CN110923481A - Amorphous film/high-entropy alloy composite material and preparation method thereof - Google Patents
Amorphous film/high-entropy alloy composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides an amorphous film/high-entropy alloy composite material and a preparation method thereof, wherein the component of the amorphous film/high-entropy alloy composite material has the following expression ZraFebNicCudAleWherein a, b, c, d and e respectively represent the atom percentage content of each corresponding component. The amorphous film/high-entropy alloy composite material prepared by the invention has good plasticity while ensuring ultrahigh strength, solves the problem of room temperature brittleness of blocky amorphous, and has excellent corrosion resistance due to the existence of a surface amorphous layer; the method provided by the invention can be used for rapidly preparing the amorphous film/high-entropy alloy composite material without any heat treatment, the preparation method is simple, the interface of the amorphous alloy and the high-entropy alloy is stable, and the strength and the plasticity are well matched; the amorphous film prepared by the inventionThe high-entropy alloy composite material has the characteristics of high strength, good plasticity and corrosion resistance, and can better meet the requirements of precision devices and the field of automobiles.
Description
Technical Field
The invention relates to the field of metal materials, in particular to an amorphous film/high-entropy alloy composite material and a preparation method thereof.
Background
The atomic arrangement in the amorphous alloy is short-range ordered and long-range disordered, and crystal defects such as crystal grains, crystal boundaries, dislocation, stacking faults and the like do not exist in the amorphous alloy. The special atomic structure enables the amorphous alloy to show excellent mechanical, magnetic and corrosion resistance properties, and has great application prospect in the fields of soft magnetic functional materials, electronic devices, corrosion resistant coatings, structural materials and the like. Amorphous alloys suffer from two serious problems-room temperature brittleness and strain softening. The room temperature brittleness and processing softening of the amorphous material limit the use of the amorphous material as a structural material, and the amorphous material is very likely to have brittle fracture failure in the using process, so that serious accidents occur.
In order to improve the plastic deformation of the bulk amorphous alloy and achieve the purpose of engineering application, the preparation of the bulk amorphous composite material is an effective method. At present, a method of introducing a second phase into an amorphous is mostly adopted to prepare an amorphous composite material, and the expansion of a single shear band is effectively hindered by adjusting the structure, size, distribution and volume fraction of the second phase. The method for introducing the second phase mainly comprises an internal generation method and an external generation method, wherein the internal generation method mainly comprises the steps of adjusting chemical components to deviate from amorphous components, controlling the cooling speed to obtain an amorphous matrix and granular crystals or dendrites, adding positive mixed thermal elements to obtain nanoscale amorphous clusters, generating a crystal phase through amorphous crystallization or in a plastic deformation stage and generating second phase particles in situ in the melt cooling process. The exogenous method is mainly to add WC, Ta, Nb and Mo refractory metal particles or prepare fiber reinforced amorphous composite materials, such as W wires and carbon steel wires for reinforcing zirconium-based amorphous materials. Patent CN 106756637 a discloses a preparation method of a high-entropy amorphous matrix composite material, the yield strength of which is 1700MPa, but the elongation is only 10%. Patent CN 106939378A discloses a method for preparing amorphous alloy/pure copper layered composite material, which utilizes a vacuum hot-pressing furnace to realize the connection of pure copper and amorphous alloy, but the preparation method is complex and the interface connection is unstable.
Disclosure of Invention
The invention overcomes the defects in the prior art and provides an amorphous film/high-entropy alloy composite material and a preparation method thereof, which combines the excellent properties of high-entropy alloy and bulk amorphous alloy, utilizes the multi-principal-element component design of the high-entropy alloy, and prepares the rod-shaped composite material with high strength, hardness, wear resistance and corrosion resistance, wherein the surface layer of the rod-shaped composite material is of an amorphous structure, and the interior of the rod-shaped composite material is of a single ordered body-centered cubic phase.
The purpose of the invention is realized by the following technical scheme.
