CN109898005B - High-strength WVTaZrHf refractory high-entropy alloy and preparation method thereof - Google Patents
High-strength WVTaZrHf refractory high-entropy alloy and preparation method thereof Download PDFInfo
- Publication number
- CN109898005B CN109898005B CN201910347837.6A CN201910347837A CN109898005B CN 109898005 B CN109898005 B CN 109898005B CN 201910347837 A CN201910347837 A CN 201910347837A CN 109898005 B CN109898005 B CN 109898005B
- Authority
- CN
- China
- Prior art keywords
- powder
- entropy alloy
- particle size
- wvtazrhf
- percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Powder Metallurgy (AREA)
Abstract
本发明公开了一种高强度的WVTaZrHf难熔高熵合金及其制备方法，其中WVTaZrHf难熔高熵合金的组元包括W、V、Ta、Zr、Hf，各组分按原子百分比构成为：W 22.5～23.5％，V 22.5～23.5％，Ta 22.5～23.5％，Zr 6‑10％，Hf 22.5～23.5％。本发明通过添加Zr、Hf元素来改善合金的结构，通过放电等离子烧结制备出具有密排六方结构的难熔高熵合金材料，进而提高难熔高熵合金的硬度和强度。
The invention discloses a high-strength WVTaZrHf refractory high-entropy alloy and a preparation method thereof. The components of the WVTaZrHf refractory high-entropy alloy include W, V, Ta, Zr, and Hf, and the components are composed of: W 22.5～23.5%, V 22.5～23.5%, Ta 22.5～23.5%, Zr 6‑10%, Hf 22.5～23.5%. The invention improves the structure of the alloy by adding Zr and Hf elements, and prepares a refractory high-entropy alloy material with a close-packed hexagonal structure by spark plasma sintering, thereby improving the hardness and strength of the refractory high-entropy alloy.
Description
Technical Field
The invention relates to a refractory high-entropy alloy and a preparation method thereof, in particular to a high-strength WVTaZrHf refractory high-entropy alloy and a preparation method thereof.
Background
Hafnium behaves very similar to zirconium, since it has an atomic radius almost equal to that of zirconium, due to the effects of lanthanide contraction. The crystal structures of hafnium and zirconium are both close-packed hexagonal structures. Hafnium has a strong ability to absorb neutrons, and can slow down the rate of nuclear chain reactions, inhibiting the "flame" of atomic reactions. Meanwhile, the composite material has strong high-temperature resistance and corrosion resistance, and the molding material has the characteristics of strong plasticity, easy processing and the like, so the composite material becomes one of important materials in the atomic energy industry and is widely applied to manufacturing control rods and protection devices of nuclear reactors at present. Zirconium has excellent corrosion resistance, extremely high melting point, ultrahigh hardness, strength and other characteristics, and is widely used in the fields of aerospace, military industry, nuclear reaction and atomic energy. Zirconium can be used as a 'vitamin' in metallurgical industry, and plays a powerful role in deoxidation, nitrogen removal and sulphur removal.
The high-entropy alloy is an alloy consisting of a plurality of main elements, particularly an alloy with more than five elements, and each main element has a high atomic percentage, generally between 5% and 35%, so that the atomic percentage of no element can exceed 50%, and the alloy becomes an alloy material with one element as the main element. Research finds that the alloy is influenced by a high-entropy effect, the mixing entropy of the high-entropy alloy with a large number of elements is often far higher than the mixing entropy of the intermetallic compound, the effect can make the intermetallic compound difficult to appear, so that the alloy is easy to form solid solution with a simple structure, the disorder degree of an alloy system consisting of a plurality of metal elements is large, the mixing entropy of the alloy system is large, the system is stable, the effective mixing of various elements is facilitated, and the components are irregularly arranged to form a simple crystalline phase, namely, a face-centered cubic crystal, a body-centered cubic crystal or a close-packed hexagonal crystal, so that the formation of a brittle phase of the intermetallic compound is inhibited.
Disclosure of Invention
The invention provides a high-strength WVTaZrHf refractory high-entropy alloy and a preparation method thereof.
