CN113636842B - High-entropy diboride-boron carbide complex phase ceramic, preparation method and application thereof - Google Patents
High-entropy diboride-boron carbide complex phase ceramic, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of complex phase ceramics, in particular to high-entropy diboride-boron carbide complex phase ceramics, a preparation method and application thereof; the complex phase ceramic comprises the following mixture of molar components: 5 to 9 of transition metal carbides (titanium carbide, zirconium carbide, hafnium carbide, niobium carbide, tantalum carbide, vanadium carbide, chromium carbide, molybdenum carbide and tungsten carbide), 0 to 1 part of each of which is mixed with 32 to 60 parts of boron powder. The transition metal carbide is powder with purity higher than 98% and granularity of 0.5-3 micron. The purity of the boron powder is more than 95 percent, and the granularity is 0.5-3 mu m. The Vickers hardness Hv5 of the high-entropy diboride-boron carbide complex phase ceramic is more than or equal to 20GPa, the bending strength is more than or equal to 420MPa, and the fracture toughness is more than or equal to 5.0MPa m 1/2 . The invention realizes the rapid in-situ self-generation preparation of the lightweight, high-strength and high-entropy diboride-boron carbide complex phase ceramic, and has low sintering temperature, thereby having wide application prospect in the fields of ultra-high temperature materials, superhard materials, ceramic cutters and the like.
Description
Technical Field
The invention relates to the technical field of complex phase ceramics, in particular to high-entropy diboride-boron carbide complex phase ceramics, a preparation method and application thereof.
Background
Ultra-high temperature materials generally refer to a class of materials that have a service temperature in excess of 2000 ℃. Typically comprising refractory metals, carbon materials and ultra high temperature ceramics (borides, carbides and nitrides of transition metals).
The high-entropy boride, carbide and nitride have high strength and high hardness, and have high entropy effect which is not possessed by the traditional ceramic material, so that excellent oxidation resistance and corrosion resistance are obtained. The method has important value for the development and application of novel ultra-high temperature heat-proof materials, wear-resistant and oxidation-resistant high-speed cutting tools, drill bits and other mechanical parts.
Although the high-entropy boride ceramic has excellent performance, the defects of difficult sintering, large brittleness, poor service reliability and the like still exist, and the defects are mainly attributed to the following reasons: first, since metal boride has a high melting point (TiB) 2 Has a melting point of 2980 ℃ and ZrB 2 Melting point of 3040 ℃ and TaB 2 Melting point 3100 ℃) of titanium, high covalent bond coordination characteristics and low self-diffusion coefficient, making it difficult to obtain dense materials with traditional sintering processes; secondly, because of the characteristic of difficult sintering, higher sintering temperature is needed, but high-temperature sintering inevitably causes grain growth and even abnormal growth while obtaining high density, thus reducing the strength of the ceramic; thirdly, due to the high-temperature sintering characteristics of the ceramic, the mature methods of fiber toughening, phase change toughening and the like are difficult to be applied to the structure design, so that the brittleness and the reliability are poor.
At present, the high-entropy diboride ceramic composite material is generally prepared by adopting a method of combining boron-carbon thermal reduction powder preparation with high-temperature sintering. The single-phase diboride high-entropy ceramic and the complex-phase diboride high-entropy ceramic prepared by the method have the defects of large grain size, easy introduction of oxygen pollution to hinder sintering densification, and limited promotion of high-entropy effect and relative material performance enhancement.
In view of the above-mentioned drawbacks, the present inventors have finally obtained the present invention through long-term research and practice.
Disclosure of Invention
The invention aims to solve the problems that the high-entropy diboride ceramic composite material prepared by the existing high-temperature sintering method has larger grain size and is easy to introduce oxygen pollution, so that the improvement of high-entropy effect and relative material performance enhancement is limited, and provides a high-entropy diboride-boron carbide composite ceramic, a preparation method and application thereof.
In order to achieve the aim, the invention provides a high-entropy diboride-boron carbide complex phase ceramic which comprises the following components: transition metal carbide powder and boron powder, wherein the transition metal carbide is any 5-9 of titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tantalum carbide, chromium carbide, molybdenum carbide and tungsten carbide.
The molar parts of the components are respectively as follows: 1-5 parts of each transition metal carbide powder, and the boron powder is 5-8 times of the total parts of the transition metal carbide.
The purity of the transition metal carbide powder is more than 98 percent, and the granularity is 0.5-3 mu m.
The purity of the boron powder is more than 95 percent, and the granularity is 0.5-3 mu m.