The amorphous film/high-entropy alloy composite material and the preparation method thereof are prepared according to the following steps:
According to the following expression ZraFebNicCudAleAnd (2) burdening, wherein a, b, c, d and e respectively represent the atomic percentage content (namely the molar ratio) of each corresponding component, a is 0.2-0.4, b-e are 0.1-0.3, and a + b + c + d + e is 1, melting the burdening by adopting a high vacuum arc melting furnace under the atmosphere of inert protective gas, wherein the melting time of raw materials is 120-240s, and repeatedly melting the raw materials into a master alloy spindle with uniform components.
In the step 1, high-purity metal raw materials (the purity is higher than 99.8 wt%, namely the purity of the simple substance zirconium, the simple substance iron, the simple substance nickel, the simple substance copper and the simple substance aluminum is more than or equal to 99.8 wt%) are selected for batching, and for active and easily oxidized metal raw materials, the surfaces of the active and easily oxidized metal raw materials are polished by using sand paper to remove oxide films of the active and easily oxidized metal raw materials, and then the active and easily oxidized metal raw materials are cleaned and then bat.
In the step 1, alloy raw materials in the water-cooled copper crucible are selected to be smelted one by one, and the raw material melt is stirred by electromagnetism in the smelting process, so that the uniformity of the chemical components of the master alloy ingot is ensured.
In step 1, inert protective gas is nitrogen, helium or argon, and the vacuum degree is pumped to 4.0X 10 before smelting-3Pa or less.
In step 1, the degree of vacuum for melting was 3.0X 10-3Pa below, the smelting time is 160-200 s.
In the step 1, after smelting, turning over each alloy ingot by using a material turning spoon for remelting, wherein the smelting frequency of each alloy ingot is not less than four times; the simple substance of zirconium, the simple substance of iron, the simple substance of nickel, the simple substance of copper and the simple substance of aluminum are cleaned and decontaminated before being placed in a smelting furnace, and the simple substance of zirconium is smelted for 2-3 times in a high vacuum smelting furnace in advance.
The preparation method comprises the steps of preparing the alloy by adopting a high-vacuum single-roller rotary quenching melt-spun machine, placing the mother alloy ingot smelted in the step 1 in a quartz tube with a small hole at the bottom end, pumping the melt-spun machine to vacuum, filling inert protective gas, heating the alloy by eddy current generated by an inductance coil to melt the alloy, pressing an injection key after the alloy is completely melted, spraying alloy liquid into a copper mold right below the quartz tube from a quartz tube nozzle under the action of pressure difference between the upper part and the bottom part of the quartz tube to rapidly cool the alloy liquid, and naturally cooling the alloy liquid to the room temperature of 20-25 ℃ to obtain a needed rod-shaped alloy sample, namely the amorphous film/high-entropy alloy composite material.
In the step 2, the copper mold is at the room temperature of 20-25 ℃, the molten alloy is rapidly cooled by the copper mold, and the rod-shaped sample formed by injection consists of an amorphous region on the surface layer and a columnar crystalline region inside the rod-shaped sample due to the fact that the cooling speed of the molten liquid close to the copper mold is high and the cooling speed of the liquid far away from the copper mold is low.
In step 2, the diameter of the amorphous film/high-entropy alloy composite rod-shaped sample is 2-10mm, the length is 40-60mm, the preferred diameter is 5-10 mm, the length is 40-60mm, and the vacuum degree is 4.0 multiplied by 10-3Pa or less.
The surface layer of the amorphous film/high-entropy alloy composite material prepared by the invention has an amorphous structure, the width (thickness) of the amorphous layer is 0.1-0.3 mm, the inside of the amorphous layer is a dendritic crystal region, and the internal structure of the amorphous layer is a single ordered body-centered cubic phase. The amorphous film/high-entropy alloy composite material forms an amorphous structure on the surface of the material, the internal dendrite is an ordered body-centered cubic phase, the amorphous thin layer and the ordered body-centered cubic solid solution in the amorphous thin layer interact with each other, the amorphous thin layer absorbs and consumes energy under the action of an external force, the expansion of cracks is delayed, the plasticity and toughness of the amorphous composite material are obviously improved, the compression strength of the amorphous film/high-entropy alloy composite material is 2100-plus-2400 MPa, the yield strength is 1680-plus-1880 MPa, and the elongation is 14-18%.
