Preparation method of ZrB2-SiC toughened B4C bulletproof piece
阅读说明：本技术 一种ZrB2-SiC增韧B4C防弹片的制备方法 (Preparation method of ZrB2-SiC toughened B4C bulletproof piece ) 是由 王海龙 李帅 王海亮 李明亮 邵刚 张锐 于 2021-08-20 设计创作，主要内容包括：本发明涉及一种ZrB-(2)-SiC增韧B-(4)C防弹片的制备方法,属于新型防弹装甲制造领域。该防弹片由以下方法获得：首先选取ZrSi-(2)、B-(4)C和C作为原料,按照摩尔比2:1:3取料混合,然后将上述混合粉体与B-(4)C粉按照体积比1:9、1.5:8.5、2:8、2.5:7.5、3:7混合,随后将混合粉体依次经湿法球磨,旋转蒸发仪干燥,筛网过筛,最后在热压炉中对粉体进行烧结,通过调控原料配比以及烧结工艺,制备获得B-(4)C-ZrB-(2)-SiC防弹片复合材料。采用该方法制备的B-(4)C-ZrB-(2)-SiC防弹片复合材料各相分布均匀,具有断裂韧性强,强度高等优点。(The invention relates to ZrB 2 Toughening of B with-SiC 4 A preparation method of a C bulletproof piece belongs to the field of novel bulletproof armor manufacturing. The shrapnel-proof sheet is obtained by the following method: firstly, ZrSi is selected 2 、B 4 Taking C and C as raw materials, mixing the raw materials according to the molar ratio of 2:1:3, and then mixing the mixed powder with B 4 Mixing the C powder according to the volume ratio of 1:9, 1.5:8.5, 2:8, 2.5:7.5 and 3:7, then carrying out wet ball milling on the mixed powder in sequence, drying by a rotary evaporator, sieving by a screen, finally sintering the powder in a hot pressing furnace, and preparing the B powder by regulating and controlling the raw material ratio and the sintering process 4 C‑ZrB 2 -SiC ballistic resistant sheet composites. B prepared by the method 4 C‑ZrB 2 the-SiC bulletproof sheet composite material has the advantages of uniform phase distribution, strong fracture toughness, high strength and the likeAnd (4) point.)
1. Contains ZrB2B of-SiC4C the bulletproof piece is characterized by comprising B volume fraction460-90% of C and ZrB in volume fraction2-SiC 10-40%。
2. Preparation of B as described in claim 14The method for preventing the shrapnel is characterized by comprising the following steps:
(1) ZrSi with the mol ratio of 2:1:32Powder, B4Powder of C powder and B in volume ratio4Mixing the powder C, and performing ball milling to obtain a suspension;
(2) drying the suspension at 40-55 ℃ for 0.5-1h, grinding, and sieving to obtain powder to be sintered;
(3) placing the powder to be sintered in a graphite mold, and carrying out hot-pressing sintering at 1700-2000 ℃ in a sintering atmosphere and 20-60 MPa; and keeping the temperature for 1-3 h;
(4) and cooling along with the furnace, and taking out and separating the ceramic sample from the mold.
3. The method of claim 2, wherein B is4The purity of the C powder is 99.9 percent, and the particle size is 0.5 mu m; the ZrB2The purity of the powder is 99.5 percent, and the particle size is 1-2 mu m; the purity of the C powder is 99.5%, and the particle size is 30 nm.
4. The method according to claim 2, wherein the ball milling process in step (1) is: putting the mixed powder into a polytetrafluoroethylene tank, adding absolute ethyl alcohol, and performing ball milling by using ball-milled zirconia balls to form turbid liquid; the ball material mass ratio is 1: 1.
5. the method according to claim 2, wherein the ball milling speed is 60-120 r/min and the time is 12-24 h.
6. The method of claim 2, wherein the suspension of step (2) is dried and passed through a 200 mesh screen.
7. The method of claim 2, wherein the hot pressing sintering process parameters in step (3) are as follows: the sintering atmosphere is argon or vacuum; the heating rate is as follows: the room temperature is 10 ℃/min to 1000 ℃; 1000-1600 ℃ and 8 ℃/min; the temperature of 1600-2000 deg.c is 5 deg.c/min.
