Multi-component transition metal boride and SiC combined composite material and preparation method thereof

Abstract

The invention discloses a multi-component transition metal boride and SiC combined composite material and a preparation method thereof. The sintering powder is prepared from raw materials, so that the sintering temperature is reduced, and sintering is promoted. The composite material is prepared from the following raw materials: TiBx powder, ZrB2 powder, HfB2 powder, VB2 powder, NbB2 powder, TaB2 powder, CrB2 powder, MoB2 powder, WB2 powder and SiC powder. During preparation, the raw materials are mixed in a planetary ball mill according to different proportions; after uniformly mixing, filling a hard alloy mold with the mixture for pre-pressing; and then, carrying out spark plasma sintering (SPS) on the pre-pressed sample. And then cooling and releasing pressure to prepare the composite material of the multi-component transition metal boride combined with SiC. According to the preparation method, sintering is promoted through vacancies in a system, the hardness and fracture toughness of the composite material formed by combining the multi-component transition metal boride and SiC are improved, the process is simplified through the one-step powder preparation mode, and the preparation period is shortened.

Description

Technical Field

[0001] The invention belongs to the technical field of composite materials, and relates to a composite material of multi-component transition metal boride combined with SiC and a preparation method thereof. Background Art

[0002] Silicon carbide ceramics have excellent properties such as high temperature strength, strong oxidation resistance, good wear resistance, good thermal stability, high thermal conductivity, high hardness, and resistance to thermal shock and chemical corrosion [Jiang Dongliang, Kuang Gao, Pan Zhensu, et al. Oxidation behavior and high temperature strength of hot-pressed silicon carbide with different additives [J]. Journal of Inorganic Materials, 1988(1):49-55]. Therefore, silicon carbide ceramics have been widely used as various corrosion-resistant containers and pipelines in the petrochemical industry; they have been successfully used as various bearings, cutting tools and mechanical sealing components in the machinery industry; and they are also considered to be the most promising candidate materials for the future manufacture of gas turbines, rocket nozzles and engines in the aerospace and automotive industries [Wang Ming, Dong Zhiguo, Zhang Xiaoyue, et al. Application of continuous fiber reinforced silicon carbide ceramic matrix composites in aeroengines [J]. Aviation Manufacturing Technology, 2014,450(6):10-13].

[0003] Zhang Yong et al. used silicon carbide powder with Al2O3 and Y2O3 sintering aids as raw materials, and quickly prepared silicon carbide ceramics through spark plasma sintering (SPS) technology, analyzed the material densification process, and focused on studying the influence of sintering process parameters on material density and mechanical properties. The results show that when the sintering temperature and pressure of the SPS process parameters are 1600 ℃ and 50 MPa, respectively, after 5 minutes of sintering, the density of silicon carbide ceramics can reach 99.1%, the hardness is HV2550, and the fracture toughness is 8.34 MPa.m 1 / 2 , the bending strength reaches 684 MPa. However, this traditional sintering aid has a significant negative impact on the high-temperature oxidation resistance and high-temperature mechanical properties of the material [Zhang Yong, He Xinbo, Qu Xuanhui, et al. Preparation of dense silicon carbide ceramics by spark plasma sintering process [J]. Mechanical Engineering Materials, 2008, 32(3):45-47].

[0004] TiB2, ZrB2, HfB2, VB2, NbB2, TaB2, CrB2, MoB2 and WB2 all have layered hexagonal crystal structures, containing alternating two-dimensional boron networks and two-dimensional metal cation layers, and their melting points are all above 2000 °C. Similar to carbides, borides also have the advantages of high hardness, high melting point and good wear resistance due to the presence of special covalent bonds, ionic bonds and metal bonds, and are widely used in high-temperature structural ceramics and other fields [Gong Yubo, Zhao Shixin, Wei Xuguang, et al. Research Progress of Multi-element Boride Ceramics [J]. Journal of Ceramics, 2022, 43(04): 567-578.].