The amorphous film/high-entropy alloy composite material prepared by the invention has good plasticity while ensuring ultrahigh strength, solves the problem of room temperature brittleness of blocky amorphous, and has excellent corrosion resistance due to the existence of a surface amorphous layer; the method provided by the invention can be used for rapidly preparing the amorphous film/high-entropy alloy composite material without any heat treatment, the preparation method is simple, the interface of the amorphous alloy and the high-entropy alloy is stable, and the strength and the plasticity are well matched; the amorphous film/high-entropy alloy composite material prepared by the invention has the characteristics of high strength, good plasticity and corrosion resistance, and can better meet the requirements of precision devices and the field of automobiles.
Drawings
FIG. 1 is an X-ray diffraction pattern of the amorphous thin film/high-entropy alloy composite material prepared by the invention.
FIG. 2 is a metallographic electron microscope photograph of the amorphous thin film/high entropy alloy composite material prepared by the present invention.
FIG. 3 is a selected-area electron diffraction pattern diagram of the amorphous thin film/high-entropy alloy composite material prepared by the present invention, wherein (a) the diffraction pattern of the outer layer of the rod-like sample is amorphous; (b) single crystal diffraction spots in the central region of the rod-like sample.
FIG. 4 is a fracture morphology photograph of the amorphous thin film/high-entropy alloy composite material prepared by the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. The high vacuum SINGLE-roll rotary quenching belt-spinning machine was used in 5, 12 months in 2014, under the conditions of SINGLE ROLLER MELT SPINNER VF-RQT50 of MAKABER & D CO.LTD.
Example 1
Preparing a master alloy ingot:
weighing the required metal simple substance according to the atomic percentage of a being 0.3 and b-e being 0.175, and pumping the vacuum degree to 3.0 multiplied by 10 before smelting-3And below Pa, closing each valve, then filling high-purity argon (with the purity of 99.99%), melting a Ti block in a central copper crucible in the furnace to remove oxygen in the smelting furnace in the smelting process, then smelting alloy raw materials in the water-cooled copper crucible one by one, using electromagnetic stirring in the smelting process, paying attention to the fact that the smelting time cannot be too long each time, keeping each sample at about 180s, turning over each alloy ingot by a material turning spoon after smelting to remelt each alloy ingot, weighing the smelted alloy ingot, and comparing the smelting loss with the total mass of the raw materials in the batching process, wherein the smelting loss cannot exceed 0.1 wt%.
Preparing a rod-shaped sample of the amorphous film/high-entropy alloy composite material:
an amorphous film/high-entropy alloy composite rod-shaped sample with the diameter of 8mm and the length of 50mm is prepared by adopting an induction heating copper die blow-casting process, the equipment is a high-vacuum single-roller rotary quenching strip throwing machine, a smelted master alloy ingot is placed in a quartz tube with a small hole with a certain diameter at the bottom end, the alloy is rapidly melted by heating eddy current generated by an inductance coil, an alloy melt is blown into a copper die by utilizing air pressure, and the temperature is naturally cooled to 20-25 ℃.
Example 2
Preparing a master alloy ingot:
weighing the required metal simple substance according to the atomic percentage of a being 0.1 and b-e being 0.05, and pumping the vacuum degree to 4.0 multiplied by 10 before smelting-3And (2) below Pa, closing each valve, then filling high-purity argon (with the purity of 99.99%), melting a Ti block in a central copper crucible in the furnace to remove oxygen in the smelting furnace in the smelting process, then smelting alloy raw materials in the water-cooled copper crucible one by one, using electromagnetic stirring in the smelting process, paying attention to that the smelting time cannot be too long each time, keeping each sample at about 120s, turning over each alloy ingot by a material turning spoon after smelting to remelt each alloy ingot so as to ensure the uniformity of chemical components of the master alloy ingot, weighing the smelted alloy ingot, and comparing the smelting loss with the total mass of the raw materials in material proportioning, wherein the smelting loss cannot exceed 0.2 wt%.
