WO2023029080A1 - Boron nitride nanotube/nanosheet-boron carbide ceramic composite material and preparation method therefor - Google Patents

Boron nitride nanotube/nanosheet-boron carbide ceramic composite material and preparation method therefor Download PDF

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WO2023029080A1
WO2023029080A1 PCT/CN2021/117936 CN2021117936W WO2023029080A1 WO 2023029080 A1 WO2023029080 A1 WO 2023029080A1 CN 2021117936 W CN2021117936 W CN 2021117936W WO 2023029080 A1 WO2023029080 A1 WO 2023029080A1
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boron nitride
nanosheet
boron
boron carbide
nitride nanotube
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王恒
曾义
杨小晗
李哲成
刘凯
徐慢
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武汉工程大学
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Definitions

  • the invention belongs to the field of advanced structural ceramic materials, and in particular relates to a boron nitride nanotube/nanosheet-boron carbide ceramic composite material and a preparation method thereof.
  • Boron carbide (B 4 C) ceramic matrix composites strengthened and toughened by low-dimensional reinforcement phases have excellent characteristics such as high specific strength, high specific modulus, high hardness, low density, high fracture toughness and high fracture work, and are a class of An important lightweight ceramic armor material is one of the important supporting materials for national defense construction and modern industry. With the continuous expansion of application fields and service environments, higher requirements are put forward for the toughness, strength and reliability of boron carbide ceramic matrix composites.
  • Boron nitride nanomaterials have the advantages of high Young's modulus and high fracture strength.
  • the fracture strength of boron nitride nanotubes (BNNTs) is 14.1-33.2GPa
  • the fracture strain is 1.5-3.4%
  • the Young's modulus is 725-1343GPa (Wei X L, et al. Adv Mater., 2010,22,4895 ), which is in good agreement with theoretical predictions (Hernández E, et al. Phys Rev Lett., 1998, 80, 4502).
  • BNNSs boron nitride nanosheets
  • Boron nitride nanotubes and nanosheets with excellent mechanical properties are effective inorganic nanoadditive phases in ceramic matrix composites.
  • Scholars from the National Institute of Materials Research in Japan took the lead in studying Al 2 O 3 and Si 3 N 4 ceramic composites containing BNNTs. The results showed that: only 0.5wt% of BNNTs were added, and Al 2 O 3 ceramics produced brittleness at 1300°C- The transition trend of ductility; Si 3 N 4 ceramics can reduce the load stress by 75% under the same deformation conditions (Huang Q, et al. Nanotechnology, 2007, 18, 485706).
  • BNNTs in ZrO 2 ceramic composites can strengthen the grain boundaries of ZrO 2 , change the fracture mode of the material (from intergranular fracture to transgranular fracture), affect the phase transition of ZrO 2 (generate phase transition toughening mechanism), and improve the ZrO 2 fracture mode.
  • 2 Toughness of ceramic composites Xu J J, et al. Mat Sci EngA., 2012, 546, 301. Tatarko P, et al. J Eur Ceam Soc., 2014, 34, 1829).
  • BNNSs produces crack bridging and passivation effects in Si 3 N 4 ceramics, improving the fracture toughness and bending strength of Si 3 N 4 ; BNNSs wrapped in Si 3 N 4 A lubricating film is formed on the grains to reduce the friction coefficient of Si 3 N 4 and improve its wear resistance (Lee B, et al. Sci. Rep., 2016, 6, 27609).
  • the boron nitride will transform from cubic phase to hexagonal phase, and the hexagonal phase boron nitride flakes formed in situ can also be formed on the B 4 C substrate.
  • the flexural strength and fracture toughness of B 4 C ceramic materials are increased by 32.7% and 58.6%, respectively (Sun J C, et al. J Eur Ceam Soc., 2020, 1103).
  • the object of the present invention is to provide a boron nitride nanotube/nanosheet-boron carbide ceramic composite material and a preparation method thereof.
  • Boron nitride nanotubes/nanosheets are uniformly dispersed in boron carbide ceramic composites, which can simultaneously exert the strength and toughness advantages of boron nitride nanotubes and nanosheets and their multi-dimensional synergistic effects, and inhibit the crystallization of boron carbide in ceramic composites. Grain growth, prolonging the crack deflection path in boron carbide ceramic materials, significantly improving the strength and toughness of boron carbide ceramic materials, providing important technical support for the expansion of boron carbide ceramic application fields and service environments.
  • the present invention adopts the following technical solutions:
  • a method for preparing a boron nitride nanotube/nanosheet-boron carbide ceramic composite material is provided, and the specific steps are as follows:
  • the boron nitride nanotube/nanosheet hybrid powder accounts for 1% to 4% of the total mass of the boron carbide powder and boron nitride nanotube/nanosheet hybrid powder; the boron nitride
  • the nanotube/nanosheet hybrid powder is a hybrid structure formed by in-situ growth of boron nitride nanotubes on boron nitride nanosheets.
  • step (1) The boron nitride nanotube/nanosheet-boron carbide composite powder obtained in step (1) is placed in an argon atmosphere for hot pressing and sintering, and then cooled to room temperature with the furnace to obtain boron nitride nanotube/nanosheet- Boron carbide ceramic composites.
  • the mass ratio of the boron carbide powder to the surfactant is (190-400):1.
  • the average particle size of the boron carbide powder is 1-10 ⁇ m.
  • the mass concentration of the surfactant in the deionized water is 0.25-0.5 mg/mL.
  • the stirring time is 1-2 hours; the ultrasonic time is 1-2 hours; the freeze-drying time is 24-48 hours.
  • the hot press sintering temperature is 1850-1950° C.
  • the sintering pressure is 30-50 MPa
  • the sintering time is 30-60 min.
  • boron nitride nanotube/nanosheet-boron carbide ceramic composite material prepared by the above-mentioned preparation method.
  • the boron nitride nanosheet-nanotube hybrid material with good interfacial bonding characteristics is evenly introduced into the boron carbide ceramic material, which can not only exert the toughening mechanism of one-dimensional boron nitride nanotubes: pull-out effect, bridging effect, load transfer 1. Generate a prestress effect to delay the cracking of the boron carbide ceramic matrix; and can also take advantage of the two-dimensional boron nitride nanosheets with a large specific surface area: "wrap" the boron carbide grains and exert an "anchor" effect.
  • the interaction between boron nitride nanotubes and nanosheets can also play a multi-dimensional synergistic effect of boron nitride nanosheet-nanotube hybrid materials, resulting in new strengthening and toughening effects, such as: inhibiting boron carbide in ceramic composites Grain growth, changing the crack deflection path of ceramic composites, and further improving the strength, toughness and reliability of boron carbide ceramic composites.
  • the solution is positively charged after the cationic surfactant is dissolved in water, and the boron carbide ceramic powder is negatively charged after being dissolved in water because of containing boron oxide
  • the heterogeneous charges attract each other to form a stable and uniform suspended boron carbide system; adding boron nitride nanotube/nanosheet hybrid powder into the liquid phase system and then stirring, ultrasonic, and freeze-drying can make
  • the boron nitride nanotube/nanosheet hybrid powder is evenly mixed with the boron carbide ceramic powder, and the structural integrity of the hybrid powder can be maintained.
  • the boron nitride nanotube/nanosheet-boron carbide ceramic composite material provided by the present invention can not only give full play to the strength and toughness advantages of boron nitride nanotube and nanosheet, but also play the role of boron nitride nanosheet-nanotube
  • the multi-dimensional synergistic effect of hybrid materials such as inhibiting the grain growth of boron carbide in ceramic composites and changing the crack deflection path of ceramic composites, can significantly improve the strength and toughness of boron carbide ceramic composites.
  • boron nitride nanotube/nanosheet-boron carbide composite powder add 0.05g cetyltrimethylammonium bromide (concentration: 0.25mg/ml) and 19.8g Boron carbide powder with an average particle size of 2.0 ⁇ m was mixed evenly to obtain a boron carbide suspension, and then 0.2 g of boron nitride nanotube/nanosheet hybrid powder was added to the suspension, stirred for 1 hour, ultrasonicated for 1 hour, and freeze-dried for 24 hours.
  • the boron nitride nanotube/nanosheet-boron carbide composite powder is obtained, wherein the boron nitride nanotube/nanosheet hybrid powder is a hybrid structure formed by in-situ growth of boron nitride nanotube on the boron nitride nanosheet, and prepared Method reference Heng Wang, et al. Large ⁇ scale synthesis and growth mechanism of boron nitride nanocomp
  • the average grain size of the boron nitride nanotube/nanosheet-boron carbide ceramic composite measured by scanning electron microscopy is 2.15 ⁇ m; the obtained boron nitride nanotube/nanosheet-boron carbide ceramic composite
  • the bending strength of the material is 542MPa; the fracture toughness of the boron nitride nanotube/nanosheet-boron carbide ceramic composite is 4.92MPa ⁇ m 1/2 measured by the unilateral notched beam method.
