WO2020077770A1 - Céramique à multiples éléments de haute entropie, son procédé de préparation, et son utilisation - Google Patents

Céramique à multiples éléments de haute entropie, son procédé de préparation, et son utilisation Download PDF

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WO2020077770A1
WO2020077770A1 PCT/CN2018/120033 CN2018120033W WO2020077770A1 WO 2020077770 A1 WO2020077770 A1 WO 2020077770A1 CN 2018120033 W CN2018120033 W CN 2018120033W WO 2020077770 A1 WO2020077770 A1 WO 2020077770A1
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ceramic
powder
oxide
solid melt
melt powder
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郭伟明
张岩
牛文彬
张威
林华泰
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广东工业大学
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Definitions

  • the invention belongs to the technical field of surface functional thin film materials, and more specifically, relates to a ceramic with multi-element high entropy and a preparation method and application thereof.
  • High-entropy ceramics have five or more kinds of components. If they become solid-phase single-phase solid-melt ceramics, they can easily obtain solid solution phases and nanostructures with high thermal stability due to their high entropy values. High-entropy ceramics have different characteristics, and their performance is superior to traditional ceramic materials. Multi-component high-entropy ceramics is a new ceramic world that can be synthesized, processed, analyzed, and applied. It has high academic research value and great industrial development potential.
  • high-entropy ceramics also have high strength, hardness, excellent wear resistance, excellent high temperature resistance, good structural stability, and good corrosion resistance and oxidation resistance.
  • Their preparation uses commercially available boride powders, and ceramic materials are sintered after high-energy ball milling. However, only a small number of reports have successfully prepared single-phase high-entropy ceramics. Therefore, there are still many places to be studied about these materials and their characteristics.
  • the ceramic has a uniform solid solution phase, stable component, high entropy ceramic with excellent mechanical properties and oxidation resistance.
  • Another object of the present invention is to provide a preparation method of the above-mentioned multi-element high-entropy ceramic.
  • Still another object of the present invention is to provide the above-mentioned applications with multi-element high-entropy ceramics.
  • a ceramic with multi-element high entropy is based on Me1 oxide, Me2 oxide, Me3 oxide, Me4 oxide, Me5 oxide and amorphous boron powder.
  • the mixed powder is mixed, and the green body obtained by molding is placed in a graphite crucible.
  • x 0.2
  • y 0.2
  • z 0.2
  • n 0.2
  • m 0.2.
  • the relative density of the ceramic is> 95%
  • the hardness is 25 to 35 GPa
  • the fracture toughness is 2 to 8 MPa ⁇ m 1/2
  • the grain size is 0.1 to 1.1 ⁇ m
  • the weight of the ceramic after heat treatment at 1000 to 1500 ° C The rate of change is 0.3 to 1%.
  • the purity of the solid melt powder (Me1xMe2yMe3zMe4nMe5m) B 2 is 99.0-99.9wt%
  • the particle size of the solid melt powder is 0.1-1 ⁇ m
  • the oxygen content of the solid melt powder is 0.1 -0.5wt%
  • the carbon content of the solid melt powder is 0.1-0.5wt%.
  • Me1, Me2, Me3, Me4 and Me5 in the solid melt powder (Me1xMe2yMe3zMe4nMe5m) B 2 are Hf, Zr, Ti, Nb, Ta, Mo or Cr.
  • the solvent is ethanol, propanol, methanol or acetone.
  • the protective atmosphere is N 2 or Ar.
  • the heating rate to 800 to 1200 ° C and the heating rate to 1400 to 1600 ° C are both 5 to 20 ° C / min, the time for holding I and II are 0.5 to 2h; the time for calcining It is 1-30 min, the calcination pressure is 10-100 MPa, and the rate of temperature increase when the temperature is raised to 1800-2200 ° C is 100-400 ° C / min.
  • the preparation method of the ceramic with multiple high entropy includes the following specific steps:
  • the invention has a multi-element high-entropy ceramic, which uses single-phase solid-melt powder (Me1xMe2yMe3zMe4nMe5m) B 2 as a raw material, and solid solution between pentad metals of Me1, Me2, Me3, Me4, and Me5. After spark plasma sintering, due to its rapid cooling rate, it is difficult to have a solid solution phase.
  • the ceramic obtained is still (Me1 2 Me2 2 Me3 2 Me4 2 Me5 2 ) B 2 single-phase multi-element high-entropy ceramic body, composition Uniform, stable composition, excellent performance, and a powder has the properties of multi-metal.
  • the present invention has the following beneficial effects:
  • the present invention adopts the ultrafine high-entropy ceramic powder self-synthesized by the solid-phase method, and prepares multiple high-entropy ceramic materials by spark plasma sintering. Studies have shown that the high-entropy ceramic powder synthesized by the solid-phase method has fine grains and uniform components . Raw material powder with small grain size and uniform composition, and the high-entropy ceramic material sintered has excellent performance.
  • the reaction raw material is a single-phase solid melt powder.
  • the method achieves the chemical uniformity of the raw material components. This also facilitates the formation of a uniform solid melt phase of its sintered material, and also saves energy and costs.
  • the high-entropy ceramic material prepared by the method of the present invention because the raw material is a solid melt powder, forming a solid melt can promote atom diffusion, can achieve compact sintering at low temperature, improve sintering performance, and improve material performance.
  • the method of the present invention uses SPS to achieve rapid preparation of high-entropy ceramic materials, greatly reducing the time for grain growth, obtaining fine-grain ceramics, low cost of raw material powder, and raw material powder relative to commercially purchased boride
