14 to 0.3: (0-0.43): (0-0.28): (0-0.29): (0-0.42): (0-0.65) mixing to form mixed powder, wherein the mixed powder comprises two or three of B, C, D or E and A;
(2) mixing acrylamide, methylene bisacrylamide, a dispersing agent and deionized water, wherein the mass ratio of the acrylamide: 0.11-0.25 deionized water, acrylamide: 30-48 parts of methylene bisacrylamide, and a dispersing agent: stirring deionized water which is 0.027-0.03 until the deionized water is completely dissolved to form a mixed solution;
(3) adding the mixed powder into the mixed solution to form water base B4C, mixing the slurry; wherein the content of boron carbide in the mixed slurry is 60-65 vol%;
step 2: preparing a biscuit:
(1) degassing the mixed slurry in vacuum for 3-10 min, adding ammonium persulfate, uniformly stirring, performing injection molding, curing in a mold, and drying at normal pressure to obtain a dried blank; wherein the adding amount of the ammonium persulfate is 0.5-0.7% of the mass of the mixed solution according to the mass ratio;
(2) carbonizing the dried blank at high temperature to obtain grain composition B4C, biscuit making; wherein the carbonization temperature is 600-900 ℃, and the carbonization heat preservation time is 2-4 h;
and step 3: preparing a boron carbide-based ceramic composite material:
(1) in particle size distribution B4C, uniformly paving simple substance silicon on the surface of the biscuit, and then carrying out high-temperature infiltration to prepare a sintered body, wherein the infiltration temperature is 1450-1600 ℃, and the temperature is kept for 30-60 min;
(2) and cooling the sintered body to room temperature, taking out, and removing redundant simple substance silicon on the surface layer to obtain the boron carbide-based ceramic composite material based on particle grading.
In the step 1(1), B4C mixed powder is composed of five specifications B4The C powder is subjected to grain grading according to a proportion, wherein B4The particle size range of the C powder A is 1.2-2.8 mu m, and the B powder B4The particle size range of the C powder B is 7-13 mu m, and the B powder B4The particle size range of the C powder C is 15-25 mu m, and the B powder C4The particle size range of the C powder D is 28-52 mu m, and the B powder D4The particle size range of the C powder E is 80-160 mu m.
In the step 1(2), the dispersant is a tetramethylammonium hydroxide aqueous solution or a polyethyleneimine aqueous solution.
In the step 1(2), the mass concentration of the aqueous solution of tetramethylammonium hydroxide or the aqueous solution of polyethyleneimine is 25%.
In the step 2(1), the curing mode is as follows: standing for 10-20 min at room temperature.
In the step 2(1), the drying temperature under normal pressure is 40-60 ℃, and the drying time is 24-48 h.
In the step 2(1), the strength of the dried blank is 40-50 MPa.
In the step 2(2), the carbonization temperature rise speed is 1-2 ℃/min.
In the step 2, the particle size distribution B4And compared with the biscuit C in injection molding, the dimensional shrinkage rate of the biscuit C is 1-5%.
In the step 2(2), the particle size distribution B4The strength of the green C is 20-30 MPa, and the density is 1.53-1.74 g/cm3。
In the step 3(1), the granularity of the simple substance silicon is less than or equal to 5 mm.
In the step 3(1), the actual addition amount of the simple substance silicon is 2 times or more of the theoretical addition amount so as to provide enough simple substance silicon and realize the sufficient infiltration of the simple substance silicon.
In the step 3(1), the theoretical addition mass of the simple substance silicon is that B4And C, completely permeating the simple substance silicon into the gaps in the blank until the simple substance silicon in the sintered body is saturated, wherein the specific calculation process is as follows: the size of the green body is basically unchanged before and after sintering due to reaction infiltration of Si. So measure B with a vernier caliper4And C, obtaining the volume V of the blank body according to the size of the blank body. B is4C blank volume removal B4And (3) the volume occupied by boron carbide in the C blank (ignoring the reaction between boron carbide and silicon), namely the volume occupied by the residual pores, namely the volume of the theoretically required simple substance Si, is multiplied by the density of 2.3, so that the theoretical addition mass of the Si is obtained.