The spark plasma sintering has the characteristics of high temperature rise speed, short sintering time, uniform structure, capability of keeping the natural state of raw materials and high density of a sintered body, and is a preparation method with high efficiency and simple process. The invention adopts a mechanical powder mixing method to obtain composite powder, and then the WVTaZrHf single-phase refractory high-entropy alloy material with good comprehensive performances such as hardness, strength and the like is prepared by discharge plasma sintering.
The invention relates to a high-strength WVTaZrHf refractory high-entropy alloy, which comprises the following components in percentage by atom: 22.5 to 23.5 percent of W, 22.5 to 23.5 percent of V, 22.5 to 23.5 percent of Ta22, 6 to 10 percent of Zr and 22.5 to 23.5 percent of Hf22.
The preparation method of the high-strength WVTaZrHf refractory high-entropy alloy comprises the following steps of:
step 1: mixed powder
Putting five metal powders of W, V, Ta, Zr and Hf into a drum mixer according to the proportion and mechanically mixing to obtain W-V-Ta-Zr-Hf composite powder;
in step 1, the original powder particle size is: the particle size of W powder is 2 μm, the particle size of V powder is 25 μm, the particle size of Ta powder is 25 μm, the particle size of Zr powder is 28 μm, and the particle size of Hf powder is 38 μm. (W melting point: 3410 ℃ C.; V melting point: 1890 ℃ C.; boiling point: 3000 ℃ C.; Ta melting point: 2996 ℃ C.; boiling point: 5425 ℃ C.; Zr melting point: 1852 ℃ C.; boiling point: 4377 ℃ C.; Hf melting point: 2227 ℃ C.; boiling point: 4602 ℃ C.)
Step 2: sintering
Filling the W-V-Ta-Zr-Hf composite powder into a graphite mold, then putting the mold into a discharge plasma sintering furnace, vacuumizing the sintering furnace, then heating to 800 ℃ at a speed of 100 ℃/min, and preserving heat for 10 minutes, wherein the pressure is controlled not to exceed 25 MPa; and then heating to 1500 ℃ at a speed of 100 ℃/min, preserving heat for 5 minutes, controlling the pressure intensity not to exceed 50MPa in sintering, cooling to room temperature after heat preservation is finished, and cooling to room temperature at a speed of 100 ℃/min after heat preservation is finished, thus obtaining the W-V-Ta-Zr-Hf high-entropy alloy material.
The invention has the beneficial effects that:
the Zr and Hf are added to improve the alloy structure, the refractory high-entropy alloy material with a close-packed hexagonal structure is prepared through spark plasma sintering, and the hardness and strength of the refractory high-entropy alloy are obviously improved. The refractory high-entropy alloy material prepared by the invention has a close-packed hexagonal structure, uniform microstructure, relative density of more than 99.9%, and microhardness value of 576.3-600.2 Hv, which is superior to that of pure tungsten material (microhardness of 320-360 Hv). The room temperature compressive strength is 1207.6-1439.4 MPa.
Drawings
FIG. 1 shows the X-ray diffraction pattern of the W-V-Ta-Zr-Hf single-phase refractory high-entropy alloy prepared in example 2 of the invention, which shows that the alloy structure prepared in the invention is a hexagonal close-packed single phase.
FIG. 2 shows a scanning electron microscope image of a W-V-Ta-Zr-Hf single-phase refractory high-entropy alloy prepared in example 2 of the present invention.
FIG. 3 shows the room temperature compression curve of the W-V-Ta-Zr-Hf single-phase refractory high-entropy alloy prepared in example 2 of the invention. The strength of the material is obviously improved, the compressive strength at room temperature is 1439.4MPa, and the elongation at break is 8%.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments.
Example 1:
in the embodiment, the WVTaZrHf single-phase refractory high-entropy alloy comprises W, V, Ta, Zr and Hf, wherein the components in atomic percentage are as follows: 22.5 percent of W, 22.5 percent of V, 22.5 percent of Ta22, 10 percent of Zr and 22.5 percent of HfHfO.