  • the average grain size of the pure boron carbide ceramic material obtained under the same hot-pressing sintering conditions (50MPa, 1950°C, 60min) was measured by the above method to be 6.05 ⁇ m, the bending strength was 398MPa, and the fracture toughness was 3.3MPa ⁇ m 1/2 .
  • the comparison shows that adding 1wt% boron nitride nanotube/nanosheet hybrid powder to the boron carbide ceramic material can inhibit the grain growth of boron carbide ceramics, and the bending strength and fracture toughness of the ceramic composite material are respectively increased by 36.2 % and 49.1% (see Table 1).
  • step (1) 0.2g boron nitride nanotubes are added to obtain boron nitride nanotube-boron carbide composite powders, and under the same hot pressing sintering conditions (50MPa, 1950 °C, 60 min) to obtain a boron nitride nanotube-boron carbide ceramic composite material (wherein the boron nitride nanotube content is 1 wt%, and the boron carbide content is 99 wt%).
  • Example 1 Using a method similar to that of Example 1, the mechanical properties of the product prepared in the example of the present invention were tested, and the bending strength and fracture toughness of the obtained boron nitride nanotube-boron carbide ceramic composite material were 481MPa and 4.31MPa ⁇ m 1/2 respectively, Compared with pure boron carbide ceramic materials without boron nitride nanotubes, they are increased by 20.9% and 30.6% respectively (see Table 1).
  • step (1) 0.2g boron nitride nanosheets are added to obtain boron nitride nanosheets-boron carbide composite powders. ° C, 60 min) to obtain a boron nitride nanosheet-boron carbide ceramic composite material (wherein the boron nitride nanosheet content is 1 wt%, and the boron carbide content is 99 wt%).
  • Example 1 Using a method similar to that of Example 1, the mechanical properties of the product prepared in the example of the present invention were tested, and the bending strength and fracture toughness of the obtained boron nitride nanosheet-boron carbide ceramic composite material were 513MPa and 4.01MPa ⁇ m 1/2 respectively, Compared with the pure boron carbide ceramic material without boron nitride nanosheets, it is increased by 28.9% and 21.5% respectively (see Table 1).
  • boron nitride nanotube/nanosheet-boron carbide composite powder add 0.1g cetyltrimethylammonium chloride (concentration: 0.5mg/ml) and 19.2g Boron carbide powder with an average particle size of 2.0 ⁇ m was mixed uniformly to obtain a boron carbide suspension, and then 0.8 g of boron nitride nanotube/nanosheet hybrid powder was added to the suspension, stirred for 2 hours, ultrasonicated for 2 hours, and freeze-dried for 48 hours A boron nitride nanotube/nanosheet-boron carbide composite powder is obtained.
  • the product prepared in the embodiment of the present invention was tested by a method similar to that of Example 1, and the results showed that the bending strength and fracture toughness of the obtained boron nitride nanotube/nanosheet-boron carbide ceramic composite material were 501MPa and 4.36MPa ⁇ m respectively /2 , which are 37.3% and 39.3% higher than pure boron carbide ceramic materials without boron nitride nanotube/nanosheet hybrid powder obtained under the same hot pressing sintering conditions (30MPa, 1950°C, 30min), respectively.
  • boron nitride nanotube/nanosheet-boron carbide composite powder add 0.1g hexadecyltrimethylammonium bromide (concentration: 0.5mg/ml) and 19.8g Boron carbide powder with an average particle size of 2.0 ⁇ m was mixed uniformly to obtain a boron carbide suspension, and then 0.2 g of boron nitride nanotube/nanosheet hybrid powder was added to the suspension, stirred for 1 hour, ultrasonicated for 2 hours, and freeze-dried for 24 hours A boron nitride nanotube/nanosheet-boron carbide composite powder is obtained.
  • the results show that the bending strength and fracture toughness of the obtained boron nitride nanotube/nanosheet-boron carbide ceramic composite material are 468MPa and 4.31MPa ⁇ m respectively /2 , which are 30.1% and 42.7% higher than pure boron carbide ceramic materials without boron nitride nanotube/nanosheet hybrid powder obtained under the same hot-pressing sintering conditions (50MPa, 1850°C, 60min), respectively.
  • boron nitride nanotube/nanosheet-boron carbide composite powder add 0.05g cetyltrimethylammonium chloride (concentration: 0.25mg/ml) and 19.2g Boron carbide powder with an average particle size of 2.0 ⁇ m was mixed uniformly to obtain a boron carbide suspension, and then 0.8 g of boron nitride nanotube/nanosheet hybrid powder was added to the suspension, stirred for 2 hours, ultrasonicated for 1 hour, and freeze-dried for 48 hours A boron nitride nanotube/nanosheet-boron carbide composite powder is obtained.
  • the product prepared in the embodiment of the present invention was tested by a method similar to that of Example 1, and the results showed that the bending strength and fracture toughness of the obtained boron nitride nanotube / nanosheet-boron carbide ceramic composite material were 439MPa and 3.88MPa ⁇ m respectively /2 , which are 31.0% and 32.0% higher than pure boron carbide ceramic materials without boron nitride nanotube/nanosheet hybrid powder obtained under the same hot-pressing sintering conditions (30MPa, 1850°C, 30min), respectively.
  • boron nitride nanotube/nanosheet-boron carbide composite powder add 0.06g cetyltrimethylammonium bromide (concentration: 0.3mg/ml) and 19.3g Boron carbide powder with an average particle size of 2.0 ⁇ m was mixed uniformly to obtain a boron carbide suspension, and then 0.7 g of boron nitride nanotube/nanosheet hybrid powder was added to the suspension, stirred for 1.5 hours, ultrasonicated for 1.5 hours, and frozen Dry for 36 hours to obtain boron nitride nanotube/nanosheet-boron carbide composite powder.
  • the product prepared in the embodiment of the present invention was tested by a method similar to that of Example 1, and the results showed that the bending strength and fracture toughness of the obtained boron nitride nanotube/nanosheet-boron carbide ceramic composite were 523MPa and 4.89MPa ⁇ m respectively /2 , which are 37.6% and 51.4% higher than pure boron carbide ceramic materials without boron nitride nanotube/nanosheet hybrid powder obtained under the same hot pressing sintering conditions (30MPa, 1950°C, 60min), respectively.
  • boron nitride nanotube/nanosheet-boron carbide composite powder add 0.07g cetyltrimethylammonium chloride (concentration: 0.35mg/ml) and 19.4g Boron carbide powder with an average particle size of 2.0 ⁇ m was mixed uniformly to obtain a boron carbide suspension, and then 0.6 g of boron nitride nanotube/nanosheet hybrid powder was added to the suspension, stirred for 1 hour, ultrasonicated for 1.5 hours, and freeze-dried After 24 hours, the boron nitride nanotube/nanosheet-boron carbide composite powder was obtained.
  • the product prepared in the embodiment of the present invention was tested by a method similar to that of Example 1, and the results showed that the bending strength and fracture toughness of the obtained boron nitride nanotube/nanosheet-boron carbide ceramic composite were 482MPa and 4.43MPa ⁇ m respectively /2 , which are 33.5% and 43.9% higher than pure boron carbide ceramic materials without boron nitride nanotube/nanosheet hybrid powder obtained under the same hot pressing sintering conditions (40MPa, 1900°C, 30min), respectively.
  • the product prepared in the embodiment of the present invention was tested by a method similar to that of Example 1, and the results showed that the bending strength and fracture toughness of the obtained boron nitride nanotube/nanosheet-boron carbide ceramic composite were 520MPa and 4.72MPa ⁇ m respectively /2 , which are 40.5% and 46.6% higher than pure boron carbide ceramic materials without boron nitride nanotube/nanosheet hybrid powder obtained under the same hot-pressing sintering conditions (50MPa, 1900°C, 60min), respectively.
  • boron nitride nanotube/nanosheet-boron carbide composite powder 0.09g cetyltrimethylammonium chloride (concentration: 0.45mg/ml), 19.7g Boron carbide powder with an average particle size of 2.0 ⁇ m was mixed uniformly to obtain a boron carbide suspension, and then 0.3 g of boron nitride nanotube/nanosheet hybrid powder was added to the suspension, stirred for 1.5 hours, ultrasonicated for 2 hours, and freeze-dried 36h to obtain boron nitride nanotube/nanosheet-boron carbide composite powder.
  • the product prepared by the embodiment of the present invention was tested by a method similar to that of Example 1, and the results showed that the bending strength and fracture toughness of the obtained boron nitride nanotube/nanosheet-boron carbide ceramic composite were 512MPa and 4.69MPa ⁇ m respectively /2 , which are 34.0% and 44.3% higher than pure boron carbide ceramic materials without boron nitride nanotube/nanosheet hybrid powder obtained under the same hot pressing sintering conditions (40MPa, 1950°C, 45min), respectively.