In the step 3(1), the sintered body and the grain composition B4The dimensional change of the biscuit C is less than 1 percent.
In the step 3(2), the prepared boron carbide-based ceramic composite material is prepared from B4C、Si、B12(B,C,Si)3And SiC.
In the step 3(2), the prepared boron carbide-based ceramic composite material has the Vickers hardness of 26.8-31.2 GPa, the bending strength of 195-365 MPa and the fracture toughness of 3.6-3.8 MPa-m1/2The bulk density is 2.50-2.51 g/cm3The open porosity is 0.16-0.25%.
According to the preparation method of the boron carbide-based ceramic composite material based on particle grading, the particle grading method can obviously improve the stacking structure of powder particles and effectively improve the density of a blank body, so that the main phase B in the composite material is improved4C content, greatly reducing the content of residual SiThe mechanical property of the composite material is improved; and through gel injection molding, the arch bridge effect and fine particle agglomeration during dry pressing can be avoided, during carbonization, organic matter macromolecules, ammonium persulfate and the like in the blank are decomposed at high temperature, generated gas escapes, only a small amount of C simple substances are remained, the C simple substances can react with Si to generate SiC during infiltration, and the prepared blank has high density, uniform structure and certain strength, so that the performance of the material is further improved.
Compared with single-particle-size powder, the boron carbide-based ceramic composite material prepared based on particle grading has the advantages that the relative density of a single-particle-size powder compact is low, the boron carbide phase is consumed in the reaction during sintering, the content of boron carbide in the composite material is not high, the content of residual Si is excessive, and the product performance is unstable and needs to be improved due to poor structural uniformity of a green body caused by the arch bridge effect among the powder.
The invention has the beneficial effects that:
(1) b prepared by the invention4The relative density of the C blank can be adjusted according to the solid-phase volume fraction of the slurry, the maximum can reach more than 70 percent and is far higher than 57 percent of that of the non-particle-level blank, and the relative density of the blank prepared by the gel injection molding method is also higher than that of the blank prepared by dry pressing on the premise of the same particle-level formula.
(2) B prepared by the invention4And C, the strength of the green body before high-temperature carbonization is 30-40 MPa, and the strength after carbonization is 10-20 MPa, so that the green body can be processed, and a product with a complex shape can be prepared.
(3) The boron carbide ceramic composite material prepared by the invention has more uniform microstructure than a composite material formed by dry pressing, and the bending strength is improved.
(4) The volume density of the boron carbide ceramic composite material prepared by the method is only 2.50-2.51 g/cm3And has high specific strength.
(5) The boron carbide ceramic composite material prepared by the preparation method of the boron carbide-based ceramic composite material based on the grain grading has the Vickers hardness of 26.8-31.2 GPa, the bending strength of 195-365 MPa and the fracture toughnessThe property is 3.6 to 3.8 MPa.m1/2The open porosity is 0.16-0.25%.
