CN112679213B - Super-multielement high-entropy ceramic and preparation method and application thereof - Google Patents
Super-multielement high-entropy ceramic and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of ceramic materials, and disclosesAn ultra-multielement high-entropy ceramic and a preparation method and application thereof are provided. The molecular formula of the high-entropy ceramic is (Hf) x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 Wherein x is more than 0 and less than 1, y is more than 0 and less than 1, z is more than 0 and less than 1, a is more than 0 and less than 1, b is more than 0 and less than 1, c is more than 0 and less than 1, d is more than 0 and less than 1, e is more than 0 and less than 1, and x + y + z + a + b + c + d + e + f =1 is satisfied; to mix HfO 2 、ZrO 2 、Ta 2 O 5 、Nb 2 O 5 、MoO 3 、WO 3 、V 2 O 5 、TiO 2 、Cr 2 O 3 Adding amorphous boron powder into an organic solvent for mixing, drying, preparing the obtained mixed powder into a blank, and preserving heat at 1400-1600 ℃ under a vacuum condition to obtain ceramic powder; the ceramic powder is made by charging into protective atmosphere at 1000-1400 deg.C by spark plasma sintering, pressurizing to 10-100 MPa, and calcining at 1800-2200 deg.C. The relative density of the super-multielement high-entropy ceramic is more than 95 percent, the hardness is 32-45 GPa, and the room temperature strength is 1000-1500 MPa.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a super-multielement high-entropy ceramic and a preparation method and application thereof.
Background
High entropy materials are a new class of crystalline solid phase materials, which contain five or more elements, and have attracted great attention of researchers due to their unique physical properties and potential application prospects. To date, much research has focused on high entropy alloys, which have excellent mechanical, corrosion and corrosion resistance properties. Compared with high-entropy alloys, high-entropy ceramics mainly include oxide ceramics, nitride ceramics, sulfide ceramics, carbide ceramics, boride ceramics and silicide ceramics. These newly discovered materials have enhanced properties in terms of electrical or mechanical properties.
The fourth and fifth groups of transition metals of carbide, boride and nitride are considered to be ultra-high temperature ceramics, high entropy ultra-high temperature ceramicsThe development of new structures and mechanical properties of porcelain is of great significance to the expansion of its application as structural components. Literature reports have successfully prepared (Hf) 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 )B 2 And (Hf) 0.2 Zr 0.2 Mo 0.2 Nb 0.2 Ti 0.2 )B 2 The quinary high-entropy boride ceramic series has a relative density of about 92% and a Vickers hardness higher than that of monobasic and binary metal diborides (up to 22.5 GPa). It is expected that more excellent mechanical properties can be obtained as the degree of densification increases. And as the number of the components increases, the high-entropy ceramic has more dislocations, so that the high-entropy ceramic is promoted to have high mechanical properties such as strength, thermal stability and high-temperature oxidation resistance, and the stability of the high-entropy structure is mainly formed by strong acting force among chemical bonds. Only quinary high-entropy ceramics have been reported so far, and the preparation and research of hexabasic and higher high-entropy ceramics have not been reported yet.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the super-multielement high-entropy ceramic is provided. The ceramic has a homogeneous solid solution phase, high strength, high hardness, ultra-multi high entropy ceramic.
The invention also aims to provide a preparation method of the above-mentioned super-multielement high-entropy ceramic.
The invention further aims to provide application of the ultra-multielement high-entropy ceramic.
The purpose of the invention is realized by the following technical scheme:
an ultra-multi-element high-entropy ceramic, the molecular formula of which is (Hf) x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 Wherein 0 is<x<1，0<y<1，0<z<1，0<a<1，0<b<1，0<c<1，0<d<1，0<e<1，0<f<1 and x + y + z + a + b + c + d + e + f =1; the high-entropy ceramic is prepared by firstly preparing metal oxide HfO 2 、ZrO 2 、Ta 2 O 5 、Nb 2 O 5 、MoO 3 、WO 3 、V 2 O 5 、TiO 2 、Cr 2 O 3 Adding amorphous boron powder into organic solvent, mixing with Si 3 N 4 The ball is used as a ball milling medium, mixed powder is obtained after drying, the mixed powder is molded into a blank, heat treatment is carried out under the vacuum condition, the temperature is raised to 1400-1600 ℃, heat preservation is carried out, and the ultra-multi high-entropy ceramic powder is obtained after grinding and sieving; the preparation method comprises the steps of heating the multielement high-entropy ceramic powder to 1000-1400 ℃ by spark plasma sintering, filling protective atmosphere, pressurizing to 10-100 MPa, heating to 1800-2200 ℃, and calcining.
Preferably, the relative density of the super-multielement high-entropy ceramic is more than 95%, the hardness is 32-45 GPa, and the room-temperature strength is 1000-1500 MPa.