The original powder particle size was: the particle size of W powder is 2 μm, the particle size of V powder is 25 μm, the particle size of Ta powder is 25 μm, the particle size of Zr powder is 28 μm, and the particle size of Hf powder is 38 μm.
The preparation method of the wvtazrf single-phase refractory high-entropy alloy in the embodiment includes the following steps:
step 1: mixed powder
Putting five metal powders of W, V, Ta, Zr and Hf into a drum mixer according to the proportion and mechanically mixing to obtain W-V-Ta-Zr-Hf composite powder;
step 2: sintering
Filling the W-V-Ta-Zr-Hf composite powder into a graphite mold, then putting the mold into a discharge plasma sintering furnace, vacuumizing the sintering furnace, then heating to 800 ℃ at a speed of 100 ℃/min, and preserving heat for 10 minutes, wherein the pressure is controlled not to exceed 25 MPa; and then heating to 1500 ℃ at a speed of 100 ℃/min, preserving heat for 5 minutes, controlling the pressure intensity not to exceed 50MPa in sintering, cooling to room temperature after heat preservation is finished, and cooling to room temperature at a speed of 100 ℃/min after heat preservation is finished, thus obtaining the W-V-Ta-Zr-Hf high-entropy alloy material.
The sintered high-entropy alloy has a close-packed hexagonal structure, uniform tissue morphology, relative density of over 99.1 percent of theoretical density, and high hardness and strength. The average hardness value of 581.2Hv is superior to that of a pure tungsten material (microhardness is 320-360 Hv), the strength of the material is obviously improved, and the compressive strength at room temperature is 1207.6 MPa.
Example 2:
in the embodiment, the WVTaZrHf single-phase refractory high-entropy alloy comprises W, V, Ta, Zr and Hf, wherein the components in atomic percentage are as follows: w23%, V23%, Ta 23%, Zr 8% and Hf 23%.
The original powder particle size was: the particle size of W powder is 2 μm, the particle size of V powder is 25 μm, the particle size of Ta powder is 25 μm, the particle size of Zr powder is 28 μm, and the particle size of Hf powder is 38 μm.
The preparation method of the wvtazrf single-phase refractory high-entropy alloy in the embodiment includes the following steps:
step 1: mixed powder
Placing five metal powders of W, V, Ta, Zr and Hf into a drum mixer according to a certain proportion and mechanically mixing to obtain W-V-Ta-Zr-Hf composite powder;
step 2: sintering
Filling the W-V-Ta-Zr-Hf composite powder into a graphite mold, then putting the mold into a discharge plasma sintering furnace, vacuumizing the sintering furnace, then heating to 800 ℃ at a speed of 100 ℃/min, and preserving heat for 10 minutes, wherein the pressure is controlled not to exceed 25 MPa; and then heating to 1500 ℃ at a speed of 100 ℃/min, preserving heat for 5 minutes, controlling the pressure intensity not to exceed 50MPa in sintering, cooling to room temperature after heat preservation is finished, and cooling to room temperature at a speed of 100 ℃/min after heat preservation is finished, thus obtaining the W-V-Ta-Zr-Hf high-entropy alloy material.
The sintered high-entropy alloy has a crystal structure of a close-packed hexagonal structure, uniform tissue, no obvious pores, relative density of over 99.9 percent of theoretical density, and high hardness and strength. The average hardness of the material is 600.2Hv, which is superior to that of a pure tungsten material (microhardness is 320-360 Hv), the strength of the material is obviously improved, the compressive strength at room temperature is 1439.4MPa, and the fracture elongation is 8%.
Example 3:
in the embodiment, the WVTaZrHf single-phase refractory high-entropy alloy comprises W, V, Ta, Zr and Hf, wherein the components in atomic percentage are as follows: 23.5% of W, 23.5% of V, 23.5% of Ta23, 6% of Zr and 23.5% of HfHfR.
The original powder particle size was: the particle size of W powder is 2 μm, the particle size of V powder is 25 μm, the particle size of Ta powder is 25 μm, the particle size of Zr powder is 28 μm, and the particle size of Hf powder is 38 μm.