Description of the drawings:
FIG. 1 is an X-ray diffraction pattern of a boron carbide-based ceramic composite material based on a grain composition prepared in examples 1-3 of the present invention, wherein (1) is the composite product of example 1, (2) is the composite product of example 2, and (3) is the composite product of example 3;
FIG. 2 shows B prepared in example 1 of the present invention4C scanning electron microscope photo of the blank, wherein, figure 2(a) is magnified 200 times, figure 2(b) is magnified 1000 times;
FIG. 3 is a scanning electron micrograph of a boron carbide-based ceramic composite material based on grain composition prepared in example 1 of the present invention, and EDS composition analysis charts of respective regions, in which (a) is a scanning electron micrograph of the boron carbide ceramic composite material, (b) is an EDS composition analysis chart of region 1, (c) is an EDS composition analysis chart of region 2, (d) is an EDS composition analysis chart of region 3, and (e) is an EDS composition analysis chart of region 4;
FIG. 4 is a scanning electron micrograph of a boron carbide-based ceramic composite material based on grain composition prepared in example 1 of the present invention, wherein FIG. 4(a) is at a magnification of 100 times, FIG. 4(b) is at a magnification of 200 times, and FIG. 4(c) is at a magnification of 500 times;
FIG. 5 is a scanning electron micrograph of a boron carbide-based ceramic composite material based on grain composition prepared in example 2 of the present invention, wherein FIG. 5(a) is at a magnification of 100 times, FIG. 5(b) is at a magnification of 200 times, and FIG. 5(c) is at a magnification of 500 times;
FIG. 6 is a scanning electron micrograph of a boron carbide-based ceramic composite material based on grain composition prepared in example 3 of the present invention, wherein FIG. 6(a) is at a magnification of 100 times, FIG. 6(b) is at a magnification of 200 times, and FIG. 6(c) is at a magnification of 500 times;
fig. 7 is a scanning electron micrograph of a boron carbide-based ceramic composite material based on grain composition prepared in example 4 of the present invention, in which fig. 7(a) is at a magnification of 100 times, fig. 7(b) is at a magnification of 200 times, and fig. 7(c) is at a magnification of 500 times.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples.
The information of each raw material used in the examples of the present invention is shown in table 1 below.
TABLE 1
Figure BDA0002117995070000041
B used in the examples of the present invention4The weight purity of the C powder is more than 93 percent, and the average particle size is 2-120 mu m.
B with an average particle size of 2 μm4The particle size range of the C powder is 1.2-2.8 mu m, and the average particle size of the C powder is 10 mu m4The particle size range of the C powder is 7-13 mu m, and the average particle size of the C powder is 20 mu m4The particle size range of the C powder is 15-25 mu m, and the average particle size of the C powder is 40 mu m4The particle size range of the C powder is 28-52 mu m, and the average particle size of the C powder is 120 mu m4The particle size range of the C powder is 80-160 mu m.
The equipment adopted for press forming in the embodiment of the invention is a WE-10A type hydraulic universal testing machine.
The equipment adopted by infiltration in the embodiment of the invention is a graphite vacuum heating furnace.
The Vickers indentation hardness test method in the embodiment of the invention is a Vickers indentation hardness method, and a 450SVD Vickers hardness tester is adopted.
The bending strength in the examples of the present invention was measured by a three-point bending strength method using an electronic universal tester AG-Xplus100kN, manufactured by japan ltd.
The method for testing fracture toughness in the examples of the present invention was the SENB method, and an electronic universal tester was AG-XPlus100kN electronic universal tester manufactured by Japan K.K.
In the embodiment of the invention, an Archimedes drainage method is adopted as the method for testing the open porosity and the volume density.
The boron carbide-based ceramic composite material prepared in the embodiment of the invention consists of B4C、Si、B12(B,C,Si)3And SiC.
In the embodiment of the invention, the granularity of the simple substance silicon is less than or equal to 5mm, and the theoretical addition mass of the simple substance siliconTo make B to4And C, completely permeating the simple substance silicon into the gaps in the blank until the simple substance silicon in the sintered body is saturated, wherein the specific calculation process is as follows: the size of the green body is basically unchanged before and after sintering due to reaction infiltration of Si. So measure B with a vernier caliper4And C, obtaining the volume V of the blank body according to the size of the blank body. B is4C blank volume removal B4And (3) the volume occupied by boron carbide in the C blank (ignoring the reaction between boron carbide and silicon), namely the volume occupied by the residual pores, namely the volume of the theoretically required simple substance Si, is multiplied by the density of 2.3, so that the theoretical addition mass of the Si is obtained.
Sintered body obtained after sintering in the examples of the present invention and grain composition B before sintering4The dimensional change of the biscuit C is less than 1 percent.
