CN117303908A - Quaternary high-entropy metal diboride and preparation method and application thereof - Google Patents
Quaternary high-entropy metal diboride and preparation method and application thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 4
- 239000011215 ultra-high-temperature ceramic Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 27
- 238000005245 sintering Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003313 weakening effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- ZSJNEUUJEWMSSS-UHFFFAOYSA-N B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].[Tm+3].[Tm+3].[Tm+3].[Tm+3] Chemical compound B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].[Tm+3].[Tm+3].[Tm+3].[Tm+3] ZSJNEUUJEWMSSS-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
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- -1 rare earth borate Chemical class 0.000 description 2
- 229910019742 NbB2 Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910008901 TmB2 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 238000000921 elemental analysis Methods 0.000 description 1
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- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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Abstract
The invention relates to a quaternary high-entropy metal diboride and a preparation method and application thereof, belonging to the technical field of ultrahigh-temperature ceramic materials. The quaternary high-entropy metal diboride prepared by the preparation method has the chemical formula (Hf) 0.2 Zr 0.2 Ta 0.2 Sc 0.2 Tm 0.2 )B 2 . Besides higher hardness and strength, the quaternary high-entropy metal diboride has the advantages that the addition of Tm atoms leads to weakening of covalent bonds, improves the brittleness of the high-entropy metal diboride, and remarkably improves the fracture toughness (8.25 MPa.m 1/2 ) Ratio HfB of 2 、ZrB 2 、NbB 2 The conventional metal diboride is about 83% higher. Therefore, the preparation method of the invention can obviously improve the toughness of the metal diboride, and the preparation methodThe method is simple and is suitable for industrial popularization and application.
Description
The application is a divisional application of the application date 2022, the application number CN202211023733.8 and the invention name of a high-toughness high-entropy metal diboride and a preparation method thereof.
Technical Field
The invention relates to a quaternary high-entropy metal diboride and a preparation method and application thereof, belonging to the technical field of ultrahigh-temperature ceramic materials.
Background
Transition metal diboride (TMB) 2 ) Belongs to a kind of superhigh temperature ceramic, and has the advantages of high melting point, high electric conductivity, high heat conductivity, excellent mechanical property, good chemical stability, etc. This unique combination of properties makes the transition metal diboride suitable for use in a variety of applications such as molten metal crucibles, cutting tools, wear parts, electrical discharge machining electrodes, hall-hero cell cathode materials, electrical equipment, armor materials, aluminum evaporation boats, nuclear neutron shielding, rocket nozzles, refractory parts, solar absorbing applications, high temperature structural parts, and the like. Although TMB 2 Has excellent hardness and strength, but as a structural application to be considered, only TMB is improved 2 Hardness and strength are insufficient. Therefore, attention must be paid to other basic mechanical properties, the most important of which is fracture toughness. However, TMB 2 Fracture toughness is generally lower due to the presence of strong covalent bonds. Thus, a more efficient, convenient and viable approach is sought to improve TMB 2 Fracture toughness versus TMB of (C) 2 It is extremely important in structural applications. High entropy metal diboride (HETMB) 2 ) Not only can expand the solid solution limit between different elements, but also can provide stability for the formation of disordered single-phase structure, and is hopeful to overcome the traditional TMB 2 Is a bottleneck in the application of (a).
Disclosure of Invention
In view of the above, the invention provides a quaternary high-entropy metal diboride, a preparation method and application thereof, wherein the metal diboride is composed of Hf, zr, ta, sc, tm and B, can be synthesized at a low temperature through a simple tube furnace, and has high density and excellent fracture toughness.
The aim of the invention is achieved by the following technical scheme.
