CN109321771B - Foam metal/high-entropy metal glass composite material with large compressive strain and preparation method thereof - Google Patents

Foam metal/high-entropy metal glass composite material with large compressive strain and preparation method thereof Download PDF

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CN109321771B
CN109321771B CN201811465587.8A CN201811465587A CN109321771B CN 109321771 B CN109321771 B CN 109321771B CN 201811465587 A CN201811465587 A CN 201811465587A CN 109321771 B CN109321771 B CN 109321771B
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entropy
metal
composite material
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CN109321771A (en
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赵维民
杨联赞
李永艳
王志峰
秦春玲
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Hebei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/08—Alloys with open or closed pores
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C3/00—Removing material from alloys to produce alloys of different constitution separation of the constituents of alloys
    • C22C3/005—Separation of the constituents of alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon

Abstract

The invention relates to a foam metal/high-entropy metal glass composite material with large compressive strain and a preparation method thereof. The composite material takes a high-entropy metal glass test bar as an internal matrix, and a foam layer is wrapped on the surface of the matrix; the atomic ratio component of the internal matrix is Ti20Zr20Hf20Cu20Pd20(ii) a The atomic ratio component of the foam layer is TixZryHfzCuwPdηThe foam layer is formed by stacking particles with the particle size of 0.35-0.6 mu m; in the preparation method, the mixed acid with low concentration is adopted, two functions of dealloying and oxidation resistance are realized simultaneously, and in addition, the dealloying process and the heat treatment process are combined together, so that the residual stress of the material is effectively removed, and the problem of layering is avoided. The invention overcomes the defects of uneven structure and components, high energy consumption and low yield of the current material.

Description

Foam metal/high-entropy metal glass composite material with large compressive strain and preparation method thereof
Technical Field
The invention relates to the field of preparation of high-entropy metal glass materials, in particular to a foam metal/high-entropy metal glass composite material with large compressive strain and a preparation method thereof.
Background
Metallic glass, also called amorphous alloy, is a metallic alloy with amorphous atomic structure, and its internal atoms are characterized by long-range disorder and short-range order, so that the material possesses some excellent mechanical properties, such as: high strength, high hardness, high strength limit, high fatigue resistance, and the like. The high-entropy alloy is a novel alloy which is defined as an alloy which is composed of at least four elements in an equal atomic ratio or a nearly equal atomic ratio form and has a solid solution structure. Recent studies have shown that there is a material design crossover between metallic glasses and high-entropy alloys, i.e. some alloys of high-entropy composition can form metallic glasses with amorphous structure under certain cooling conditions, and such alloys are called high-entropy metallic glasses. Due to the high entropy effect existing among the components, the high entropy metallic glass shows special physical properties which some binary or ternary traditional metallic glasses do not have, and is considered to be an engineering structure material with great application prospect. However, such alloys lack macroscopic plasticity at room temperature, causing brittle fracture which severely limits their practical applications. Notably, the deformation of high entropy metallic glasses at room temperature is non-uniform and when compressed or stretched, highly localized shear bands rapidly expand, leading to catastrophic failure. Therefore, the improvement of the plasticity of the high-entropy metal glass and the guarantee of the safety of the high-entropy metal glass in the service process become the key point of the current research. In the prior art, the plastic improvement of the material is mostly realized by adjusting the microstructure of the alloy, such as alloying, heat treatment or deformation treatment, but the amorphous characteristics of the material are also changed by the methods. Therefore, on the premise of keeping the amorphous characteristics of the material, the idea of improving the room temperature plasticity of the material by a material surface modification method is very important.