The preparation method of the wvtazrf single-phase refractory high-entropy alloy in the embodiment includes the following steps:
step 1: mixed powder
Placing five metal powders of W, V, Ta, Zr and Hf into a drum mixer according to a certain proportion and mechanically mixing to obtain W-V-Ta-Zr-Hf composite powder;
step 2: sintering
Filling the W-V-Ta-Zr-Hf composite powder into a graphite mold, then putting the mold into a discharge plasma sintering furnace, vacuumizing the sintering furnace, then heating to 800 ℃ at a speed of 100 ℃/min, and preserving heat for 10 minutes, wherein the pressure is controlled not to exceed 25 MPa; and then heating to 1500 ℃ at a speed of 100 ℃/min, preserving heat for 5 minutes, controlling the pressure intensity not to exceed 50MPa in sintering, cooling to room temperature after heat preservation is finished, and cooling to room temperature at a speed of 100 ℃/min after heat preservation is finished, thus obtaining the W-V-Ta-Zr-Hf high-entropy alloy material.
The sintered high-entropy alloy has a close-packed hexagonal structure, uniform structure, large grains, no obvious pores, relative density of over 99.6 percent of theoretical density, and high hardness and strength. The average hardness value of 576.3Hv is superior to that of a pure tungsten material (microhardness is 320-360 Hv), the strength of the material is obviously improved, and the compressive strength at room temperature is 1327.3 MPa.
Claims (2)
1. A high-strength WVTaZrHf refractory high-entropy alloy is characterized in that:
the WVTaZrHf refractory high-entropy alloy comprises the following components in percentage by atom: 22.5 to 23.5 percent of W, 22.5 to 23.5 percent of V, 22.5 to 23.5 percent of Ta, 6 to 10 percent of Zr and 22.5 to 23.5 percent of Hf;
the WVTaZrHf refractory high-entropy alloy is prepared by a method comprising the following steps:
step 1: mixed powder
Putting five metal powders of W, V, Ta, Zr and Hf into a drum mixer according to the proportion and mechanically mixing to obtain W-V-Ta-Zr-Hf composite powder;
step 2: sintering
Filling the W-V-Ta-Zr-Hf composite powder into a graphite mold, then putting the mold into a discharge plasma sintering furnace, vacuumizing the sintering furnace, then heating to 800 ℃ and preserving heat for 10 minutes, wherein the pressure is controlled not to exceed 25 MPa; then heating to 1500 ℃ and preserving heat for 5 minutes, controlling the pressure not to exceed 50MPa in sintering, and cooling to room temperature after heat preservation is finished to obtain the W-V-Ta-Zr-Hf high-entropy alloy material;
in step 1, the original powder particle size is: the particle size of W powder is 2 μm, the particle size of V powder is 25 μm, the particle size of Ta powder is 25 μm, the particle size of Zr powder is 28 μm, and the particle size of Hf powder is 38 μm.
2. The wvtazrf refractory high-entropy alloy of claim 1, wherein:
in step 2, the heating rate is controlled to be 100 ℃/min; the cooling rate after the heat preservation is 100 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910347837.6A CN109898005B (en) | 2019-04-28 | 2019-04-28 | High-strength WVTaZrHf refractory high-entropy alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910347837.6A CN109898005B (en) | 2019-04-28 | 2019-04-28 | High-strength WVTaZrHf refractory high-entropy alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109898005A CN109898005A (en) | 2019-06-18 |
| CN109898005B true CN109898005B (en) | 2021-01-15 |
Family
ID=66956426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910347837.6A Active CN109898005B (en) | 2019-04-28 | 2019-04-28 | High-strength WVTaZrHf refractory high-entropy alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109898005B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343932B (en) * | 2019-08-28 | 2021-06-08 | 合肥工业大学 | A kind of WVTaZrSc refractory high entropy alloy with high strength and preparation method thereof |
| CN110538945B (en) * | 2019-09-19 | 2021-04-13 | 中国人民解放军陆军装甲兵学院 | Refractory high-entropy alloy stranded wire material, application and preparation method thereof |
| CN113652595B (en) * | 2021-08-23 | 2022-10-04 | 太原理工大学 | High-strength and high-toughness TiZrHfNbTaW x Refractory high-entropy alloy and preparation method thereof |