Preparation method of quaternary high-entropy metal diboride with chemical formula (Hf) 0.2 Zr 0.2 Ta 0.2 Sc 0.2 Tm 0.2 )B 2 The method comprises the steps of carrying out a first treatment on the surface of the The preparation method comprises the following steps:
will HfO 2 ，ZrO 2 ，Ta 2 O 5 ，Sc 2 O 3 ，Tm 2 O 3 And B 4 C powder is mixed according to the stoichiometric ratio of the chemical formula, and B is 4 The actual adding amount of the C powder is B calculated according to the stoichiometric ratio 4 115-135% of the mass of the powder C, and uniformly mixing to obtain mixed powder; filling the mixed powder into a graphite crucible, and preserving heat for 1-3 h in a tubular furnace under the argon atmosphere and at the temperature of 1600 ℃; obtaining quaternary high-entropy metal diboride powder; the method comprises the steps of carrying out a first treatment on the surface of the
Loading the quaternary high-entropy metal diboride powder into a graphite mold, and sintering the powder in vacuum or inert gas protective atmosphere by adopting discharge induction plasma sintering to obtain the quaternary high-entropy metal diboride; the sintering temperature is 1900-2200 ℃, the pressure is 30-50 MPa, and the heat preservation and pressure maintaining time is 20-30 min;
the phase structure of the quaternary high-entropy metal diboride is hexagonal AlB 2 A shaped structure.
Preferably, the mixing is to mix HfO 2 、ZrO 2 、Ta 2 O 5 、Sc 2 O 3 、Tm 2 O 3 And B 4 C, ball-milling and mixing the powder in a ball-milling tank; the ball-milling mixing ball-material ratio is 3-6:1, the rotating speed is 300-500 rpm, and the time is 2-6 h.
Preferably, the heating rate when heating to 1600 ℃ is 5 ℃/min to 10 ℃/min.
Preferably, the sintering further comprises grinding and sieving the quaternary high entropy metal diboride powder; the number of the sieved sieves is 100-300 meshes.
Preferably, the HfO 2 、ZrO 2 、Ta 2 O 5 、Sc 2 O 3 、Tm 2 O 3 And B 4 The particle size of the C powder is 0.5-3 mu m.
The invention also provides application of the quaternary high-entropy metal diboride prepared by the preparation method in the ultrahigh-temperature ceramic material.
The beneficial effects are that:
(1)TmB 2 as rare earth diboride, tmB is obtained because the phase structure thereof cannot exist at normal temperature and normal pressure 2 Cannot be applied. The invention firstly proposes that TmB2 and other three transition metal diboride TMB 2 (tm=hf, ta, zr, sc) solid-solutions to form high entropy metal diborides, which can exert not only TmB 2 And also improves the fracture toughness of the metal diboride by a high entropy structure. This is mainly due to TmB 2 With TMB 2 (tm=hf, ta, zr, sc) has good phase stability, and TmB 2 Compared with other TMB 2 Has lower melting point, and improves the sinterability and the compactness of the high-entropy metal diboride.
(2) The high-entropy metal diboride designed by the invention has the advantages that the brittleness of the high-entropy metal diboride is improved due to the reduction of covalent bonds caused by the addition of Tm atoms, and the fracture toughness is obviously improved; the Tm atoms have a larger radius than the other four Tm atoms, resulting in higher lattice distortion, resulting in solid solution strengthening and crack propagation, thereby increasing their hardness.
(3) The excessive B is added in the preparation process of the high-entropy metal diboride 4 C, B, which is an oxide of boron generated during the carbothermic reaction of boron 2 O 3 And BO, the rapid volatilization under vacuum and high temperature leads to loss of boron source, furthermore in order to react the metal oxide with B 4 C can fully react without residual metal oxide, so excessive B is added 4 C。
(4) The high-entropy metal diboride can be prepared into powder in a tube furnace at a lower temperature (1600 ℃), the preparation process is easy to operate, the preparation cost is low, and the method is suitable for industrial popularization.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows the composition of (Hf) prepared in example 1 0.2 Zr 0.2 Ta 0.2 Sc 0.2 Tm 0.2 )B 2 X-ray diffraction (XRD) patterns of the powder;
FIG. 2 shows the composition of example 1 (Hf 0.2 Zr 0.2 Ta 0.2 Sc 0.2 Tm 0.2 )B 2 X-ray diffraction (XRD) patterns of the mass;
FIG. 3 shows the composition of example 1 (Hf 0.2 Zr 0.2 Ta 0.2 Sc 0.2 Tm 0.2 )B 2 Elemental analysis (for a block).
