CN115302124A - NiCrNbMoTa refractory high-entropy alloy and preparation method thereof - Google Patents
NiCrNbMoTa refractory high-entropy alloy and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K9/00—Arc welding or cutting
- B23K9/04—Welding for other purposes than joining, e.g. built-up welding
- B23K9/044—Built-up welding on three-dimensional surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K9/00—Arc welding or cutting
- B23K9/16—Arc welding or cutting making use of shielding gas
- B23K9/167—Arc welding or cutting making use of shielding gas and of a non-consumable electrode
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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Abstract
The invention discloses a NiCrNbMoTa refractory high-entropy alloy and a preparation method thereof, wherein the NiCrNbMoTa refractory high-entropy alloy comprises the elements of Ni, cr, nb, mo and Ta, and the molar percentage of the elements is 20-30% of Ni, 5-10% of Cr, 30-40% of Nb, 10-20% of Mo and 10-20% of Ta. Five metal elements of Ni, cr, nb, mo and Ta are selected as alloy composition elements, the alloy composition elements can be used for preparing high-temperature-resistant materials, nbMoTaNiCr cable-type welding wires are obtained by adopting a stranded wire method, and compared with the traditional alloy, the NiCrNbMoTa refractory high-entropy alloy obtained by adopting a TIG rotating arc additive manufacturing technology has the advantages of uniform structure, improved comprehensive properties of hardness, strength and the like, and good application prospect.
Description
Technical Field
The invention belongs to the field of additive manufacturing, and particularly relates to a NiCrNbMoTa refractory high-entropy alloy and a preparation method thereof.
Background
With the rapid development of the fields of aerospace, nuclear power, military industry and the like, the demand for high-temperature structural materials with better performance is increasing. Currently, nickel-base superalloys are used in applications where the operating temperature can be as high as 1100 ℃. However, nickel-base superalloys cannot operate at higher temperatures due to their melting point. Therefore, it is important to find materials with higher melting points and better high temperature properties. The traditional alloy design system tends to be perfect, but the development requirement of high-end equipment is difficult to meet.
The high-entropy alloy is an alloy material prepared by mixing at least five or more than five metal elements according to an equal atomic ratio or a nearly equal atomic ratio. The lowest atomic content of each element is not less than 5 percent, the highest atomic content of each element cannot exceed 35 percent, and the mixing entropy is more than 1.5R. 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. The high-entropy alloy has four effects, namely a thermodynamic high-entropy effect, a structural lattice distortion effect, a kinetic delayed diffusion effect and a performance 'cocktail' effect. As one of three major breakthroughs of the alloying theory in recent decades, the traditional alloy design concept and the unique high entropy effect are overturned, so that the alloy has excellent performances of high temperature resistance, high strength, high hardness, corrosion resistance, irradiation resistance and the like. 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 mainly comprises a vacuum arc melting method, a powder metallurgy method, a cladding method, a magnetron sputtering method and the like. The vacuum arc melting method is the most widely applied high-entropy alloy preparation technology, and laboratory researches mostly adopt the method to prepare the high-entropy alloy. The principle of the method is an electrothermal metallurgy method for smelting metal by utilizing electric energy to generate electric arcs between electrodes or between the electrodes and the smelted materials. 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 vacuum arc melting method is only used for preparing small high-entropy alloy ingots, large-size alloy sample pieces cannot be prepared, and complex structural parts cannot be prepared. The powder metallurgy method is also a common method for preparing refractory high-entropy alloy at present, and comprises the steps of taking principal component metal powder as a raw material, designing components of each component according to a specific proportion, mixing and ball-milling the raw material by using a high-energy ball mill, and forming and sintering to obtain the massive high-entropy alloy. The key problem which is not solved by the existing powder metallurgy method is that the alloy powder is easy to be polluted in the ball milling process, and grinding balls, container walls, ball milling media, process control agents and the like can pollute the sample, generate impurities and finally influence the mechanical property of the super-entropy alloy. In addition, the powder preparation can be carried out under inert gas or vacuum, so as to prevent the powder from being oxidized and nitrided.
