阅读说明：本技术 一种难熔高熵合金绞股丝材、其应用及制备方法 (Refractory high-entropy alloy stranded wire material, application and preparation method thereof ) 是由 柳建 蔡志海 屈会强 刘军 仝永刚 郭杰 秦航 于 2019-09-19 设计创作，主要内容包括：本发明涉及一种难熔高熵合金绞股丝材、其应用及制备方法,该难熔高熵合金绞股丝材由5-7种不同的高熔点纯金属丝或含高熔点金属的合金丝绞合而成,本发明难熔高熵合金绞股丝材制备具有工艺简单,易操作,效率高,成本低的优点；该难熔高熵合金绞股丝材具有多种应用,可应用来焊接相应的合金形成高熵合金焊缝；也可采用堆焊的形式制备难熔高熵合金,也可在此基础上采用叠层制造技术制备大尺寸,复杂形状的难熔高熵合金零部件。相较于真空电弧熔炼以及激光熔覆等方法,本发明基于难熔高熵合金绞股丝材实现的增材制造技术更加方便、快捷,有效促进了高熵合金的工程应用。(The invention relates to a refractory high-entropy alloy stranded wire material, and an application and a preparation method thereof, wherein the refractory high-entropy alloy stranded wire material is formed by stranding 5-7 different high-melting-point pure metal wires or alloy wires containing high-melting-point metals; the refractory high-entropy alloy stranded wire has various applications, and can be applied to welding corresponding alloys to form high-entropy alloy welding seams; the refractory high-entropy alloy can also be prepared in a surfacing mode, and large-size and complex-shaped refractory high-entropy alloy parts can also be prepared by adopting a lamination manufacturing technology on the basis. Compared with methods such as vacuum arc melting and laser cladding, the additive manufacturing technology realized on the basis of the refractory high-entropy alloy stranded wire material is more convenient and faster, and the engineering application of the high-entropy alloy is effectively promoted.)

1. A refractory high-entropy alloy stranded wire is characterized by being formed by stranding 5-7 different high-melting-point metal wires or alloy wires containing high-melting-point metals.

2. the refractory high entropy alloy stranded wire of claim 1, wherein the refractory metal comprises tungsten, molybdenum, niobium, tantalum, vanadium, zirconium, rhenium, hafnium, titanium, iridium.

3. A high entropy alloy stranded wire material according to claim 2, wherein the high melting point metal wire has a purity higher than 99.9%.

4. The refractory high-entropy alloy stranded wire according to claim 1, wherein the diameter of the high-melting-point metal wire or the high-melting-point metal-containing alloy wire is 0.4mm to 1.0 mm.

5. The refractory high-entropy alloy stranded wire according to claim 1, wherein the refractory high-entropy alloy stranded wire is formed by stranding 4 to 6 peripheral high-melting-point metal wires or peripheral high-melting-point metal-containing alloy wires around a central high-melting-point metal wire or a central high-melting-point metal-containing alloy wire.

6. The refractory high-entropy alloy stranded wire according to claim 5, wherein the diameters of the peripheral high-melting-point metal wires or the peripheral high-melting-point metal-containing alloy wires are the same, and the diameter of the central high-melting-point metal wire or the central high-melting-point metal-containing alloy wire is not less than the diameter of the peripheral high-melting-point metal wires or the peripheral high-melting-point metal-containing alloy wires.

7. A method for preparing the refractory high-entropy alloy stranded wire material as claimed in any one of claims 1 to 6, wherein the method comprises:

A. Preparing a refractory high-entropy alloy stranded wire material;

B. Preparing refractory high-entropy alloy stranded wires by stranding, wherein when two metal wires or alloy wires of the same material exist in the raw materials, the metal wires or the alloy wires of the same material are positioned at the alignment position, the wire-withdrawing speed in the stranding process is 5-10 m/min, and the stranding distance is 10-15 mm.

8. use of the refractory high entropy alloy stranded wire of any one of claims 1 to 6 in the field of welding to make a refractory high entropy alloy weld.

9. The refractory high-entropy alloy stranded wire material of any one of claims 1 to 6, for preparing a large-size and complex-shape high-entropy alloy in the technical field of additive manufacturing.

10. Use of the refractory high entropy alloy stranded wire of any one of claims 1 to 6 in the preparation of high temperature resistant alloy materials.

Technical Field

The invention belongs to the technical field of additive manufacturing, and relates to a refractory high-entropy alloy stranded wire material, a preparation method thereof and application thereof in the technical field of welding, surfacing and arc cladding forming for preparing high-entropy alloy.