Detailed Description
The present invention will be further described with reference to the following detailed description, wherein the processes are conventional, and wherein the starting materials are commercially available from the open market, unless otherwise specified.
In the following examples:
HfO 2 ，ZrO 2 ，Ta 2 O 5 ，Sc 2 O 3 ，Tm 2 O 3 and B 4 The particle size of the powder C is 500 nm-3 mu m;
the elastic modulus is measured by adopting a pulse excitation resonance method, and the size of a test sample is cuboid of 3mm multiplied by 15mm multiplied by 40 mm;
the bending strength is obtained through a three-point bending experiment, the testing equipment is a universal mechanical testing machine, the size of a strip sample for testing is 3mm multiplied by 4mm multiplied by 36mm, the span is 30mm, and the moving speed of a pressure head is 0.5mm/min; wherein, before testing, the sample is polished on three sides, and the pulled surface is subjected to 45-degree chamfering treatment to reduce the possibility of edge damage;
the fracture toughness is obtained through a three-point bending experiment, the testing equipment is a universal mechanical testing machine, a single-side notched beam method is adopted for testing, the sample size is 3mm multiplied by 6mm multiplied by 40mm, the notched depth is 3mm, the width is 0.15mm, the span is 24mm, and the moving speed of the pressure head is 0.05mm/min.
Example 1
(1) Will HfO 2 ，ZrO 2 ，Ta 2 O 5 ，Sc 2 O 3 ，Tm 2 O 3 And B 4 Adding the powder C into a nylon ball milling tank according to a chemical formula ratio, ball-milling and mixing for 5 hours at a rotating speed of 350rpm, so as to obtain uniformly mixed powder;
(2) Filling the mixed powder into a graphite crucible, putting into a tube furnace, flushing argon as a protective atmosphere, heating to 1600 ℃ at a heating rate of 10 ℃/min, and preserving the temperature for 3 hours to obtain (Hf) 0.2 Zr 0.2 Ta 0.2 Sc 0.2 Tm 0.2 )B 2 Powder;
(3) Will (Hf) 0.2 Zr 0.2 Ta 0.2 Sc 0.2 Tm 0.2 )B 2 Filling the powder into a graphite mold, sintering under argon protective atmosphere by adopting discharge induction plasma sintering, wherein the sintering temperature is 2000 ℃, the sintering pressure is 50MPa, and the sintering time is 30min, so as to obtain single-phase (Hf) 0.2 Zr 0.2 Ta 0.2 Sc 0.2 Tm 0.2 )B 2 A block body.
For (Hf) obtained in step (2) 0.2 Zr 0.2 Ta 0.2 Sc 0.2 Tm 0.2 )B 2 XRD characterization of the powder, as can be seen in FIG. 1, (Hf) 0.2 Zr 0.2 Ta 0.2 Sc 0.2 Tm 0.2 )B 2 The main diffraction peak of the powder is hexagonal AlB 2 A type structure, and a certain amount of intermediate rare earth borate exists.
(Hf) obtained in step (3 0.2 Zr 0.2 Ta 0.2 Sc 0.2 Tm 0.2 )B 2 The mass was XRD characterized and found (Hf 0.2 Zr 0.2 Ta 0.2 Sc 0.2 Tm 0.2 )B 2 The bulk rare earth borate disappears, and the main phase structure is hexagonal AlB 2 A type structure, and a small amount of thulium tetraborate is present.