The existing refractory high-entropy alloy preparation has the defects of complex process, high cost and small one-time preparation amount, and the actual engineering application requirements of the refractory 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 refractory high-entropy alloy. Compared with metal powder, the metal wire has the advantages of high utilization rate, no environmental pollution, difficult oxidation, convenient 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 drawing cannot be realized.
Therefore, the process for preparing the refractory high-entropy alloy needs to be further explored.
Disclosure of Invention
Aiming at various defects in the prior art and solving the problems, the NiCrNbMoTa refractory high-entropy alloy and the preparation method thereof are provided, the NiCrNbMoTa refractory high-entropy alloy comprises elements of Ni, cr, nb, mo and Ta, and the NbMoTaNiCr refractory high-entropy alloy with good performance is prepared by adopting a TIG rotating wire arc additive manufacturing process, and has uniform structure and improved comprehensive properties such as hardness, strength and the like.
In order to achieve the above purpose, the invention provides the following technical scheme:
the NiCrNbMoTa refractory high-entropy alloy comprises the following elements of Ni, cr, nb, mo and Ta, wherein the mole percentage content of each element is 20-30% of Ni, 5-10% of Cr, 30-40% of Nb, 10-20% of Mo and 10-20% of Ta.
Optionally, the mole percentage of each element is Ni 28.16%, cr 7.04%, nb 37.7%, mo14.5%, and Ta 12.6%.
The preparation method of the NiCrNbMoTa refractory high-entropy alloy comprises the following steps:
s1, stranding high-melting-point metal wires or alloy wires containing high-melting-point metals to obtain a refractory high-entropy alloy cable type welding wire, wherein the high-melting-point metals comprise Nb, mo and Ta;
and S2, carrying out surfacing treatment on the cable-type welding wire of the refractory high-entropy alloy obtained in the step S1 to obtain the NiCrNbMoTa refractory high-entropy alloy.
Optionally, in step S1, the purity of the high-melting-point metal wire is higher than 99.9%, and the diameter of the high-melting-point metal wire or the alloy wire containing the high-melting-point metal is 0.4mm to 1.0mm.
Optionally, in step S1, the refractory high-entropy alloy cable-type welding wire is formed by twisting a plurality of peripheral high-melting-point metal wires or peripheral alloy wires containing high-melting-point metal around a central high-melting-point metal wire or central alloy wire containing high-melting-point metal, and the peripheral high-melting-point metal wires or the peripheral alloy wires containing high-melting-point metal are located in the peripheral high-melting-point metal wires or the peripheral alloy wires containing high-melting-point metal, and two high-melting-point metal wires or two alloy wires containing high-melting-point metal with the same material are arranged at intervals or in opposite directions.
Optionally, the refractory high-entropy alloy cable-type welding wire is formed by twisting 3 Nb wires, 2 Ni-Cr alloy wires, 1 Ta wire, and 1 Mo wire.
Optionally, in the refractory high-entropy alloy cable-type welding wire, 1 Ni-Cr alloy wire is used as a central wire, and the other 1 Ni-Cr alloy wire, 3 Nb wires, 1 Ta wire, and 1 Mo wire are used as peripheral wires.
Optionally, in step S2, the surfacing process is performed by performing arc cladding on the refractory high-entropy alloy cable-type welding wire on the base material by using a TIG rotating arc additive manufacturing process.
Optionally, performing arc cladding forming on the refractory high-entropy alloy cable-type welding wire on the base material by adopting a TIG rotating wire arc additive manufacturing process specifically comprises the following steps:
s21, polishing, cleaning and fixing the titanium alloy plate, putting the cable type welding wire into an automatic wire feeder, and moving a tungsten electrode of a welding gun to the initial position of surfacing;
s22, setting a wire feeding angle and a wire feeding speed;
and S23, connecting cooling water, introducing high-purity argon, controlling the flow of the high-purity argon, setting TIG welding current, tungsten electrode rotation rate of a welding gun and material increase speed, and performing material increase manufacturing on the cable-type welding wire of the refractory high-entropy alloy obtained in the step S1 to obtain the NiCrNbMoTa refractory high-entropy alloy.