  • the powder is fine, it diffuses faster during the sintering process, and it is easier to sinter a single-phase high-entropy ceramic material, which will make the structure of the high-entropy ceramic material smaller and improve the performance of the material.
  • Fig. 1 is an XRD pattern of (Hf 0.2 Mo 0.2 Ta 0.2 Nb 0.2 Ti 0.2 ) B 2 high-entropy solid melt powder prepared in Example 2.
  • FIG. 2 is an XRD pattern of the B 2 high-entropy ceramic prepared in Example 2 after SPS sintering (Hf 0.2 Mo 0.2 Ta 0.2 Nb 0.2 Ti 0.2 ).
  • the green body is placed in a graphite crucible, and heated to 1200 ° C at a rate of 10 ° C / min for 1h, and then heated to 1600 ° C for 1h at a rate of 10 ° C / min, after vacuum heat treatment Obtained (Hf 0.2 Zr 0.2 Nb 0.2 Ta 0.2 Cr 0.2 ) B 2 ultrafine high-entropy ceramic solid melt powder.
  • the particle size of the multi-component high-entropy ceramic solid melt powder of this example was measured by laser particle size analysis to be 0.34 ⁇ m, and the oxygen content of the solid melt powder was 0.1 wt% measured by a carbon-oxygen analyzer.
  • the carbon of the solid melt powder The content is 0.02 wt%.
  • the prepared ceramic material with multiple high entropy forms a uniform single-phase solid melt.
  • the relative density is 99%, the hardness is 30 GPa, the fracture toughness is 6 MPa ⁇ m 1/2 , the grain size is 0.50 ⁇ m, the ceramic has good oxidation resistance, and the weight increases by 0.85% after heat treatment at 1200 ° C.
  • the green body is placed in a graphite crucible, and heated to 1100 ° C at a rate of 10 ° C / min for 1h, and then heated to 1550 ° C for 1h at a rate of 10 ° C / min, after vacuum heat treatment (Hf 0.2 Mo 0.2 Ta 0.2 Nb 0.2 Ti 0.2 ) B 2 ultrafine high-entropy solid melt powder was obtained.
  • FIG. 1 is an XRD pattern of (Hf 0.2 Mo 0.2 Ta 0.2 Nb 0.2 Ti 0.2 ) B 2 high-entropy solid melt powder prepared in this example.
  • (a) is oxide mixed powder
  • (b) is (Hf 0.2 Mo 0.2 Ta 0.2 Nb 0.2 Ti 0.2 ) B 2 multivariate high-entropy solid melt powder, it can be seen from FIG.
  • FIG. 2 is an XRD pattern of the B 2 high-entropy ceramic after SPS sintering (Hf 0.2 Mo 0.2 Ta 0.2 Nb 0.2 Ti 0.2 ) prepared in this example.
  • (a) is (Hf 0.2 Mo 0.2 Ta 0.2 Nb 0.2 Ti 0.2 ) B 2 multi-component high-entropy solid melt powder
  • (b) is (Hf 0.2 Mo 0.2 Ta 0.2 Nb 0.2 Ti 0.2 ) B 2 multi-component high-entropy ceramic .
  • B 2 multi-component high-entropy solid melt powder has only one phase, compared with HfB 2 standard PDF card 65-86778, (Hf 0.2 Mo 0.2 Ta 0.2 Nb 0.2 Ti 0.2 )
  • the peak of B 2 shifts to a high angle, and the multicomponent high-entropy solid melt powder is a uniform solid melt phase. It shows that the multi-component high-entropy solid melt powder is still a homogeneous solid melt phase after SPS sintering.
  • the particle size of the solid melt powder of this embodiment was measured by laser particle size analysis to be 0.10 ⁇ m, the oxygen content of the solid melt powder was 0.08 wt%, and the carbon content of the solid melt powder was 0.01 wt% measured by a carbon-oxygen analyzer ,
  • the prepared ceramic material with multiple high entropy forms a uniform single-phase solid melt, its relative density is 99%, hardness 35GPa, fracture toughness 5MPa ⁇ m 1/2 , grain size is 0.10 ⁇ m, ceramic resistance The oxidation performance is good, and the weight increases by 0.35% after heat treatment at 1200 ° C.
  • the green body is put into a graphite crucible, and heated to 1000 ° C at a rate of 10 ° C / min for 1h, and then heated to 1550 ° C for 1h at a rate of 10 ° C / min.
  • vacuum heat treatment Hf 0.2 Zr 0.2 Nb 0.2 Mo 0.2 Cr 0.2
  • B 2 ultrafine high-entropy solid melt powder
  • the particle size of the solid melt powder of this embodiment was measured by laser particle size analysis to be 0.80 ⁇ m, and the oxygen content of the solid melt powder measured by a carbon-oxygen analyzer was 0.01 wt%, and the carbon content of the solid melt powder was 0.03 wt% ,
  • the prepared ceramic material with multiple high entropy forms a uniform single-phase solid melt, its relative density is 99%, hardness 25GPa, fracture toughness 8MPa ⁇ m 1/2 , grain size is 1.10 ⁇ m, ceramic resistance The oxidation performance is good, and the weight increases by 0.71% after heat treatment at 1200 ° C.
  • the green body is put into a graphite crucible, and heated to 1200 ° C at a rate of 10 ° C / min for 1h, and then heated to 1550 ° C for 1h at a rate of 10 ° C / min. Obtained (Hf 0.2 Ti 0.2 Nb 0.2 Ta 0.2 Cr 0.2 ) B 2 ultrafine high-entropy ceramic solid solution powder.
  • the particle size of the solid melt powder of this example was measured by laser particle size analysis to be 0.39 ⁇ m, the oxygen content of the solid melt powder measured by a carbon-oxygen analyzer was 0.15 wt%, and the carbon content of the solid solution powder was 0.01 wt%.
  • Preparation The obtained solid melt material with multiple high entropy forms a uniform single-phase solid melt with a relative density of 99%, a hardness of 30 GPa, a fracture toughness of 4.23 MPa ⁇ m 1/2 , and a grain size of 0.45 ⁇ m.
  • the oxidation resistance is good, and the weight is increased by 0.72% after heat treatment at 1400 ° C.
  • the green body is put into a graphite crucible, and heated to 1150 ° C for 1h at a rate of 10 ° C / min, and then heated to 1550 ° C for 1h at a rate of 10 ° C / min, after vacuum heat treatment Obtained (Hf 0.2 Zr 0.2 Ti 0.2 Ta 0.2 Cr 0.2 ) B 2 ultrafine high-entropy ceramic solid melt powder.
  • the particle size of the solid solution powder of this example was measured by laser particle size analysis to be 0.39 ⁇ m, the oxygen content of the solid melt powder was 0.13 wt%, and the carbon content of the solid melt powder was 0.02 wt% measured by a carbon-oxygen analyzer.
  • Preparation The obtained ceramic material with multiple high entropy forms a uniform single-phase solid melt, its relative density is 99%, the hardness is 35GPa, the fracture toughness is 6MPa ⁇ m 1/2 , the grain size is 0.52 ⁇ m, the oxidation resistance of the ceramic Good, the weight increased by 0.3% after heat treatment at 1500 °C.