Preferably, the purities of the metal oxide and the amorphous boron powder are both 96.0-99.9 wt%, and the particle sizes of the metal oxide and the amorphous boron powder are both 0.1-10 μm; the particle size of the ultra-multi-element high-entropy ceramic powder is 0.1-0.5 mu m, and the oxygen content in the ultra-multi-element high-entropy ceramic powder is 0.1-1 wt%.
Preferably, the amorphous boron powder is mixed with HfO 2 、ZrO 2 And TiO 2 The molar ratios of (2) to (4): 1, the amorphous boron powder and Nb 2 O 5 、V 2 O 5 And Ta 2 O 5 The molar ratios of (1) to (7) are all: 1, the amorphous boron powder and Cr 2 O 3 The molar ratio of (8-9): 1, the amorphous boron powder and MoO 3 And WO 3 The molar ratios of (4-5): 1.
preferably, the organic solvent is ethanol, propanol, methanol or acetone.
Preferably, the protective atmosphere is N 2 Or Ar.
Preferably, the rate of heating to 1400-1600 ℃ is 5-20 ℃/min, the time of calcination is 1-30 min, and the rate of heating to 1800-2200 ℃ and the rate of cooling are 100-400 ℃/min.
The preparation method of the super-multielement high-entropy ceramic comprises the following specific steps:
s1. TheMetal oxide HfO 2 、ZrO 2 、Ta 2 O 5 、Nb 2 O 5 、MoO 3 、WO 3 、V 2 O 5 、TiO 2 、Cr 2 O 3 Mixing with boron powder and organic solvent for 10-24 h, and adding Si 3 N 4 The ball is a ball milling medium, and the ball material ratio is (2-5): 1, drying to obtain mixed powder;
s2, molding the mixed powder into a blank, carrying out heat treatment under a vacuum condition, heating to 1400-1600 ℃ at a heating rate of 5-20 ℃/min, keeping the temperature for 0.5-2 h, grinding and sieving to obtain (Hf) x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 Ultra-multicomponent high entropy ceramic powder;
s3. Will (Hf) x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 Placing the ultra-multielement high-entropy ceramic powder into a graphite mould, heating to 1000-1400 ℃ at the speed of 100-400 ℃/min by adopting spark plasma sintering, filling protective atmosphere, heating to 1800-2200 ℃ at the speed of 100-400 ℃/min, preserving heat for 1-30 min, pressurizing to 10-100 MPa, and calcining to obtain (Hf) Hf x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 A super-multielement high entropy ceramic.
The application of the ultra-multielement high-entropy ceramic in the field of preparing ultra-high temperature (> 2000 ℃) ultra-hard (> 30 GPa) structural parts.
The super-multicomponent high-entropy ceramic is prepared by taking metal oxide and boron powder as raw materials and adopting a boron thermal reduction method to prepare (Hf) x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 The preparation method comprises the steps of directly preparing solid solution powder by a solid phase method from the ultra-multi-element high-entropy ceramic powder, and preparing (Hf) after spark plasma sintering x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 An ultra-multi-element high-entropy ceramic material. Due to its havingNine components, the disorder degree of the material is greatly increased, more dislocations exist in the system, and more transformations exist in each layer of the crystal structure, so that the performance of the material is greatly improved.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention successfully prepares single-phase nine-element solid solution powder by a simple solid-phase method of boron thermal reaction, which is the first ultra-multi-element high-entropy ceramic powder so far, and has the advantages of simple method, stable components, small powder particle size and high purity. Solves the problems that the highest number of components of the existing high-entropy ceramic powder is 5, the stability of the material is influenced by increasing the number of the components, and the single-phase solid solution material is difficult to prepare.
2. Usually due to WB 2 、MoB 2 、CrB 2 And VB 2 And HfB 2 、ZrB 2 And TiB 2 The crystal structures of the powder are different and are difficult to be dissolved into a single solid solution in a solid solution mode, and the superpolymer high-entropy powder and the ceramic prepared by the invention unexpectedly break through the superpolymer high-entropy superslurality of WB 2 、MoB 2 、CrB 2 、VB 2 On HfB 2 /ZrB 2 The single-phase solid solution (Hf) is prepared x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 A super-multielement high entropy ceramic.
3. Prepared by the invention of (Hf) x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 The invention relates to an ultra-multi high-entropy ceramic, which utilizes self-synthesized high-entropy ceramic powder, wherein the powder is solid solution powder, so that the sintering driving force is improved, and the single-phase high-entropy ceramic is easier to prepare x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 A super-multielement high entropy ceramic.
4. The invention is madePrepared from (Hf) x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 As the components of the ultra-multi-element high-entropy ceramic are increased, the high-entropy ceramic system has more dislocations, so that the system is difficult to slide, the ultra-multi-element high-entropy ceramic is promoted to have high strength and hardness, and the stability of the high-entropy structure is mainly formed by strong acting force among chemical bonds.