Optionally, in step S22, the wire feeding angle is 30 °, and the wire feeding speed is 8mm/S.
Optionally, in step S23, the purity of the high-purity argon is not less than 99.9%, the gas flow is 20L/min, the arc rotation rate is 300r/min, the welding machine current is 150A, and the material increase speed is 90mm/min.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, three refractory metal elements of Ni, cr, nb, mo and Ta are selected as alloy constituent elements, so that the alloy can be used for high-temperature resistant materials, and the NbMoTaNiCr refractory high-entropy alloy with good performance is prepared by adopting a TIG rotating wire arc additive manufacturing process, so that the structure is uniform, the comprehensive properties such as hardness and strength are improved, and compared with the traditional alloy, the alloy has higher strength, plasticity and hardness at normal temperature, and has good application prospects.
(2) By adopting a TIG rotating arc additive manufacturing process and combining a reasonable arrangement form of all metal wires or alloy wires in the refractory high-entropy alloy cable type welding wire, the obtained Ni 28.16 Cr 7.04 Nb 37.7 Mo 14.5 Ta 12.6 The refractory high-entropy alloy has higher high-temperature mechanical property, oxidation resistance, strength and hardness, and ensures the obtained Ni 28.16 Cr 7.04 Nb 37.7 Mo 14.5 Ta 12.6 The electric arc cladding quality of each part of the refractory high-entropy alloy is uniform, thereby improving the Ni content 28.16 Cr 7.04 Nb 37.7 Mo 14.5 Ta 12.6 And (3) cladding forming quality of refractory high-entropy alloy.
(3) Ni prepared by the invention 28.16 Cr 7.04 Nb 37.7 Mo 14.5 Ta 12.6 The alloy material structure is a face-centered cubic structure, the metallographic structure is uniform, and the microhardness value is 910HV. The yield strength at 750 ℃ is 597MPa, and the strength of the material is not increased along with the increase of the temperatureObviously reduced generation and stronger thermal stability.
(4) The refractory high-entropy alloy prepared by the method has the advantages of low cost of selected raw materials, simple and easy preparation method and wide application prospect.
Drawings
FIG. 1 is a schematic cross-sectional view of a refractory high-entropy alloy cable-type welding wire according to an embodiment 1 of the present invention;
FIG. 2 shows Ni in example 1 of the present invention 28.16 Cr 7.04 Nb 37.7 Mo 14.5 Ta 12.6 XRD pattern of the alloy;
FIG. 3 shows Ni in example 1 of the present invention 28.16 Cr 7.04 Nb 37.7 Mo 14.5 Ta 12.6 A hardness test chart of the alloy;
FIG. 4 shows Ni in the present invention 28.16 Cr 7.04 Nb 37.7 Mo 14.5 Ta 12.6 750 ℃ compressive stress-strain plot of the alloy;
FIG. 5 shows Ni in example 1 of the present invention 28.16 Cr 7.04 Nb 37.7 Mo 14.5 Ta 12.6 DSC profile of the alloy;
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following embodiments of the present invention are described clearly and completely, and other similar embodiments obtained by those skilled in the art without making creative efforts based on the embodiments in the present application shall fall within the protection scope of the present application.
Detailed description of the preferred embodiment 1
The embodiment provides a NiCrNbMoTa refractory high-entropy alloy, which comprises the following elements of Ni, cr, nb, mo and Ta in percentage by mole, wherein the elements comprise, by mole, 20-30% of Ni, 5-10% of Cr, 30-40% of Nb, 10-20% of Mo and 10-20% of Ta.