Technical Field
The invention belongs to the technical field of manufacturing of bulletproof armor, and particularly relates to ZrB2Toughening of B with-SiC4C, preparing the bulletproof piece.
Background
Bulletproof ceramic material (Al)2O3、SiC、B4C, etc.) have low density, high hardness, high strength, high elastic modulus, etc. properties relative to conventional metal materials, and are green and energy-saving in production, and therefore have been sought in recent years. With Al2O3Compared with SiC bulletproof ceramics, the boron carbide ceramics has the advantages of higher hardness, smaller density, stronger impact resistance and the like, so the boron carbide ceramics has wider application prospect in the fields of high-temperature structural materials, light personnel, vehicle bulletproof armor materials and the like. However B4The high content of C covalent bonds results in difficult sintering and poor toughness, which limits its wide application.
At present, high-performance B is prepared4The common method for C composite material is to directly add SiC and ZrB2、TiB2TiC, etc. second phase or addition thereof can reduce B4C sintering temperature and inducing to produce sintering aid for increasing B4C compactness, strength and toughness, however, the introduction of a low strength phase is inevitable. For example, Sung Min So et al, prepared B by hot-pressing sintering4C-SiC composite material, when B4When C and SiC are uniformly dispersed in the composite material, the growth of crystal grains is inhibited, and a sintered body with fine and uniform crystal grains and high strength is obtained, but the toughening effect is insufficient. Existing B4The C-based composite material directly takes the second phase as an additive, so that the sintering temperature cannot be obviously reduced, and the mechanical property of the material is obviously improved.
Thus, how to provide a sintering method such that ZrB is produced2Is uniformly distributed in B with SiC toughening phase4In the C matrix with B4C has good associativity and can promote B4The toughness of the C bulletproof ceramic material and the capability of reducing the sintering temperature are problems which need to be solved by the technical personnel in the field.
Disclosure of Invention
The present invention is based on the above technical problem, and the present invention aims to provide an in-situ methodReaction sintering to form ZrB2And SiC reinforcing and toughening B4The method for compounding the ceramic with the C bulletproof piece has the advantages that the phase purity of the composite material is high, the component distribution is uniform, and the B bulletproof piece is ensured4The low density of the C ceramic and the increase of the B4The bending strength and the fracture toughness of the C composite material reduce the sintering temperature.
In view of the above, the present invention provides a ZrB-containing material2B of-SiC4The C bulletproof sheet contains a volume fraction of B460-90% of C and ZrB in volume fraction2-SiC 10-40%。
According to a second aspect of the invention, it is proposed to prepare a catalyst comprising ZrB2B of-SiC4The method for preventing the shrapnel comprises the following steps:
(1) ZrSi with the mol ratio of 2:1:32Powder, B4Powder of C powder and B in volume ratio4Mixing the powder C, and performing ball milling to obtain a suspension;
(2) drying the suspension at 40-55 deg.C for 0.5-1h, grinding, and sieving to obtain powder to be sintered;
(3) placing the powder to be sintered in a graphite mold, and carrying out hot-pressing sintering at the temperature of 1700-2000 ℃ and the pressure of 20-60 MPa in the sintering atmosphere; and keeping the temperature for 1-3 h;
(4) and cooling along with the furnace, and taking out and separating the ceramic sample from the mold.
Reaction equation 2ZrSi of the present invention2 +B4C+3C=2ZrB2+4SiC。
Preferably, the sintering temperature is 1900 in step (2)oC, keeping the temperature for 60 min.
According to one embodiment of the invention, B4The purity of the C powder is 99.9 percent, and the particle size is 0.5 mu m; ZrB2The purity of the powder is 99.5 percent, and the particle size is 1-2 mu m; the purity of the C powder is 99.5 percent, and the particle size is 30 nm.
Preferred B4The granularity of C is 0.5 mu m grade, B470% of C powder and ZrB2The content of-SiC was 30%.