Background

The performance lag of the aero-engine caused by the lag of the high-temperature resistant material is always the main reason for restricting the problem of heart disease of warplane performance in China. The high thrust and the ultrahigh sound speed are inevitable trends of development of air-space equipment in the future, and higher requirements are provided for high temperature resistance, corrosion resistance, toughness and strength of materials. However, the use temperature of the high-temperature alloy used currently is lower than 1200 ℃ due to the limitation of the melting point of the alloy, and the high-temperature alloy can not meet the requirement of the performance development of air-space equipment in the future.

The high-entropy alloy is an alloy material prepared by mixing at least five or more (5 to 13) elements as main elements according to an equal molar ratio or a nearly equal molar ratio. The minimum atomic content of each element is not less than 5% and not more than 35% at most, so the alloy is also called multi-principal element alloy and multi-principal element high-entropy alloy. The concept of the high-entropy alloy breaks through the traditional alloy design concept mainly based on one element, so that the research of the alloy material enters a brand-new era. High entropy alloys have four major effects: the high-entropy alloy has excellent comprehensive properties such as high strength, high hardness, high wear resistance/corrosion resistance and the like due to the high entropy effect, the lattice distortion effect, the delayed diffusion effect and the cocktail effect. Particularly, the refractory high-entropy alloy is considered to be a revolutionary material in the field of aeronautical engines due to excellent high-temperature resistance and mechanical properties.

The preparation technology of the high-entropy alloy at present mainly comprises a vacuum arc melting method, a mechanical alloying-powder metallurgy method, a cladding method, a spraying method, a sputtering method and the like. The vacuum arc melting method is the most widely applied high-entropy alloy preparation technology, and the laboratory researches mostly adopt the method to prepare the high-entropy alloy. It is an electrothermal metallurgical method for smelting metal by using electric energy to produce electric arc between electrodes or between electrode and the material to be smelted. The vacuum arc melting method has the technical advantages that alloy ingots cannot be oxidized and alloy components are uniform, but the melting process is complex, the method is only used for preparing small high-entropy alloy ingots at present, large-size alloy sample pieces cannot be prepared, and complex structural parts cannot be prepared. The mechanical alloying method is a powder preparation technology, and after the high-entropy alloy powder is prepared by the method, high-entropy alloy block materials and components can be prepared by a powder metallurgy method, and high-entropy alloy coatings can also be prepared by a cladding method or a spraying method.

the mechanical alloying and powder metallurgy method can be used for preparing high-entropy alloy sample pieces with larger sizes and regular shapes, but the preparation of high-entropy alloy components with complex shapes is difficult. Cladding method, spraying method and sputtering method are the main preparation methods of high-entropy alloy coating. However, the cladding method and the spraying method are premised on preparing high-entropy alloy powder by an arc melting and gas atomization method or a mechanical alloying method. Therefore, the defects of complex process, high cost and small one-time preparation amount exist in the preparation of the high-entropy alloy at present, and the actual engineering application requirements of the high-temperature-resistant high-entropy alloy cannot be met. Therefore, the development of a high-efficiency and low-cost design and preparation technology is also a key problem to be solved urgently in the development of the high-entropy alloy. The vacuum arc melting method has the technical advantages that the alloy ingot cannot be oxidized and the alloy components are uniform, but the complex structural part cannot be prepared. Compared with metal powder, the metal wire has the advantages of high utilization rate (close to 100%), no environmental pollution, no oxidation, convenience in storage and the like. The use of wire forming to produce parts is more economical and cost effective, and the range of product sizes produced by wire forming is much larger than that produced by powder fusion techniques. The development of the high-entropy alloy wire is beneficial to realizing the engineering preparation and application of the high-entropy alloy material, and has very important practical significance and economic value.

However, the ductility and toughness of the refractory high-entropy alloy at room temperature are poor, and the drawing cannot be realized. At present, no report on a preparation method and technology of refractory high-entropy alloy wires exists.

Disclosure of Invention

The invention aims to provide a refractory high-entropy alloy wire, and an application and a preparation method thereof. By adopting the high-entropy alloy wire material and combining with an additive manufacturing technology, the preparation of a large-area and thick-size high-entropy alloy coating and the preparation of large-size and complex-shape high-entropy alloy parts can be realized.

the high-entropy alloy stranded wire material provided by the invention is formed by stranding 5-7 different high-melting-point metal wires or alloy wires containing high-melting-point metals.