Wherein, nb element has good corrosion resistance, can improve the alloy strength, and has a structure of BCC; the Mo element is hard and tough, has strong oxidation resistance, is relatively stable at normal temperature, can have enough strength and creep resistance at high temperature, and has a BCC structure at high temperature; ta element has tough texture, high ductility and extremely strong corrosion resistance, does not react with aqua regia and concentrated nitric acid, and has a BCC structure at high temperature; cr element is ductile, has high corrosion resistance and oxidation resistance, is slowly oxidized in air even in a red hot state, is insoluble in water, and can play a role of protection when plated on metal. Based on the performance advantages of Ni, cr, nb, mo, and Ta, the present embodiment combines Ni, cr, nb, mo, and Ta, and reasonably controls the mole percentage of each element in the alloy, so as to obtain an alloy with good high-temperature mechanical properties, oxidation resistance, strength, and hardness. The better mole percentage content is obtained through the test process, and the refractory high-entropy alloy which is more than or less than the mole percentage content of each element has poor performance in the aspects of high-temperature mechanical property, oxidation resistance, strength, hardness and the like compared with the refractory high-entropy alloy which is composed of 20-30% of Ni, 5-10% of Cr, 30-40% of Nb, 10-20% of Mo and 10-20% of Ta. The selected elements of Ni, cr, nb, mo and Ta have low cost, and the manufacturing cost of the obtained refractory high-entropy alloy is reduced while the high-temperature mechanical property, the oxidation resistance, the strength and the hardness of the existing refractory high-entropy alloy are improved, so that the refractory high-entropy alloy has good practicability.
In this example, the molar percentages of the elements are 28.16% Ni, 7.04% Cr, 37.7% Nb, 14.5% Mo, and 12.6% Ta.
The preparation method of the NiCrNbMoTa refractory high-entropy alloy comprises the following steps of:
s1, stranding high-melting-point metal wires or alloy wires containing high-melting-point metals to obtain the refractory high-entropy alloy cable type welding wire, wherein the high-melting-point metals comprise Ni, cr, nb, mo and Ta.
Optionally, the purity of the high-melting-point metal wire is higher than 99.9%, and the diameter of the high-melting-point metal wire or the alloy wire containing the high-melting-point metal is 0.4 mm-1.0 mm.
Optionally, in step S1, the refractory high-entropy alloy cable-type welding wire is formed by twisting a plurality of peripheral high-melting-point metal wires or alloy wires containing high-melting-point metal around a central high-melting-point metal wire or alloy wire containing high-melting-point metal, and the peripheral high-melting-point metal wires or alloy wires containing high-melting-point metal are positioned in the peripheral high-melting-point metal wires or alloy wires containing high-melting-point metal, and the two high-melting-point metal wires or alloy wires containing high-melting-point metal with the same material are arranged at intervals or in opposite directions, so as to improve element uniformity at each position in the refractory high-entropy alloy cable-type welding wire as much as possible, thereby improving uniformity of the refractory high-entropy alloy obtained by subsequent cladding forming, and improving quality thereof. The yarn receiving speed in the twisting process is 5-10 m/min, and the twisting distance is 10-15 mm.
In the embodiment, the refractory high-entropy alloy cable-type welding wire is formed by twisting 3 Nb wires, 2 Ni-Cr alloy wires, 1 Ta wire and 1 Mo wire through special twisting equipment, the twisting distance is 12mm, the diameter of each single-stranded wire is 0.5mm, and the purity of each single-stranded wire is not lower than 99.9%. The mol percentage of each element of the NiCrNbMoTa refractory high-entropy alloy is 28.16 percent of Ni, 7.04 percent of Cr, 37.7 percent of Nb, 14.5 percent of Mo and 12.6 percent of Ta according to a calculation formula of the atomic percentage of each element in the welding wire.
The raw materials selected in the experiment are metal wires with 5 elements, the diameter of each wire is 0.5mm, the purity is not lower than 99.9%, and in order to ensure that each metal wire has a certain elongation and is not twisted and broken in the wire twisting process, each metal wire is subjected to annealing treatment.
And S2, carrying out surfacing treatment on the cable-type welding wire of the refractory high-entropy alloy obtained in the step S1 to obtain the NiCrNbMoTa refractory high-entropy alloy.