5. Prepared by the invention of (Hf) x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 The high entropy ceramics is characterized by that when the solute atoms are dissolved in the base body in the form of solid solution, they are strengthened, and because the component elements are increased, the strengthening action when the solute atoms are disorderly distributed in the base body and the strengthening action when the solute atoms are preferentially distributed near the crystal defect or are orderly arranged exist, and when the external force is applied, the number of solute atoms on the unit area slip surface is increased, the relative atomic size difference is large, and the relative atomic valence and some chemical and physical differences between solute and solvent are large, so that the performance of said material can be greatly raised.
Drawings
FIG. 1 shows (Hf) obtained in example 1 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/9 W 1/9 V 1/9 Ti 1/9 Cr 1/9 )B 2 SEM photograph of the ultra-multi-component high-entropy ceramic powder.
FIG. 2 shows (Hf) obtained in example 1 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/9 W 1/9 V 1/9 Ti 1/9 Cr 1/9 )B 2 XRD patterns of the ultra-multi-element high-entropy ceramic powder and the ceramic.
FIG. 3 is (Hf) obtained in example 1 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/9 W 1/9 V 1/9 Ti 1/9 Cr 1/9 )B 2 And (3) a surface scanning distribution diagram of the ultra-multielement high-entropy ceramic.
FIG. 4 shows (Hf) in comparative example 2 0.2 Zr 0.2 W 0.2 Mo 0.2 Ti 0.2 )B 2 XRD pattern of quinary high entropy ceramic powder.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
1. With HfO 2 (purity of powder 99.9%, particle diameter 2 μm), zrO 2 (purity of powder 99.9%, particle diameter 1 μm), cr 2 O 3 (purity of powder 99.9%, particle diameter 10 μm), nb 2 O 5 (purity of powder 99.9%, particle diameter 1 μm) powder, V 2 O 5 (purity of powder 99.9%, particle diameter 1 μm) powder, WO 3 (purity of powder 99.9%, particle diameter 1 μm) powder, moO 3 (purity of powder 99.9%, particle diameter 1 μm) powder, tiO 2 (purity of powder 99.9%, particle diameter 4 μm) and Ta 2 O 5 (purity of powder 99.9%, particle size 1 μm) powder and B (purity of powder 99.9%, particle size 2 μm) were mixed with ethanol to prepare Si 3 N 4 The ball is a ball milling medium, and the ball material ratio is 2:1 and mixing for 24 hours.
2. Boron powder and HfO 2 、ZrO 2 And TiO 2 All molar ratios of 3.67:1, boron powder and Nb 2 O 5 、V 2 O 5 And Ta 2 O 5 All molar ratios of (A) to (B) are 8.07:1, boron powder and Cr 2 O 3 Is 8.8:1, boron powder and MoO 3 And WO 3 Is 4.4:1.
3. molding the mixed powder into a blank, performing heat treatment under vacuum condition, heating to 1600 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, grinding and sieving to obtain (Hf) 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/9 W 1/9 V 1/9 Ti 1/9 Cr 1/9 )B 2 Ultra-multicomponent high-entropy ceramic powder.
4. Will (Hf) 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/9 W 1/9 V 1/9 Ti 1/9 Cr 1/9 )B 2 Placing the ultra-multielement high-entropy ceramic powder into a graphite mould, filling Ar protective atmosphere when the temperature is raised to 1200 ℃ at the speed of 150 ℃/min by adopting spark plasma sintering, raising the temperature to 2000 ℃ at the speed of 150 ℃/min, preserving the heat for 10min, and pressurizing and calcining at 30MPa to obtain (Hf) 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/9 W 1/9 V 1/ 9 Ti 1/9 Cr 1/9 )B 2 An ultra-multielement high entropy ceramic.
FIG. 1 shows (Hf) obtained in this example 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/9 W 1/9 V 1/9 Ti 1/9 Cr 1/9 )B 2 SEM photograph of the ultra-multi-component high-entropy ceramic powder shows that the powder has fine and uniform particle size distribution and particle size of about 0.25 μm, as can be seen from FIG. 1. FIG. 2 shows (Hf) obtained in this example 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/9 W 1/9 V 1/9 Ti 1/9 Cr 1/9 )B 2 XRD patterns of the ultra-multi-element high-entropy ceramic powder and the ceramic. Wherein, (a) is the ultra-multi-element high-entropy ceramic powder, and (b) is the ultra-multi-element high-entropy ceramic. As can be seen from FIG. 2, the ultra-multi-component high-entropy ceramic powder has a small amount of undissolved HfB 2 Phase, successfully prepared (Hf) 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/9 W 1/9 V 1/ 9 Ti 1/9 Cr 1/9 )B 2 The ultra-multi-element high-entropy ceramic powder is sintered at 2000 ℃, and is formed by HfB 2 Solid solution of the phases, resulting in a decrease of the lattice constant, (Hf) 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/9 W 1/9 V 1/9 Ti 1/9 Cr 1/9 )B 2 The diffraction peak of the (Hf) is moved to a high angle to successfully prepare a single-phase solid solution (Hf) 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/9 W 1/9 V 1/9 Ti 1/9 Cr 1/9 )B 2 Super-multielement high-entropy pottery. FIG. 3 shows (Hf) obtained in this example 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/9 W 1/9 V 1/9 Ti 1/9 Cr 1/9 )B 2 And (3) a surface scanning distribution diagram of the ultra-multielement high-entropy ceramic. As can be seen from FIG. 3, nine elements of Hf, zr, ta, nb, mo, W, V, ti and Cr are uniformly distributed, and pores on the surface of the ceramic are less.