Example 1
The preparation method of the boron carbide-based ceramic composite material based on the particle grading comprises the following steps: b having an average particle diameter of 2 μm, 10 μm, 20 μm, 40 μm4And uniformly mixing the powder C with absolute ethyl alcohol according to the proportion of 0.14:0.43:0.14:0.29, fully drying, and grinding into powder for later use.
Mixing acrylamide, methylene bisacrylamide and tetramethylammonium hydroxide with deionized water according to a mass ratio of acrylamide to deionized water of 0.15 to 48 and a mass ratio of tetramethylammonium hydroxide aqueous solution to deionized water of 0.027, stirring until the mixture is completely dissolved to form a mixed solution, adding the mixed solution into the mixed solution, and adding the mixed solution into the mixed solution, wherein the mixed solution is prepared by adding different specifications B4C mixed powder prepared from powder C to form water base B4C, mixing the slurry; wherein the content of boron carbide in the mixed slurry is 60 vol%.
And (3) degassing the mixed slurry in vacuum for 5min, and adding an ammonium persulfate solution, wherein the adding mass of the ammonium persulfate solution is 0.5% of the mixed dissolving mass. Uniformly stirring, injecting into a mold, curing in the mold, drying at 40 deg.C under normal pressure for 48 hr, vacuum carbonizing at high temperature with heating rate of 1 deg.C/min and carbonization temperature of 600 deg.C, and maintaining for 3 hr to obtain grain composition B4Biscuit C, grain composition B4The dimensional shrinkage of the green body and the injection mold was 3%.
Grading the particles into B4Placing the C blank in graphiteIn the crucible, simple substance silicon blocks or silicon powder are spread on the blank body for high-temperature infiltration to prepare a sintered body; wherein the dosage of Si is 2 times of the theoretical required value, the infiltration temperature is 1500 ℃, and the temperature is kept for 30 min;
and cooling the sintered body along with the furnace, taking out, and removing redundant simple substance silicon on the surface layer to obtain the boron carbide-based ceramic composite material based on particle grading.
B prepared in this example4The density of the C blank body is 1.6g/cm3The strength is 20MPa, the strength before carbonization is 40MPa, and the scanning electron micrograph of the blank is shown as figure 2, wherein, figure 2(a) is magnified 200 times, and figure 2(b) is magnified 1000 times; the boron carbide composite material prepared in the example has a Vickers hardness of 26.8GPa, a bending strength of 365MPa and a fracture toughness of 3.8 MPa-m1 /2Bulk density of 2.50g/cm3An open porosity of 0.16%, an X-ray diffraction pattern of the composite material is shown in fig. 1(1), a scanning electron micrograph and an EDS composition analysis pattern of each region are shown in fig. 3, fig. 3(a) is a scanning electron micrograph of the boron carbide ceramic composite material, fig. 3(b) is an EDS composition analysis pattern of the region 1, fig. 3(c) is an EDS composition analysis pattern of the region 2, fig. 3(d) is an EDS composition analysis pattern of the region 3, and fig. 3(e) is an EDS composition analysis pattern of the region 4; the scanning electron micrograph of the composite material is shown in FIG. 4, wherein FIG. 4(a) is a magnification of 100 times, FIG. 4(b) is a magnification of 200 times, and FIG. 4(c) is a magnification of 500 times; .
Comparative example 1
The dry pressing preparation method of the reaction combined boron carbide ceramic composite material comprises the following steps: b having an average particle diameter of 2 μm, 10 μm, 20 μm, 40 μm4And uniformly mixing the C powder with deionized water according to the proportion of 0.14:0.43:0.14:0.29, adding 5 wt% of polyvinyl alcohol aqueous solution, uniformly stirring, fully drying, grinding into powder for later use, wherein the mass of the polyvinyl alcohol aqueous solution is 15% of the mass of the powder.
Putting a proper amount of powder into a die, and molding under the pressure of 200MPa to obtain a grain composition B4C, green body.