Optionally, in step S2, the surfacing process is performed by performing arc cladding on the refractory high-entropy alloy cable-type welding wire on the base material by using a TIG rotating arc additive manufacturing process.
Optionally, performing arc cladding forming on the refractory high-entropy alloy cable-type welding wire on the base material by adopting a TIG rotating wire arc additive manufacturing process specifically comprises the following steps:
s21, polishing, cleaning and fixing the titanium alloy plate, putting the cable type welding wire into an automatic wire feeder, and moving a tungsten electrode of a welding gun to the initial position of surfacing;
s22, setting a wire feeding angle and a wire feeding speed;
and S23, connecting cooling water, introducing high-purity argon, controlling the flow of the argon, setting TIG welding current, the tungsten electrode rotation rate of a welding gun and the material increase speed, and performing cable type welding wire material increase manufacturing on the refractory high-entropy alloy obtained in the step S1 to obtain the NiCrNbMoTa refractory high-entropy alloy.
Optionally, in step S22, the wire feeding angle is 30 °, and the wire feeding speed is 8mm/S.
Optionally, in step S23, the purity of the high-purity argon is not less than 99.9%, the gas flow is 20L/min, the arc rotation rate is 300r/min, the welding machine current is 150A, and the material increase speed is 90mm/min.
Designing orthogonal experiments according to the existing experimental equipment, totaling a plurality of groups, obtaining the optimal process parameters under the condition of obtaining the optimal forming quality through continuous optimization, and preparing the Ni 28.16 Cr 7.04 Nb 37.7 Mo 14.5 Ta 12. And (3) alloying.
Because the metal wire or the alloy wire positioned at the periphery is melted most fully by adopting the rotating electric arc, the molybdenum wire and the tantalum wire have the highest melting point compared with other metal wires or alloy wires in the embodiment, and the electric arc cladding forming is facilitated. Meanwhile, the ductility and toughness of the Ni-Cr alloy wires are considered, so 1 Ni-Cr alloy wire is selected as a central wire, and the other 3 Nb wires, 1 Ni-Cr alloy wire, 1 Ta wire and 1 Mo wire are selected as peripheral wires, wherein the 3 Nb wires are arranged at intervals, and the cross section of each refractory high-entropy alloy cable welding wire is shown in figure 1. By adopting a TIG rotating arc additive manufacturing process and combining a reasonable arrangement form of all metal wires or alloy wires in the refractory high-entropy alloy cable type welding wire, the obtained Ni 28.16 Cr 7.04 Nb 37.7 Mo 14.5 Ta 12.6 The refractory high-entropy alloy has higher high-temperature mechanical property, oxidation resistance, strength and hardness, and ensures the obtained Ni 28.16 Cr 7.04 Nb 37.7 Mo 14.5 Ta 12.6 The electric arc cladding quality of each part of the refractory high-entropy alloy is uniform, thereby improving the Ni content 28.16 Cr 7.04 Nb 37.7 Mo 14.5 Ta 12.6 And (3) cladding forming quality of refractory high-entropy alloy.
At present, the cable type welding wire is mainly designed in a mode that 1 welding wire is arranged in the center and 6 welding wires are arranged around the center, and the main reason of the design is to ensure that the welding wire has excellent weldability by considering the high symmetry of the welding wire. The refractory high-entropy alloy cable-type welding wire is designed by combining the physical and chemical characteristics of all elements. Because the conductivity, melting point and other properties of each element are different, the welding wire is stranded in a symmetrical distribution mode to ensure the weldability of the welding wire. If Ta or Nb wires are used as central wires, large current is needed for material increase, so that heat input is increased, and splashing is generated during material increase; if the current is small, the Ta wire as the center wire cannot be completely melted, and the surface forming quality is poor.
