CN113088787B

CN113088787B - Single-phase WNbMoTaZr series refractory high-entropy alloy and preparation method thereof

Info

Publication number: CN113088787B
Application number: CN202110348397.3A
Authority: CN
Inventors: 陈顺华; 李天�; 吴玉程; 杨海东; 秦永强; 张俊生; 唐火红; 张聚臣; 常伟杰
Original assignee: Hefei University of Technology
Current assignee: Hefei University of Technology
Priority date: 2021-03-31
Filing date: 2021-03-31
Publication date: 2022-05-10
Anticipated expiration: 2041-03-31
Also published as: CN113088787A

Abstract

The invention discloses a single-phase WNbMoTaZr refractory high-entropy alloy and a preparation method thereof, wherein the element composition comprises W, Nb, Mo, Ta and Zr, and the molar ratio of W to Nb to Mo to Ta to Zr is 1:1:1: 0.1-0.5. The alloy of the invention has higher strength, plasticity and hardness, good thermal stability and huge application potential in high temperature environment.

Description

Single-phase WNbMoTaZr series refractory high-entropy alloy and preparation method thereof

Technical Field

The invention belongs to the technical field of metal materials and preparation thereof, and particularly relates to a single-phase WNbMoTaZr series refractory high-entropy alloy and a preparation method thereof.

Background

The high-entropy alloy is a novel metal material and is proposed for the first time by Chinese scholars in the root of Lei Yi. Different from the design concept of the traditional alloy, the high-entropy alloy is composed of a plurality of main elements, the mole ratio of each element is between 5% and 35%, and because of the distinctive alloy components and design modes, a plurality of alloys with different components can be formed, and the high-entropy alloy has huge application potential. Because the high entropy alloy has high mixed entropy due to the composition of a plurality of different elements, the alloy tends to form a solid solution structure and is not easy to form intermetallic compounds. Since alloys are composed of a variety of major metallic elements, high entropy alloys are also referred to as multi-principal element alloys. The high-entropy alloy has high strength, high hardness, strong corrosion resistance, radiation resistance and the like. At present, the high-entropy alloy is applied to the fields of aerospace, transportation and the like.

The refractory high-entropy alloy has the potential of becoming a high-temperature structural material because each component element has high melting point and has better mechanical property at high temperature. The WNbMoTa high-entropy alloy is a typical refractory high-entropy alloy, has good strength at room temperature and high temperature, but has poor plasticity at room temperature, and the application of the WNbMoTa high-entropy alloy as an engineering structure material is seriously influenced. Therefore, the development of the refractory high-entropy alloy with higher strength and better plasticity has important significance on the basis.

Disclosure of Invention

Based on the problems in the prior art, the invention provides a single-phase WNbMoTaZr series refractory high-entropy alloy and a preparation method thereof, aiming at improving the hardness, the strength and the plasticity of the obtained alloy compared with the WNbMoTa high-entropy alloy.

In order to achieve the purpose, the invention adopts the following technical scheme:

the single-phase WNbMoTaZr refractory high-entropy alloy comprises W, Nb, Mo, Ta and Zr, wherein the molar ratio of W to Nb to Mo to Ta to Zr is 1:1:1: 0.1-0.5.

The preparation method of the WNbMoTaZr refractory high-entropy alloy comprises the following steps:

step 1, pretreating metal raw materials

Removing oxide layers on the surfaces of high-purity W, Nb, Mo, Ta and Zr block raw materials by using a file and abrasive paper, then ultrasonically cleaning the polished raw materials in alcohol, and finally taking out the raw materials and air-drying or blow-drying the raw materials;

step 2, weighing

Weighing raw materials according to the total mass of the required alloy and the proportion of each element;

step 3, smelting

31, sequentially putting the metal raw materials of all elements into a water-cooled copper crucible of a vacuum arc melting furnace from low to high according to the melting point of each element in the alloy, putting a high-purity titanium ingot into the other crucible, and closing the furnace chamber;

step 32, firstly opening the mechanical pump to vacuumize to below 5Pa, and then opening the molecular pump to vacuumize to 8 × 10^-4Pa below; then filling high-purity argon until the pressure of the furnace chamber is 0.95 Mpa;

step 33, smelting the titanium ingot for 1-2 minutes after arc striking, fully absorbing residual oxygen in the cavity, moving the electric arc to a raw material, and smelting the alloy until all the raw materials are fused together and maintained for 5-10 minutes;

step 34, overturning the alloy ingot by using a manipulator, and repeating the step 33; the components of the alloy ingot are uniform by repeated melting, and the WNbMoTaZr series refractory high-entropy alloy is obtained.