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Abstract

A boron nitride nanotube/nanosheet-boron carbide ceramic composite material and a preparation method therefor, the method comprising: sequentially adding a surfactant and boron carbide powder to deionized water; mixing evenly to obtain a boron carbide suspension; continuously adding boron nitride nanotube/nanosheet hybrid powder, stirring, performing ultrasonic treatment, and freeze-drying to obtain boron nitride nanotube/nanosheet-boron carbide composite powder; finally placing same in an argon atmosphere for hot pressing and sintering, and cooling down to room temperature along with a furnace, so as to obtain a boron nitride nanotube/nanosheet-boron carbide ceramic composite material. The boron nitride nanotube/nanosheet hybrid powder is a hybrid structure formed by in-situ generation of boron nitride nanotubes on boron nitride nanosheets. In the ceramic composite material obtained in the method, the boron nitride nanotubes/nanosheets are uniformly dispersed in the boron carbide ceramic composite material, so that the strength and toughness advantages of the boron nitride nanotubes and nanosheets and multi-dimensional synergistic effects thereof can all be expressed at the same time, thereby significantly improving the strength and toughness of the boron carbide ceramic material.

Description

[根据细则37.2由ISA制定的发明名称]　氮化硼纳米管/纳米片-碳化硼陶瓷复合材料及其制备方法[Title of the invention established by ISA under Rule 37.2] Boron nitride nanotube/nanosheet-boron carbide ceramic composite material and method for its preparation 技术领域technical field
本发明属于先进结构陶瓷材料领域，具体涉及一种氮化硼纳米管/纳米片-碳化硼陶瓷复合材料及其制备方法。The invention belongs to the field of advanced structural ceramic materials, and in particular relates to a boron nitride nanotube/nanosheet-boron carbide ceramic composite material and a preparation method thereof.
背景技术Background technique
低维增强相强韧化的碳化硼(B 4C)陶瓷基复合材料具有高比强度、高比模量、高硬度、低密度，以及高断裂韧性和高断裂功等优良特性，是一类重要的轻质陶瓷装甲材料，是国防建设与现代工业的重要支撑材料之一。随着应用领域和服役环境的不断拓展，对碳化硼陶瓷基复合材料的韧性、强度和可靠性提出了更高的要求。 Boron carbide (B 4 C) ceramic matrix composites strengthened and toughened by low-dimensional reinforcement phases have excellent characteristics such as high specific strength, high specific modulus, high hardness, low density, high fracture toughness and high fracture work, and are a class of An important lightweight ceramic armor material is one of the important supporting materials for national defense construction and modern industry. With the continuous expansion of application fields and service environments, higher requirements are put forward for the toughness, strength and reliability of boron carbide ceramic matrix composites.
氮化硼纳米材料(纳米管、纳米片)具有高杨氏模量和高断裂强度的优点，如：利用透射电子显微镜-原子力显微镜(TEM-AFM)测得直径为11.9～44.3nm的单根氮化硼纳米管(BNNTs)的断裂强度为14.1～33.2GPa，断裂应变为1.5～3.4％，杨氏模量为725～1343GPa(Wei X L,et al.Adv Mater.,2010,22,4895)，与理论预测较为吻合(Hernández E,et al.Phys Rev Lett.,1998,80,4502)。利用AFM研究氮化硼纳米片(BNNSs)的力学性能发现：氮化硼层间较大的滑移能可以阻止片层间的移动，厚度变化(1～9层)对BNNSs的力学性能影响不大，断裂强度为70.5±5.5GPa，杨氏模量为0.865±0.073TPa(Falin A,et al.Nat Commun.,2017,8,15815)。Boron nitride nanomaterials (nanotubes, nanosheets) have the advantages of high Young's modulus and high fracture strength. The fracture strength of boron nitride nanotubes (BNNTs) is 14.1-33.2GPa, the fracture strain is 1.5-3.4%, and the Young's modulus is 725-1343GPa (Wei X L, et al. Adv Mater., 2010,22,4895 ), which is in good agreement with theoretical predictions (Hernández E, et al. Phys Rev Lett., 1998, 80, 4502). Using AFM to study the mechanical properties of boron nitride nanosheets (BNNSs), it was found that the large slip energy between boron nitride layers can prevent the movement between layers, and the thickness change (1-9 layers) has little effect on the mechanical properties of BNNSs. Large, with a breaking strength of 70.5±5.5GPa and a Young’s modulus of 0.865±0.073TPa (Falin A, et al. Nat Commun., 2017, 8, 15815).
力学性能优异的氮化硼纳米管和纳米片是陶瓷基复合材料中有效的无机纳米添加相。日本国立材料研究所的学者率先研究了含BNNTs的Al 2O 3和Si 3N 4陶瓷复合材料，结果表明：仅添加0.5wt％的BNNTs，Al 2O 3陶瓷在1300℃下产生了脆性-延性的转变趋势；Si 3N 4陶瓷在同样的变形条件下能降低75％的载荷应力(Huang Q,et al.Nanotechnology,2007,18,485706)。BNNTs在ZrO 2陶瓷复合材料中能强化ZrO 2的晶界、改变材料的断裂方式(由沿晶断裂变为穿晶断裂)、影响ZrO 2的相变(产生相变增韧机制)、提高ZrO 2陶瓷复合材料的韧性(Xu J J,et al.Mat Sci EngA.,2012,546,301.Tatarko P,et al.J Eur Ceam Soc.,2014,34,1829)。对于含氮化硼纳米片的Si 3N 4陶瓷材料，BNNSs在Si 3N 4陶瓷中产生裂纹桥接和钝化效应，提高Si 3N 4的断裂韧性和弯曲强度；BNNSs包裹在Si 3N 4晶粒上形成润滑膜，降低Si 3N 4的摩擦系数，提高其耐磨性(Lee B,et al.Sci.Rep.,2016,6,27609)。在B 4C陶瓷中加入5wt％的立方相氮化硼进行放电等离子烧结，氮化硼会由立方相转变为六方相，原位形成 的六方相氮化硼薄片在B 4C基体上也能够吸收裂纹扩展所需能量，B 4C陶瓷材料的弯曲强度和断裂韧性分别提高了32.7％和58.6％(Sun J C,et al.J Eur Ceam Soc.,2020,1103)。 Boron nitride nanotubes and nanosheets with excellent mechanical properties are effective inorganic nanoadditive phases in ceramic matrix composites. Scholars from the National Institute of Materials Research in Japan took the lead in studying Al 2 O 3 and Si 3 N 4 ceramic composites containing BNNTs. The results showed that: only 0.5wt% of BNNTs were added, and Al 2 O 3 ceramics produced brittleness at 1300°C- The transition trend of ductility; Si 3 N 4 ceramics can reduce the load stress by 75% under the same deformation conditions (Huang Q, et al. Nanotechnology, 2007, 18, 485706). BNNTs in ZrO 2 ceramic composites can strengthen the grain boundaries of ZrO 2 , change the fracture mode of the material (from intergranular fracture to transgranular fracture), affect the phase transition of ZrO 2 (generate phase transition toughening mechanism), and improve the ZrO 2 fracture mode. 2 Toughness of ceramic composites (Xu J J, et al. Mat Sci EngA., 2012, 546, 301. Tatarko P, et al. J Eur Ceam Soc., 2014, 34, 1829). For Si 3 N 4 ceramic materials containing boron nitride nanosheets, BNNSs produces crack bridging and passivation effects in Si 3 N 4 ceramics, improving the fracture toughness and bending strength of Si 3 N 4 ; BNNSs wrapped in Si 3 N 4 A lubricating film is formed on the grains to reduce the friction coefficient of Si 3 N 4 and improve its wear resistance (Lee B, et al. Sci. Rep., 2016, 6, 27609). Adding 5wt% cubic boron nitride to B 4 C ceramics for spark plasma sintering, the boron nitride will transform from cubic phase to hexagonal phase, and the hexagonal phase boron nitride flakes formed in situ can also be formed on the B 4 C substrate. By absorbing the energy required for crack propagation, the flexural strength and fracture toughness of B 4 C ceramic materials are increased by 32.7% and 58.6%, respectively (Sun J C, et al. J Eur Ceam Soc., 2020, 1103).
因此，如何设计简单添加方式以便最大程度的发挥氮化硼纳米管和纳米片作为无机纳米添加相在碳化硼陶瓷基复合材料中的作用，进一步提升碳化硼陶瓷复合材料的强度、韧性和可靠性，是当务之急。Therefore, how to design a simple addition method to maximize the role of boron nitride nanotubes and nanosheets as inorganic nano-additive phases in boron carbide ceramic matrix composites, and further improve the strength, toughness and reliability of boron carbide ceramic composites , is imperative.