In the prior art, CN106637376A discloses a method for preparing a metal glass nano porous structure, in which high-concentration (1.5-2.5M) sulfuric acid is used as a corrosive solution, and a porous layer is prepared on the surface of metal glass by an electrochemical hydrothermal method. Firstly, the process selects strong acid as corrosive liquid, and has great potential threat to the environment and the health of workers. Secondly, it is low in yield and not suitable for large-scale production. Finally, the alloy prepared is not high-entropy metallic glass, and does not have some special physical properties of the high-entropy metallic glass. Paper Materials Science&Engineering a2016, 673, 141 discloses a method for improving plasticity of high-entropy metallic glass by covering the surface of a high-entropy metallic glass test bar with a Ni-P film by an electroless plating method. The method requires pretreatment of the test bar prior to electroless plating. Specifically, the test rod needs to be sensitized in a mixed solution of stannous chloride and hydrochloric acid for 15min, and then transferred to a mixed solution of palladium chloride and hydrochloric acid for activation for 15 min. After the pretreatment is finished, the test bar is soaked in a mixed solution of ammonium bifluoride, nickel sulfate, sodium hydroxide, citric acid, sodium dihydrogen phosphate and thiourea for 3 hours for chemical plating of the Ni-P film. The preparation process involves a large amount of chemical reagents, increases the preparation cost and the complexity of the process, and increases the burden of post-treatment of waste liquid and the potential threat to environmental pollution. The Journal of Non-Crystalline Solids 2018, 488, 63 discloses a method for remelting a metallic glass surface layer by a laser remelting method so as to improve the plasticity of an alloy. The method requires melting the surface layer of the metal using a relatively high power laser beam and then melting the surface layer of the metal by 10 deg.f5–108Cooling was carried out at a cooling rate of K/s. The process has high requirements on equipment, the process needs to be precisely controlled, and the requirements on equipment advancement and high technical level of operators are increased. Secondly, the material prepared by the method needs to be rapidly cooled, so that the energy consumption is extremely high, and the cost is increased. Finally, the alloy prepared is not high-entropy metallic glass, and does not have some special physical properties of the high-entropy metallic glass. The paper Intermetallics 2016, 77, 1 discloses a method for preparing a nano-porous metal/metal glass composite material by a dealloying method so as to improve the compressive strain of the alloy, wherein a large amount of Cu is doped in the composite material synthesized by the method2O impurities and a nano porous layer wrapped on the surface of the metal glass substrate have a layering phenomenon, and the performance of the material as an engineering structure material is influenced by the nonuniformity of components. Secondly, the prepared alloy is not high-entropy metal glass and does not have some special physical properties of the high-entropy metal glass.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a foam metal/high-entropy metal glass composite material with large compressive strain and a preparation method thereof. The composite material takes a high-entropy metal glass test bar as a substrate, and the surface of the composite material is wrapped by a foam layer with a certain thickness. The foam layer is stacked by particles with the particle size of 0.35-0.6 mu m to form a foam metal structure, and the thickness of the foam layer reaches 9.17-14.53 mu m. In the preparation method, the mixed acid with low concentration is adopted, two functions of dealloying and oxidation resistance are realized simultaneously, and the dealloying process and the heat treatment process are combined together, so that the residual stress is effectively removed, and the layering problem is avoided. The invention solves the defects of complex process, high cost, advanced equipment, precise control of the process, high requirement on the technical level of operators, large burden on waste liquid treatment, potential threat to environment and worker health, uneven structure and components of the prepared material, high energy consumption and low yield in the prior art.
The technical scheme of the invention is as follows:
a foam metal/high-entropy metal glass composite material with large compressive strain takes a high-entropy metal glass test bar as an internal matrix, and a foam layer is wrapped on the surface of the matrix;
wherein the component of the inner matrix is Ti20Zr20Hf20Cu20Pd20Subscript numbers respectively represent the atomic percentage of corresponding metal elements in the alloy, and the diameter is 1.0-1.5 mm;
the foam layer comprises TixZryHfzCuwPdηWherein the atomic percentage of the components is that x is more than or equal to 1.79 and less than or equal to 3.28, y is more than or equal to 1.93 and less than or equal to 3.67, z is more than or equal to 1.23 and less than or equal to 3.46, w is more than or equal to 43.31 and less than or equal to 46.91, η is more than or equal to 46.25 and less than or equal to 48.14, x + y + z + w + η is equal to 100, and the thickness is 9.17-14.53 mu m.
The foam layer is formed by stacking particles with the particle size of 0.35-0.6 mu m;
the composite material with large compressive strain has the compressive fracture strength of 1058-1349 MPa and the compressive strain of 4.3-6.9%.