Preferably, in step 1, the purity of the W, Nb, Mo, Ta and Zr bulk raw materials is not less than 99.95%.

Preferably, in step 2, the weight is accurate to. + -. 0.001 g.

Preferably, in step 31, the vacuum arc melting furnace is a WK series vacuum arc melting furnace.

Preferably, in step 32, the purity of the high-purity argon gas is not less than 99.9%.

Preferably, in the step 33, the arc striking current is 20-30A, and the smelting current is 250-300A.

Preferably, in step 34, the number of times of melting is not less than 10.

The invention has the beneficial effects that:

1. five refractory elements of W, Nb, Mo, Ta and Zr are selected as alloy components, the smelted alloy has good high-temperature mechanical property, and compared with WNbMoTa high-entropy alloy, the alloy has higher strength, plasticity and hardness at normal temperature, and has good application prospect.

2. The preparation method of the refractory high-entropy alloy is simple and feasible, and has wide application prospect.

3. The WNbMoTaZr refractory high-entropy alloy has a single BCC phase structure in a crystal phase.

Drawings

FIG. 1 is a schematic diagram of hardness measurement point locations;

FIG. 2 is WNbMoTaZr in example 1_0.3XRD pattern of the alloy;

FIG. 3 is WNbMoTaZr in example 1_0.3A compressive stress-strain plot of the alloy;

FIG. 4 shows WNbMoTaZr in example 1_0.3A DSC curve of the alloy;

FIG. 5 shows WNbMoTaZr in example 2_0.5XRD pattern of the alloy;

FIG. 6 is WNbMoTaZr in example 2_0.5A compressive stress-strain plot of the alloy;

FIG. 7 shows WNbMoTaZr in example 2_0.5DSC curve of the alloy.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. The following disclosure is merely exemplary and illustrative of the inventive concept, and those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Example 1

The composition of the high-entropy alloy in the embodiment is WNbMoTaZr_0.3Wherein the molar ratio of W, Nb, Mo, Ta and Zr is 1:1:1:1: 0.3.

This example WNbMoTaZr_0.3The preparation method of the high-entropy alloy ingot comprises the following steps:

step 1: pretreatment of metal raw material

Removing oxide layers on the surfaces of high-purity W, Nb, Mo, Ta and Zr blocky raw materials by using a file and abrasive paper, putting the polished raw materials into a beaker containing absolute ethyl alcohol, and putting the beaker into an ultrasonic cleaning machine for cleaning for 5 minutes to remove impurities and stains on the metal surface; finally, taking out the raw materials and drying the raw materials by a blower.

Step 2, weighing

And calculating the mass required by each element according to the molar ratio of each element according to the total mass of the required alloy, and weighing each raw material by using a high-precision electronic balance.

Step 3, smelting

And 31, sequentially putting the metal raw materials of all the elements into a water-cooled copper crucible of a vacuum arc melting furnace from low to high according to the melting points of all the elements in the alloy, putting a high-purity titanium ingot into the other crucible, and closing the furnace chamber.

Step 32, firstly opening the mechanical pump to vacuumize to below 5Pa, and then opening the molecular pump to vacuumize to 8 × 10^-4Pa below; then high-purity argon is filled until the pressure of the furnace chamber is 0.95 Mpa.

And step 33, smelting the titanium ingot for 1-2 minutes after arc striking (the arc striking current is 25A), fully absorbing residual oxygen in the cavity, moving the electric arc to the raw materials, and smelting the alloy (the smelting current is 280A) until all the raw materials are fused together and maintaining for 6 minutes.

Step 34, overturning the alloy ingot by using a manipulator, and repeating the step 33; repeatedly smelting for 10 times to ensure that the components of the alloy ingot are uniform, thus obtaining WNbMoTaZr_0.3Refractory high entropy alloy.

WNbMoTaZr obtained in this example_0.3The structural characterization and mechanical property test of the alloy are as follows:

1. about 0.3g of powder was prepared from an alloy ingot by a mechanical method, and the phase structure of the alloy was analyzed by obtaining the X-ray diffraction pattern of the alloy by a fixed target X-ray diffractometer.

2. Cutting three cuboid compression samples of 3mm multiplied by 6mm from an alloy ingot by using a medium-speed wire cutting machine, polishing the surfaces of the cut samples by using sand paper of 240 meshes, 400 meshes, 800 meshes and 2000 meshes in sequence to remove a deteriorated layer, and performing a compression experiment on the polished samples by using a material electronic universal tester to obtain an engineering stress-strain curve of the samples.