发明内容Contents of the invention
本发明的目的在于提供一种氮化硼纳米管/纳米片-碳化硼陶瓷复合材料及其制备方法。氮化硼纳米管/纳米片在碳化硼陶瓷复合材料中均匀分散，能同时发挥氮化硼纳米管和纳米片的强韧化优势及其多维度协同效应，抑制陶瓷复合材料中碳化硼的晶粒生长，延长碳化硼陶瓷材料中裂纹偏转路径，显著提升碳化硼陶瓷材料的强度和韧性，为碳化硼陶瓷应用领域和服役环境的拓展提供重要技术支撑。The object of the present invention is to provide a boron nitride nanotube/nanosheet-boron carbide ceramic composite material and a preparation method thereof. Boron nitride nanotubes/nanosheets are uniformly dispersed in boron carbide ceramic composites, which can simultaneously exert the strength and toughness advantages of boron nitride nanotubes and nanosheets and their multi-dimensional synergistic effects, and inhibit the crystallization of boron carbide in ceramic composites. Grain growth, prolonging the crack deflection path in boron carbide ceramic materials, significantly improving the strength and toughness of boron carbide ceramic materials, providing important technical support for the expansion of boron carbide ceramic application fields and service environments.
为了解决上述技术问题，本发明采用以下技术方案：In order to solve the above technical problems, the present invention adopts the following technical solutions:
提供一种氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的制备方法，具体步骤如下：A method for preparing a boron nitride nanotube/nanosheet-boron carbide ceramic composite material is provided, and the specific steps are as follows:
(1)在去离子水中依次加入表面活性剂和碳化硼粉体，混合均匀得碳化硼悬浮液，然后向碳化硼悬浮液中加入氮化硼纳米管/纳米片杂化粉体，搅拌、超声、冷冻干燥得到氮化硼纳米管/纳米片-碳化硼复合粉体，其中所述表面活性剂为十六烷基三甲基溴化铵或十六烷基三甲基氯化铵；按质量百分比计，所述氮化硼纳米管/纳米片杂化粉体占所述碳化硼粉体和氮化硼纳米管/纳米片杂化粉体总质量的1～4％；所述氮化硼纳米管/纳米片杂化粉体为氮化硼纳米片上原位生长氮化硼纳米管形成的杂化结构。(1) Add surfactant and boron carbide powder in deionized water in sequence, mix uniformly to obtain boron carbide suspension, then add boron nitride nanotube/nanosheet hybrid powder to the boron carbide suspension, stir, and sonicate , freeze-drying to obtain boron nitride nanotube/nanosheet-boron carbide composite powder, wherein the surfactant is cetyltrimethylammonium bromide or cetyltrimethylammonium chloride; by mass In terms of percentage, the boron nitride nanotube/nanosheet hybrid powder accounts for 1% to 4% of the total mass of the boron carbide powder and boron nitride nanotube/nanosheet hybrid powder; the boron nitride The nanotube/nanosheet hybrid powder is a hybrid structure formed by in-situ growth of boron nitride nanotubes on boron nitride nanosheets.
(2)将步骤(1)所得氮化硼纳米管/纳米片-碳化硼复合粉体置于氩气气氛下热压烧结，然后随炉冷却至室温，得到氮化硼纳米管/纳米片-碳化硼陶瓷复合材料。(2) The boron nitride nanotube/nanosheet-boron carbide composite powder obtained in step (1) is placed in an argon atmosphere for hot pressing and sintering, and then cooled to room temperature with the furnace to obtain boron nitride nanotube/nanosheet- Boron carbide ceramic composites.
上述方案中，所述步骤(1)中，碳化硼粉体和表面活性剂的质量比为(190～400)：1。In the above scheme, in the step (1), the mass ratio of the boron carbide powder to the surfactant is (190-400):1.
上述方案中，所述步骤(1)中，碳化硼粉体的平均粒径为1～10μm。In the above solution, in the step (1), the average particle size of the boron carbide powder is 1-10 μm.
上述方案中，所述步骤(1)中，表面活性剂在去离子水中的质量浓度为0.25～0.5mg/mL。In the above scheme, in the step (1), the mass concentration of the surfactant in the deionized water is 0.25-0.5 mg/mL.
上述方案中，所述步骤(1)中，搅拌时间为1～2h；超声时间为1～2h；冷冻干燥时间为24～48h。In the above scheme, in the step (1), the stirring time is 1-2 hours; the ultrasonic time is 1-2 hours; the freeze-drying time is 24-48 hours.
上述方案中，所述步骤(2)中，热压烧结温度为1850～1950℃，烧结压力为30～50MPa，烧结时间为30～60min。In the above solution, in the step (2), the hot press sintering temperature is 1850-1950° C., the sintering pressure is 30-50 MPa, and the sintering time is 30-60 min.
提供一种上述所述的制备方法制备得到的氮化硼纳米管/纳米片-碳化硼陶瓷复合材料。Provided is a boron nitride nanotube/nanosheet-boron carbide ceramic composite material prepared by the above-mentioned preparation method.
在碳化硼陶瓷材料中均匀引入具有良好界面结合特性的氮化硼纳米片-纳米管杂化材料，既可以发挥一维氮化硼纳米管的增韧机制：拔出效应、桥接效应、载荷转移、产生预应力效应延缓碳化硼陶瓷基体开裂；又可以发挥大比表面积的二维氮化硼纳米片的优势：对碳化硼晶粒产生“包裹”并发挥“锚接”效应。此外，氮化硼纳米管和纳米片的相互作用还能发挥氮化硼纳米片-纳米管杂化材料的多维度协同效应，产生新的增强增韧效应，如：抑制陶瓷复合材料中碳化硼的晶粒生长、改变陶瓷复合材料的裂纹偏转路径，进一步提升碳化硼陶瓷复合材料的强度、韧性和可靠性。The boron nitride nanosheet-nanotube hybrid material with good interfacial bonding characteristics is evenly introduced into the boron carbide ceramic material, which can not only exert the toughening mechanism of one-dimensional boron nitride nanotubes: pull-out effect, bridging effect, load transfer 1. Generate a prestress effect to delay the cracking of the boron carbide ceramic matrix; and can also take advantage of the two-dimensional boron nitride nanosheets with a large specific surface area: "wrap" the boron carbide grains and exert an "anchor" effect. In addition, the interaction between boron nitride nanotubes and nanosheets can also play a multi-dimensional synergistic effect of boron nitride nanosheet-nanotube hybrid materials, resulting in new strengthening and toughening effects, such as: inhibiting boron carbide in ceramic composites Grain growth, changing the crack deflection path of ceramic composites, and further improving the strength, toughness and reliability of boron carbide ceramic composites.
本发明的有益效果为：The beneficial effects of the present invention are:
1.本发明制备氮化硼纳米管/纳米片-碳化硼复合粉体时，阳离子表面活性剂溶于水后溶液呈正电性，碳化硼陶瓷粉体因含有硼氧化物溶于水后呈负电性，异种电荷相互吸引，可以形成稳定、均匀的悬浮态碳化硼体系；在该液相体系中加入氮化硼纳米管/纳米片杂化粉体后经搅拌、超声、冷冻干燥，既能使氮化硼纳米管/纳米片杂化粉体与碳化硼陶瓷粉体均匀混合，又能保持该杂化粉体的结构完整性。1. When the present invention prepares boron nitride nanotube/nanosheet-boron carbide composite powder, the solution is positively charged after the cationic surfactant is dissolved in water, and the boron carbide ceramic powder is negatively charged after being dissolved in water because of containing boron oxide The heterogeneous charges attract each other to form a stable and uniform suspended boron carbide system; adding boron nitride nanotube/nanosheet hybrid powder into the liquid phase system and then stirring, ultrasonic, and freeze-drying can make The boron nitride nanotube/nanosheet hybrid powder is evenly mixed with the boron carbide ceramic powder, and the structural integrity of the hybrid powder can be maintained.
2.本发明提供的氮化硼纳米管/纳米片-碳化硼陶瓷复合材料，能同时发挥氮化硼纳米管和纳米片的强韧化优势外，还能发挥氮化硼纳米片-纳米管杂化材料的多维度协同效应，如：抑制陶瓷复合材料中碳化硼的晶粒生长、改变陶瓷复合材料的裂纹偏转路径，对于碳化硼陶瓷复合材料的强度和韧性有显著提升作用。2. The boron nitride nanotube/nanosheet-boron carbide ceramic composite material provided by the present invention can not only give full play to the strength and toughness advantages of boron nitride nanotube and nanosheet, but also play the role of boron nitride nanosheet-nanotube The multi-dimensional synergistic effect of hybrid materials, such as inhibiting the grain growth of boron carbide in ceramic composites and changing the crack deflection path of ceramic composites, can significantly improve the strength and toughness of boron carbide ceramic composites.
具体实施方式Detailed ways
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。In order to better understand the present invention, the content of the present invention is further illustrated below in conjunction with the examples, but the content of the present invention is not limited to the following examples.