The preparation method of the foam metal/high-entropy metal glass composite material with large compressive strain comprises the following steps:
firstly, preparing a high-entropy metallic glass test bar
According to the formula Ti20Zr20Hf20Cu20Pd20The components are that high-purity Ti, Zr, Hf, Cu and Pd with corresponding mass are respectively weighed as raw materials and put into a furnace, before smelting, the vacuum degree in the furnace is controlled to be 3.5 × 10-3Setting the arc striking current to be 50A under MPa, then smelting the raw material metal under the current increased to 60-80A, keeping the molten state for 30-40 s each time, repeatedly smelting for 3-5 times, then increasing the current to 100-120A, sucking the molten metal into a copper mold under the suction casting pressure of 0.1-0.2 MPa, and obtaining Ti with the diameter of 1.0-1.5 mm20Zr20Hf20Cu20Pd20A high-entropy metal glass test bar;
secondly, preparing the foam metal/high-entropy metal glass composite material by dealloying
Cutting the high-entropy metal glass test bar prepared in the previous step, placing the cut high-entropy metal glass test bar in a reaction kettle of mixed acid solution, and performing dealloying for 2-6 days at a constant temperature to obtain a foam metal/high-entropy metal glass composite material;
wherein the temperature in the reaction kettle is 150-200 ℃; the mixed acid solution is formed by mixing HF solution and HCl solution with equal volumes, wherein the concentration of the HF solution is 0.01-0.03M, and the concentration of the HCl solution is 0.005-0.01M.
The purities of the high-purity Ti, Zr, Hf, Cu and Pd are all more than 99.9 wt.%.
The raw materials and equipment used in the foam metal/high-entropy metal glass composite material with large compressive strain and the preparation method thereof are obtained by known ways, and the operation process is mastered by those skilled in the art.
The invention has the substantive characteristics that:
the invention provides a foam metal/high-entropy metal glass composite material without any oxide inclusion and a preparation method thereof, wherein the foam metal/high-entropy metal glass composite material is obtained by taking low-concentration mixed acid as a corrosive liquid and combining a dealloying and heat treatment process, and the composite material has large compressive strain. TheThe composite material takes an internal high-entropy metal glass test bar as a matrix, and the surface of the matrix is wrapped with a foam layer with a certain thickness. The structure fully utilizes the excellent energy absorption characteristic of the foam layer, and the material still maintains higher-level compressive fracture strength while the room-temperature compressive strain is greatly improved. In the preparation method, the mixed corrosive liquid is prepared by skillfully adding a trace amount of hydrochloric acid into low-concentration hydrofluoric acid. Wherein, hydrofluoric acid is used for removing elements with higher chemical activity on the surface layer of the high-entropy metallic glass, and hydrochloric acid is used for removing oxides (Cu) generated in the process of dealloying2O, etc.) impurities, ultimately resulting in a metal-based foam layer that is free of any oxide impurities. Secondly, the invention breakthroughly implements the synchronous heat treatment process on the test bar in the dealloying process, effectively avoids the phenomena of cracking, layering and untight connection of the foam layer caused by the release of residual stress, and finally prepares the foam metal/high-entropy metal glass composite material with the uniform structure and good integrity of the foam layer and the tight connection with the matrix.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention relates to a foam metal/high-entropy metal glass composite material with large compressive strain and a preparation method thereof. The foam layer has uniform components and good integrity, and does not crack, delaminate or be untight in connection with a matrix.
(2) According to the foam metal/high-entropy metal glass composite material with large compressive strain and the preparation method thereof, the mixed acid with low concentration is selected as the corrosive liquid in the preparation process, so that the potential threat to the environment and the health of workers is reduced. Wherein, hydrofluoric acid is used for removing elements with higher chemical activity on the surface layer of the high-entropy metallic glass, and hydrochloric acid is used for removing oxides (Cu) generated in the process of dealloying2O, etc.) impurities, and finally obtaining the foam metal layer without any oxide impurities on the surface of the high-entropy metallic glass.
(3) According to the foam metal/high-entropy metal glass composite material with large compressive strain and the preparation method thereof, the excellent energy absorption characteristic of the foam metal layer is fully utilized, the room-temperature compressive strain of the alloy is improved, the compressive strain is increased by 4.3-6.9%, compared with the original high-entropy metal glass, the compressive strain is increased by 72-176%, and the material still maintains high-level compressive fracture strength while the compressive strain of the material is greatly improved.