Preparing a rod-shaped sample of the amorphous film/high-entropy alloy composite material:
an induction heating copper mold blowing casting process is adopted to prepare an amorphous film/high-entropy alloy composite rod-shaped sample with the diameter of 5mm and the length of 40mm, the device is a high-vacuum single-roller rotary quenching strip throwing machine, a smelted master alloy ingot is placed in a quartz tube with a small hole with a certain diameter at the bottom end, the alloy is rapidly melted through eddy current heating generated by an inductance coil, an alloy melt is blown into a copper mold by utilizing air pressure, and the temperature is naturally cooled to 20-25 ℃.
Example 3
Preparing a master alloy ingot:
weighing the required metal simple substances according to the atomic percentages of a-0.5 and b-e-0.4, and pumping the vacuum degree to 3.5 multiplied by 10 before smelting-3And below Pa, closing each valve, then filling high-purity argon (with the purity of 99.99%), melting a Ti block in a central copper crucible in the furnace to remove oxygen in the smelting furnace in the smelting process, then smelting alloy raw materials in the water-cooled copper crucible one by one, using electromagnetic stirring in the smelting process, paying attention to that the smelting time cannot be too long each time, keeping each sample at about 240s to ensure the uniformity of chemical components of the master alloy ingot, overturning each alloy ingot by a material turning spoon after smelting for remelting, wherein the smelting frequency of each alloy ingot is not less than five times, weighing the smelted alloy ingot, and compared with the total mass of the raw materials in batching, the smelting loss cannot exceed 0.05 wt%.
Preparing a rod-shaped sample of the amorphous film/high-entropy alloy composite material:
an induction heating copper mold blowing casting process is adopted to prepare an amorphous film/high-entropy alloy composite rod-shaped sample with the diameter of 10mm and the length of 60mm, the device is a high-vacuum single-roller rotary quenching strip throwing machine, a smelted master alloy ingot is placed in a quartz tube with a small hole with a certain diameter at the bottom end, the alloy is rapidly melted through eddy current heating generated by an inductance coil, an alloy melt is blown into a copper mold by utilizing air pressure, and the temperature is naturally cooled to 20-25 ℃.
Example 4
Preparing a master alloy ingot:
weighing the needed metal simple substance according to the atomic percentage of a being 0.2 and b-e being 0.1,before smelting, the vacuum degree is pumped to 3.0X 10-3And (2) below Pa, closing each valve, then filling high-purity argon (with the purity of 99.99%), during the smelting process, firstly melting a Ti block in a central copper crucible in the furnace to remove oxygen in the smelting furnace, then smelting alloy raw materials in the water-cooled copper crucible one by one, using electromagnetic stirring during the smelting process, paying attention to that the smelting time cannot be too long each time, keeping each sample at about 200s, turning over each alloy ingot by using a material turning spoon to remelt each alloy ingot after smelting in order to ensure the uniformity of the chemical components of the master alloy ingot, weighing the smelted alloy ingot, and comparing with the total mass of the raw materials during batching, wherein the smelting loss cannot exceed 0.12 wt%.
Preparing a rod-shaped sample of the amorphous film/high-entropy alloy composite material:
an amorphous film/high-entropy alloy composite rod-shaped sample with the diameter of 6mm and the length of 45mm is prepared by adopting an induction heating copper die blow-casting process, the equipment is a high-vacuum single-roller rotary quenching strip throwing machine, a smelted master alloy ingot is placed in a quartz tube with a small hole with a certain diameter at the bottom end, the alloy is rapidly melted by heating eddy current generated by an inductance coil, an alloy melt is blown into a copper die by utilizing air pressure, and the temperature is naturally cooled to 20-25 ℃.