Grading the particles into B4Placing the C blank in a graphite crucible, spreading simple substance silicon blocks or silicon powder on the blank, and carrying out high-temperature infiltration to prepare the productObtaining a sintered body; wherein the dosage of Si is 2 times of the theoretical required value, the infiltration temperature is 1550 ℃, and the temperature is kept for 30 min;
and cooling the sintered body along with the furnace, taking out, and removing redundant simple substance silicon on the surface layer to obtain the boron carbide-based ceramic composite material based on particle grading.
Particle size distribution B obtained in this example4The density of the C blank body is 1.58g/cm3The boron carbide composite material obtained in this example had a Vickers hardness of 27.9GPa, a bending strength of 320MPa, and a fracture toughness of 3.4MPa m1/2Bulk density of 2.51g/cm3The open porosity was 0.23%.
Example 2
The preparation method of the boron carbide-based ceramic composite material based on the particle grading comprises the following steps: b having an average particle diameter of 2 μm, 10 μm, 20 μm, 120 μm4And uniformly mixing the powder C with absolute ethyl alcohol according to the proportion of 0.19:0.14:0.25:0.42, fully drying, and grinding into powder for later use.
Mixing acrylamide, methylene bisacrylamide and tetramethylammonium hydroxide with deionized water according to a mass ratio of 0.16 to 50, and stirring until the mixture is completely dissolved, adding the mixture in advance, wherein the mass ratio of the acrylamide to the deionized water is 0.029, and the mass ratio of the aqueous solution of the tetramethylammonium hydroxide to the deionized water is different from that of the aqueous solution of the methylene bisacrylamide4C mixed powder prepared from powder C to form water base B4C, mixing the slurry; wherein the content of boron carbide in the mixed slurry is 63 vol%.
And (3) degassing the mixed slurry in vacuum for 5min, and adding an ammonium persulfate solution, wherein the adding mass of the ammonium persulfate solution is 0.6% of the mixed dissolving mass. Uniformly stirring, injecting into a mold, curing in the mold, drying at 40 ℃ under normal pressure for 48h, performing vacuum high-temperature carbonization at the temperature rise rate of 1 ℃/min and the carbonization temperature of 600 ℃, and preserving heat for 3h to obtain the grain composition B4Biscuit C, grain composition B4The dimensional shrinkage of the green body and the injection mold was 2%.
Grading the particles into B4C, placing the blank in a graphite crucible, laying simple substance silicon blocks or silicon powder on the blank, and carrying out high-temperature infiltration to prepare a sintered body; wherein the amount of Si is2 times of the theoretical required value, the infiltration temperature is 1550 ℃, and the temperature is kept for 30 min;
and cooling the sintered body along with the furnace, taking out, and removing redundant simple substance silicon on the surface layer to obtain the boron carbide-based ceramic composite material based on particle grading.
Particle size distribution B obtained in this example4The density of the C blank body is 1.73g/cm3The strength is 15MPa, and the strength before carbonization is 36 MPa; the boron carbide composite material prepared in the example has a Vickers hardness of 28.9GPa, a bending strength of 211MPa and a fracture toughness of 3.7 MPa-m1/2Bulk density of 2.50g/cm3The open porosity was 0.25%, the X-ray diffraction pattern of the composite material is shown in fig. 1(2), and the scanning electron micrograph of the composite material is shown in fig. 5, in which fig. 5(a) is a magnification of 100 times, fig. 5(b) is a magnification of 200 times, and fig. 5(c) is a magnification of 500 times.
Example 3
The preparation method of the boron carbide-based ceramic composite material based on the particle grading comprises the following steps: b having an average particle diameter of 2 μm, 10 μm, 120 μm4And uniformly mixing the powder C with absolute ethyl alcohol according to the ratio of 0.2:0.15:0.65, fully drying, and grinding into powder for later use.