The high melting point metal comprises tungsten, molybdenum, niobium, tantalum, vanadium, zirconium, rhenium, hafnium, titanium and iridium.

Preferably, the refractory high-entropy alloy stranded wire material is formed by stranding different high-melting-point metal wires of tungsten, molybdenum, niobium, tantalum and titanium.

The diameter of the high-melting-point metal wire is 0.4 mm-1.0 mm, and the purity of the high-melting-point metal wire is higher than 99.9%.

Furthermore, the refractory high-entropy alloy stranded wire material is formed by stranding 4-6 peripheral high-melting-point metal wires or alloy wires containing high-melting-point metal at the periphery around a central high-melting-point metal wire or alloy wire containing high-melting-point metal at the center. The central wire is generally selected from wires with higher hardness and relatively poorer plasticity and toughness, and the specific number of the surrounding wires can be configured according to the design condition of the high-entropy alloy components.

The diameters of the peripheral high-melting-point metal wires or the peripheral alloy wires are the same, and the diameter of the central metal wire is generally not less than that of the peripheral metal wires or the peripheral alloy wires containing high-melting-point metal. If the diameter of the central wire is smaller than that of the peripheral wires, the situation that the central wire is independently suspended and the center of the stranded wire material is possibly caused.

the invention provides a preparation method of a refractory high-entropy alloy stranded wire material, which comprises the following steps:

A. Preparing a refractory high-entropy alloy stranded wire material;

B. The refractory high-entropy alloy stranded wire material is prepared by stranding, wherein when two metal wires or alloy wires of the same material exist in the raw materials, the metal wires or the alloy wires of the same material are located at the opposite positions, preferably, the wire-withdrawing speed in the stranding process is 5-10 m/min, and the strand pitch is 10-15 mm.

The invention provides an application of the refractory high-entropy alloy stranded wire material in preparing a high-entropy alloy weld joint in the field of welding.

The invention provides application of the refractory high-entropy alloy stranded wire material in preparing high-entropy alloy by adopting a surfacing or arc cladding forming technology.

The invention provides an application of the refractory high-entropy alloy stranded wire material in preparation of a high-temperature-resistant alloy material.

The invention has the beneficial effects that: the invention creatively combines the stranded welding wire technology with the high-entropy alloy to obtain the stranded wire material for preparing the refractory high-entropy alloy. The preparation process of the refractory high-entropy alloy stranded wire material has the advantages of simple process, easy operation, high processing efficiency and low cost; the refractory high-entropy alloy stranded wire has multiple applications, and on one hand, the wire can be used for welding corresponding alloys to form high-entropy alloy welding seams; on the other hand, the refractory high-entropy alloy can be prepared in a surfacing mode, and on the basis, a large-size and complex-shape refractory high-entropy alloy part can be prepared by adopting a lamination manufacturing technology. Compared with methods such as vacuum arc melting and laser cladding, the additive manufacturing technology realized on the basis of the refractory high-entropy alloy stranded wire material is more convenient and faster, and the engineering application of the high-entropy alloy is effectively promoted.

Drawings

FIG. 1 is a schematic cross-sectional view of a refractory high-entropy alloy stranded wire in example 1 of the present invention.

FIG. 2 is a front view of a refractory high-entropy alloy stranded wire in example 1 of the present invention.

FIG. 3 is a photograph of a weld bead of a high entropy alloy of example 2 of the present invention.

FIG. 4 shows EDS analysis and test results of the distribution of Ti as a high-entropy alloy element in example 2 of the present invention.

FIG. 5 shows the EDS analysis and test results of the distribution of Mo in the high-entropy alloy element of example 2 of the invention.

FIG. 6 shows EDS analysis and test results of the distribution of W in the high-entropy alloy according to example 2 of the present invention.

FIG. 7 shows the EDS analysis and test results of the distribution of Nb in the high-entropy alloy element of example 2 of the invention.

FIG. 8 shows the EDS analysis and test results of the distribution of Ta as the high-entropy alloy element in example 2 of the present invention.

FIG. 9 shows the XRD analysis and test results of the phase structure of the high-entropy alloy in example 2 of the present invention.

FIG. 10 shows the 1000 ℃ compressive strength test results of the high-entropy alloy of example 2 of the present invention.

FIG. 11 is a schematic cross-sectional view of a refractory high-entropy alloy stranded wire in example 3 of the present invention.

Detailed Description

The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. Unless otherwise specified, the starting materials described in the examples of the present application are all commercially available products.