Example 5
Preparing a master alloy ingot:
weighing the required metal simple substances according to the atomic percentages of a-0.3 and b-e-0.2, and pumping the vacuum degree to 2.5 multiplied by 10 before smelting-3And below Pa, closing each valve, then filling high-purity argon (with the purity of 99.99%), melting a Ti block in a central copper crucible in the furnace to remove oxygen in the smelting furnace in the smelting process, then smelting alloy raw materials in the water-cooled copper crucible one by one, using electromagnetic stirring in the smelting process, paying attention to the fact that the smelting time cannot be too long each time, keeping each sample at about 160s, turning over each alloy ingot by a material turning spoon after smelting to remelt each alloy ingot, weighing the smelted alloy ingot, and comparing the smelting loss with the total mass of the raw materials in the batching process, wherein the smelting loss cannot exceed 0.15 wt%.
Preparing a rod-shaped sample of the amorphous film/high-entropy alloy composite material:
an amorphous film/high-entropy alloy composite rod-shaped sample with the diameter of 7mm and the length of 55mm is prepared by adopting an induction heating copper die blow-casting process, the equipment is a high-vacuum single-roller rotary quenching strip throwing machine, a smelted master alloy ingot is placed in a quartz tube with a small hole with a certain diameter at the bottom end, the alloy is rapidly melted by heating eddy current generated by an inductance coil, an alloy melt is blown into a copper die by utilizing air pressure, and the temperature is naturally cooled to 20-25 ℃.
Example 6
Preparing a master alloy ingot:
weighing the required metal simple substances according to the atomic percentages of a-0.4 and b-e-0.3, and pumping the vacuum degree to 2.0 multiplied by 10 before smelting-3And (2) below Pa, closing each valve, then filling high-purity argon (with the purity of 99.99%), melting a Ti block in a central copper crucible in the furnace to remove oxygen in the smelting furnace in the smelting process, then smelting alloy raw materials in the water-cooled copper crucible one by one, using electromagnetic stirring in the smelting process, paying attention to that the smelting time cannot be too long each time, keeping each sample at about 170s, turning over each alloy ingot by a material turning spoon after smelting to remelt each alloy ingot so as to ensure the uniformity of chemical components of the master alloy ingot, weighing the smelted alloy ingot, and comparing the smelting loss with the total mass of the raw materials in material proportioning, wherein the smelting loss cannot exceed 0.1 wt%.
Preparing a rod-shaped sample of the amorphous film/high-entropy alloy composite material:
an amorphous film/high-entropy alloy composite rod-shaped sample with the diameter of 8mm and the length of 50mm is prepared by adopting an induction heating copper die blow-casting process, the equipment is a high-vacuum single-roller rotary quenching strip throwing machine, a smelted master alloy ingot is placed in a quartz tube with a small hole with a certain diameter at the bottom end, the alloy is rapidly melted by heating eddy current generated by an inductance coil, an alloy melt is blown into a copper die by utilizing air pressure, and the temperature is naturally cooled to 20-25 ℃.
The amorphous film/high-entropy alloy composite material rod-shaped sample prepared by the method is characterized by using a MiniFlex500 diffractometer and adopting a Cu targetAs a target material
The tube voltage and the tube current are respectively 40kV and 15mA, the scanning speed is 4 DEG/min, and the scanning angle is 20-80 deg. Firstly, a high-entropy alloy/block amorphous composite rod-shaped sample with the diameter of phi 8mm is prepared by a copper mold spray casting process, and a diamond slicer is used for cutting a slice with the thickness of 2mm to perform the measurement of X-ray diffraction. As can be seen from fig. 1, the surface layer of the rod-like sample prepared by the process has a typical amorphous diffuse broadening peak and no sharp crystallization peak, indicating that the surface layer of the sample has an amorphous structure. The core structure of the sample is a single ordered body-centered cubic phase, and an obvious (100) crystal face can be seen in an XRD (X-ray diffraction) pattern, so that the body-centered cubic structure is ordered, and the (100) crystal face which is originally delustred is diffracted.