实施例1Example 1
一种氮化硼纳米管/纳米片-碳化硼陶瓷复合材料及其制备方法，具体步骤如下：A boron nitride nanotube/nanosheet-boron carbide ceramic composite material and a preparation method thereof, the specific steps are as follows:
(1)氮化硼纳米管/纳米片-碳化硼复合粉体的制备：在200ml去离子水中依次加入0.05g十六烷基三甲基溴化铵(浓度为0.25mg/ml)和19.8g平均粒径为2.0μm的碳化硼粉体，混合均匀得碳化硼悬浮液，然后向悬浮液中加入0.2g氮化硼纳米管/纳米片杂化粉体，搅拌1h、超声1h、冷冻干燥24h得到氮化硼纳米管/纳米片-碳化硼复合粉体，其中氮化硼纳米管/纳米片杂化粉体为氮化硼纳米片上原位生长氮化硼纳米管形成的杂化结构，制备方法参考文献Heng Wang,et al.Large‐scale synthesis and growth mechanism of boron nitride  nanocomposite assembled by nanosheets and nanotubes,Journal ofthe American Ceramic Society,2020,103(10),5594-5598。(1) Preparation of boron nitride nanotube/nanosheet-boron carbide composite powder: add 0.05g cetyltrimethylammonium bromide (concentration: 0.25mg/ml) and 19.8g Boron carbide powder with an average particle size of 2.0 μm was mixed evenly to obtain a boron carbide suspension, and then 0.2 g of boron nitride nanotube/nanosheet hybrid powder was added to the suspension, stirred for 1 hour, ultrasonicated for 1 hour, and freeze-dried for 24 hours The boron nitride nanotube/nanosheet-boron carbide composite powder is obtained, wherein the boron nitride nanotube/nanosheet hybrid powder is a hybrid structure formed by in-situ growth of boron nitride nanotube on the boron nitride nanosheet, and prepared Method reference Heng Wang, et al. Large‐scale synthesis and growth mechanism of boron nitride nanocomposite assembled by nanosheets and nanotubes, Journal of the American Ceramic Society, 2020, 103(10), 5594-5598.
(2)氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的制备：将步骤(1)所得氮化硼纳米管/纳米片-碳化硼复合粉体置于圆柱状石墨模具中，在热压烧结炉中施加50MPa压力、1950℃烧结60min，随炉冷却至室温，得到直径为48mm、厚度为4.5mm的氮化硼纳米管/纳米片-碳化硼陶瓷复合材料，其中氮化硼纳米管/纳米片含量为1wt％，碳化硼含量为99wt％。(2) Preparation of boron nitride nanotube/nanosheet-boron carbide ceramic composite material: place the boron nitride nanotube/nanosheet-boron carbide composite powder obtained in step (1) in a cylindrical graphite mould, heat Apply a pressure of 50 MPa in a pressure sintering furnace, sinter at 1950°C for 60 minutes, and cool to room temperature with the furnace to obtain a boron nitride nanotube/nanosheet-boron carbide ceramic composite material with a diameter of 48mm and a thickness of 4.5mm, wherein the boron nitride nanotube The nanosheet content is 1wt%, and the boron carbide content is 99wt%.
利用扫描电子显微镜测得氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的平均晶粒尺寸为2.15μm；利用三点弯曲法测得所得氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的弯曲强度为542MPa；利用单边切口梁法测得氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的断裂韧性为4.92MPa·m 1/2。 The average grain size of the boron nitride nanotube/nanosheet-boron carbide ceramic composite measured by scanning electron microscopy is 2.15 μm; the obtained boron nitride nanotube/nanosheet-boron carbide ceramic composite The bending strength of the material is 542MPa; the fracture toughness of the boron nitride nanotube/nanosheet-boron carbide ceramic composite is 4.92MPa·m 1/2 measured by the unilateral notched beam method.
利用上述方法测得相同热压烧结条件(50MPa，1950℃，60min)下所得纯碳化硼陶瓷材料的平均晶粒尺寸为6.05μm，弯曲强度为398MPa，断裂韧性为3.3MPa·m 1/2。对比可知，在碳化硼陶瓷材料中加入1wt％的氮化硼纳米管/纳米片杂化粉体，能抑制碳化硼陶瓷晶粒长大，且陶瓷复合材料的弯曲强度和断裂韧性分别提高了36.2％和49.1％(见表1)。 The average grain size of the pure boron carbide ceramic material obtained under the same hot-pressing sintering conditions (50MPa, 1950°C, 60min) was measured by the above method to be 6.05μm, the bending strength was 398MPa, and the fracture toughness was 3.3MPa·m 1/2 . The comparison shows that adding 1wt% boron nitride nanotube/nanosheet hybrid powder to the boron carbide ceramic material can inhibit the grain growth of boron carbide ceramics, and the bending strength and fracture toughness of the ceramic composite material are respectively increased by 36.2 % and 49.1% (see Table 1).
对比例1Comparative example 1
具体步骤同实施例1，不同之处在于，步骤(1)中，添加0.2g氮化硼纳米管，得到氮化硼纳米管-碳化硼复合粉体，在相同热压烧结条件(50MPa，1950℃，60min)下得到氮化硼纳米管-碳化硼陶瓷复合材料(其中氮化硼纳米管含量为1wt％，碳化硼含量为99wt％)。The specific steps are the same as in Example 1, the difference is that in step (1), 0.2g boron nitride nanotubes are added to obtain boron nitride nanotube-boron carbide composite powders, and under the same hot pressing sintering conditions (50MPa, 1950 °C, 60 min) to obtain a boron nitride nanotube-boron carbide ceramic composite material (wherein the boron nitride nanotube content is 1 wt%, and the boron carbide content is 99 wt%).
采用与实施例1相似的方法对本发明实施例制备的产物进行力学性能测试，所得氮化硼纳米管-碳化硼陶瓷复合材料的弯曲强度和断裂韧性分别为481MPa和4.31MPa·m 1/2，分别比不含氮化硼纳米管的纯碳化硼陶瓷材料提高20.9％和30.6％(见表1)。 Using a method similar to that of Example 1, the mechanical properties of the product prepared in the example of the present invention were tested, and the bending strength and fracture toughness of the obtained boron nitride nanotube-boron carbide ceramic composite material were 481MPa and 4.31MPa·m 1/2 respectively, Compared with pure boron carbide ceramic materials without boron nitride nanotubes, they are increased by 20.9% and 30.6% respectively (see Table 1).
对比例2Comparative example 2
具体步骤同实施例1，不同之处在于，步骤(1)中，添加0.2g氮化硼纳米片，得到氮化硼纳米片-碳化硼复合粉体，在相同热压烧结条件(50MPa，1950℃，60min)下得到氮化硼纳米片-碳化硼陶瓷复合材料(其中氮化硼纳米片含量为1wt％，碳化硼含量为99wt％)。The specific steps are the same as in Example 1, except that in step (1), 0.2g boron nitride nanosheets are added to obtain boron nitride nanosheets-boron carbide composite powders. ° C, 60 min) to obtain a boron nitride nanosheet-boron carbide ceramic composite material (wherein the boron nitride nanosheet content is 1 wt%, and the boron carbide content is 99 wt%).
采用与实施例1相似的方法对本发明实施例制备的产物进行力学性能测试，所得氮化硼纳米片-碳化硼陶瓷复合材料的弯曲强度和断裂韧性分别为513MPa和4.01MPa·m 1/2，分别比不含氮化硼纳米片的纯碳化硼陶瓷材料提高28.9％和21.5％(见表1)。 Using a method similar to that of Example 1, the mechanical properties of the product prepared in the example of the present invention were tested, and the bending strength and fracture toughness of the obtained boron nitride nanosheet-boron carbide ceramic composite material were 513MPa and 4.01MPa·m 1/2 respectively, Compared with the pure boron carbide ceramic material without boron nitride nanosheets, it is increased by 28.9% and 21.5% respectively (see Table 1).
表1碳化硼陶瓷复合材料的弯曲强度、断裂韧性及其提升率对比Table 1 Comparison of flexural strength, fracture toughness and improvement rate of boron carbide ceramic composites
Figure PCTCN2021117936-appb-000001
Figure PCTCN2021117936-appb-000001
实施例2Example 2
一种氮化硼纳米管/纳米片-碳化硼陶瓷复合材料及其制备方法，具体步骤如下：A boron nitride nanotube/nanosheet-boron carbide ceramic composite material and a preparation method thereof, the specific steps are as follows:
(1)氮化硼纳米管/纳米片-碳化硼复合粉体的制备：在200ml去离子水中依次加入0.1g十六烷基三甲基氯化铵(浓度为0.5mg/ml)和19.2g平均粒径为2.0μm的碳化硼粉体，混合均匀得碳化硼悬浮液，然后向悬浮液中加入0.8g氮化硼纳米管/纳米片杂化粉体，搅拌2h、超声2h、冷冻干燥48h得到氮化硼纳米管/纳米片-碳化硼复合粉体。(1) Preparation of boron nitride nanotube/nanosheet-boron carbide composite powder: add 0.1g cetyltrimethylammonium chloride (concentration: 0.5mg/ml) and 19.2g Boron carbide powder with an average particle size of 2.0 μm was mixed uniformly to obtain a boron carbide suspension, and then 0.8 g of boron nitride nanotube/nanosheet hybrid powder was added to the suspension, stirred for 2 hours, ultrasonicated for 2 hours, and freeze-dried for 48 hours A boron nitride nanotube/nanosheet-boron carbide composite powder is obtained.
