Zirconium-based amorphous alloy material, preparation method thereof, structural part and thin-wall machined part

Abstract

The invention provides a zirconium-based amorphous alloy material, a preparation method of the zirconium-based amorphous alloy material, a structural part and a thin-wall machined part. The chemical formula of the zirconium-based amorphous alloy material is (ZraCubAlcMd) 100-xRx, wherein 0.57 < = a < = 0.65, 0.20 < = b < = 0.30, 0.08 < = c < = 0.16, 0.001 < = d < = 0.05, and 0 < x < = 2; m comprises one or more of Nb, Ti and Hf, and R is a rare earth element. According to the zirconium-based amorphous alloy material provided by the invention, the composition and proportion of the zirconium-based amorphous alloy material are optimized, the influence of oxygen concentration on the zirconium-based amorphous alloy material can be reduced by adding the rare earth metal with a specific proportion, and the amorphous forming difficulty of the zirconium-based amorphous alloy material is reduced; and the zirconium-based amorphous alloy material with relatively high amorphous forming ability is obtained.

Description

Technical Field

[0001] The present application relates to the technical field of alloy materials, and in particular to a zirconium-based amorphous alloy material and a preparation method thereof, structural parts, and thin-walled processed parts. Background Art

[0002] Zirconium-based bulk amorphous alloys have attracted considerable attention in engineering applications due to their exceptional properties, including high strength, high hardness, and corrosion resistance. However, these alloys have exhibited limited glass-forming ability and toughness, failing to meet production requirements. This is due to the low vacuum levels in industrial die-casting and zirconium's strong affinity for oxygen, which leads to varying degrees of oxidation in the alloy. This makes it difficult for zirconium-based alloys to form amorphous structures in low vacuum environments. Only alloy systems with high glass-forming ability (d > 10 mm) under laboratory conditions are suitable for industrial production. Due to these preparation and compositional issues, conventional zirconium-based bulk amorphous alloys remain limited to widespread application. Conventional alloys suitable for industrial die-casting contain elements such as Be and Ni, which are toxic to humans, further limiting their application. Therefore, the development of Be- and Ni-free bulk amorphous alloy systems with strong glass-forming ability and high strength and toughness is of great significance. Summary of the Invention

[0003] Based on this, it is necessary to provide a zirconium-based amorphous alloy material with high amorphous forming ability and its preparation method, structural parts and thin-walled processed parts.

[0004] The present application provides a zirconium-based amorphous alloy material, the chemical formula of which is (Zr a Cu b Al c M d ) 100-x R x ;

[0005] Among them, 0.57≤a≤0.65, 0.20≤b≤0.30, 0.08≤c≤0.16, 0.001≤d≤0.05, 0<x≤2;

[0006] M includes one or more of Nb, Ti and Hf, and R is a rare earth element.

[0007] In one embodiment, R includes one or more of Y, Er, Ga, and Dy.

[0008] In one embodiment, R is Y.

[0009] In one embodiment, one or more of the following conditions are met:

[0010] (1) 0.59≤a≤0.62;

[0011] (2) 0.22≤b≤0.28;

[0012] (3) 0.1≤c≤0.14;

[0013] (4) 0.001≤d≤0.04;

[0014] (5) 0<x≤2.

[0015] In one embodiment, the zirconium-based amorphous alloy material satisfies one or more of the following conditions:

[0016] (1) The maximum amorphous forming capacity is 1mm~10mm;

[0017] (2) The maximum compressive strength at room temperature is 1.3 GPa~2.3 GPa;

[0018] (3) Yield strength is 1.2 GPa~1.8 GPa;

[0019] (4) Plasticity is 0.2%~20%.

[0020] The present application also provides a method for preparing a zirconium-based amorphous alloy material, comprising the following steps:

[0021] According to the chemical formula (Zr a Cu b Al c M d ) 100-x R x The nominal composition provides each metal element, wherein 0.57≤a≤0.65, 0.20≤b≤0.30, 0.08≤c≤0.16, 0.001≤d≤0.05, 0<x≤2; M includes one or more of Nb, Ti and Hf, and R is a rare earth element;

[0022] The metal elements are mixed and subjected to a first smelting process to prepare an alloy material.