The high-entropy alloy/block amorphous composite rod-shaped sample with the diameter of phi 8mm is prepared by a copper mold spray casting process, a cylinder with the thickness of 10mm is cut by a diamond slicer, the sample is corroded by 4% nitric acid alcohol after being ground and polished, and metallographic structure observation is carried out by a SmartZoom5 digital microscope. It can be seen from the metallographic photograph of fig. 2 that the rod-like sample was divided into a bright outer amorphous region and an inner dendritic region. The width of the amorphous layer is 0.1 mm-0.3 mm.
Preparing a high-entropy alloy/block amorphous composite rod-shaped sample with the diameter of phi 8mm by a copper mold spray casting process, cutting a thin sheet with the thickness of 0.3mm by a diamond slicer, and grinding the thin sheet to the thickness of about 0.06mm by 400#, 800#, 1000# abrasive paper; punching out a wafer with the diameter of phi 3mm from the edge and the center of a sheet sample respectively, and carrying out double-spraying electrolytic thinning on a double-spraying electrolytic thinning instrument, wherein the used electrolyte is 5% perchloric acid alcohol solution, the temperature is controlled between minus 25 ℃ and 30 ℃, and the double-spraying voltage is 50V to 70V. Microscopic analysis was performed on a JEM-2100 type Transmission Electron Microscope (TEM). The diffraction pattern of FIG. 3(a) is a ring-like halo of diffuse scattering, indicating that the outer layer of the rod-like sample is amorphous; the single crystal diffraction spots of FIG. 3(b) correspond to XRD results, which are consistent with the diffraction pattern of ordered body-centered cubic phases.
Room temperature uniaxial compression experiment-first, the diameter phi is obtained by the preparation of copper mold spray casting technology2mm high-entropy alloy/block amorphous composite rod-shaped sample, and then preparing a compressed sample by using a diamond slicer according to the requirement of the height-diameter ratio of 2: 1. A total of 3 compressed samples were prepared, which were prepared to ensure parallelism of the top and bottom. In the compression test, a rod-shaped sample is placed in a self-made reverse compressor, and an extensometer is arranged on a bayonet of the reverse compressor. The device adopted in the compression test is a WDW-100 electronic universal material machine, a uniaxial compression test is carried out under the room temperature condition, and the strain rate is set to be 4.2 multiplied by 10-4s-1. The data of mechanical property parameters including yield strength, compressive strength and total elongation obtained by three compression tests are shown in table 1, the average value of the compressive strength of the developed high-entropy alloy/block amorphous composite rod-shaped sample is 2200MPa, the average value of the yield strength is 1754MPa, and the average value of the total elongation is 15.9%, so that excellent matching of strength and plasticity is shown. 16.9% is the maximum compressive strain in the three-time compression test, and it can be seen from fig. 4 that the fracture center has obvious plastic deformation, the amorphous region at the edge can effectively delay the crack propagation, and the plasticity of the composite rod-shaped sample is improved. The material has higher yield strength of 1711Mpa and better comprehensive mechanical property, thereby providing more possibilities for subsequent engineering practical application.
TABLE 1 compressive mechanical Properties of high-entropy alloy/bulk amorphous composite rod-like samples of the present invention
Corrosion performance testing, firstly, preparing a high-entropy alloy/block amorphous composite rod-shaped sample with the diameter of phi 8mm by a copper mold spray casting process, cutting a cylinder with the thickness of 5mm by a diamond slicer, and then, carefully grinding the sample by using metallographic abrasive paper of 800#, 1200# and 2000# in sequence. Putting the ground sample into alcohol, cleaning the sample by using an ultrasonic cleaner, drying and weighing the sample, and then respectively immersing the sample into 3.5 percent NaCl solution, 1 percent HF solution and 2 percent HNO3The sample was kept for 48 hours and then taken out, and the surface state and weight change of the sample before and after the etching were analyzed. As can be seen from Table 2, the alloys were in different corrosion solutionsThe mass change is small, and the surface of the alloy is almost unchanged, which shows that the high-entropy alloy/block amorphous composite rod sample prepared by the method has excellent corrosion resistance. The amorphous surface layer of the amorphous film/high-entropy alloy composite rod-shaped sample spontaneously forms a uniform passivation interlayer due to the single-phase disordered characteristic in the structure, and can prevent corrosion of a corrosion medium, so that the amorphous film/high-entropy alloy composite material shows excellent corrosion resistance, namely, the amorphous film/high-entropy alloy composite material is applied as a corrosion-resistant material.