(2)氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的制备：将步骤(1)所得氮化硼纳米管/纳米片-碳化硼复合粉体置于圆柱状石墨模具中，在热压烧结炉中施加30MPa压力、1950℃烧结30min，随炉冷却至室温，得到直径为48mm、厚度为4.5mm的氮化硼纳米管/纳米片-碳化硼陶瓷复合材料，其中氮化硼纳米管/纳米片含量为4wt％，碳化硼含量为96wt％。(2) Preparation of boron nitride nanotube/nanosheet-boron carbide ceramic composite material: place the boron nitride nanotube/nanosheet-boron carbide composite powder obtained in step (1) in a cylindrical graphite mould, heat Apply a pressure of 30 MPa in a pressure sintering furnace, sinter at 1950°C for 30 minutes, and cool to room temperature with the furnace to obtain a boron nitride nanotube/nanosheet-boron carbide ceramic composite material with a diameter of 48mm and a thickness of 4.5mm, wherein the boron nitride nanotube The nanosheet content is 4wt%, and the boron carbide content is 96wt%.
采用与实施例1相似的方法对本发明实施例制备的产物进行测试，结果表明所得氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的弯曲强度和断裂韧性分别是501MPa和4.36MPa·m 1/2，分别比相同热压烧结条件(30MPa，1950℃，30min)所得不含氮化硼纳米管/纳米片杂化粉体的纯碳化硼陶瓷材料提高37.3％和39.3％。 The product prepared in the embodiment of the present invention was tested by a method similar to that of Example 1, and the results showed that the bending strength and fracture toughness of the obtained boron nitride nanotube/nanosheet-boron carbide ceramic composite material were 501MPa and 4.36MPa·m respectively /2 , which are 37.3% and 39.3% higher than pure boron carbide ceramic materials without boron nitride nanotube/nanosheet hybrid powder obtained under the same hot pressing sintering conditions (30MPa, 1950°C, 30min), respectively.
实施例3Example 3
一种氮化硼纳米管/纳米片-碳化硼陶瓷复合材料及其制备方法，具体步骤如下：A boron nitride nanotube/nanosheet-boron carbide ceramic composite material and a preparation method thereof, the specific steps are as follows:
(1)氮化硼纳米管/纳米片-碳化硼复合粉体的制备：在200ml去离子水中依次加入0.1g十六烷基三甲基溴化铵(浓度为0.5mg/ml)和19.8g平均粒径为2.0μm的碳化硼粉体，混合均匀得碳化硼悬浮液，然后向悬浮液中加入0.2g氮化硼纳米管/纳米片杂化粉体，搅拌1h、超声2h、冷冻干燥24h得到氮化硼纳米管/纳米片-碳化硼复合粉体。(1) Preparation of boron nitride nanotube/nanosheet-boron carbide composite powder: add 0.1g hexadecyltrimethylammonium bromide (concentration: 0.5mg/ml) and 19.8g Boron carbide powder with an average particle size of 2.0 μm was mixed uniformly to obtain a boron carbide suspension, and then 0.2 g of boron nitride nanotube/nanosheet hybrid powder was added to the suspension, stirred for 1 hour, ultrasonicated for 2 hours, and freeze-dried for 24 hours A boron nitride nanotube/nanosheet-boron carbide composite powder is obtained.
(2)氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的制备：将步骤(1)所得氮化硼纳米管/纳米片-碳化硼复合粉体置于圆柱状石墨模具中，在热压烧结炉中施加50MPa压力、 1850℃烧结60min，随炉冷却至室温，得到直径为48mm、厚度为4.5mm的氮化硼纳米管/纳米片-碳化硼陶瓷复合材料，其中氮化硼纳米管/纳米片含量为1wt％，碳化硼含量为99wt％。(2) Preparation of boron nitride nanotube/nanosheet-boron carbide ceramic composite material: place the boron nitride nanotube/nanosheet-boron carbide composite powder obtained in step (1) in a cylindrical graphite mould, heat Apply a pressure of 50 MPa in a pressure sintering furnace, sinter at 1850°C for 60 minutes, and cool to room temperature with the furnace to obtain a boron nitride nanotube/nanosheet-boron carbide ceramic composite material with a diameter of 48mm and a thickness of 4.5mm, wherein the boron nitride nanotube The nanosheet content is 1wt%, and the boron carbide content is 99wt%.
采用与实施例1相似的方法对本发明实施例制备的产物进行测试，结果表明所得氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的弯曲强度和断裂韧性分别是468MPa和4.31MPa·m 1/2，分别比相同热压烧结条件(50MPa，1850℃，60min)所得不含氮化硼纳米管/纳米片杂化粉体的纯碳化硼陶瓷材料提高30.1％和42.7％。 Adopt the method similar to Example 1 to test the product prepared by the embodiment of the present invention, the results show that the bending strength and fracture toughness of the obtained boron nitride nanotube/nanosheet-boron carbide ceramic composite material are 468MPa and 4.31MPa·m respectively /2 , which are 30.1% and 42.7% higher than pure boron carbide ceramic materials without boron nitride nanotube/nanosheet hybrid powder obtained under the same hot-pressing sintering conditions (50MPa, 1850°C, 60min), respectively.
实施例4Example 4
一种氮化硼纳米管/纳米片-碳化硼陶瓷复合材料及其制备方法，具体步骤如下：A boron nitride nanotube/nanosheet-boron carbide ceramic composite material and a preparation method thereof, the specific steps are as follows:
(1)氮化硼纳米管/纳米片-碳化硼复合粉体的制备：在200ml去离子水中依次加入0.05g十六烷基三甲基氯化铵(浓度为0.25mg/ml)和19.2g平均粒径为2.0μm的碳化硼粉体，混合均匀得碳化硼悬浮液，然后向悬浮液中加入0.8g氮化硼纳米管/纳米片杂化粉体，搅拌2h、超声1h、冷冻干燥48h得到氮化硼纳米管/纳米片-碳化硼复合粉体。(1) Preparation of boron nitride nanotube/nanosheet-boron carbide composite powder: add 0.05g cetyltrimethylammonium chloride (concentration: 0.25mg/ml) and 19.2g Boron carbide powder with an average particle size of 2.0 μm was mixed uniformly to obtain a boron carbide suspension, and then 0.8 g of boron nitride nanotube/nanosheet hybrid powder was added to the suspension, stirred for 2 hours, ultrasonicated for 1 hour, and freeze-dried for 48 hours A boron nitride nanotube/nanosheet-boron carbide composite powder is obtained.
(2)氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的制备：将步骤(1)所得氮化硼纳米管/纳米片-碳化硼复合粉体置于圆柱状石墨模具中，在热压烧结炉中施加30MPa压力、1850℃烧结30min，随炉冷却至室温，得到直径为48mm、厚度为4.5mm的氮化硼纳米管/纳米片-碳化硼陶瓷复合材料，其中氮化硼纳米管/纳米片含量为4wt％，碳化硼含量为96wt％。(2) Preparation of boron nitride nanotube/nanosheet-boron carbide ceramic composite material: place the boron nitride nanotube/nanosheet-boron carbide composite powder obtained in step (1) in a cylindrical graphite mould, heat Apply a pressure of 30MPa in a pressure sintering furnace, sinter at 1850°C for 30 minutes, and cool to room temperature with the furnace to obtain a boron nitride nanotube/nanosheet-boron carbide ceramic composite material with a diameter of 48mm and a thickness of 4.5mm, wherein the boron nitride nanotube The nanosheet content is 4wt%, and the boron carbide content is 96wt%.
采用与实施例1相似的方法对本发明实施例制备的产物进行测试，结果表明所得氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的弯曲强度和断裂韧性分别是439MPa和3.88MPa·m 1/2，分别比相同热压烧结条件(30MPa，1850℃，30min)所得不含氮化硼纳米管/纳米片杂化粉体的纯碳化硼陶瓷材料提高31.0％和32.0％。 The product prepared in the embodiment of the present invention was tested by a method similar to that of Example 1, and the results showed that the bending strength and fracture toughness of the obtained boron nitride nanotube / nanosheet-boron carbide ceramic composite material were 439MPa and 3.88MPa·m respectively /2 , which are 31.0% and 32.0% higher than pure boron carbide ceramic materials without boron nitride nanotube/nanosheet hybrid powder obtained under the same hot-pressing sintering conditions (30MPa, 1850°C, 30min), respectively.