[0023] In one embodiment, after preparing the alloy material, the method further comprises:

[0024] Mixing the alloy material and the master alloy ingot, and performing a casting process, wherein the casting temperature is greater than the melting point of the master alloy ingot;

[0025] Wherein, the chemical formula of the intermediate alloy ingot is Cu m R n , m+n=100 and m is less than n.

[0026] In one embodiment, one or both of the following conditions are met:

[0027] (1) The chemical formula of the intermediate alloy ingot is Cu 37 R 63 ;

[0028] (2) The mass ratio of the alloy material to the intermediate alloy ingot is (90-99.9):(0.01-0.6).

[0029] Furthermore, the present application provides a structural component, wherein the material of the structural component includes the zirconium-based amorphous alloy material as described above or the zirconium-based amorphous alloy material prepared by the above preparation method.

[0030] Furthermore, the present application provides a thin-walled workpiece, wherein the material of the thin-walled workpiece includes the zirconium-based amorphous alloy material as described above or the zirconium-based amorphous alloy material prepared by the above preparation method.

[0031] The zirconium-based amorphous alloy material provided in the present application optimizes the composition and proportion of the zirconium-based amorphous alloy material and adds a specific proportion of rare earth metals to reduce the influence of oxygen concentration on the zirconium-based amorphous alloy material, thereby reducing the difficulty of amorphous formation of the zirconium-based amorphous alloy material and obtaining a zirconium-based amorphous alloy material with higher amorphous forming ability. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the specific implementation methods of the present application or the technical solutions in the prior art, the following is a brief introduction to the drawings required for use in the specific implementation methods or the description of the prior art. Obviously, the drawings described below are some implementation methods of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0033] Figure 1 The XRD patterns of the zirconium-based amorphous alloy materials with a diameter of 2 mm in Examples 1 to 5 and Comparative Example 1 are shown.

[0034] Figure 2 (a) is the XRD graph of the zirconium-based amorphous alloy material with a diameter of 10 mm in Examples 1 to 5 and (b) is the XRD graph of Comparative Example 1.

[0035] Figure 3 The differential scanning calorimetry test diagram of the zirconium-based amorphous alloy material with a diameter of 2 mm in Examples 1 to 5 and Comparative Example 1, wherein T x is the crystallization temperature, T g is the glass transition temperature.

[0036] Figure 4 1 and 2 are stress-strain curves of the zirconium-based amorphous alloy materials of Examples 1 to 5 and Comparative Example 1, where 2% is the scale of the strain.

[0037] Figure 5(a) is the comparative example 1, and (b) to (f) are scanning electron microscope images of the fracture morphologies of the zirconium-based amorphous alloy materials corresponding to Examples 1 to 5, respectively.

[0038] Figure 6 Actual pictures of industrial die-casting of zirconium-based amorphous alloy materials of Examples 1 to 5.

[0039] Figure 7 This is a physical picture of the industrial die-casting of the zirconium-based amorphous alloy material in comparative example 1.

[0040] Figure 8 This is the XRD pattern of the industrial die-cast sample of the zirconium-based amorphous alloy material in Example 2.

[0041] Figure 9 This is the phase diagram of Al-Y binary alloy.

[0042] Figure 10 This is the micromorphology of the alloy after Al-Y alloy was used as an intermediate alloy and cycled three times.

[0043] Figure 11 This is the Cu-Y binary alloy phase diagram.

[0044] Figure 12 This is the micromorphology of the alloy after Cu-Y alloy was cycled three times as an intermediate alloy. DETAILED DESCRIPTION

[0045] To facilitate understanding of the present application, a more comprehensive description of the present application will be provided below with reference to the accompanying drawings. The accompanying drawings illustrate preferred embodiments of the present application. However, the present application may be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and comprehensive understanding of the disclosure of the present application.