TABLE 2 high entropy alloy/bulk amorphous composite rod sample of the present invention was prepared in 3.5% NaCl aqueous solution, 1 wt% HF aqueous solution, 2 wt% HNO3Mass change after soaking in aqueous solution for 48h
The preparation of the amorphous film/high-entropy alloy composite material can be realized by adjusting the process parameters according to the content of the invention, and the performance basically consistent with the invention is shown by tests. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. The amorphous film/high-entropy alloy composite material is characterized in that the surface layer of the amorphous film/high-entropy alloy composite material has an amorphous structure, the thickness of the amorphous layer is 0.1-0.3 mm, the inner part of the amorphous layer is a dendritic region, the inner structure of the amorphous layer is a single ordered body-centered cubic phase, the compression strength is 2100-2400MPa, the yield strength is 1680-1880MPa, the elongation is 14-18%, and the amorphous film/high-entropy alloy composite material is prepared according to the following steps:
step 1, preparing a master alloy ingot
According to the following expression ZraFebNicCudAleThe ingredients are prepared, wherein a, b, c, d and e respectively represent the atom percentage content (i.e. the molar ratio) of each corresponding component, a is 0.2-0.4, b to e are 0.1-0.3,and a + b + c + d + e is 1, the ingredients are smelted by adopting a high vacuum arc smelting furnace under the atmosphere of inert protective gas, the smelting time of the raw materials is 120-240s, and the raw materials are repeatedly smelted into a master alloy spindle with uniform components;
step 2, preparing amorphous film/high-entropy alloy composite material
The preparation method comprises the steps of preparing the alloy by adopting a high-vacuum single-roller rotary quenching melt-spun machine, placing the mother alloy ingot smelted in the step 1 in a quartz tube with a small hole at the bottom end, pumping the melt-spun machine to vacuum, filling inert protective gas, heating the alloy by eddy current generated by an inductance coil to melt the alloy, pressing an injection key after the alloy is completely melted, spraying alloy liquid into a copper mold right below the quartz tube from a quartz tube nozzle under the action of pressure difference between the upper part and the bottom part of the quartz tube to rapidly cool the alloy liquid, and naturally cooling the alloy liquid to the room temperature of 20-25 ℃ to obtain a needed rod-shaped alloy sample, namely the amorphous film/high-entropy alloy composite material.
2. The amorphous thin film/high-entropy alloy composite material of claim 1, wherein in step 1, a high-purity metal raw material (with a purity higher than 99.8 wt%, that is, the purity of the simple substance zirconium, the simple substance iron, the simple substance nickel, the simple substance copper, and the simple substance aluminum is greater than or equal to 99.8 wt%) is selected for mixing, and for an active and easily-oxidized metal raw material, an oxide film of the active and easily-oxidized metal raw material is removed by polishing the surface with sand paper, and then the mixture is mixed after cleaning.
3. The amorphous thin film/high-entropy alloy composite material as claimed in claim 1, wherein in step 1, the raw alloy materials in the water-cooled copper crucible are selected to be melted one by one, and the raw material melt is stirred by electromagnetism during the melting process, so as to ensure the uniformity of the chemical components of the master alloy ingot.
4. An amorphous thin film/high entropy alloy composite material as claimed in claim 1, wherein in step 1, the inert shielding gas is nitrogen, helium or argon, and the vacuum degree is pumped to 4.0 x 10 before melting-3Pa or less, and the degree of vacuum of melting is preferably 3.0X 10-3Pa below, the smelting time is 160-200 s.