实施例5Example 5
一种氮化硼纳米管/纳米片-碳化硼陶瓷复合材料及其制备方法，具体步骤如下：A boron nitride nanotube/nanosheet-boron carbide ceramic composite material and a preparation method thereof, the specific steps are as follows:
(1)氮化硼纳米管/纳米片-碳化硼复合粉体的制备：在200ml去离子水中依次加入0.06g十六烷基三甲基溴化铵(浓度为0.3mg/ml)和19.3g平均粒径为2.0μm的碳化硼粉体，混合均匀得碳化硼悬浮液，然后向悬浮液中加入0.7g氮化硼纳米管/纳米片杂化粉体，搅拌1.5h、超声1.5h、冷冻干燥36h得到氮化硼纳米管/纳米片-碳化硼复合粉体。(1) Preparation of boron nitride nanotube/nanosheet-boron carbide composite powder: add 0.06g cetyltrimethylammonium bromide (concentration: 0.3mg/ml) and 19.3g Boron carbide powder with an average particle size of 2.0 μm was mixed uniformly to obtain a boron carbide suspension, and then 0.7 g of boron nitride nanotube/nanosheet hybrid powder was added to the suspension, stirred for 1.5 hours, ultrasonicated for 1.5 hours, and frozen Dry for 36 hours to obtain boron nitride nanotube/nanosheet-boron carbide composite powder.
(2)氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的制备：将步骤(1)所得氮化硼纳米管/纳米片-碳化硼复合粉体置于圆柱状石墨模具中，在热压烧结炉中施加30MPa压力、 1950℃烧结60min，随炉冷却至室温，得到直径为48mm、厚度为4.5mm的氮化硼纳米管/纳米片-碳化硼陶瓷复合材料，其中氮化硼纳米管/纳米片含量为3.5wt％，碳化硼含量为96.5wt％。(2) Preparation of boron nitride nanotube/nanosheet-boron carbide ceramic composite material: place the boron nitride nanotube/nanosheet-boron carbide composite powder obtained in step (1) in a cylindrical graphite mould, heat Apply a pressure of 30 MPa in a pressure sintering furnace, sinter at 1950°C for 60 minutes, and cool to room temperature with the furnace to obtain a boron nitride nanotube/nanosheet-boron carbide ceramic composite material with a diameter of 48mm and a thickness of 4.5mm, wherein the boron nitride nanotube The nanosheet content is 3.5wt%, and the boron carbide content is 96.5wt%.
采用与实施例1相似的方法对本发明实施例制备的产物进行测试，结果表明所得氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的弯曲强度和断裂韧性分别是523MPa和4.89MPa·m 1/2，分别比相同热压烧结条件(30MPa，1950℃，60min)所得不含氮化硼纳米管/纳米片杂化粉体的纯碳化硼陶瓷材料提高37.6％和51.4％。 The product prepared in the embodiment of the present invention was tested by a method similar to that of Example 1, and the results showed that the bending strength and fracture toughness of the obtained boron nitride nanotube/nanosheet-boron carbide ceramic composite were 523MPa and 4.89MPa·m respectively /2 , which are 37.6% and 51.4% higher than pure boron carbide ceramic materials without boron nitride nanotube/nanosheet hybrid powder obtained under the same hot pressing sintering conditions (30MPa, 1950°C, 60min), respectively.
实施例6Example 6
一种氮化硼纳米管/纳米片-碳化硼陶瓷复合材料及其制备方法，具体步骤如下：A boron nitride nanotube/nanosheet-boron carbide ceramic composite material and a preparation method thereof, the specific steps are as follows:
(1)氮化硼纳米管/纳米片-碳化硼复合粉体的制备：在200ml去离子水中依次加入0.07g十六烷基三甲基氯化铵(浓度为0.35mg/ml)和19.4g平均粒径为2.0μm的碳化硼粉体，混合均匀得碳化硼悬浮液，然后向悬浮液中加入0.6g氮化硼纳米管/纳米片杂化粉体，搅拌1h、超声1.5h、冷冻干燥24h得到氮化硼纳米管/纳米片-碳化硼复合粉体。(1) Preparation of boron nitride nanotube/nanosheet-boron carbide composite powder: add 0.07g cetyltrimethylammonium chloride (concentration: 0.35mg/ml) and 19.4g Boron carbide powder with an average particle size of 2.0 μm was mixed uniformly to obtain a boron carbide suspension, and then 0.6 g of boron nitride nanotube/nanosheet hybrid powder was added to the suspension, stirred for 1 hour, ultrasonicated for 1.5 hours, and freeze-dried After 24 hours, the boron nitride nanotube/nanosheet-boron carbide composite powder was obtained.
(2)氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的制备：将步骤(1)所得氮化硼纳米管/纳米片-碳化硼复合粉体置于圆柱状石墨模具中，在热压烧结炉中施加40MPa压力、1900℃烧结30min，随炉冷却至室温，得到直径为48mm、厚度为4.5mm的氮化硼纳米管/纳米片-碳化硼陶瓷复合材料，其中氮化硼纳米管/纳米片含量为3wt％，碳化硼含量为97wt％。(2) Preparation of boron nitride nanotube/nanosheet-boron carbide ceramic composite material: place the boron nitride nanotube/nanosheet-boron carbide composite powder obtained in step (1) in a cylindrical graphite mould, heat Apply a pressure of 40 MPa in a pressure sintering furnace, sinter at 1900°C for 30 minutes, and cool to room temperature with the furnace to obtain a boron nitride nanotube/nanosheet-boron carbide ceramic composite material with a diameter of 48mm and a thickness of 4.5mm, wherein the boron nitride nanotube The nanosheet content is 3wt%, and the boron carbide content is 97wt%.
采用与实施例1相似的方法对本发明实施例制备的产物进行测试，结果表明所得氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的弯曲强度和断裂韧性分别是482MPa和4.43MPa·m 1/2，分别比相同热压烧结条件(40MPa，1900℃，30min)所得不含氮化硼纳米管/纳米片杂化粉体的纯碳化硼陶瓷材料提高33.5％和43.9％。 The product prepared in the embodiment of the present invention was tested by a method similar to that of Example 1, and the results showed that the bending strength and fracture toughness of the obtained boron nitride nanotube/nanosheet-boron carbide ceramic composite were 482MPa and 4.43MPa·m respectively /2 , which are 33.5% and 43.9% higher than pure boron carbide ceramic materials without boron nitride nanotube/nanosheet hybrid powder obtained under the same hot pressing sintering conditions (40MPa, 1900°C, 30min), respectively.
实施例7Example 7
一种氮化硼纳米管/纳米片-碳化硼陶瓷复合材料及其制备方法，具体步骤如下：A boron nitride nanotube/nanosheet-boron carbide ceramic composite material and a preparation method thereof, the specific steps are as follows:
(1)氮化硼纳米管/纳米片-碳化硼复合粉体的制备：在200ml去离子水中依次加入0.08g十六烷基三甲基溴化铵(浓度为0.4mg/ml)、19.6g平均粒径为2.0μm的碳化硼粉体，混合均匀得碳化硼悬浮液，然后向悬浮液中加入0.4g氮化硼纳米管/纳米片杂化粉体，搅拌1.5h、超声1h、冷冻干燥48h得到氮化硼纳米管/纳米片-碳化硼复合粉体。(1) Preparation of boron nitride nanotube/nanosheet-boron carbide composite powder: Add 0.08g cetyltrimethylammonium bromide (concentration: 0.4mg/ml), 19.6g Boron carbide powder with an average particle size of 2.0 μm was mixed uniformly to obtain a boron carbide suspension, and then 0.4 g of boron nitride nanotube/nanosheet hybrid powder was added to the suspension, stirred for 1.5 hours, ultrasonicated for 1 hour, and freeze-dried After 48 hours, the boron nitride nanotube/nanosheet-boron carbide composite powder was obtained.
(2)氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的制备：将步骤(1)所得氮化硼纳米管/纳米片-碳化硼复合粉体置于圆柱状石墨模具中，在热压烧结炉中施加50MPa压力、 1900℃烧结60min，随炉冷却至室温，得到直径为48mm、厚度为4.5mm的氮化硼纳米管/纳米片-碳化硼陶瓷复合材料，其中氮化硼纳米管/纳米片含量为2wt％，碳化硼含量为98wt％。(2) Preparation of boron nitride nanotube/nanosheet-boron carbide ceramic composite material: place the boron nitride nanotube/nanosheet-boron carbide composite powder obtained in step (1) in a cylindrical graphite mould, heat Apply a pressure of 50 MPa in a sintering furnace, sinter at 1900°C for 60 minutes, and cool to room temperature with the furnace to obtain a boron nitride nanotube/nanosheet-boron carbide ceramic composite material with a diameter of 48mm and a thickness of 4.5mm, wherein the boron nitride nanotube The nanosheet content is 2wt%, and the boron carbide content is 98wt%.
采用与实施例1相似的方法对本发明实施例制备的产物进行测试，结果表明所得氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的弯曲强度和断裂韧性分别是520MPa和4.72MPa·m 1/2，分别比相同热压烧结条件(50MPa，1900℃，60min)所得不含氮化硼纳米管/纳米片杂化粉体的纯碳化硼陶瓷材料提高40.5％和46.6％。 The product prepared in the embodiment of the present invention was tested by a method similar to that of Example 1, and the results showed that the bending strength and fracture toughness of the obtained boron nitride nanotube/nanosheet-boron carbide ceramic composite were 520MPa and 4.72MPa·m respectively /2 , which are 40.5% and 46.6% higher than pure boron carbide ceramic materials without boron nitride nanotube/nanosheet hybrid powder obtained under the same hot-pressing sintering conditions (50MPa, 1900°C, 60min), respectively.
实施例8Example 8
一种氮化硼纳米管/纳米片-碳化硼陶瓷复合材料及其制备方法，具体步骤如下：A boron nitride nanotube/nanosheet-boron carbide ceramic composite material and a preparation method thereof, the specific steps are as follows:
(1)氮化硼纳米管/纳米片-碳化硼复合粉体的制备：在200ml去离子水中依次加入0.09g十六烷基三甲基氯化铵(浓度为0.45mg/ml)、19.7g平均粒径为2.0μm的碳化硼粉体，混合均匀得碳化硼悬浮液，然后向悬浮液中加入0.3g氮化硼纳米管/纳米片杂化粉体，搅拌1.5h、超声2h、冷冻干燥36h得到氮化硼纳米管/纳米片-碳化硼复合粉体。(1) Preparation of boron nitride nanotube/nanosheet-boron carbide composite powder: 0.09g cetyltrimethylammonium chloride (concentration: 0.45mg/ml), 19.7g Boron carbide powder with an average particle size of 2.0 μm was mixed uniformly to obtain a boron carbide suspension, and then 0.3 g of boron nitride nanotube/nanosheet hybrid powder was added to the suspension, stirred for 1.5 hours, ultrasonicated for 2 hours, and freeze-dried 36h to obtain boron nitride nanotube/nanosheet-boron carbide composite powder.
(2)氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的制备：将步骤(1)所得氮化硼纳米管/纳米片-碳化硼复合粉体置于圆柱状石墨模具中，在热压烧结炉中施加40MPa压力、1950℃烧结45min，随炉冷却至室温，得到直径为48mm、厚度为4.5mm的氮化硼纳米管/纳米片-碳化硼陶瓷复合材料，其中氮化硼纳米管/纳米片含量为1.5wt％，碳化硼含量为98.5wt％。(2) Preparation of boron nitride nanotube/nanosheet-boron carbide ceramic composite material: place the boron nitride nanotube/nanosheet-boron carbide composite powder obtained in step (1) in a cylindrical graphite mould, heat Apply a pressure of 40 MPa in a pressure sintering furnace, sinter at 1950°C for 45 minutes, and cool to room temperature with the furnace to obtain a boron nitride nanotube/nanosheet-boron carbide ceramic composite material with a diameter of 48mm and a thickness of 4.5mm, wherein the boron nitride nanotube The nanosheet content is 1.5wt%, and the boron carbide content is 98.5wt%.
采用与实施例1相似的方法对本发明实施例制备的产物进行测试，结果表明所得氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的弯曲强度和断裂韧性分别是512MPa和4.69MPa·m 1/2，分别比相同热压烧结条件(40MPa，1950℃，45min)所得不含氮化硼纳米管/纳米片杂化粉体的纯碳化硼陶瓷材料提高34.0％和44.3％。 The product prepared by the embodiment of the present invention was tested by a method similar to that of Example 1, and the results showed that the bending strength and fracture toughness of the obtained boron nitride nanotube/nanosheet-boron carbide ceramic composite were 512MPa and 4.69MPa·m respectively /2 , which are 34.0% and 44.3% higher than pure boron carbide ceramic materials without boron nitride nanotube/nanosheet hybrid powder obtained under the same hot pressing sintering conditions (40MPa, 1950°C, 45min), respectively.
显然，上述实施例仅仅是为清楚地说明所作的实例，而并非对实施方式的限制。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而因此所引申的显而易见的变化或变动仍处于本发明创造的保护范围之内。Apparently, the above-mentioned embodiments are only examples for clear illustration, rather than limiting the implementation. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above description. It is not necessary and impossible to exhaustively list all the implementation manners here. However, the obvious changes or modifications thus extended are still within the scope of protection of the present invention.

Claims (7)

  1. 一种氮化硼纳米管/纳米片-碳化硼陶瓷复合材料的制备方法，其特征在于，具体步骤如下：A method for preparing a boron nitride nanotube/nanosheet-boron carbide ceramic composite material, characterized in that the specific steps are as follows:
    (1)在去离子水中依次加入表面活性剂和碳化硼粉体，混合均匀得碳化硼悬浮液，然后向碳化硼悬浮液中加入氮化硼纳米管/纳米片杂化粉体，搅拌、超声、冷冻干燥得到氮化硼纳米管/纳米片-碳化硼复合粉体，其中：所述表面活性剂为十六烷基三甲基溴化铵或十六烷基三甲基氯化铵；按质量百分比计，所述氮化硼纳米管/纳米片杂化粉体占所述碳化硼粉体和氮化硼纳米管/纳米片杂化粉体总质量的1～4％；所述氮化硼纳米管/纳米片杂化粉体为氮化硼纳米片上原位生长氮化硼纳米管形成的杂化结构。(1) Add surfactant and boron carbide powder in deionized water in sequence, mix uniformly to obtain boron carbide suspension, then add boron nitride nanotube/nanosheet hybrid powder to the boron carbide suspension, stir, and sonicate , freeze-drying to obtain boron nitride nanotube/nanosheet-boron carbide composite powder, wherein: the surfactant is cetyltrimethylammonium bromide or cetyltrimethylammonium chloride; In terms of mass percentage, the boron nitride nanotube/nanosheet hybrid powder accounts for 1% to 4% of the total mass of the boron carbide powder and boron nitride nanotube/nanosheet hybrid powder; The boron nanotube/nanosheet hybrid powder is a hybrid structure formed by in-situ growth of boron nitride nanotubes on boron nitride nanosheets.
    (2)将步骤(1)所得氮化硼纳米管/纳米片-碳化硼复合粉体置于氩气气氛下热压烧结，然后随炉冷却至室温，得到氮化硼纳米管/纳米片-碳化硼陶瓷复合材料。(2) The boron nitride nanotube/nanosheet-boron carbide composite powder obtained in step (1) is placed in an argon atmosphere for hot pressing and sintering, and then cooled to room temperature with the furnace to obtain boron nitride nanotube/nanosheet- Boron carbide ceramic composites.
  2. 根据权利要求1所述的制备方法，其特征在于，所述步骤(1)中，碳化硼粉体和表面活性剂的质量比为(190～400)：1。The preparation method according to claim 1, characterized in that, in the step (1), the mass ratio of the boron carbide powder to the surfactant is (190-400):1.
  3. 根据权利要求1所述的制备方法，其特征在于，所述步骤(1)中，碳化硼粉体的平均粒径为1～10μm。The preparation method according to claim 1, characterized in that, in the step (1), the average particle size of the boron carbide powder is 1-10 μm.
  4. 根据权利要求1所述的制备方法，其特征在于，所述步骤(1)中，表面活性剂在去离子水中的质量浓度为0.25～0.5mg/mL。The preparation method according to claim 1, characterized in that, in the step (1), the mass concentration of the surfactant in the deionized water is 0.25-0.5 mg/mL.
  5. 根据权利要求1所述的制备方法，其特征在于，所述步骤(1)中，搅拌时间为1～2h；超声时间为1～2h；冷冻干燥时间为24～48h。The preparation method according to claim 1, characterized in that, in the step (1), the stirring time is 1-2 hours; the ultrasonic time is 1-2 hours; and the freeze-drying time is 24-48 hours.
  6. 根据权利要求1所述的制备方法，其特征在于，所述步骤(2)中，热压烧结温度为1850～1950℃，烧结压力为30～50MPa，烧结时间为30～60min。The preparation method according to claim 1, characterized in that, in the step (2), the hot pressing sintering temperature is 1850-1950° C., the sintering pressure is 30-50 MPa, and the sintering time is 30-60 min.
  7. 一种权利要求1-6任一项所述的制备方法制备得到的氮化硼纳米管/纳米片-碳化硼陶瓷复合材料。A boron nitride nanotube/nanosheet-boron carbide ceramic composite material prepared by the preparation method described in any one of claims 1-6.
PCT/CN2021/117936 2021-08-30 2021-09-13 Boron nitride nanotube/nanosheet-boron carbide ceramic composite material and preparation method therefor WO2023029080A1 (en)

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