The invention also discloses a preparation method of the high-entropy diboride-boron carbide complex phase ceramic, which comprises the following steps:
s1: putting transition metal carbide powder, boron powder and absolute ethyl alcohol into a ball milling tank, adding zirconia grinding balls, and mixing for 24 hours on a ball milling mixer at the speed of 100 r/min;
s2: evaporating the slurry mixed in the step S1 to dryness, and then drying for 24h at 80 ℃;
s3: grinding the dried mixed powder in the step S2 in a mortar, and sieving the ground mixed powder by a standard sieve of 200 meshes;
s4: putting the mixed powder sieved in the step S3 into a graphite die, heating to 1900-2200 ℃ in a discharge plasma sintering furnace at the speed of 100-200 ℃/min, simultaneously pressurizing at 30-50 MPa, keeping for 1-20 min, and then cooling and decompressing;
s5: and demolding the complex-phase ceramic block from the graphite mold and taking out.
The invention also discloses application of the high-entropy diboride-boron carbide complex phase ceramic in the fields of ultra-high temperature materials, superhard materials and ceramic cutters.
Compared with the prior art, the invention has the beneficial effects that:
1. the in-situ reaction self-generation process adopted by the invention realizes the sintering densification of the complex phase ceramic while generating the high-entropy diboride and the boron carbide in situ. The sintering densification temperature can be reduced, the oxygen pollution caused by powder mixing can be reduced, and the in-situ self-generated high-entropy diboride and boron carbide have fine (about 1 micron, shown in figure 2) grains and good compatibility;
2. the high-entropy diboride-boron carbide complex phase ceramic prepared by the method has lower density, higher hardness, strength and fracture toughness than single-phase high-entropy diboride ceramic with the same components;
3. the Vickers hardness Hv5 of the prepared complex phase ceramic is more than or equal to 20GPa, the bending strength is more than or equal to 420MPa, and the fracture toughness is more than or equal to 5.0MPa m 1/2 . Compared with single-phase high-entropy diboride ceramic with the same components (Hv 5=19.44 +/-0.50 GPa, fracture toughness =2.83 +/-0.15 MPa m 1/2 ) The high-entropy diboride-boron carbide complex phase ceramic prepared by the invention has the advantages of light weight, high strength and toughness;
4. the invention realizes the in-situ reaction rapid preparation of the high-performance high-entropy diboride-boron carbide complex phase ceramic, and has low sintering temperature and obvious grain refinement effect, thereby having wide application prospect in the fields of ultra-high temperature materials, superhard materials, ceramic cutters and the like.
Drawings
FIG. 1 is an X-ray diffraction pattern of a high-entropy diboride-boron carbide complex phase ceramic in examples 1, 2 and 3;
FIG. 2 is a scanning electron micrograph of a high-entropy diboride-boron carbide complex phase ceramic and the energy spectrum results of the corresponding region in example 2;
FIG. 3 is a scanning electron micrograph of the indentation crack propagation path of the high-entropy diboride-boron carbide complex phase ceramic in example 1.
Detailed Description
The above and further features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
Example 1
The molar parts of the raw materials are as follows: 1 part of titanium carbide, 1 part of zirconium carbide, 1 part of hafnium carbide, 1 part of niobium carbide, 1 part of tantalum carbide and 32 parts of boron powder. The preparation process comprises the following steps: (1) Putting carbide powder and boron powder into a polyethylene bottle, adding zirconia grinding balls and absolute ethyl alcohol, and carrying out ball milling and mixing for 24 hours; (2) Evaporating the mixed slurry on a rotary evaporator to dryness, and then putting the dried slurry into an air-blowing drying oven to dry for 24 hours at the temperature of 80 ℃; (3) sieving the dried powder through a standard sieve with 200 meshes; (4) Loading the sieved powder into a graphite die, heating to 2000 ℃ at a speed of 100 ℃/min in a discharge plasma sintering furnace, simultaneously pressurizing to 40MPa, carrying out vacuum sintering for 6 minutes, and then cooling and decompressing; and (5) demolding, and taking out the sintered ceramic sample.
The X-ray diffraction pattern of the obtained in-situ authigenic high-entropy diboride-boron carbide complex phase ceramic is shown in figure 1a, wherein the main phases comprise high-entropy diboride and boron carbide. The density of the complex phase ceramic is 4.9g/cm 3 Vickers hardness (Hv 5) of 20.65 +/-1.83 GPa, bending strength of 422 +/-48 MPa and fracture toughness of 5.48 +/-0.50 MPa m 1/2 . As shown in figure 3, submicron-grade high-entropy diboride and boron carbide grains in the material have the effects of deflecting and branching cracks, and are beneficial to improving the fracture toughness. As a comparison, the single-phase diboride high-entropy ceramic material prepared by adopting boron-carbon thermal reduction powder preparation and combining with an SPS sintering method has the density of 8.2g/cm 3 The Vickers hardness (Hv 5) is 19.44 +/-0.50 GPa, and the fracture toughness is 2.83 +/-0.15 MPa m 1/2 . The data show that the in-situ autogenous high-entropy diboride-boron carbide complex phase ceramic prepared by the invention has lower density, higher Vickers hardness, bending strength and fracture toughness.