According to one embodiment of the invention, the ball milling process in step (1) is as follows: the ball milling process in the step (1) is as follows: putting the mixed powder into a polytetrafluoroethylene tank, adding absolute ethyl alcohol, ball-milling zirconia balls by using a roller ball mill to form turbid liquid; the ball material mass ratio is 1: 1.
according to one embodiment of the invention, the ball milling speed is 60-120 r/min, and the time is 12-24 h.
Preferably, the ball milling and mixing time in the step (1) is 24 hours, and the rotating speed of the ball mill is 100 r/min.
According to one embodiment of the invention, the suspension in step (2) is dried and passed through a 200 mesh screen.
After the ball milling of the invention is finished, the slurry and ZrO2Ball milling and ball separation are carried out, then a rotary evaporator is adopted to dry the slurry, and the dried mixed powder is screened by a 200-mesh screen for later use.
According to one embodiment of the invention, the parameters of the hot pressing sintering process in the step (3) are as follows: the sintering atmosphere is argon; the heating rate is as follows: the room temperature is 10 ℃/min to 1000 ℃; 1000-1600 ℃ and 8 ℃/min; the temperature of 1600-2000 deg.c is 5 deg.c/min.
Through the technical scheme, the invention provides the method for generating ZrB through in-situ reaction2Toughening of B with-SiC4The preparation method of the C bulletproof piece has the following technical effects:
(1) the invention adopts ZrSi2Powder, B4The powder C and the powder C are used as additive raw materials, and the raw materials are subjected to in-situ reaction sintering to generate B4C-ZrB2-SiC composite material, with direct use of a second phase ceramic additive and B4Compared with the method of mixing C powder, ZrB generated by in-situ reaction2And SiC crystal grains are finer and more uniformly distributed, and B4The grain boundary bonding of C is more compact, and the generated ZrB2Most of the SiC crystal grains are rod-shaped or lath-shaped, and B can be effectively improved4C, toughness. B prepared by the invention4C-ZrB2The bending strength of the-SiC composite ceramic is 350-500 MPa, the Vickers hardness is 17-25 GPa, and the fracture toughness is 3.5-5.5 MPa.m1/2;
(2) The invention provides a ZrB2-SiC toughening B generated by in-situ reaction4The preparation method of the C bulletproof piece has the advantages of good repeatability, simple steps and easy realization.
Drawings
FIG. 1 is B prepared according to examples 1 to 5 of the present invention4C-ZrB2-SiC composite XRD;
FIG. 2 shows the volume fraction of 70% B used in example 54C、30%（2ZrSi2 +B4C + 3C) formula prepared B4C-ZrB2-SiC sintered body fracture SEM.
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, a more particular description of the invention will be rendered by reference to the appended drawings. It should be noted that the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and therefore the scope of the present invention is not limited by the specific embodiments disclosed below.
B used in the examples of the present invention4The C powder is purchased from Zhengzhou Songshan boron science and technology Limited company, and has the average grain diameter of 0.5 mu m and the purity of 99.9 percent. ZrSi used2The powder is purchased from Beijing Huaweiruike chemical Co., Ltd, and has a particle size of 1-2 μm and a purity of 99.5%. The C powder is purchased from Beijing Huaweiruike chemical Co., Ltd, and has an average particle size of 30 nm and a purity of 99.5%.
Example 1
B4C-ZrB2The SiC bulletproof sheet material consists of the following raw materials in volume fraction: b is490% of C powder and 10% of additive.
B4C-ZrB2The preparation method of the-SiC bulletproof sheet composite material comprises the following steps:
1) preparing mixed powder of an additive and raw materials: selecting ZrSi2Powder, B4Taking the powder C and the powder C as raw materials, weighing the raw materials according to the molar ratio of 2:1:3, and weighing the powder B according to the volume ratio4Mixing the powder C;
2) ball milling: b is to be4C and the prepared additive are placed in a polytetrafluoroethylene tank, and ZrO with equal mass is added2Ball milling with absolute ethanol asBall milling media, wherein ball milling is carried out by adopting a roller ball mill for 24 hours at a rotating speed of 100 r/min;
3) and (3) drying: after the ball milling is finished, the slurry and ZrO2Ball milling and ball separation, drying the slurry by adopting a rotary evaporator, and sieving the dried mixed powder by using a 200-mesh screen for later use;
4) and (3) sintering: weighing B according to the formula4C powder and additive, placing the mixed powder into a graphite die, and then carrying out hot-pressing sintering at the sintering temperature of 1900 DEG CoC, keeping the pressure at 30 MPa for 60 min, cooling along with the furnace after sintering, taking out the mold, and separating the sintered body from the mold to obtain B4C-ZrB2-SiC ballistic resistant sheet composites.