This example (Hf) was determined by laser particle size analysis 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/9 W 1/9 V 1/9 Ti 1/9 Cr 1/9 )B 2 The particle size of the ultra-multi-component high-entropy ceramic powder is 0.25 μm, and is measured by a carbon-oxygen analyzer (Hf) 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/9 W 1/9 V 1/ 9 Ti 1/9 Cr 1/9 )B 2 The oxygen content of the ultra-multi-component high-entropy ceramic powder is 0.3wt%. (Hf) 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/9 W 1/9 V 1/ 9 Ti 1/9 Cr 1/9 )B 2 The relative density of the super-multielement high-entropy ceramic is 99%, the hardness is 43GPa, and the room temperature strength is 1500MPa.
Example 2
1. With HfO 2 (purity of powder 99.9%, particle diameter 2 μm), zrO 2 (purity of powder 99.9%, particle diameter 1 μm), cr 2 O 3 (purity of powder 99.9%, particle diameter 1 μm), nb 2 O 5 (purity of powder 99.9%, particle diameter 1 μm) powder, V 2 O 5 (purity of powder 99.9%, particle diameter 1 μm) powder, WO 3 (purity of powder 99.9%, particle diameter 1 μm) powder, moO 3 (purity of powder 99.9%, particle diameter 2 μm) powder, tiO 2 (purity of powder 99.9%, particle size 4 μm) and Ta 2 O 5 (purity of powder 99.9%, particle size 1 μm) powder and B (purity of powder 96.9%, particle size 10 μm) were mixed with ethanol to prepare Si 3 N 4 The ball is a ball milling medium, and the ball material ratio is 3:1 and mixing for 24 hours.
2. Boron powder and HfO 2 、ZrO 2 And TiO 2 The molar ratio of (A) to (B) is 3.78:1,boron powder and Nb 2 O 5 、V 2 O 5 And Ta 2 O 5 The molar ratio of (A) to (B) is 8.34:1, boron powder and Cr 2 O 3 Is 8.9:1, boron powder and MoO 3 And WO 3 Is 4.2:1.
3. molding the mixed powder into a blank, performing heat treatment under vacuum condition, heating to 1500 ℃ at a heating rate of 15 ℃/min, keeping the temperature for 1h, grinding and sieving to obtain (Hf) 1/9 Zr 2/9 Ta 1/18 Nb 1/18 Mo 1/9 W 1/9 V 1/9 Ti 1/9 Cr 1/9 )B 2 An ultra-multi-element high-entropy ceramic powder.
4. Will (Hf) 1/9 Zr 2/9 Ta 1/18 Nb 1/18 Mo 1/9 W 1/9 V 1/9 Ti 1/9 Cr 1/9 )B 2 Placing the ultra-multi-element high-entropy ceramic powder into a graphite mold, heating to 1200 deg.C at 200 deg.C/min by spark plasma sintering, introducing Ar protective atmosphere, heating to 2000 deg.C at 200 deg.C/min, maintaining for 15min, and calcining under 30MPa to obtain (Hf) (Hf is prepared 1/9 Zr 2/9 Ta 1/18 Nb 1/18 Mo 1/9 W 1/9 V 1/ 9 Ti 1/9 Cr 1/9 )B 2 An ultra-multielement high entropy ceramic.
This example (Hf) was determined by laser particle size analysis 1/9 Zr 2/9 Ta 1/18 Nb 1/18 Mo 1/9 W 1/9 V 1/9 Ti 1/9 Cr 1/9 )B 2 The particle size of the ultra-multi-component high-entropy ceramic powder is 0.26 μm, measured by carbon-oxygen analyzer (Hf) 1/9 Zr 2/9 Ta 1/18 Nb 1/18 Mo 1/9 W 1/9 V 1/9 Ti 1/ 9 Cr 1/9 )B 2 The oxygen content of the ultra-multi-element high-entropy ceramic powder is 0.4wt%. (Hf) 1/9 Zr 2/9 Ta 1/18 Nb 1/18 Mo 1/9 W 1/9 V 1/9 Ti 1/ 9 Cr 1/9 )B 2 The relative density of the super-multielement high-entropy ceramic is 98 percent, the hardness is 40GPa, and the room temperature strength is 1300MPa.