In the embodiment, based on the Nb wires, the Ni-Cr alloy wires, the Ta wires and the Mo wires as raw materials of the cable type welding wires made of the refractory high-entropy alloy, a TIG rotating wire arc additive manufacturing process is adopted, firstly, the large-size refractory high-entropy alloy can be prepared, secondly, the rotating wire arc can be subjected to heat input periodic change, and then the effect of stirring a molten pool is achieved, meanwhile, the rotating arc can ensure that the arc is stable, arc breakage is not generated, the melting efficiency of the wires is ensured, and the refractory high-entropy alloy is prepared better.
In contrast, when the MIG additive process is adopted for additive, the weld joint formability is poor, and the splashing is severe and discontinuous; MIG arcs are prone to arc interruption.
Ni obtained in example 28.16 Cr 7.04 Nb 37.7 Mo 14.5 Ta 12.6 The structural characterization and the mechanical property test of the refractory high-entropy alloy are as follows:
1. cutting the alloy into blocks of 8mm × 8mm × 2mm by using a wire cutting machine, respectively grinding the blocks by using 200#, 800#, 1000#, 1500# and 2000# sandpaper, then polishing the samples by using an aluminum oxide polishing solution, and performing phase structure analysis on the prepared refractory high-entropy alloy by adopting x-ray diffraction (XRD) (D/Max-2600), wherein the result is shown in FIG. 2;
2. the microhardness of a sample is detected by adopting an HV50Z type Vickers microhardness tester, the sample is processed into a cube small block with the size of 10mm multiplied by 6mm, the surface of the sample is ground to be flat and ensure the upper level and the lower level by utilizing abrasive paper grinding abrasive paper of 200#, 800#, 1000#, 1500# and 2000#, and the test surface is polished. The hardness of the obtained samples is tested by using a micro Vickers hardness tester, six points are equidistantly measured on each sample, and the test result is shown in figure 3;
3. using a neutral wire cutting machine to cut Ni 28.16 Cr 7.04 Nb 37.7 Mo 14.5 Ta 12.6 Cutting three cylindrical alloy samples with phi 4 multiplied by 6mm from the alloy, sequentially grinding the surfaces of the cut samples by using abrasive paper grinding abrasive paper respectively in 200#, 800#, 1000#, 1500# and 2000#, so as to remove a deteriorated layer, measuring the high-temperature compression performance of the refractory high-entropy alloy by using a Gleeble-3500 thermal simulation testing machine for the ground samples, and obtaining an engineering stress-strain curve of the samples, wherein the result is shown in figure 4;
4. using a wire cutting machine to cut Ni 28.16 Cr 7.04 Nb 37.7 Mo 14.5 Ta 12.6 The alloy is cut into cuboid samples with the size of 4mm multiplied by 2mm, the surfaces of the cut samples are sequentially polished by abrasive paper of 200#, 800#, 1000#, 1500# and 2000#, and the DSC curve of the alloy is obtained by measuring with a synchronous thermal analyzer after polishing, and the result is shown in figure 5.
The test results were analyzed as follows:
as shown in FIGS. 2 to 5, ni prepared in this example 28.16 Cr 7.04 Nb 37.7 Mo 14.5 Ta 12.6 The crystal structure of the refractory high-entropy alloy is a face-centered cubic structure, DSC curve results show that exothermic peaks and endothermic peaks appear at 600-650 ℃, the alloy undergoes phase change at the temperature, the crystal form is stable along with the temperature rise, and other peaks do not appear, which indicates that Ni prepared by the embodiment 28.16 Cr 7.04 Nb 37.7 Mo 14.5 Ta 12.6 The refractory high-entropy alloy forming layer has higher thermal stability. Ni prepared in this example 28.16 Cr 7.04 Nb 37.7 Mo 14.5 Ta 12.6 The mean hardness value of the refractory high-entropy alloy is 910HV. At 750 ℃, the yield strength is 597MPa, and the breaking strain is 6.5 percent.
The present invention has been described in detail, and it should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Claims (10)
1. The NiCrNbMoTa refractory high-entropy alloy is characterized in that the NiCrNbMoTa refractory high-entropy alloy comprises the elements of Ni, cr, nb, mo and Ta, wherein the mole percentage of the elements is 20-30% of Ni, 5-10% of Cr, 30-40% of Nb, 10-20% of Mo and 10-20% of Ta.