| CN114941099B (en) * | 2022-05-26 | 2023-03-21 | 合肥工业大学 | A high-strength and high-hardness W-Ta-V-Zr system refractory high-entropy alloy and its preparation method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170314097A1 (en) * | 2016-05-02 | 2017-11-02 | Korea Advanced Institute Of Science And Technology | High-strength and ultra heat-resistant high entropy alloy (hea) matrix composites and method of preparing the same |
| CN105950945B (en) * | 2016-06-29 | 2018-04-13 | 华南理工大学 | A kind of high intensity high-entropy alloy NbMoTaWVCr and preparation method thereof |
| CN107096923B (en) * | 2017-04-28 | 2019-04-12 | 西安交通大学 | The preparation method of high-melting-point high-entropy alloy spherical powder based on laser gain material manufacture |
| US20190024198A1 (en) * | 2017-07-19 | 2019-01-24 | The Industry & Academic Cooperation In Chungnam National University (Iac) | Precipitation Hardening High Entropy Alloy and Method of Manufacturing the Same |
-
2019
- 2019-04-28 CN CN201910347837.6A patent/CN109898005B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| Microstructure, phase stability and mechanical properties;Zhidong Han等;《Progress in Natural Science: Materials International》;20151031;第365-369页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109898005A (en) | 2019-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109898005B (en) | High-strength WVTaZrHf refractory high-entropy alloy and preparation method thereof | |
| CN106435323B (en) | A kind of oxide dispersion intensifying ODS high-entropy alloys and preparation method thereof | |
| CN104372230B (en) | High-strength high-toughness ultrafine-grained high-entropy alloy and preparation method thereof | |
| CN112941351B (en) | Preparation method of powder metallurgy titanium and titanium alloy with ultrahigh fatigue strength | |
| CN109338172A (en) | A kind of high-entropy alloy reinforced 2024 aluminum matrix composite material and preparation method thereof | |
| CN102925780A (en) | Titanium-nickel-aluminum alloy material and its preparation process | |
| CN103305722B (en) | A kind of tough titanium group high temperature Alloy And Preparation Method of height of bimorph construction and application | |
| CN107971499A (en) | The method for preparing spherical titanium aluminium-based alloyed powder end | |
| CN108588534B (en) | A kind of in-situ self-generated carbide dispersion reinforced multi-principal alloy and preparation method thereof | |
| CN104961467A (en) | High-toughness ceramic matrix composite and preparing method and application thereof | |
| CN107475547A (en) | A kind of preparation method of double yardstick titanium alloy materials | |
| CN114032409B (en) | A kind of preparation method of low cost and high performance titanium oxide alloy material | |
| CN112941366B (en) | Method for preparing high-performance powder metallurgy titanium and titanium alloy from ultrafine titanium powder | |
| CN106906379B (en) | Double mesostructure titanium alloys based on whiskers high-toughenedization in situ and preparation and application | |
| CN113373364A (en) | Particle-reinforced refractory high-entropy composite material and preparation method thereof | |
| CN108546863A (en) | A kind of more pivot high temperature alloys and preparation method thereof | |
| CN110669977A (en) | Light super-tough high-strength NbTiVAlxZry as-cast high-entropy alloy | |
| CN114799155B (en) | Preparation method of ceramic particle reinforced refractory high entropy alloy | |
| CN105177385A (en) | Nb-Si-Ti-W-Hf composite material and preparation method thereof | |
| CN107119202A (en) | A kind of method for improving titanium alloy intensity | |
| CN110343932B (en) | A kind of WVTaZrSc refractory high entropy alloy with high strength and preparation method thereof | |
| CN114836665B (en) | Ta-W-Hf-Re-C alloy and preparation method of bar thereof | |
| CN107937840B (en) | A kind of titanium aluminum alloy composite material and preparation method thereof | |
| CN106636985B (en) | A kind of metal glass composite material and preparation method thereof | |
| CN106756646A (en) | A kind of Strengthening and Toughening metal glass composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |