阅读说明：本技术 一种结构功能一体化的高熵合金及其制备方法 (High-entropy alloy with integrated structure and function and preparation method thereof ) 是由 潘虎成 滕常青 吴璐 邓志勇 张伟 毛建军 覃检涛 伍晓勇 于 2020-07-30 设计创作，主要内容包括：本发明公布了一种结构功能一体化的基于Al-Nb-Zr-Mo-V-Hf体系高熵合金,属于高熵合金材料领域,其组分按质量百分比为：铝：4～15%；铌：20～30%；锆：20～60%；钼：5～15%；钒：1～5%,余量为铪元素(0.01～20.0%)和不可避免的杂质；针对目前典型BCC结构难熔高熵合金如TaNbMoW、TaNbMoWV等含有大量高密度金属元素,合金密度大,成本高,室温塑性差,难以作为结构材料应用的瓶颈问题,同时以外的研究为对可吸收中子的高熵合金研究未给予充分的重视,本发明提出一种基于Al-Nb-Zr-Mo-V-Hf体系的高熵合金,并充分考虑Hf元素的特殊作用,从而实现高熵合金的结构功能一体化。(The invention discloses a structure-function integrated high-entropy alloy based on an Al-Nb-Zr-Mo-V-Hf system, which belongs to the field of high-entropy alloy materials and comprises the following components in percentage by mass: aluminum: 4-15%; niobium: 20-30%; zirconium: 20-60%; molybdenum: 5-15%; vanadium: 1 to 5 percent of hafnium element (0.01 to 20.0 percent) and inevitable impurities; the invention provides a high-entropy alloy based on an Al-Nb-Zr-Mo-V-Hf system, and fully considers the special function of Hf element, thereby realizing the structural function integration of the high-entropy alloy.)

1. The Al-Nb-Zr-Mo-V-Hf system based high-entropy alloy with integrated structure and function is characterized by comprising the following components in percentage by mass: aluminum: 4-15%; niobium: 20-30%; zirconium: 20-60%; molybdenum: 5-15%; vanadium: 1 to 5%, and the balance of hafnium element (0.01 to 20.0%) and inevitable impurities.

2. The Al-Nb-Zr-Mo-V-Hf system high-entropy alloy with integrated structure and function according to claim 1, is characterized by comprising the following components in percentage by mass: aluminum: 4-15%; niobium: 20-30%; zirconium: 20-45%; molybdenum: 5-10%; vanadium: 1 to 5%, and the balance of hafnium element (0.01 to 10.0%) and inevitable impurities.

3. The Al-Nb-Zr-Mo-V-Hf system high-entropy alloy with integrated structure and function according to claim 2 is characterized by comprising the following components in percentage by mass: aluminum: 4 percent; niobium: 30 percent; zirconium: 45 percent; molybdenum: 10 percent; vanadium: 1%, and the balance of hafnium element (10.0%) and inevitable impurities.

4. The Al-Nb-Zr-Mo-V-Hf system high-entropy alloy with integrated structure and function according to claim 1, is characterized by comprising the following components in percentage by mass: aluminum: 4-10%; niobium: 20-30%; zirconium: 20-60%; molybdenum: 5-15%; vanadium: 1 to 4.99%, and the balance of hafnium element (0.01 to 20.0%) and inevitable impurities.

5. The Al-Nb-Zr-Mo-V-Hf system high-entropy alloy with integrated structure and function according to claim 4 is characterized by comprising the following components in percentage by mass: aluminum: 10 percent; niobium: 20 percent; zirconium: 60 percent; molybdenum: 5 percent; vanadium: 4.99%, and the balance of hafnium element (0.01%) and inevitable impurities.

6. The Al-Nb-Zr-Mo-V-Hf system high-entropy alloy with integrated structure and function according to claim 1, is characterized by comprising the following components in percentage by mass: aluminum: 4-15%; niobium: 20-30%; zirconium: 20-39%; molybdenum: 5-15%; vanadium: 1 to 5%, and the balance of hafnium element (0.01 to 20.0%) and inevitable impurities.

7. The Al-Nb-Zr-Mo-V-Hf system high-entropy alloy with integrated structure and function according to claim 6 is characterized by comprising the following components in percentage by mass: aluminum: 15 percent; niobium: 20 percent; zirconium: 39 percent; molybdenum: 5 percent; vanadium: 1%, and the balance of hafnium element (20.0%) and inevitable impurities.

8. The Al-Nb-Zr-Mo-V-Hf system high-entropy alloy with integrated structure and function according to claim 1, is characterized by comprising the following components in percentage by mass: aluminum: 4-15%; niobium: 20-30%; zirconium: 20-60%; molybdenum: 5-15%; vanadium: 1 to 5%, and the balance of hafnium element (0.01 to 15.0%) and inevitable impurities.

9. The Al-Nb-Zr-Mo-V-Hf system high-entropy alloy with integrated structure and function according to claim 1, is characterized by comprising the following components in percentage by mass: aluminum: 4-10%; niobium: 20-25%; zirconium: 20-46%; molybdenum: 5-9%; vanadium: 1 to 2%, and the balance of hafnium element (0.01 to 8.0%) and inevitable impurities.

10. The method for preparing the structure-function integrated Al-Nb-Zr-Mo-V-Hf system high-entropy alloy according to any one of claims 1-9, specifically comprising the following steps:

(1) preparing raw materials: weighing required alloy raw materials according to the Al-Nb-Zr-Mo-V-Hf system high-entropy alloy proportion;

(2) arc melting: under the protection of protective gas, rapidly heating and melting Al, Zr, Nb, Mo, V and Zr-Hf intermediate alloy; in order to obtain alloy ingots with uniform components, all samples are repeatedly smelted for five times, and the samples are turned over after each smelting; in order to avoid the influence on the structure and the performance of the sample caused by the difference of smelting time and smelting current, after all alloy elements are completely melted into liquid state in each smelting of the sample, the current is directly closed after the smelting is kept for 1 min; ensure that the surface of all the samples after melting remains bright, i.e. no significant oxidation of the alloy occurs during the melting preparation.

Technical Field

The invention belongs to the field of high-entropy alloy materials, and particularly relates to a novel high-entropy alloy with integrated structure and function and a preparation method thereof.

Background

The radiation resistance is one of the key properties of the reactor cladding material and is also a difficulty in current research. The research on the ion irradiation outside the reactor finds that the irradiation resistance of the high-entropy alloy is possibly superior to that of the existing cladding material, and the kinetically slow diffusion effect of the high-entropy alloy is probably the main mechanism of the excellent irradiation resistance of the high-entropy alloy. Xia and the like research the irradiation damage condition of AlCoCrFeNi series high-entropy alloy under the irradiation of gold ions. It was found that the microstructure studies remained stable even at irradiation doses up to 50 dpa. The study also compared the radiation resistance of high entropy alloys with alloys commonly used in various types of reactors. It can be seen that the radiation swelling rate of the high entropy alloy is lowest at the same dpa, and is far lower than that of 316 stainless steel and Fe-15Cr-20Ni alloy. Matheus et al investigated the foaming of FeCrMnNi (FCC) -based high entropy alloys and 348(FCC) austenitic stainless steels with a cocrystal structure containing four elements of Fe, Cr, Mn, Ni under irradiation with helium and xenon ions using in situ transmission electron microscopy. By contrast, the growth rate of He and Xe bubbles is relatively low in fecrmmnni high entropy alloys. Researchers believe this is because the poor diffusion kinetics in high entropy alloys result in high entropy alloys having better resistance to fission gases. Researches show that under the irradiation effect, the high-entropy alloy with the structure of FCC, BCC or BCC + FCC mixture and the like can keep the stability of the phase structure, and the research of Egami and the like proves that the Zr-Hf-Nb alloy has high irradiation resistance through charged ion irradiation experiments.

In addition, in the aspect of thermal neutron absorption characteristics, the absorption cross section of the thermal neutrons of the Hf element is 115 bar, which is 1-2 orders of magnitude higher than that of other alloy elements (Zr: 0.18 bar; Ti: 5.6 bar; Al: 0.22 bar), so that the Hf-containing high-entropy alloy can better serve some special functional requirements. Therefore, the high-entropy alloy has the advantages of high radiation damage resistance and the like besides the advantages of high strength and high plasticity which are traditionally considered, and can also show the characteristics of high neutron absorption cross section and the like through the addition of proper elements such as Hf and the like, so that special parts in the nuclear power field show the performance characteristics of integration of structural characteristics and functional characteristics.

However, most of previous researches are focused on ternary systems such as Zr-Hf-Nb, the elongation of the alloy is poor, and researches on six-element system high-strength and high-toughness and high-entropy alloy represented by Al-Nb-Zr-Mo-V-Hf are rarely reported; in addition, since other studies have not sufficiently considered the neutron absorption capability of the Hf-containing high-entropy alloy, the addition amount of the Hf element tends to have a large randomness. Therefore, the high-entropy alloy based on the Al-Nb-Zr-Mo-V-Hf system is developed, and the special function of the Hf element is fully considered, so that the structural function integration of the high-entropy alloy is realized, and the high-entropy alloy has important significance for the development and application of high-end nuclear materials.

Disclosure of Invention

The invention provides a high-entropy alloy based on an Al-Nb-Zr-Mo-V-Hf system, and fully considers the special function of Hf element, thereby realizing the structural function integration of the high-entropy alloy.

The invention relates to an Al-Nb-Zr-Mo-V-Hf system-based high-entropy alloy with integrated structure and function, which comprises the following components in percentage by mass: aluminum: 4-15%; niobium: 20-30%; zirconium: 20-60%; molybdenum: 5-15%; vanadium: 1 to 5%, and the balance of hafnium element (0.01 to 20.0%) and inevitable impurities.