Mixing acrylamide, methylene bisacrylamide and tetramethylammonium hydroxide with deionized water, stirring until the mass ratio of the acrylamide to the deionized water is 0.16, the mass ratio of the acrylamide to the methylene bisacrylamide is 48, and the mass ratio of the tetramethylammonium hydroxide aqueous solution to the deionized water is 0.027 according to the mass ratio, stirring until the mixture is completely dissolved, adding the mixture in advance, and adding the mixture into the mixture to obtain the composite material with different specifications B4C mixed powder prepared from powder C to form water base B4C, mixing the slurry; wherein the content of boron carbide in the mixed slurry is 60 vol%.
And (3) degassing the mixed slurry in vacuum for 5min, and adding an ammonium persulfate solution, wherein the adding mass of the ammonium persulfate solution is 0.5% of the mass of the mixed solution. Uniformly stirring, injecting into a mold, curing in the mold, drying at normal pressure of 50 ℃ for 32h, carbonizing at high temperature in vacuum at the rate of 2 ℃/min and the carbonization temperature of 600 ℃, and preserving heat for 4h to obtain the grain composition B4Biscuit C, grain composition B4The dimensional shrinkage of the biscuit C during injection molding is 3 percent。
Grading the particles into B4C, placing the blank in a graphite crucible, laying simple substance silicon blocks or silicon powder on the blank, and carrying out high-temperature infiltration to prepare a sintered body; wherein the dosage of Si is 2 times of the theoretical required value, the infiltration temperature is 1550 ℃, and the temperature is kept for 30 min;
and cooling the sintered body along with the furnace, taking out, and removing redundant simple substance silicon on the surface layer to obtain the boron carbide-based ceramic composite material based on particle grading.
Particle size distribution B obtained in this example4The density of the C blank is 1.74g/cm3The strength is 10MPa, and the strength before carbonization is 30 MPa; the boron carbide composite material prepared in the example has a Vickers hardness of 31.2GPa, a bending strength of 195MPa and a fracture toughness of 3.6 MPa-m1/2Bulk density of 2.51g/cm3The open porosity was 0.22%, the X-ray diffraction pattern of the composite material is shown in fig. 1(3), and the scanning electron micrograph of the composite material is shown in fig. 6, in which fig. 6(a) is a magnification of 100 times, fig. 6(b) is a magnification of 200 times, and fig. 6(c) is a magnification of 500 times.
Example 4
The preparation method of the boron carbide-based ceramic composite material based on the particle grading comprises the following steps: b having an average particle diameter of 2 μm, 20 μm, 120 μm4And uniformly mixing the powder C with absolute ethyl alcohol according to the proportion of 0.3:0.28:0.42, fully drying, and grinding into powder for later use.
Mixing acrylamide, methylene bisacrylamide and tetramethylammonium hydroxide with deionized water according to the mass ratio of 0.18 to 40 to 0.027, stirring until the mixture is completely dissolved, adding the mixture of different specifications B4C mixed powder prepared from powder C to form water base B4C, mixing the slurry; wherein the content of boron carbide in the mixed slurry is 60 vol%.
And (3) degassing the mixed slurry in vacuum for 5min, and adding an ammonium persulfate solution, wherein the adding mass of the ammonium persulfate solution is 0.7% of the mass of the mixed solution. Uniformly stirring, injecting into a mold, curing in the mold, drying at 60 ℃ under normal pressure for 24 hours,carrying out vacuum high-temperature carbonization at the temperature rise rate of 2 ℃/min and the carbonization temperature of 700 ℃, and preserving heat for 4h to obtain the grain composition B4Biscuit C, grain composition B4The dimensional shrinkage of the green body and the injection mold was 3%.
Grading the particles into B4C, placing the blank in a graphite crucible, laying simple substance silicon blocks or silicon powder on the blank, and carrying out high-temperature infiltration to prepare a sintered body; wherein the dosage of Si is 2 times of the theoretical required value, the infiltration temperature is 1550 ℃, and the temperature is kept for 30 min;
and cooling the sintered body along with the furnace, taking out, and removing redundant simple substance silicon on the surface layer to obtain the boron carbide-based ceramic composite material based on particle grading.