(4) The foam metal/high-entropy metal glass composite material with large compressive strain and the preparation method thereof have simple material preparation process, and can realize mass preparation of the foam metal/high-entropy metal glass composite material with large compressive strain only by simply regulating and controlling dealloying parameters (dealloying time, dealloying temperature and corrosive liquid type and concentration) in a reaction kettle. The design of the process reduces energy consumption, reduces the requirements on the advancement of equipment, the precise control of the process and the high technical level of operators, improves the yield and is suitable for large-scale production.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is an XRD pattern of a high-entropy metallic glass test bar obtained in example 1.
FIG. 2 is a low-magnification SEM topography of the foam metal/high-entropy metal glass composite material prepared in example 1.
FIG. 3 is a high-magnification SEM topography of the foam metal/high-entropy metal glass composite material prepared in example 1.
FIG. 4 is an SEM topography of a foam layer of the foam metal/high-entropy metal glass composite prepared in example 1.
FIG. 5 is a graph of the spectrum analysis of the foam layer of the foam metal/high entropy metal glass composite material prepared in example 1.
FIG. 6 is a graph of compressive stress-strain curves of the foam metal/high entropy metallic glass composite prepared in example 1.
FIG. 7 is an SEM topographic map of the fracture morphology of the foam metal/high-entropy metallic glass composite material prepared in example 1.
Detailed Description
Example 1
Firstly, preparing a high-entropy metallic glass test bar
According to Ti20Zr20Hf20Cu20Pd20The components (wherein, subscript numbers are respectively the atomic percentage of corresponding metal elements in the alloy, the same in the following examples), high-purity (mass fraction is more than 99.9 wt.%) Ti, Zr, Hf, Cu and Pd metals with corresponding mass are respectively weighed, before smelting, the vacuum degree in the furnace is controlled to be 3.5 × 10-3MPa. Setting the arcing current to be 50A, then formally smelting the sample under the current increased to 60A, keeping the melting state for 30s each time, and repeating the smelting for 3 times, thereby ensuring the uniformity of the components of the alloy ingot. Finally, clamping the alloy ingot to a smelting suction casting station by using a manipulator in the furnace, increasing the current to 100A, sucking molten metal into a copper mold under the suction casting pressure of 0.1MPa, and obtaining Ti with the diameter of 1mm20Zr20Hf20Cu20Pd20A high-entropy metal glass test bar;
secondly, preparing the foam metal/high-entropy metal glass composite material by dealloying
And intercepting the high-entropy metal glass test bar prepared in the previous step for 3mm, and placing the high-entropy metal glass test bar into a reaction kettle containing a mixed solution, wherein the mixed solution is formed by mixing HF and HCl solution, the volume ratio of the HF to the HCl solution is 1:1, the concentration of the HF solution is 0.01M, and the concentration of the HCl solution is 0.005M. And (3) performing dealloying for 6 days at a constant temperature of 150 ℃ to obtain the foam metal/high-entropy metal glass composite material.
FIG. 1 shows Ti obtained in example 120Zr20Hf20Cu20Pd20The XRD pattern of the test bar shows that X-rays show a single diffuse scattering peak, so that the high-entropy alloy with the composition is proved to be in an amorphous structure. FIG. 2 is a low-magnification SEM topography of the foam metal/high-entropy metal glass composite material prepared in example 1. FIG. 3 is a high-magnification SEM topography of the foam metal/high-entropy metal glass composite material prepared in example 1. The figure shows that the material is tightly bonded where the foam layer is composited with the inner matrix. Wherein the foam layer has a uniform structure, no delamination and a thickness of 9.17 μm. FIG. 4 shows the surface foam of the foam metal/high-entropy metal glass composite material prepared in example 1The SEM topography of the layer shows that the foam layer is formed by tightly packing particles with the particle size of about 0.35 mu m, has good integrity and does not have any cracking phenomenon. FIG. 4 is a graph showing the spectral analysis of the foam layer having a composition of Ti2.60Zr2.64Hf2.09Cu45.51Pd47.56It is shown that the alloy mainly consists of Cu and Pd elements and a small amount of Ti, Zr and Hf elements which are not completely corroded, and does not contain any oxide impurities. The mechanical tests of the high-entropy metallic glass and the foam metal/high-entropy metallic glass composite material prepared in example 1 are shown in fig. 6. The compressive fracture strength of the high-entropy metal glass reaches 1710MPa, but the compressive strain is only 2.5%, while the compressive strain of the foam metal/high-entropy metal glass composite material prepared by the method is greatly improved to 5.4% on the premise that the compressive fracture strength is kept to 1125MPa, which is improved by 116% compared with the original high-entropy metal glass, and the foam metal/high-entropy metal glass composite material prepared by the method has good comprehensive mechanical properties. The sectional morphology of the foam metal/high-entropy metal glass composite material prepared in example 1 was detected, and the result is shown in fig. 7. The fact that the plurality of shear cracks terminate to expand at the front edge of the connection between the foam layer and the matrix shows that the foam layer serves as a buffer zone in the process of shear crack expansion, on one hand, redundant energy in the matrix is absorbed, on the other hand, the effect of delaying the rapid expansion of the shear cracks is achieved, and finally the compression strain at room temperature of the composite material is greatly improved.
Example 2
Firstly, smelting, suction casting and preparing the high-entropy metallic glass test bar
According to Ti20Zr20Hf20Cu20Pd20Respectively weighing high-purity (mass fraction is more than 99.9 wt.%) Ti, Zr, Hf, Cu and Pd, and before smelting, controlling vacuum degree in furnace to be 3.5 × 10-3MPa. Setting the arcing current to be 50A, and then formally smelting the sample under the current increased to 70A, keeping the melting state for 35s each time, and repeating the smelting for 3 times, thereby ensuring the uniformity of the components of the alloy ingot. Finally, theClamping an alloy ingot to a smelting suction casting station by using a manipulator in the furnace, increasing the current to 110A, and sucking molten metal into a copper mold under the suction casting pressure of 0.15MPa to obtain Ti with the diameter of 1.5mm20Zr20Hf20Cu20Pd20A high-entropy metal glass test bar;
secondly, preparing the foam metal/high-entropy metal glass composite material by dealloying
Intercepting the high-entropy metal glass test bar prepared in the previous step for 3mm, and placing the high-entropy metal glass test bar into a reaction kettle containing a mixed solution of 0.02M HF and 0.0075M HCl, wherein the volume ratio of HF to HCl solution is 1: 1. And performing dealloying for 4 days at a constant temperature of 175 ℃ to obtain the foam metal/high-entropy metal glass composite material.
The appearance of the foam metal/high-entropy metal glass composite material prepared by the embodiment is observed, and the material is tightly connected at the composite position of the foam layer and the internal matrix. Wherein the foam layer has uniform structure, no delamination, and a thickness of 14.53 μm. The foam layer is formed by tightly stacking particles with the particle size of about 0.5 mu m, has good integrity and does not have any cracking phenomenon. Secondly, the composition of the foam layer is Ti1.79Zr1.93Hf1.23Cu46.91Pd48.14It is shown that the alloy mainly consists of Cu and Pd elements and a small amount of Ti, Zr and Hf elements which are not completely corroded, and does not contain any oxide impurities.
The foam metal/high-entropy metal glass composite material prepared by the embodiment is used for carrying out compression performance test, and the composite material is found to show good comprehensive mechanical properties. Wherein, the compression fracture strength and the compression strain of the composite material are 1125MPa and 6.9 percent respectively, and the compression strain is improved by 176 percent compared with the original high-entropy metal glass.
Example 3
Firstly, smelting, suction casting and preparing the high-entropy metallic glass test bar
According to Ti20Zr20Hf20Cu20Pd20Respectively weighing high-purity (mass fraction is more than 99.9 wt.%) Ti, Zr, Hf, Cu and Pd, and before smelting, controlling vacuum degree in furnace to be 3.5 × 10-3MPa. Get upThe arc current is set to be 50A, the sample is formally smelted under the current increased to 80A, the smelting is repeated for 3 times each time the sample is kept in the molten state for 40s, and therefore the uniformity of the components of the alloy ingot is guaranteed. Finally, clamping the alloy ingot to a smelting suction casting station by using a manipulator in the furnace, increasing the current to 120A, sucking molten metal into a copper mold under the suction casting pressure of 0.2MPa, and obtaining Ti with the diameter of 1.5mm20Zr20Hf20Cu20Pd20A high-entropy metal glass test bar;
secondly, preparing the foam metal/high-entropy metal glass composite material by dealloying
Intercepting the high-entropy metal glass test bar prepared in the previous step for 3mm, and placing the high-entropy metal glass test bar into a reaction kettle containing a mixed solution of 0.03M HF and 0.01M HCl, wherein the volume ratio of HF to HCl solution is 1: 1. And (3) performing dealloying for 2 days at a constant temperature of 200 ℃ to obtain the foam metal/high-entropy metal glass composite material.
The appearance of the foam metal/high-entropy metal glass composite material prepared by the embodiment is observed, and the material is tightly connected at the composite position of the foam layer and the internal matrix. Wherein the foam layer has uniform structure, no delamination, and a thickness of 12.38 μm. The foam layer is formed by tightly stacking particles with the particle size of about 0.6 mu m, has good integrity and does not have any cracking phenomenon. Secondly, the composition of the foam layer is Ti3.28Zr3.67Hf3.46Cu43.31Pd46.25It is shown that the alloy mainly consists of Cu and Pd elements and a small amount of Ti, Zr and Hf elements which are not completely corroded, and does not contain any oxide impurities.
The foam metal/high-entropy metal glass composite material prepared by the embodiment is used for carrying out compression performance test, and the composite material is found to show good comprehensive mechanical properties. Wherein the compressive fracture strength and the compressive strain of the composite material are 1058.6MPa and 4.3 percent respectively, and the compressive strain of the composite material is improved by 72 percent compared with the original high-entropy metal glass.
Comparative example 1: the melting current is 80A, other conditions are the same as those of the example 1, and the high-entropy metallic glass test bar cannot be successfully cast by suction.
Comparative example 2: the suction casting pressure is 0.05MPa, other conditions are the same as those in example 1, and the high-entropy metallic glass test bar cannot be prepared by suction casting successfully.
Comparative example 3: the corrosion temperature is selected to be room temperature (25 ℃), the microscopic morphology of the corrosion sample is observed under the same other conditions as in example 1, and the material is found to have obvious cracks at the composite position of the foam layer and the internal matrix, so that the foam layer is easy to fall off. In addition, a large number of irregular arc-shaped cracks appear in the foam layer. The occurrence of the cracks and fissures damages the integrity of the whole structure, so that the foam layer can not protect the matrix. The compressive fracture strength and the compressive strain of the composite material are 1178MPa and 2.1 percent respectively, and the room-temperature compressive strain of the material is reduced while the compressive fracture strength is reduced.
Comparative example 4: the corrosion temperature is 500 ℃, other conditions are the same as those of the example 1, the microscopic morphology of a corrosion sample is observed, and the fact that the particles forming the foam layer are obviously coarsened at high temperature is found, the particle size reaches 1.2 mu m, and the protective effect of the foam layer on an internal matrix is greatly weakened by the thick structure. The compression fracture strength and the compression strain of the composite material are 1284MPa and 2.6 percent respectively, the room temperature compression strain of the material is only slightly improved while the compression fracture strength is greatly reduced, and the comprehensive mechanical property of the material is greatly reduced in comparison.
Comparative example 5: 0.01M HF as corrosive liquid is selected, the surface micro-morphology of a corrosive sample is observed under the same other conditions as in example 1, the material morphology is approximately the same as that of the material prepared in example 1, but the EDS detection result shows that the component of the foam layer of the composite material prepared in the comparative example is Ti1.25Zr1.37Hf1.02Cu24.17Pd25.88O46.31Indicating that the foam layer is subject to a higher degree of oxidation. At the same time, XRD detection results show that the composite material is doped with a large amount of Cu2O impurities, material composition non-uniformity.
Comparative example 6: the HF concentration is 0.1M, other conditions are the same as those of the embodiment 1, the surface micro-morphology of the corrosion sample is observed, and the thickness of the foam layer is up to 21.83 mu M, but the foam layer becomes loose, the phenomenon of over corrosion also occurs on the local part, and the protection effect on the matrix is greatly reduced. The compressive fracture strength and the compressive strain of the material are 768MPa and 3.5 percent respectively, the room-temperature compressive strain of the material is only slightly improved while the compressive fracture strength of the material is greatly reduced, and the comprehensive mechanical property of the material is reduced in comparison.
Comparative example 7: the time for dealloying is 2 days, other conditions are the same as those of example 1, the surface micro-morphology of the corrosion sample is observed, and the material is found to be tightly connected at the composite position of the foam layer and the internal matrix, the foam layer is not cracked, and the material shows better integrity, but the thickness of the foam layer is only 2.83 microns, and the material cannot generate effective protection effect on the internal matrix. The compressive fracture strength and the compressive strain of the material are 1564MPa and 4.9 percent respectively, the room temperature compressive strain of the material is slightly reduced while the compressive fracture strength of the material is reduced by a small margin, and the comprehensive mechanical property of the material is reduced.
In summary, the matrix of the present invention is Ti in atomic ratio20Zr20Hf20Cu20Pd20The foam layer of the high-entropy metal glass alloy does not contain any oxide impurity, has uniform structure and good integrity, does not have cracking and layering phenomena, is tightly connected with a matrix, and plays a certain role in protecting the matrix. Firstly, preparing a high-entropy metal glass precursor test rod by using an arc melting and suction casting method. And then, placing the test bar in a reaction kettle containing a mixed solution of low-concentration hydrofluoric acid and hydrochloric acid for dealloying. Wherein, the low-concentration hydrofluoric acid is used for removing elements with higher chemical activity on the surface layer of the high-entropy metal glass, and the trace hydrochloric acid is used for removing oxides generated in the process of dealloying, so that the foam metal layer without any oxide impurities is finally obtained. In the dealloying process, the temperature is constant at 150-200 ℃, the process design effectively avoids the phenomenon that the foam layer cracks, delaminates or is not tightly connected due to the release of residual stress in the dealloying process, and finally the foam metal/high-entropy metal glass composite material which is uniform and complete in structure and is tightly combined with the matrix is prepared. The compression strain of the composite material prepared by the method is as high as 4.3-6.9%, and compared with the original high-entropy metal glass, the compression strain increase of the composite material is as high as 72-176%.
The above examples and comparative examples illustrate a foam metal/high-entropy metal glass composite material with large compressive strain and a preparation method thereof, which are finally developed through repeated practice by continuously trying the components of the high-entropy metal glass and the dealloying process, strictly controlling each process step and carrying out multiple times of practice.
The invention is not the best known technology.

Claims (4)

1. A foam metal/high-entropy metal glass composite material with large compressive strain is characterized in that the composite material takes a high-entropy metal glass test bar as an internal matrix, and a foam layer is wrapped on the surface of the matrix;
wherein the component of the inner matrix is Ti20Zr20Hf20Cu20Pd20Subscript numbers respectively represent the atomic percentage of corresponding metal elements in the alloy, and the diameter is 1.0-1.5 mm;
the foam layer comprises TixZryHfzCuwPdηWherein the atomic percentage of the components is that x is more than or equal to 1.79 and less than or equal to 3.28, y is more than or equal to 1.93 and less than or equal to 3.67, z is more than or equal to 1.23 and less than or equal to 3.46, w is more than or equal to 43.31 and less than or equal to 46.91, η is more than or equal to 46.25 and less than or equal to 48.14, x + y + z + w + η is equal to 100, and the thickness is 9.17-14.53 mu m;
the preparation method of the foam metal/high-entropy metal glass composite material with large compressive strain comprises the following steps:
firstly, preparing a high-entropy metallic glass test bar
According to the formula Ti20Zr20Hf20Cu20Pd20The components are that high-purity Ti, Zr, Hf, Cu and Pd with corresponding mass are respectively weighed as raw materials and put into a furnace, before smelting, the vacuum degree in the furnace is controlled to be 3.5 × 10-3Setting the arc striking current to be 50A under MPa, then smelting the raw material metal under the current increased to 60-80A, keeping the molten state for 30-40 s each time, repeatedly smelting for 3-5 times, then increasing the current to 100-120A, sucking the molten metal into a copper mold under the suction casting pressure of 0.1-0.2 MPa, and obtaining Ti with the diameter of 1.0-1.5 mm20Zr20Hf20Cu20Pd20A high-entropy metal glass test bar;
secondly, preparing the foam metal/high-entropy metal glass composite material by dealloying
Cutting the high-entropy metal glass test bar prepared in the previous step, placing the cut high-entropy metal glass test bar in a reaction kettle of mixed acid solution, and performing dealloying for 2-6 days at a constant temperature to obtain a foam metal/high-entropy metal glass composite material;
wherein the temperature in the reaction kettle is 150-200 ℃; the mixed acid solution is formed by mixing HF solution and HCl solution with equal volumes, wherein the concentration of the HF solution is 0.01-0.03M, and the concentration of the HCl solution is 0.005-0.01M.