Example 3
1. With HfO 2 (purity of powder 99.9%, particle diameter 1 μm), zrO 2 2 (purity of powder 99.9%, particle diameter 1 μm), cr 2 O 3 (purity of powder 99.9%, particle diameter 10 μm), nb 2 O 5 (purity of powder 99.9%, particle diameter 1 μm) powder, V 2 O 5 (purity of powder 99.9%, particle diameter 1 μm) powder, WO 3 (purity of powder 99.9%, particle size 3 μm) powder, moO 3 (purity of powder 99.9%, particle diameter 2 μm) powder, tiO 2 (purity of powder 99.9%, particle diameter 4 μm) and Ta 2 O 5 (purity of powder 99.9%, particle size 1 μm) powder and B (purity of powder 99.9%, particle size 2 μm) were mixed with ethanol to form Si 3 N 4 The ball is a ball milling medium, and the ball material ratio is 4:1, mixing for 28h.
2. Boron powder and HfO 2 、ZrO 2 And TiO 2 The molar ratio of (A) to (B) is 3.9:1, boron powder and Nb 2 O 5 、V 2 O 5 And Ta 2 O 5 The molar ratio of (A) to (B) is 9:1, boron powder and Cr 2 O 3 Is 8.5:1, boron powder and MoO 3 And WO 3 Is 4.4:1.
3. molding the mixed powder into a blank, performing heat treatment under vacuum condition, heating to 1550 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 2h, grinding and sieving to obtain (Hf) 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/18 W 1/18 V 3/9 Ti 1/18 Cr 1/18 )B 2 An ultra-multi-element high-entropy ceramic powder.
4. Will (Hf) 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/18 W 1/18 V 3/9 Ti 1/18 Cr 1/18 )B 2 Placing the ultra-multi-element high-entropy ceramic powder into a graphite mold, heating to 1200 deg.C at a rate of 250 deg.C/min by spark plasma sintering, introducing Ar protective atmosphere, heating to 2200 deg.C at a rate of 150 deg.C/min, holding for 10min, and calcining under 50MPa to obtain (Hf) (Hf, hf) 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/18 W 1/ 18 V 3/9 Ti 1/18 Cr 1/18 )B 2 A super-multielement high entropy ceramic.
This example (Hf) was determined by laser particle size analysis 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/18 W 1/18 V 3/9 Ti 1/18 Cr 1/18 )B 2 The particle size of the ultra-multi-component high-entropy ceramic powder is 0.31 μm, measured by carbon-oxygen analyzer (Hf) 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/18 W 1/18 V 3/ 9 Ti 1/18 Cr 1/18 )B 2 The oxygen content of the ultra-multi-element high-entropy ceramic powder is 0.5wt%. (Hf) 1/9 Zr 1/9 Ta 1/9 Nb 1/9 Mo 1/18 W 1/18 V 3/ 9 Ti 1/18 Cr 1/18 )B 2 The relative density of the super-multielement high-entropy ceramic is 95.5 percent, the hardness is 35GPa, and the room temperature strength is 1000MPa.
Example 4
1. With HfO 2 (purity of powder 99.9%, particle diameter 2 μm), zrO 2 (purity of powder 99.9%, particle diameter 1 μm), cr 2 O 3 (purity of powder 99.9%, particle diameter 7 μm), nb 2 O 5 (purity of powder 99.9%, particle diameter 4 μm) powder, V 2 O 5 (purity of powder 99.9%, particle diameter 1 μm) powder, WO 3 (purity of powder 99.9%, particle diameter 1 μm) powder, moO 3 (purity of powder: 99.9%, particle size: 1 μm) powder, tiO 2 (purity of powder 99.9%, particle diameter 4 μm) and Ta 2 O 5 (purity of powder 99.9%, particle size 1 μm) powder and B (purity of powder 98%, particle size 5 μm) were mixed with ethanol to form Si 3 N 4 The ball is a ball milling medium, and the ball material ratio is 4:1 and mixing for 24 hours.
2. Boron powder and HfO 2 、ZrO 2 And TiO 2 2 The molar ratio of (A) to (B) is 4:1, boron powder and Nb 2 O 5 、V 2 O 5 And Ta 2 O 5 The molar ratio of (A) to (B) is 8:1, boron powder and Cr 2 O 3 Is 8.8:1, boron powder and MoO 3 And WO 3 Is 4.4:1.
3. molding the mixed powder into a blank, performing heat treatment under vacuum condition, heating to 1600 ℃ at a heating rate of 10 ℃/min, preserving heat for 2h, grinding and sieving to obtain (Hf) 2/9 Zr 2/9 Ta 1/18 Nb 1/18 Mo 1/18 W 1/18 V 1/18 Ti 1/18 Cr 2/9 )B 2 An ultra-multi-element high-entropy ceramic powder.