B prepared in this example4C-ZrB2The Vickers hardness of the-SiC bulletproof sheet composite material is 19 GPa, the bending strength is 370 MPa, and the fracture toughness is 3.6 MPa.m1/2。
Example 2
B4C-ZrB2the-SiC bulletproof sheet composite material consists of the following raw materials in percentage by volume: b is485% of C powder and 15% of additive.
B4C-ZrB2The preparation method of the-SiC bulletproof sheet composite material comprises the following steps:
1) preparing mixed powder of an additive and raw materials: selecting ZrSi2Powder, B4Taking the powder C and the powder C as raw materials, weighing the raw materials according to the molar ratio of 2:1:3, and weighing the powder B according to the volume ratio4Mixing the powder C;
2) ball milling: b is to be4C and the prepared additive are placed in a polytetrafluoroethylene tank, and ZrO with equal mass is added2Ball milling is carried out on the ball milling balls by adopting a roller ball mill with the absolute ethyl alcohol as a ball milling medium, the ball milling time is 24 hours, and the rotating speed is 120 r/min;
3) and (3) drying: after the ball milling is finished, the slurry and ZrO2Ball milling and ball separation, drying the slurry by adopting a rotary evaporator, and sieving the dried mixed powder by using a 200-mesh screen for later use;
4) and (3) sintering: weighing B according to the formula4C powder and additive, placing the mixed powder into graphite mouldA tool; then hot-pressed and sintered at the sintering temperature of 1900oC, keeping the pressure at 30 MPa for 60 min, cooling along with the furnace after sintering, taking out the mold, and separating the sintered body from the mold to obtain B4C-ZrB2-SiC ballistic resistant sheet composites.
B prepared in this example4C-ZrB2The Vickers hardness of the-SiC bulletproof sheet composite material is 19 GPa, the bending strength is 380 MPa, and the fracture toughness is 3.7 MPa.m1/2。
Example 3
B4C-ZrB2the-SiC bulletproof sheet composite material consists of the following raw materials in percentage by volume: b is480% of C powder and 20% of additive.
B4C-ZrB2The preparation method of the-SiC bulletproof sheet composite material comprises the following steps:
1) preparing mixed powder of an additive and raw materials: selecting ZrSi2Powder, B4Taking the powder C and the powder C as raw materials, weighing the raw materials according to the molar ratio of 2:1:3, and weighing the powder B according to the volume ratio4Mixing the powder C;
2) ball milling: b is to be4C and the prepared additive are placed in a polytetrafluoroethylene tank, and ZrO with equal mass is added2Ball milling is carried out on the ball milling balls by adopting a roller ball mill with the absolute ethyl alcohol as a ball milling medium, the ball milling time is 24 hours, and the rotating speed is 100 r/min;
3) and (3) drying: after the ball milling is finished, the slurry and ZrO2Ball milling and ball separation, drying the slurry by adopting a rotary evaporator, and sieving the dried mixed powder by using a 200-mesh screen for later use;
4) and (3) sintering: weighing B according to the formula4C, placing the mixed powder in a graphite die; then hot pressed and sintered at 1950oC, keeping the temperature and the pressure for 60 min under the pressure of 30 MPa, cooling along with the furnace after sintering is finished, taking out the mold, and separating the sintered body from the mold to obtain the B4C-ZrB2-SiC ballistic resistant sheet composites.
B prepared in this example4C-ZrB2The Vickers hardness of the-SiC bulletproof sheet composite material is 20 GPa, the bending strength is 390 MPa, and the fracture toughness is 3.8 MPam1/2。
Example 4
B4C-ZrB2the-SiC bulletproof sheet composite material consists of the following raw materials in volume fraction: b is475% of C powder and 25% of additive.