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Abstract

La présente invention concerne une céramique à multiples éléments de haute entropie, son procédé de préparation, et son utilisation. Un oxyde de Me1, un oxyde de Me2, un oxyde de Me3, un oxyde de Me4, un oxyde de Me5 et une poudre de bore amorphe sont utilisés comme matières premières pour la céramique. La céramique est préparée par broyage à boulets et mélange des matières premières et compactage du mélange résultant en un corps cru ; par soumission du corps cru au traitement thermique dans un creuset en graphite sous vide pour obtenir une poudre fondue solide de (Me1xMe2yMe3zMe4nMe5m)B2 ; et par soumission de la poudre fondue solide au frittage par plasma d'étincelles par chauffage de la poudre fondue solide à 1 000 à 1 400 °C, puis en fournissant une atmosphère protectrice, suivi du chauffage jusqu'à 1 800 à 2 200 °C pour conduire la calcination, où 0,1 ≤ x ≤ 0,9, 0,1 ≤ y ≤ 0,9, 0,1 ≤ z ≤ 0,9, 0,1 ≤ n ≤ 0,9, et 0,1 ≤ m ≤ 0,9. La céramique à multiples éléments de haute entropie obtenue présente une densité relative > 95 %, une dureté de 25 à 35 GPa, une ténacité à la fracture de 2 à 8 MPa•m1/2, une taille de grain de 0,1 à 1,1 µm, et un taux de changement de poids de 0,3 à 1 % après traitement thermique à 1 000 à 1 500 °C.
PCT/CN2018/120033 2018-10-15 2018-12-10 Céramique à multiples éléments de haute entropie, son procédé de préparation, et son utilisation WO2020077770A1 (fr)

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