4. Will (Hf) 2/9 Zr 2/9 Ta 1/18 Nb 1/18 Mo 1/18 W 1/18 V 1/18 Ti 1/18 Cr 2/9 )B 2 Placing the ultra-multielement high-entropy ceramic powder into a graphite mould, filling Ar protective atmosphere when the temperature is raised to 1200 ℃ at the speed of 150 ℃/min by adopting spark plasma sintering, raising the temperature to 1800 ℃ at the speed of 150 ℃/min, preserving the heat for 15min, and performing calcination under the pressure of 50MPa to obtain (Hf) 2/9 Zr 2/9 Ta 1/18 Nb 1/18 Mo 1/ 18 W 1/18 V 1/18 Ti 1/18 Cr 2/9 )B 2 An ultra-multielement high entropy ceramic.
(Hf) obtained in this example by laser particle size analysis 2/9 Zr 2/9 Ta 1/18 Nb 1/18 Mo 1/18 W 1/18 V 1/18 Ti 1/ 18 Cr 2/9 )B 2 The particle size of the ultra-multi-component high-entropy ceramic powder is 0.32 μm, and is measured by a carbon-oxygen analyzer (Hf) 2/9 Zr 2/9 Ta 1/18 Nb 1/ 18 Mo 1/18 W 1/18 V 1/18 Ti 1/18 Cr 2/9 )B 2 The oxygen content of the ultra-multi-element high-entropy ceramic powder is 0.6wt%. (Hf) 2/9 Zr 2/9 Ta 1/ 18 Nb 1/18 Mo 1/18 W 1/18 V 1/18 Ti 1/18 Cr 2/9 )B 2 The relative density of the ultra-multi-element high-entropy ceramic is 97.5 percent, the hardness is 39GPa, and the room-temperature strength is 1200MPa.
Example 5
1. With HfO 2 (purity of powder 99.9%, particle diameter 2 μm), zrO 2 (purity of powder 99.9%, particle diameter 10 μm), cr 2 O 3 (purity of powder 99.9%, pellets)Diameter 3 μm), nb 2 O 5 (purity of powder 99.9%, particle size 1 μm) powder, V 2 O 5 (purity of powder 99.9%, particle diameter 1 μm) powder, WO 3 (purity of powder 99.9%, particle diameter 1 μm) powder, moO 3 (purity of powder 99.9%, particle diameter 6 μm) powder, tiO 2 (purity of powder 99.9%, particle size 4 μm) and Ta 2 O 5 (purity of powder 99.9%, particle diameter 1 μm) powder and B (purity of powder 97%, particle diameter 7 μm) were mixed with ethanol to prepare Si 3 N 4 The ball is a ball milling medium, and the ball material ratio is 5:1 and mixing for 24 hours.
2. Boron powder and HfO 2 、ZrO 2 And TiO 2 The molar ratio of (A) to (B) is 4:1, boron powder and Nb 2 O 5 、V 2 O 5 And Ta 2 O 5 The molar ratio of (A) to (B) is 8.07:1, boron powder and Cr 2 O 3 Is 8.8:1, boron powder and MoO 3 And WO 3 In a molar ratio of 5:1.
3. molding the mixed powder into a blank, performing heat treatment under vacuum condition, heating to 1600 ℃ at a heating rate of 20 ℃/min, preserving heat for 1h, grinding and sieving to obtain (Hf) 1/9 Zr 1/9 Ta 1/9 Nb 1/18 Mo 1/18 W 3/9 V 1/9 Ti 1/18 Cr 1/18 )B 2 Ultra-multicomponent high-entropy ceramic powder.
4. Will (Hf) 1/9 Zr 1/9 Ta 1/9 Nb 1/18 Mo 1/18 W 3/9 V 1/9 Ti 1/18 Cr 1/18 )B 2 Placing the ultra-multi-element high-entropy ceramic powder into a graphite mold, heating to 1200 deg.C at 150 deg.C/min by spark plasma sintering, introducing Ar protective atmosphere, heating to 2000 deg.C at 200 deg.C/min, maintaining for 5min, and calcining under 30MPa to obtain (Hf) 1/9 Zr 1/9 Ta 1/9 Nb 1/18 Mo 1/18 W 3/ 9 V 1/9 Ti 1/18 Cr 1/18 )B 2 A super-multielement high entropy ceramic.
This example (Hf) was determined by laser particle size analysis 1/9 Zr 1/9 Ta 1/9 Nb 1/18 Mo 1/18 W 3/9 V 1/9 Ti 1/18 Cr 1/18 )B 2 The particle size of the ultra-multi-component high-entropy ceramic powder is 0.22 μm, measured by carbon-oxygen analyzer (Hf) 1/9 Zr 1/9 Ta 1/9 Nb 1/18 Mo 1/18 W 3/9 V 1/ 9 Ti 1/18 Cr 1/18 )B 2 The oxygen content of the ultra-multi-element high-entropy ceramic powder is 0.2wt%. (Hf) 1/9 Zr 1/9 Ta 1/9 Nb 1/18 Mo 1/18 W 3/9 V 1/ 9 Ti 1/18 Cr 1/18 )B 2 The relative density of the super-multielement high-entropy ceramic is 98.5 percent, the hardness is 42GPa, and the room temperature strength is 1400MPa.