3. Cutting a plate with the thickness of 2mm and parallel upper and lower surfaces from the alloy ingot by using a medium wire cutting machine, sequentially polishing the surface of the cut sample by using 240-mesh, 400-mesh, 800-mesh and 2000-mesh abrasive paper to remove a deteriorated layer, and polishing for 5 minutes by using a mechanical polishing machine to enable the surface to be measured to be smooth and flat. The hardness of the samples was measured using a micro vickers hardness tester, and six points were measured equidistantly for each sample along the direction shown in fig. 1.

4. About 0.3g of powder was prepared from the alloy ingot by a mechanical method, and measured by a synchronous thermal analyzer to obtain a DSC curve of the alloy.

The results of the above tissue structure characterization and mechanical property test are shown in fig. 2, fig. 3, fig. 4 and table 1. This example WNbMoTaZr_0.3The high-entropy alloy crystal structure is a single body-centered cubic structure, has a uniform tissue structure and does not have obvious pores or impurities. DSC results show that the alloy has good thermal stability in the range of room temperature to 1400 ℃.The average value of the hardness of the alloy is 518HV, which is superior to pure tungsten (the hardness is 320-360 HV) and WNbMoTa high-entropy alloy (the hardness is 450 HV). The yield strength of the alloy reaches 1407Mpa, the compression plasticity is about 8.4 percent, and the alloy is superior to WNbMoTa high-entropy alloy (the yield strength is 1211Mpa, and the compression plasticity is about 1 percent).

Example 2

The composition of the high-entropy alloy in the embodiment is WNbMoTaZr_0.5Wherein the molar ratio of W, Nb, Mo, Ta and Zr is 1:1:1:1: 0.5.

This example WNbMoTaZr_0.5The preparation method of the high-entropy alloy ingot is the same as that of example 1.

WNbMoTaZr obtained in this example_0.5The method for the structural characterization and mechanical property test of the alloy is the same as that of example 1, and the test results are shown in fig. 5, fig. 6, fig. 7 and table 1. WNbMoTaZr of this example_0.5The crystal structure of the high-entropy alloy is still a single body-centered cubic structure, the organization structure is uniform, and obvious pores and impurities are not generated. DSC results show that the alloy has good thermal stability in the range of room temperature to 1400 ℃. The average value of the hardness of the alloy is 546HV, which is superior to pure tungsten (the hardness is 320-360 HV) and WNbMoTa high-entropy alloy (the hardness is 450 HV). The yield strength of the alloy reaches 1584MPa, the compression plasticity is about 11.4 percent, and the alloy is superior to WNbMoTa high-entropy alloy (the yield strength is about 1211MPa, and the compression plasticity is about 1 percent).

TABLE 1 hardness of alloys obtained in two examples

The present invention is not limited to the above exemplary embodiments, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A single-phase WNbMoTaZr refractory high-entropy alloy is characterized in that: the high-entropy alloy comprises W, Nb, Mo, Ta and Zr, wherein the molar ratio of W to Nb to Mo to Ta to Zr is 1:1:1: 0.1-0.5, and the high-entropy alloy is of a single-phase BBC structure; the preparation method of the single-phase WNbMoTaZr refractory high-entropy alloy comprises the following steps:

step 1, pretreating metal raw materials

step 2, weighing

step 3, smelting

step 32, firstly opening the mechanical pump to vacuumize to below 5Pa, and then opening the molecular pump to vacuumize to 8 x 10^-4Pa below; then filling high-purity argon until the pressure of the furnace chamber is 0.95 Mpa;

step 34, overturning the alloy ingot by using a manipulator, and repeating the step 33; the above steps are repeated for not less than 10 times to make the components of the alloy ingot uniform, and the WNbMoTaZr series refractory high-entropy alloy is obtained.

2. The single-phase WNbMoTaZr refractory high-entropy alloy of claim 1, wherein: in the step 1, the purities of the W, Nb, Mo, Ta and Zr bulk raw materials are not lower than 99.95%.

3. The single-phase WNbMoTaZr refractory high-entropy alloy of claim 1, wherein: in step 2, the weight is accurate to +/-0.001 g.

4. The single-phase WNbMoTaZr refractory high-entropy alloy of claim 1, wherein: in step 31, the vacuum arc melting furnace is a WK series vacuum arc melting furnace.

5. The single-phase WNbMoTaZr refractory high-entropy alloy of claim 1, wherein: in step 32, the purity of the high-purity argon is not less than 99.9%.

6. The single-phase WNbMoTaZr refractory high-entropy alloy of claim 1, wherein: in step 33, the arc striking current is 20-30A, and the smelting current is 250-300A.