5. An amorphous thin film/high entropy alloy composite material as claimed in claim 1, wherein in step 2, the temperature of the copper mold is 20-25 ℃, the molten alloy is rapidly cooled by the copper mold, and the rod-shaped sample formed by injection consists of an amorphous region on the surface layer and a columnar crystalline region inside the rod-shaped sample due to the fact that the cooling speed of the molten liquid close to the copper mold is high and the cooling speed of the liquid far from the copper mold is low; the diameter of the amorphous film/high-entropy alloy composite rod-shaped sample is 2-10mm, the length is 40-60mm, the preferred diameter is 5-10 mm, the length is 40-60mm, and the vacuum degree is 4.0 multiplied by 10-3Pa or less.
6. The preparation method of the amorphous film/high-entropy alloy composite material is characterized by comprising the following steps of:
step 1, preparing a master alloy ingot
According to the following expression ZraFebNicCudAleMixing materials, wherein a, b, c, d and e respectively represent the atomic percentage content (i.e. the molar ratio) of each corresponding component, a is 0.2-0.4, b-e are 0.1-0.3, and a + b + c + d + e is 1, melting the mixed materials by adopting a high vacuum arc melting furnace under the atmosphere of inert protective gas, wherein the melting time of raw materials is 120-240s, and repeatedly melting the mixed materials into a master alloy spindle with uniform components;
step 2, preparing amorphous film/high-entropy alloy composite material
The preparation method comprises the steps of preparing the alloy by adopting a high-vacuum single-roller rotary quenching melt-spun machine, placing the mother alloy ingot smelted in the step 1 in a quartz tube with a small hole at the bottom end, pumping the melt-spun machine to vacuum, filling inert protective gas, heating the alloy by eddy current generated by an inductance coil to melt the alloy, pressing an injection key after the alloy is completely melted, spraying alloy liquid into a copper mold right below the quartz tube from a quartz tube nozzle under the action of pressure difference between the upper part and the bottom part of the quartz tube to rapidly cool the alloy liquid, and naturally cooling the alloy liquid to the room temperature of 20-25 ℃ to obtain a needed rod-shaped alloy sample, namely the amorphous film/high-entropy alloy composite material.
7. The method for preparing the amorphous thin film/high-entropy alloy composite material according to claim 6, wherein in the step 1, the purities of the simple substance zirconium, the simple substance iron, the simple substance nickel, the simple substance copper and the simple substance aluminum are respectively more than or equal to 99.8 wt%, and for active and easily oxidized metal raw materials, the surfaces of the active and easily oxidized metal raw materials are polished by sand paper to remove oxide films of the active and easily oxidized metal raw materials, and then the active and easily oxidized metal raw materials are cleaned and mixed; the alloy raw materials in the water-cooled copper crucible are smelted one by one, and the raw material solution is stirred by electromagnetism in the smelting process, so that the uniformity of the chemical components of the master alloy ingot is ensured.
8. A method for preparing an amorphous thin film/high entropy alloy composite material as claimed in claim 6, wherein in step 1, the inert shielding gas is nitrogen, helium or argon, and the degree of vacuum is pumped to 4.0 x 10 before melting-3Pa or less, and the degree of vacuum of melting is preferably 3.0X 10-3Pa below, the smelting time is 160-200 s.
9. A method for preparing an amorphous thin film/high entropy alloy composite material as claimed in claim 6, wherein in step 2, the temperature of the copper mold is 20-25 ℃, and the molten alloy is rapidly cooled by the copper mold; the diameter of the amorphous film/high-entropy alloy composite rod-shaped sample is 2-10mm, the length is 40-60mm, the preferred diameter is 5-10 mm, the length is 40-60mm, and the vacuum degree is 4.0 multiplied by 10-3Pa or less.
10. Use of the amorphous thin film/high entropy alloy composite material of any one of claims 1 to 5 in the preparation of corrosion resistant materials.
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