[0005] Shi Haofan et al. prepared ZrB2-SiC-G ultra-high temperature ceramic bulk material by hot pressing sintering at 1900 °C. The fracture toughness of the ceramic material was tested by three-point bending test using the single-edge notched beam method, and the fracture toughness of the material was 4.2MPa / m 1 / 2 . [Shi Haofan, Zhang Yuxia, Shen Gucheng, Wang Lingling, Kong Dewen. Research on fracture behavior of ZrB2-SiC-G ceramic composites [J]. Construction Technology, 2018, 47(S2): 24-26.]. Li Bin et al. prepared TiB2-ZrB2-SiC composites by spark plasma sintering. The results showed that the composite powder had a small particle size after two ball millings and was evenly distributed without agglomeration. (TixZry)B2 solid solution phase was generated in the sintered material. When the volume fraction of zirconium boride was 30%, the generated solid solution played a good role in grain refinement and interface fusion in the composite material, making the flexural strength and fracture toughness of TZS30 composite material higher than that of TZS0 composite material. However, its fracture toughness is still less than 4 MPa / m 1 / 2 , cannot meet more industrial use needs [Li Bin, You Huiyuan, Yang Haijun, Chang Jiadong, Wang Chuanbin. Microstructure and mechanical properties of TiB2 / ZrB2 / SiC composite functional materials [J]. Powder Metallurgy Materials Science and Engineering, 2014, 19(05): 818-824.].

[0006] In order to improve the intrinsic brittleness of silicon carbide and transition metal borides, the present invention adopts mechanical alloying to mix TiBx powder, ZrB2 powder, HfB2 powder, VB2 powder, NbB2 powder, TaB2 powder, CrB2 powder, MoB2 powder, WB2 powder and SiC powder raw materials, adopts SPS sintering technology to prepare a multi-component transition metal boride combined with SiC composite material, and uses TiBx powder to modify the powder, so as to utilize the vacancies in the system to reduce the sintering temperature and promote sintering, thereby improving the fracture toughness, hardness, corrosion resistance and other properties of the composite material, and at the same time simplifies the process and reduces the production cost of the composite material. Summary of the invention

[0007] The present invention adopts a one-step method to prepare a composite material of a multi-component transition metal boride combined with SiC, simplifies the preparation process, and based on the existence of vacancies in the system, can increase the configuration entropy of the system, thereby reducing the sintering temperature and promoting sintering. The novel composite material of a multi-component transition metal boride combined with SiC is prepared by TiBx powder, ZrB2 powder, HfB2 powder, VB2 powder, NbB2 powder, TaB2 powder, CrB2 powder, MoB2 powder, WB2 powder, and SiC powder raw materials. Among them, the TiBx powder is prepared by mechanical alloying, and the particle size is about 100 nm. The purity of TiB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of ZrB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of VB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of NbB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of HfB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of TaB2 powder is 99.5%, and the particle size is 3 μm; the purity of CrB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of MoB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of WB2 powder is 99.5%, and the particle size is 3μm; the purity of SiC powder is 99.5%, and the particle size is 1 μm.

[0008] The present invention also discloses a method for preparing a composite material of a multi-component transition metal boride combined with SiC, comprising the following steps: S1. After adding dispersant to the raw material powders of each preset mass fraction, the powders were placed in a WC carbide ball mill for ball milling. The ball-to-material mass ratio was 20:1, the rotation speed was 450 r / min, the ball milling was performed for 20 hours, each rotation was 30 minutes, and the machine was stopped for 30 minutes for heat dissipation to obtain a mixed powder; S2. Pre-press the mixed powder prepared in step S1 at a pre-pressing pressure of 500 MPa for 60 s; then, subject the pre-pressed sample to spark plasma sintering (SPS) at a sintering pressure of 40 MPa, a sintering temperature of 1900 °C, and a holding time of 10 min; then, cool and release the pressure to obtain a composite material of multi-component transition metal boride combined with SiC.

[0009] Furthermore: the dispersant is industrial ethanol with a purity of ≥99.7%, and 0.2-0.5 mL of the dispersant is added to every 10 g of powder.