Comparative example 1
1. With HfO 2 (purity of powder 99.9%, particle size 2 μm), zrO 2 2 (purity of powder 99.9%, particle diameter 10 μm), nb 2 O 5 (purity of powder 99.9%, particle diameter 1 μm) powder, tiO 2 (purity of powder 99.9%, particle diameter 4 μm) and Ta 2 O 5 (purity of powder 99.9%, particle size 1 μm) powder and B (purity of powder 97%, particle size 7 μm) were mixed with ethanol to prepare Si 3 N 4 The ball is a ball milling medium, and the ball material ratio is 5:1 and mixing for 24 hours.
2. Boron powder and HfO 2 、ZrO 2 And TiO 2 The molar ratio of (A) to (B) is 4:1, boron powder and Nb 2 O 5 All molar ratios of (A) to (B) are 8.07:1.
3. molding the mixed powder into a blank, performing heat treatment under vacuum condition, heating to 1600 ℃ at a heating rate of 20 ℃/min, keeping the temperature for 1h, grinding and sieving to obtain (Hf) 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 )B 2 Five-element high-entropy ceramic powder.
4. Will (Hf) 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 )B 2 Placing quinary high-entropy ceramic powder into a graphite mold, heating to 1200 deg.C at 150 deg.C/min by spark plasma sintering, charging Ar protective atmosphere, heating to 2000 deg.C at 200 deg.C/min, maintaining for 5min, and calcining under 30MPa to obtain (Hf) 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 )B 2 Five-membered high entropy ceramics.
Comparative example (Hf) determined by laser particle size analysis 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 )B 2 The particle size of the five-membered high-entropy ceramic powder is 0.22 μm, and is measured by a carbon-oxygen analyzer (Hf) 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 )B 2 The oxygen content of the quinary high-entropy ceramic powder is 0.2wt%. (Hf) 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 )B 2 The quinary high-entropy ceramic has the relative density of 92 percent, the compactness is lower, the hardness is only 20GPa, and the room-temperature strength is only 500MPa, while the high-entropy ceramic prepared by the embodiments 1-5 can improve the performance of the high-entropy ceramic and has excellent performance.
Comparative example 2
1. With HfO 2 (purity of powder 99.9%, particle diameter 2 μm), zrO 2 (purity of powder 99.9%, particle diameter 10 μm), WO 3 (purity of powder 99.9%, particle diameter 1 μm) powder, moO 3 (purity of powder 99.9%, particle diameter 6 μm) powder, tiO 2 (purity of powder 99.9%, particle size 4 μm) and B (purity of powder 97%, particle size 7 μm) were mixed with ethanol to form Si 3 N 4 The ball is a ball milling medium, and the ball material ratio is 5:1 and mixing for 24 hours.
2. Boron powder and HfO 2 、ZrO 2 And TiO 2 The molar ratio of (A) to (B) is 4:1, boron powder and WO 3 In a molar ratio of 5:1.
3. molding the mixed powder into a blank, performing heat treatment under vacuum condition, heating to 1600 ℃ at a heating rate of 20 ℃/min, preserving heat for 1h, grinding and sieving to obtain (Hf) 0.2 Zr 0.2 W 0.2 Mo 0.2 Ti 0.2 )B 2 Five-element high-entropy ceramic powder.
4. Will (Hf) 0.2 Zr 0.2 W 0.2 Mo 0.2 Ti 0.2 )B 2 Placing five-element high-entropy ceramic powder into a graphite mold, heating to 1200 deg.C at 150 deg.C/min by spark plasma sintering, introducing Ar protective atmosphere, and heating at 200 deg.C/minHeating to 2000 deg.C, maintaining the temperature for 5min, and calcining under 30MPa to obtain (Hf) 0.2 Zr 0.2 W 0.2 Mo 0.2 Ti 0.2 )B 2 Five-membered high entropy ceramics.
This example (Hf) was determined by laser particle size analysis 0.2 Zr 0.2 W 0.2 Mo 0.2 Ti 0.2 )B 2 The particle size of the five-membered high-entropy ceramic powder is 0.67 μm, and is measured by a carbon-oxygen analyzer (Hf) 0.2 Zr 0.2 W 0.2 Mo 0.2 Ti 0.2 )B 2 The oxygen content of the quinary high-entropy ceramic powder is 0.2wt%. (Hf) 0.2 Zr 0.2 W 0.2 Mo 0.2 Ti 0.2 )B 2 The quinary high-entropy ceramic has the relative density of 95 percent, the hardness of 25GPa and the room-temperature strength of 620MPa, and the performance is lower than that of the ultra-multiple high-entropy ceramic prepared in the examples 1-5.