2. The NiCrNbMoTa refractory high-entropy alloy of claim 1, wherein the molar percentages of the respective elements are Ni 28.16%, cr 7.04%, nb 37.7%, mo14.5%, and Ta 12.6%.
3. The method for preparing the NiCrNbMoTa refractory high-entropy alloy according to any one of claims 1 to 2, comprising the following steps:
s1, stranding high-melting-point metal wires or alloy wires containing high-melting-point metals to obtain a refractory high-entropy alloy cable type welding wire, wherein the high-melting-point metals comprise Nb, mo and Ta;
and S2, carrying out surfacing treatment on the refractory high-entropy alloy cable-type welding wire obtained in the step S1 to obtain the NiCrNbMoTa refractory high-entropy alloy.
4. The method for preparing the NiCrNbMoTa refractory high-entropy alloy according to claim 3, wherein in step S1, the purity of the high-melting-point metal wire is higher than 99.9%, and the diameter of the high-melting-point metal wire or the high-melting-point alloy wire is 0.4 mm-1.0 mm.
5. The NiCrNbMoTa refractory high-entropy alloy preparation method according to claim 3, wherein in step S1, the refractory high-entropy alloy cable-type welding wire is formed by twisting a plurality of peripheral high-melting-point metal wires or peripheral high-melting-point metal-containing alloy wires around a central high-melting-point metal wire or central high-melting-point metal-containing alloy wire, wherein the peripheral high-melting-point metal wires or peripheral high-melting-point metal-containing alloy wires are provided, and two high-melting-point metal wires or high-melting-point metal-containing alloy wires with the same material are arranged at intervals or in opposite directions.
6. The preparation method of the NiCrNbMoTa refractory high-entropy alloy according to claim 5, wherein the refractory high-entropy alloy cable-type welding wire is formed by twisting 3 Nb wires, 2 Ni-Cr alloy wires, 1 Ta wire and 1 Mo wire.
7. The preparation method of the NiCrNbMoTa refractory high-entropy alloy wire as claimed in claim 6, wherein 1 Ni-Cr alloy wire is used as a central wire, and the other 1 Ni-Cr alloy wire, 3 Nb wires, 1 Ta wire and 1 Mo wire are used as peripheral wires in the refractory high-entropy alloy cable-type welding wire.
8. The preparation method of the NiCrNbMoTa refractory high-entropy alloy according to claim 3, wherein in the step S2, a surfacing process is performed on a refractory high-entropy alloy cable-type welding wire on a base material by adopting a TIG rotating wire arc additive manufacturing process.
9. The preparation method of the NiCrNbMoTa refractory high-entropy alloy according to claim 8, wherein the arc cladding forming of the cable-type refractory high-entropy alloy welding wire on the base material by adopting a TIG rotating wire arc additive manufacturing process specifically comprises the following steps:
s21, polishing, cleaning and fixing the titanium alloy plate, putting the cable type welding wire into a wire feeder, and moving a welding gun tungsten electrode to the initial position of overlaying welding;
s22, setting a wire feeding angle and a wire feeding speed;
and S23, connecting cooling water, introducing high-purity argon, controlling the flow of the high-purity argon, setting TIG welding current, tungsten electrode rotation rate of a welding gun and material increase speed, and performing material increase manufacturing on the cable-type welding wire of the refractory high-entropy alloy obtained in the step S1 to obtain the NiCrNbMoTa refractory high-entropy alloy.
10. The method for preparing the NiCrNbMoTa refractory high-entropy alloy according to claim 9, wherein in step S22, the wire feeding angle is 30 degrees, and the wire feeding speed is 8mm/S; in step S23, the purity of the high-purity argon is not lower than 99.9%, the gas flow is 20L/min, the arc rotation rate is 300r/min, the welding machine current is 150A, and the material increase speed is 90mm/min.
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