[0010] Further: the specific sintering process and parameters in step S2 are: first, slowly apply pressure to the sample to 40MPa; then, heat from room temperature to 600℃ at a heating rate of 100℃ / min, and keep at 600℃ for 5 minutes; then heat from 600℃ to 1900℃ at a heating rate of 100℃ / min, and keep at the terminal temperature for 10 minutes; cool with the furnace to obtain a blank; perform surface grinding and deburring on the prepared blank to obtain a new multi-component transition metal boride combined with SiC composite material The main purpose of the present invention is to provide a high-toughness multi-component transition metal boride combined with SiC composite material powder and sintered body material, which can obtain a composite material with good density and excellent performance under a simpler process and a lower sintering temperature. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0012] Figure 1 is an XRD pattern of the composite material of multi-component transition metal boride and SiC in Example 1; Figure 2 This is a SEM image of the composite material of multi-component transition metal boride and SiC in Example 1. DETAILED DESCRIPTION

[0013] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0014] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is by no means intended to limit the present invention and its application or use. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0015] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprising" and / or "including" are used in this specification, it indicates the presence of features, steps, operations, devices, components and / or combinations thereof.

[0016] Unless otherwise specifically stated, the relative arrangement, numerical expressions and numerical values ​​of the parts and steps described in these embodiments do not limit the scope of the present invention. At the same time, it should be clear that, for ease of description, the sizes of the various parts shown in the drawings are not drawn according to the actual proportional relationship. The technology, methods and equipment known to ordinary technicians in the relevant field may not be discussed in detail, but in appropriate cases, the technology, methods and equipment should be regarded as a part of the authorization specification. In all examples shown and discussed here, any specific value should be interpreted as being merely exemplary, rather than as a limitation. Therefore, other examples of exemplary embodiments may have different values. It should be noted that similar reference numerals and letters represent similar items in the following drawings, so once a certain item is defined in an accompanying drawing, it does not need to be further discussed in subsequent drawings.

[0017] The detection equipment described in the present invention are all instruments used in conventional detection means, such as X-ray diffractometer, hardness tester, scanning electron microscope, etc.

[0018] The present invention adopts a one-step method to prepare a composite material of a multi-component transition metal boride combined with SiC, simplifies the preparation process, and based on the existence of vacancies in the system, can increase the configuration entropy of the system, thereby reducing the sintering temperature and promoting sintering. The novel composite material of a multi-component transition metal boride combined with SiC is prepared by TiBx powder, ZrB2 powder, HfB2 powder, VB2 powder, NbB2 powder, TaB2 powder, CrB2 powder, MoB2 powder, WB2 powder, and SiC powder raw materials. Among them, the TiBx powder is prepared by mechanical alloying, and the particle size is about 100 nm. The purity of TiB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of ZrB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of VB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of NbB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of HfB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of TaB2 powder is 99.5%, and the particle size is 3 μm; the purity of CrB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of MoB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of WB2 powder is 99.5%, and the particle size is 3μm; the purity of SiC powder is 99.5%, and the particle size is 1 μm.

[0019] Exemplary embodiments, features and performance aspects of the present invention will be described in detail below.

[0020] The raw material powders of each preset mass fraction composition were added with dispersant and then placed in a WC carbide ball mill for ball milling. The ball-to-material mass ratio was 20:1, the rotation speed was 450 r / min, the ball milling was performed for 20 hours, each rotation was 60 minutes, and the machine was stopped for 30 minutes for heat dissipation to obtain a mixed powder. The prepared mixed powder was pre-pressed with a pre-pressing pressure of 500 MPa and a pre-pressing time of 60 seconds. Then, the pre-pressed sample was subjected to SPS sintering with a sintering pressure of 40 MPa, a sintering temperature of 1700-1900 °C, and a holding time of 10 minutes. Then, the temperature was lowered and the pressure was released to obtain a sintered body of a composite material of multi-component transition metal boride combined with SiC.