FIG. 4 shows (Hf) in this comparative example 0.2 Zr 0.2 W 0.2 Mo 0.2 Ti 0.2 )B 2 XRD pattern of five-membered high-entropy ceramic powder, as can be seen from FIG. 4, the five-membered W-containing system is difficult to be dissolved into single-phase solid solution ceramic, which exists (Mo, W) in addition to the high-entropy phase 2 B 5 ，WB，m-(Hf,Zr)O 2 And MoB 2 Phase, and the ultra-multi-element high-entropy ceramic powder prepared by the borothermic carbothermic reduction method has increased elements and also contains WB 2 Component, albeit WB 2 Has a crystal structure different from that of other borides, which exceeds WB 2 The solid solution limit of (2) can still prepare the solid solution super-multi-element high-entropy ceramic powder, as shown in figure 2. Prepared by the invention of (Hf) x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 The super-multi-element high-entropy ceramic utilizes self-synthesized high-entropy ceramic powder which is solid solution powder, improves the sintering driving force, enables the single-phase high-entropy ceramic to be prepared more easily, and is prepared by spark plasma sintering (Hf) x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 The super-multielement high-entropy ceramic has high cooling speed, and can stabilize high-entropy ceramic components to formWork produced a single phase (Hf) x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 A super-multielement high entropy ceramic. Relative density of the obtained super-multi-element high-entropy ceramic>95 percent, the hardness is 32-45 GPa, and the room temperature strength is 1000-1500 MPa.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes and modifications are intended to be included in the scope of the present invention.
Claims (6)
1. A preparation method of an ultra-multielement high-entropy ceramic is characterized by comprising the following specific steps:
s1, mixing metal oxide HfO 2 、ZrO 2 、Ta 2 O 5 、Nb 2 O 5 、MoO 3 、WO 3 、V 2 O 5 、TiO 2 、Cr 2 O 3 Mixing with amorphous boron powder and organic solvent for 10-24 h to obtain Si 3 N 4 The ball is a ball milling medium, and the ball material ratio is (2-5): 1, drying to obtain mixed powder; amorphous boron powder and HfO 2 、ZrO 2 And TiO 2 2 The molar ratios of (2) to (4): 1, amorphous boron powder and Nb 2 O 5 、V 2 O 5 And Ta 2 O 5 The molar ratios of (1) to (7) are all (9): 1, amorphous boron powder and Cr 2 O 3 The molar ratio of (8-9): amorphous boron powder and MoO 3 And WO 3 The molar ratios of (4-5): 1;
s2, molding the mixed powder into a blank, carrying out heat treatment under a vacuum condition, heating to 1400-1600 ℃ at a heating rate of 5-20 ℃/min, keeping the temperature for 0.5-2 h, grinding and sieving to obtain (Hf) x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 Ultra-multicomponent high entropy ceramic powder;
s3. Will (Hf) x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 Placing the ultra-multielement high-entropy ceramic powder into a graphite mould, heating to 1000-1400 ℃ at the speed of 100-400 ℃/min by adopting spark plasma sintering, filling protective atmosphere, heating to 1800-2200 ℃ at the speed of 100-400 ℃/min, preserving heat for 1-30 min, pressurizing to 10-100 MPa, and calcining to obtain (Hf) Hf x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 An ultra-multielement high entropy ceramic; the molecular formula of the high-entropy ceramic is (Hf) x Zr y Ta z Nb a Mo b W c V d Ti e Cr f )B 2 Wherein 0 is<x<1，0<y<1，0<z<1，0<a<1，0<b<1，0<c<1，0<d<1，0<e<1，0<f<1 and x + y + z + a + b + c + d + e + f =1; the particle size of the ultra-multi-element high-entropy ceramic powder is 0.1-0.5 mu m, and the oxygen content in the ultra-multi-element high-entropy ceramic powder is 0.1-1 wt%.
2. The preparation method of the high-entropy ceramic, according to claim 1, wherein the relative density of the high-entropy ceramic in step S3 is greater than 95%, the hardness is 32-45 GPa, and the room-temperature strength is 1000-1500 MPa.
3. The method for preparing the multielement high-entropy ceramic according to claim 1, wherein the purities of the metal oxide and the amorphous boron powder in the step S1 are both 96-99.9 wt%, and the particle sizes of the metal oxide and the amorphous boron powder are both 0.1-10 μm; the organic solvent is ethanol, propanol, methanol or acetone.
4. The method for preparing the multielement high-entropy ceramic according to claim 1, wherein the protective atmosphere in the step S3 is N 2 Or Ar.
5. An ultra-multivariate high-entropy ceramic, characterized in that the high-entropy ceramic is prepared by the method of any one of claims 1 to 4.
6. The application of the ultra-multi-element high-entropy ceramic in claim 5 in the field of manufacturing ultra-high temperature and ultra-hard structural parts.
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