The technical scheme is further improved and optimized, and the components of the material comprise the following components in percentage by mass: aluminum: 4-15%; niobium: 20-30%; zirconium: 20-45%; molybdenum: 5-10%; vanadium: 1 to 5%, and the balance of hafnium element (0.01 to 10.0%) and inevitable impurities.

The technical scheme is further improved and optimized, and the components of the material comprise the following components in percentage by mass: aluminum: 4 percent; niobium: 30 percent; zirconium: 45 percent; molybdenum: 10 percent; vanadium: 1%, and the balance of hafnium element (10.0%) and inevitable impurities.

The technical scheme is further improved and optimized, and the components of the material comprise the following components in percentage by mass: aluminum: 4-10%; niobium: 20-30%; zirconium: 20-60%; molybdenum: 5-15%; vanadium: 1 to 4.99%, and the balance of hafnium element (0.01 to 20.0%) and inevitable impurities.

The technical scheme is further improved and optimized, and the components of the material comprise the following components in percentage by mass: aluminum: 10 percent; niobium: 20 percent; zirconium: 60 percent; molybdenum: 5 percent; vanadium: 4.99%, and the balance of hafnium element (0.01%) and inevitable impurities.

The technical scheme is further improved and optimized, and the components of the material comprise the following components in percentage by mass: aluminum: 4-15%; niobium: 20-30%; zirconium: 20-39%; molybdenum: 5-15%; vanadium: 1 to 5%, and the balance of hafnium element (0.01 to 20.0%) and inevitable impurities.

The technical scheme is further improved and optimized, and the components of the material comprise the following components in percentage by mass: aluminum: 15 percent; niobium: 20 percent; zirconium: 39 percent; molybdenum: 5 percent; vanadium: 1%, and the balance of hafnium element (20.0%) and inevitable impurities.

The technical scheme is further improved and optimized, and the components of the material comprise the following components in percentage by mass: aluminum: 4-15%; niobium: 20-30%; zirconium: 20-60%; molybdenum: 5-15%; vanadium: 1 to 5%, and the balance of hafnium element (0.01 to 15.0%) and inevitable impurities.

The technical scheme is further improved and optimized, and the components of the material comprise the following components in percentage by mass: aluminum: 4-10%; niobium: 20-25%; zirconium: 20-46%; molybdenum: 5-9%; vanadium: 1 to 2%, and the balance of hafnium element (0.01 to 8.0%) and inevitable impurities.

The Al-Nb-Zr-Mo-V-Hf system based high-entropy alloy with integrated structure and function has the following tensile yield strength: 760 to 1216MPa, elongation: 5 to 15 percent.

The invention discloses a preparation method of an Al-Nb-Zr-Mo-V-Hf system based high-entropy alloy with integrated structure and function, which specifically comprises the following steps:

(1) preparing raw materials: weighing required alloy raw materials according to the Al-Nb-Zr-Mo-V-Hf system high-entropy alloy proportion;

(2) arc melting: under the protection of protective gas, rapidly heating and melting Al, Zr, Nb, Mo, V and Zr-Hf intermediate alloy; in order to obtain alloy ingots with uniform components, all samples are repeatedly smelted for five times, and the samples are turned over after each smelting. In order to avoid that the structure and the performance of the sample are possibly influenced to a certain extent due to the difference of smelting time and smelting current, the current is directly closed after all alloy elements are completely melted into liquid state in each smelting of the sample and the smelting is kept for 1 min. Ensure that the surface of all the samples after melting remains bright, i.e. no significant oxidation of the alloy occurs during the melting preparation.

Has the advantages that:

the Al-Nb-Zr-Mo-V-Hf system high-entropy alloy provided by the invention is a novel nuclear material with integrated structure and function, and due to the addition of Al element, compared with the traditional BCC structure refractory high-entropy alloys TaNbMoW and TaNbMoWV, the extensibility at room temperature is greatly improved; in addition, with the addition of Hf element, the yield strength level of the high-entropy alloy of the system can be greatly improved, and meanwhile, the high-entropy alloy also retains better plastic deformation capability, has the elongation up to 15 percent and has good industrial application prospect; more importantly, the high-entropy alloy containing the Hf element can also strongly absorb thermal neutrons in a reactor, so that the high-entropy alloy provides an optimal candidate material with high toughness and high neutron absorption characteristics for parts with special purposes in the military industry. Therefore, the high-entropy alloy based on the Al-Nb-Zr-Mo-V-Hf system realizes the structural function integration of the high-entropy alloy by fully considering the special function of the Hf element, and has important significance for the development and application of high-end nuclear materials.

Detailed Description

The present invention will be described in further detail in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

On the contrary, the invention is intended to cover alternatives, modifications, equivalents and alternatives which may be included within the spirit and scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present invention, certain specific details are set forth in order to provide a better understanding of the present invention. It will be apparent to one skilled in the art that the present invention may be practiced without these specific details. The present invention will be further described with reference to the following embodiments.