[0021] Example 1 The raw material formula is weighed according to the following mass percentages:

[0022] S1. Add dispersant to the raw material powder composed of the mass fraction in Table 1 and put it into a WC hard alloy ball mill for ball milling. The ball-to-material mass ratio is 10:1, the speed is 400 r / min, and the ball milling is carried out for 20 h. The forward and reverse rotations are alternately operated for 60 min each time, and the machine is stopped for 30 min for heat dissipation to obtain a mixed powder. S2. Pre-press the mixed powder prepared in step S1, the pre-pressing pressure is 500 MPa, and the pre-pressing time is 60 s. Then, the pre-pressed sample is subjected to SPS sintering, the sintering pressure is 40 MPa, and the heating system is as follows: first, the temperature is increased from room temperature to 600 ℃ at a heating rate of 100 ℃ / min, and kept at 600 ℃ for 5 min; then the temperature is increased from 600 ℃ to 1900 ℃ at a heating rate of 100 ℃ / min, and kept at 10 min. Cool with the furnace to obtain a blank. The prepared blank is subjected to surface grinding and deburring treatment to obtain a composite material of multi-component transition metal boride combined with SiC. After the sintered multi-component transition metal boride combined with SiC composite material sample is ground and polished, the microstructure and performance are tested and analyzed. The results show that the density is 97.4%, the hardness is 19.25 GPa, and the fracture toughness is 8.05 MPa·m 1 / 2 . Figure 1 is an XRD pattern of the composite material of multi-component transition metal boride and SiC in Example 1; Figure 2 The SEM image of the composite material of multi-component transition metal boride combined with SiC in Example 1 The results of the above examples are analyzed, and it is found that the composite material with a raw material sintering temperature of 1900° C. has the best comprehensive performance. The present invention can prepare a composite material with excellent performance through a simple preparation method.

[0023] The present invention is described above by way of example, but the present invention is not limited to the details of the above embodiments, and the present invention can be implemented in other specific forms without departing from the basic features of the present invention. Any changes or modifications made based on the present invention belong to the scope of protection claimed by the present invention.

Claims

1. A composite material of multi-component transition metal boride combined with SiC, characterized in that: The multi-component transition metal boride combined with SiC composite material is prepared using TiBx powder, ZrB2 powder, HfB2 powder, VB2 powder, NbB2 powder, TaB2 powder, CrB2 powder, MoB2 powder, WB2 powder, and SiC powder as raw materials.

2. The composite material of multi-component transition metal boride combined with SiC according to claim 1, characterized in that: Among them, TiBx powder is made by mechanical alloying and has a particle size of about 100 nm; the purity of TiB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of ZrB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of VB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of NbB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of HfB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of TaB2 powder is 99.5%, and the particle size is 3 μm; the purity of CrB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of MoB2 powder is 99.5%, and the particle size is 1-3 μm; the purity of WB2 powder is 99.5%, and the particle size is 3 μm; the purity of SiC powder is 99.5%, and the particle size is 1 μm.

3. A method for preparing a composite material of a multi-component transition metal boride combined with SiC as claimed in any one of claims 1 to 2, characterized in that: The following steps are involved: S1. After adding dispersant to the raw material powders of each preset mass fraction, the powders were placed in a WC carbide ball mill for ball milling. The ball-to-material mass ratio was 20:1, the rotation speed was 450 r / min, the ball milling was performed for 20 hours, each rotation was 30 minutes, and the machine was stopped for 30 minutes for heat dissipation to obtain a mixed powder; S2. Pre-press the mixed powder prepared in step S1 at a pre-pressing pressure of 500 MPa for 60 s; then, subject the pre-pressed sample to spark plasma sintering (SPS) at a sintering pressure of 40 MPa, a sintering temperature of 1900 °C, and a holding time of 10 min; then, cool and release the pressure to obtain a composite material of multi-component transition metal boride combined with SiC.

4. The method for preparing the composite material of multi-component transition metal boride and SiC according to claim 3, characterized in that: The dispersant is industrial ethanol with a purity of ≥99.7%, and 0.2-0.5 mL of the dispersant is added to every 10 g of powder.

5. The method for preparing the composite material of multi-component transition metal boride and SiC according to claim 3, characterized in that: The specific sintering process and parameters in step S2 are as follows: first, slowly apply pressure to the sample to 40 MPa; then, heat the sample from room temperature to 600 °C at a heating rate of 100 °C / min, and keep the sample at 600 °C for 5 min; then heat the sample from 600 °C to 1900 °C at a heating rate of 100 °C / min, and keep the sample at the terminal temperature for 10 min; cool the sample in the furnace to obtain a blank; perform surface grinding and deburring on the prepared blank to obtain a novel multi-component transition metal boride-combined SiC composite material.

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