2. The foamed metal/high-entropy metal glass composite material with large compressive strain as claimed in claim 1, wherein the foamed layer is formed by stacking particles having a particle size of 0.35 to 0.6 μm.
3. The foamed metal/high entropy metallic glass composite material with large compressive strain as claimed in claim 1, wherein the compressive fracture strength of the composite material with large compressive strain is 1058-1349 MPa, and the compressive strain is 4.3-6.9%.
4. The metal foam/high-entropy metal glass composite material with large compressive strain as claimed in claim 1, wherein the purities of the high-purity Ti, Zr, Hf, Cu and Pd metals are each greater than 99.9 wt.% in mass fraction in the preparation method.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1566394A (en) * 2003-06-25 2005-01-19 中国科学院金属研究所 Polycomponent amorphous alloy with equal atomic ratio feature
KR100760339B1 (en) * 2006-05-19 2007-10-04 한국과학기술연구원 Nanometer-sized porous metallic glasses and method for manufactruring the same
US7521037B1 (en) * 2006-08-01 2009-04-21 Brookhaven Science Associates, Llc Regeneration of aluminum hydride
KR20160014130A (en) * 2014-07-28 2016-02-11 세종대학교산학협력단 High entropy alloy having excellent strength and ductility
CN106086712A (en) * 2016-05-31 2016-11-09 深圳大学 TiZrHf system high entropy amorphous alloy material and preparation method thereof
CN108295854A (en) * 2018-01-30 2018-07-20 河北工业大学 A kind of multi-stage porous nano porous copper load nano cuprous oxide wire composite material and preparation method
CN108597892A (en) * 2018-04-28 2018-09-28 河北工业大学 A kind of nano porous copper load copper-based oxide composite of morphology controllable and preparation method and application

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9033024B2 (en) * 2012-07-03 2015-05-19 Apple Inc. Insert molding of bulk amorphous alloy into open cell foam

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1566394A (en) * 2003-06-25 2005-01-19 中国科学院金属研究所 Polycomponent amorphous alloy with equal atomic ratio feature
KR100760339B1 (en) * 2006-05-19 2007-10-04 한국과학기술연구원 Nanometer-sized porous metallic glasses and method for manufactruring the same
US7521037B1 (en) * 2006-08-01 2009-04-21 Brookhaven Science Associates, Llc Regeneration of aluminum hydride
KR20160014130A (en) * 2014-07-28 2016-02-11 세종대학교산학협력단 High entropy alloy having excellent strength and ductility
CN106086712A (en) * 2016-05-31 2016-11-09 深圳大学 TiZrHf system high entropy amorphous alloy material and preparation method thereof
CN108295854A (en) * 2018-01-30 2018-07-20 河北工业大学 A kind of multi-stage porous nano porous copper load nano cuprous oxide wire composite material and preparation method
CN108597892A (en) * 2018-04-28 2018-09-28 河北工业大学 A kind of nano porous copper load copper-based oxide composite of morphology controllable and preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Ti-Zr-Hf-Cu-M 合金系大块玻璃合金的形成;张颖楠等;《稀有金属快报》;20021231(第12期);第15页 *

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