Particle size distribution B obtained in this example4The density of the C blank is 1.55g/cm3The strength is 10MPa, and the strength before carbonization is 33 MPa; the boron carbide composite material prepared in the example had a Vickers hardness of 29.5GPa, a bending strength of 205MPa, and a fracture toughness of 3.7MPa m1/2Bulk density of 2.50g/cm3The open porosity was 0.20%, and the scanning electron micrograph of this composite material is shown in FIG. 7, in which FIG. 7(a) is a magnification of 100 times, FIG. 7(b) is a magnification of 200 times, and FIG. 7(c) is a magnification of 500 times.
Example 5
The preparation method of the boron carbide-based ceramic composite material based on the particle grading comprises the following steps: b having an average particle diameter of 2 μm, 10 μm or 45 μm4And uniformly mixing the powder C with absolute ethyl alcohol according to the proportion of 0.26:0.32:0.42, fully drying, and grinding into powder for later use.
Mixing acrylamide, methylene bisacrylamide and tetramethylammonium hydroxide with deionized water, stirring until the mass ratio of the acrylamide to the deionized water is 0.18, the mass ratio of the acrylamide to the methylene bisacrylamide is 45, and the mass ratio of the tetramethylammonium hydroxide aqueous solution to the deionized water is 0.028 according to the mass ratio, completely dissolving, adding the mixture in advance, and adding the mixture into the mixture to obtain the emulsion with different specifications of B4C mixed powder prepared from powder C to form water base B4C, mixing the slurry; wherein the content of boron carbide in the mixed slurry is 60 vol%.
Vacuum degassing the mixed slurry for 5min, and adding ammonium persulfateAnd (3) adding ammonium persulfate solution into the mixed solution, wherein the mass of the ammonium persulfate solution is 0.6 percent of the mass of the mixed solution. Uniformly stirring, injecting into a mold, curing in the mold, drying at 60 ℃ under normal pressure for 24h, carbonizing at high temperature under vacuum at the rate of 1.5 ℃/min and the temperature of 700 ℃, and keeping the temperature for 4h to obtain the grain composition B4Biscuit C, grain composition B4The dimensional shrinkage of the green body and the injection mold was 3%.
Grading the particles into B4C, placing the blank in a graphite crucible, laying simple substance silicon blocks or silicon powder on the blank, and carrying out high-temperature infiltration to prepare a sintered body; wherein the dosage of Si is 2 times of the theoretical required value, the infiltration temperature is 1480 ℃, and the temperature is kept for 30 min;
and cooling the sintered body along with the furnace, taking out, and removing redundant simple substance silicon on the surface layer to obtain the boron carbide-based ceramic composite material based on particle grading.
Particle size distribution B obtained in this example4The density of the C blank is 1.53g/cm3The strength is 12MPa, and the strength before carbonization is 35 MPa; the method for preparing the boron carbide-based ceramic composite material based on the grain composition prepared by the embodiment has the advantages that the Vickers hardness of the boron carbide composite material is 26.7GPa, the bending strength is 310MPa, and the fracture toughness is 3.8 MPa.m1/2Bulk density of 2.50g/cm3The open porosity was 0.17%.

Claims (8)

1. A preparation method of a boron carbide-based ceramic composite material based on particle grading is characterized by comprising the following steps:
step 1: preparing mixed slurry:
(1) taking B with different particle sizes4C powder comprising B4C powder A, B4C powder B, B4C powder C, B4C powders D and B4C powder E, wherein B4The average particle size of the powder A is 2 mu m, and the average particle size of the powder B is4The average particle size of the C powder B is 10 mu m, and the B4The average particle size of C powder is 20 μm, and B powder4The average particle size of the C powder D is 40 mu m, and the B powder D4The average particle size of the powder C E is 120 mu m, and the mass ratio of A: b: c: d: e = (0.14-0.3): (0-0.43): (0-0.28): (0-0.42): (0 to 0.65) of,mixing to form mixed powder, wherein the mixed powder comprises two or three of B, C, D or E and A;
(2) mixing acrylamide, methylene bisacrylamide, a dispersing agent and deionized water, wherein the mass ratio of the acrylamide: deionized water = 0.11-0.25, acrylamide: methylene bisacrylamide = 30-48, dispersant: deionized water = 0.027-0.03, and is stirred until being completely dissolved to form a mixed solution, wherein the dispersant is a tetramethylammonium hydroxide aqueous solution;
(3) adding the mixed powder into the mixed solution to form water base B4C, mixing the slurry; wherein the content of boron carbide in the mixed slurry is 60-63 vol%;
step 2: preparing a biscuit:
(1) degassing the mixed slurry in vacuum for 3-10 min, adding ammonium persulfate, uniformly stirring, performing injection molding, curing in a mold, and drying at normal pressure to obtain a dried blank; wherein the adding amount of the ammonium persulfate is 0.5-0.7% of the mass of the mixed solution according to the mass ratio;
(2) carbonizing the dried blank at high temperature to obtain grain composition B4C, biscuit making; wherein the carbonization temperature is 600 ℃, the carbonization temperature rise speed is 1-2 ℃/min, and the carbonization heat preservation time is 3-4 h;
and step 3: preparing a boron carbide-based ceramic composite material:
(1) in particle size distribution B4C, uniformly paving simple substance silicon on the surface of the blank, and then carrying out high-temperature infiltration to prepare a sintered body, wherein the infiltration temperature is 1450-1600 ℃, and the temperature is kept for 30-60 min;
(2) and cooling the sintered body to room temperature, taking out, and removing redundant simple substance silicon on the surface layer to obtain the boron carbide-based ceramic composite material based on particle grading.
2. The method for preparing a boron carbide-based ceramic composite material according to claim 1, wherein in step 1(1), B4C mixed powder is composed of five specifications B4The C powder is subjected to grain grading according to a proportion, wherein B4The particle size range of the C powder A is 1.2-2.8 mu m, and the B powder B4Granules of powder C and powder BThe degree range is 7-13 mu m, B4The particle size range of the C powder C is 15-25 mu m, and the B powder C4The particle size range of the C powder D is 28-52 mu m, and the B powder D4The particle size range of the C powder E is 80-160 mu m.
3. The method according to claim 1, wherein the aqueous tetramethylammonium hydroxide solution is 25% by mass in step 1 (2).
4. The method for preparing the boron carbide-based ceramic composite material based on particle grading according to claim 1, wherein in the step 2(1), the drying temperature under normal pressure is 40-60 ℃, the drying time is 24-48 h, and the strength of a dried blank is 40-50 MPa.
5. The method for preparing a boron carbide-based ceramic composite material according to claim 1, wherein in step 2(2), the particle size distribution B is4The strength of the green C is 20-30 MPa, and the density is 1.53-1.74 g/cm3。
6. The method for preparing boron carbide-based ceramic composite material based on particle grading according to claim 1, wherein in step 3(1), the particle size of elemental silicon is less than or equal to 5mm, the actual addition amount of elemental silicon is 2 times or more of the theoretical addition amount so as to provide enough elemental silicon and realize sufficient infiltration of elemental silicon, and the theoretical addition mass of elemental silicon is such that B is4And C, completely permeating the simple substance silicon into the gaps in the blank until the simple substance silicon in the sintered body is saturated.
7. The method for preparing boron carbide-based ceramic composite material according to claim 1, wherein in step 3(2), the boron carbide-based ceramic composite material is prepared from B4C、Si、B12(B,C,Si)3And SiC.
8. The method for preparing a boron carbide-based ceramic composite material based on particle grading according to claim 1, wherein in step 3(2), the prepared boron carbide-based ceramic composite material has a Vickers hardness of 26.8-31.2 GPa, a bending strength of 195-365 MPa, and a fracture toughness of 3.6-3.8 MPa-m1/2The bulk density is 2.50-2.51 g/cm3The open porosity is 0.16-0.25%.
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