B4C-ZrB2The preparation method of the-SiC bulletproof sheet composite material comprises the following steps:
1) preparing mixed powder of an additive and raw materials: selecting ZrSi2Powder, B4Taking the powder C and the powder C as raw materials, weighing the raw materials according to the molar ratio of 2:1:3, and weighing the powder B according to the volume ratio4Mixing the powder C;
2) ball milling: b is to be4C and the prepared additive are put into a polytetrafluoroethylene tank, and ZrO with equal mass is added2Ball milling is carried out on the ball milling balls by adopting a roller ball mill with the absolute ethyl alcohol as a ball milling medium, the ball milling time is 24 hours, and the rotating speed is 100 r/min;
3) and (3) drying: after the ball milling is finished, the slurry and ZrO2Ball milling and ball separation, drying the slurry by adopting a rotary evaporator, and sieving the dried mixed powder by using a 200-mesh screen for later use;
4) and (3) sintering: weighing B according to the formula4C, placing the mixed powder in a graphite die; then hot-pressed and sintered at the sintering temperature of 1900oC, keeping the pressure at 30 MPa for 120 min, cooling along with the furnace after sintering, taking out the mold, and separating the sintered body from the mold to obtain compact B4C-ZrB2-SiC ballistic resistant sheet composites.
B prepared in this example4C-ZrB2The Vickers hardness of the-SiC bulletproof sheet composite material is 22 GPa, the bending strength is 430 MPa, and the fracture toughness is 4.5 MPa.m1/2。
Example 5
B4C-ZrB2the-SiC bulletproof sheet composite material consists of the following raw materials in percentage by volume: b is470% of C powder and 30% of additive.
B4C-ZrB2The preparation method of the-SiC bulletproof sheet composite material comprises the following steps:
1) preparing mixed powder of an additive and raw materials: selection of ZrSi2Powder, B4Taking the powder C and the powder C as raw materials, weighing the raw materials according to the molar ratio of 2:1:3, and weighing the powder B according to the volume ratio4Mixing the powder C;
2) ball milling: b is to be4C and the prepared additive are placed in a polytetrafluoroethylene tank, and ZrO with equal mass is added2Ball milling is carried out on the ball milling balls by adopting a roller ball mill with the absolute ethyl alcohol as a ball milling medium, the ball milling time is 24 hours, and the rotating speed is 120 r/min;
3) and (3) drying: after the ball milling is finished, the slurry and ZrO2Ball milling and ball separation, drying the slurry by adopting a rotary evaporator, and sieving the dried mixed powder by using a 200-mesh screen for later use;
4) and (3) sintering: weighing B according to the formula4C, placing the mixed powder in a graphite die; then hot-pressed and sintered at the sintering temperature of 1900oC, keeping the pressure at 30 MPa for 60 min, cooling along with the furnace after sintering, taking out the mold, and separating the sintered body from the mold to obtain B4C-ZrB2-SiC ballistic resistant sheet composites.
B prepared in this example4C-ZrB2The Vickers hardness of the-SiC bulletproof sheet composite material is 22 GPa, the bending strength is 460 MPa, and the fracture toughness is 5.6 MPa.m1/2。
Example 6
B obtained in examples 1 to 54C-ZrB2XRD (X-ray diffraction) tests are carried out on the-SiC bulletproof sheet composite material, the results are the same as those in figure 1, and the results in figure 1 show that the composite material prepared by the method is pure phase, and the component elements are B respectively4C、ZrB2SiC, no residue of the reactants.
B prepared in example 54C-ZrB2SEM scanning of-SiC bulletproof sheet composite material fracture, and results show that the generated ZrB2Most of the SiC crystal grains are rod-shaped or lath-shaped, the mechanism of action when the ceramic is broken is pull out and bridged, and B can be effectively promoted4C, toughness.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention. It should be understood that numerous modifications and variations may be devised by those skilled in the art without departing from the inventive concepts herein, and it is intended to cover such modifications and variations as fall within the true spirit and scope of the appended claims. Therefore, the technical solutions that can be obtained by logical analysis, reasoning or limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
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