EDS mode of scanning electron microscope was used to determine the ratio of (Hf 0.2 Zr 0.2 Ta 0.2 Sc 0.2 Tm 0.2 )B 2 The block was subjected to elemental powder, and it was found from the test results of fig. 3 that the four metallic elements of Hf, ta, zr and Sc were uniformly distributed, and no agglomeration or segregation was found, but that Tm element was slightly biased, which was caused by the presence of a small amount of thulium tetraborate.
For (Hf) prepared in step (3) 0.2 Zr 0.2 Ta 0.2 Sc 0.2 Tm 0.2 )B 2 The blocks were subjected to mechanical properties, the test results being shown in Table 1. As can be seen from Table 1, (Hf) 0.2 Zr 0.2 Ta 0.2 Sc 0.2 Tm 0.2 )B 2 The overall mechanical properties are very excellent, with a fracture toughness of 8.25 MPa.m 1/2 Ratio HfB of 2 (4MPa·m 1/2 )，ZrB 2 (4MPa·m 1/2 )，NbB2(4.5MPa·m 1/2 ) The conventional metal diboride is about 83% higher. Thus, the present invention relates to (Hf 0.2 Zr 0.2 Ta 0.2 Sc 0.2 Tm 0.2 )B 2 The toughness of the metal diboride can be obviously improved, and the preparation process is simple and is suitable for industrial popularization and application.
TABLE 1
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (6)
1. A preparation method of quaternary high-entropy metal diboride is characterized in that the chemical formula of the quaternary high-entropy metal diboride is (Hf) 0.2 Zr 0.2 Ta 0.2 Sc 0.2 Tm 0.2 )B 2 The method comprises the steps of carrying out a first treatment on the surface of the The preparation method comprises the following steps:
will HfO 2 ，ZrO 2 ，Ta 2 O 5 ，Sc 2 O 3 ，Tm 2 O 3 And B 4 C powder is mixed according to the stoichiometric ratio of the chemical formula, and B is 4 The actual adding amount of the C powder is B calculated according to the stoichiometric ratio 4 115-135% of the mass of the powder C, and uniformly mixing to obtain mixed powder; filling the mixed powder into a graphite crucible, and preserving heat for 1-3 h in a tubular furnace under the argon atmosphere and at the temperature of 1600 ℃; obtaining quaternary high-entropy metal diboride powder; the method comprises the steps of carrying out a first treatment on the surface of the
Loading the quaternary high-entropy metal diboride powder into a graphite mold, and sintering the powder in vacuum or inert gas protective atmosphere by adopting discharge induction plasma sintering to obtain the quaternary high-entropy metal diboride; the sintering temperature is 1900-2200 ℃, the pressure is 30-50 MPa, and the heat preservation and pressure maintaining time is 20-30 min;
the phase structure of the quaternary high-entropy metal diboride is hexagonal AlB 2 A shaped structure.
2. The preparation method according to claim 1, wherein the mixing is to mix HfO 2 、ZrO 2 、Ta 2 O 5 、Sc 2 O 3 、Tm 2 O 3 And B 4 C, ball-milling and mixing the powder in a ball-milling tank; the ball-milling mixing ball-material ratio is 3-6:1, the rotating speed is 300-500 rpm, and the time is 2-6 h.
3. The method according to claim 1, wherein the heating rate when heating to 1600 ℃ is 5 ℃/min to 10 ℃/min.
4. The method of claim 1, wherein the pre-sintering further comprises grinding and sieving the quaternary high entropy metal diboride powder; the number of the sieved sieves is 100-300 meshes.
5. The production method according to claim 1 or 2, characterized in that the HfO 2 、ZrO 2 、Ta 2 O 5 、Sc 2 O 3 、Tm 2 O 3 And B 4 The particle size of the C powder is 0.5-3 mu m.
6. The use of the quaternary high-entropy metal diboride prepared by the preparation method of any one of claims 1 to 5 in ultra-high temperature ceramic materials.
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