Example 2
The raw materials have the following mole parts: 1 part of titanium carbide, 1 part of zirconium carbide, 1 part of hafnium carbide, 1 part of niobium carbide, 1 part of tantalum carbide, 1 part of vanadium carbide and 38.5 parts of boron powder. The preparation process is the same as in example 1 and is not repeated herein.
The X-ray diffraction pattern of the obtained in-situ authigenic high-entropy diboride-boron carbide complex phase ceramic is shown in figure 1b, and the main phases comprise high-entropy diboride and boron carbide. The grain size of high-entropy diboride and boron carbide in the composite ceramic is about 1 μm, and all metal elements in the high-entropy phase are uniformly distributed (attached)Fig. 2). The Vickers hardness (Hv 5) of the complex phase ceramic is 21.3 +/-0.8 GPa, the bending strength is 478 +/-49 MPa, and the fracture toughness is 5.80 +/-0.55 MPa m 1/2 。
Example 3
The weight portions of the raw materials are as follows: 1 part of titanium carbide, 1 part of zirconium carbide, 1 part of hafnium carbide, 1 part of niobium carbide, 1 part of tantalum carbide, 0.25 part of tungsten carbide and 33.6 parts of boron powder. The preparation process is the same as in example 1 and is not repeated herein.
The X-ray diffraction pattern of the obtained in-situ autogenous high-entropy diboride-boron carbide complex phase ceramic is shown in figure 1c, and the main phases comprise the high-entropy diboride and the boron carbide. The Vickers hardness (Hv 5) of the complex phase ceramic is 20.9 +/-0.5 GPa, the bending strength is 561 +/-72 MPa, and the fracture toughness is 4.45 +/-0.61 MPa m 1/2 。
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. The high-entropy diboride-boron carbide complex phase ceramic is characterized by comprising the following components: the transition metal carbide powder comprises transition metal carbide powder and boron powder, wherein the transition metal carbide is any 5-9 of titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tantalum carbide, chromium carbide, molybdenum carbide and tungsten carbide, and the transition metal carbide comprises the following components in parts by mole: 1-5 parts of each transition metal carbide powder, and 5-8 times of the boron powder as the total part of the transition metal carbide.
2. The high-entropy diboride-boron carbide composite ceramic according to claim 1, wherein the transition metal carbide powder has a purity of > 98% and a particle size of 0.5-3 μm.
3. The high-entropy diboride-boron carbide complex phase ceramic according to claim 1, wherein the boron powder has a purity of > 95% and a particle size of 0.5-3 μm.
4. A method for preparing a high-entropy diboride-boron carbide complex phase ceramic as defined in any one of claims 1 to 3, comprising the steps of:
s1: putting transition metal carbide powder, boron powder and absolute ethyl alcohol into a ball milling tank, adding zirconia grinding balls, and mixing for 24 hours on a ball milling mixer at the speed of 100 r/min;
s2: evaporating the slurry mixed in the step S1 to dryness, and then drying for 24 hours at 80 ℃;
s3: grinding the dried mixed powder in the step S2 in a mortar, and sieving the ground mixed powder by a standard sieve of 200 meshes;
s4: putting the mixed powder sieved in the step S3 into a graphite die, heating to 1900-2200 ℃ in a discharge plasma sintering furnace at the speed of 100-200 ℃/min, pressurizing at 30-50 MPa at the same time, keeping for 1-20 min, and cooling and decompressing;
s5: and demolding and taking out the complex-phase ceramic block from the graphite mold.
5. Use of the high-entropy diboride-boron carbide complex phase ceramic according to any one of claims 1 to 3 in the fields of ultra-high temperature materials, superhard materials and ceramic cutters.
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| CN114262229B (en) * | 2022-01-04 | 2022-09-16 | 哈尔滨工业大学 | Preparation method and application of high-strength and high-toughness diboride-carbide complex-phase high-entropy ceramic |
| CN114736022B (en) * | 2022-04-29 | 2023-04-18 | 武汉理工大学 | High-density, high-strength and ultrahigh-hardness boron carbide/high-entropy diboride complex phase ceramic and preparation method thereof |
| CN115141967B (en) * | 2022-06-13 | 2023-11-14 | 哈尔滨工业大学（深圳） | High-entropy alloy composite material and preparation method and application thereof |
| CN115872749B (en) * | 2022-11-30 | 2023-12-19 | 武汉科技大学 | High-entropy boride enhancement B 4 C composite ceramic and in-situ synthesis method thereof |
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