[0046] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application pertains. The terms used herein in the specification of this application are for the purpose of describing specific embodiments only and are not intended to limit this application.

[0047] As used herein, the term "and / or" includes any one of two or more of the listed items, as well as any and all combinations of the listed items, including any combination of any two, any more, or all of the listed items. For example, "A and / or B" includes A, B, and the combination of A and B.

[0048] In this document, unless otherwise specified, "one or more" means any one of the listed items or any combination of the listed items. Similarly, "one or more" and other expressions that mean "one or more" are also understood in the same way unless otherwise specified.

[0049] Herein, terms such as "further," "further," "particularly," "for example," "such as," "example," and "for instance" are used for descriptive purposes to indicate a connection between the preceding and following technical solutions in terms of their coverage. However, they should not be construed as limiting the preceding technical solution or the scope of protection herein. Herein, unless otherwise specified, "A (such as B)" means that B is a non-limiting example of A, and it should be understood that A is not limited to B.

[0050] As used herein, "optionally," "optional," and "optional" mean optional, that is, any one of the two parallel options of "with" or "without." If multiple "optional" items appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "optional" item is independent of the other. In this application, descriptions such as "optionally contain" and "optionally include" mean "containing or not containing." "Optional component X" means the presence or absence of component X, or the presence or absence of component X.

[0051] In this document, the terms "first," "second," "third," and "fourth," etc., are used for descriptive purposes only and should not be understood as indicating or implying relative importance or quantity, nor as implicitly indicating the importance or quantity of the technical features indicated. Furthermore, "first," "second," "third," and "fourth," etc., serve only as non-exhaustive enumeration and description and should not constitute a closed-ended limitation on quantity.

[0052] In this article, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0053] As used herein, when referring to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​within the numerical interval is deemed to be continuous and includes the two numerical endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every numerical value between the two numerical endpoints. Unless otherwise specified, when a numerical interval refers only to integers within the numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe a feature or characteristic, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. "Numerical interval" allows for a broad range of numerical interval types including percentage intervals, ratio intervals, and ratio intervals.

[0054] Herein, the term "room temperature" or "normal temperature" generally refers to 4°C to 35°C, for example, 20°C ± 5°C. In some embodiments herein, "room temperature" or "normal temperature" refers to 10°C to 30°C. In some embodiments herein, "room temperature" or "normal temperature" refers to 20°C to 30°C.

[0055] In this document, if a method flow involves multiple steps, unless otherwise specified herein, there is no strict order restriction on the execution of these steps, and they can be performed in an order other than the order described. Moreover, any step can include multiple sub-steps or multiple stages, and these sub-steps or stages do not necessarily need to be completed at the same time, but can be performed at different times, and their execution order does not necessarily need to be sequential, but can be performed in rotation, alternation, or simultaneously with other steps or parts of sub-steps or stages of other steps.

[0056] The present application provides a zirconium-based amorphous alloy material, the chemical formula of which is (Zr a Cu b Al c M d ) 100-x R x ;

[0057] Among them, 0.57≤a≤0.65, 0.20≤b≤0.30, 0.08≤c≤0.16, 0.001≤d≤0.05, 0<x≤2;

[0058] M includes one or more of Nb, Ti and Hf, and R is a rare earth element.

[0059] The zirconium-based amorphous alloy material provided in the present application optimizes the composition and proportion of the zirconium-based amorphous alloy material and adds a specific proportion of rare earth metals to reduce the influence of oxygen concentration on the zirconium-based amorphous alloy material, thereby reducing the difficulty of amorphous formation of the zirconium-based amorphous alloy material and obtaining a zirconium-based amorphous alloy material with higher amorphous forming ability.

[0060] Furthermore, M is Ti.

[0061] In a specific example, R includes one or more of Y, Er, Ga, and Dy. Furthermore, R is Y.

[0062] In a specific example, 0.59≤a≤0.62. Specifically, a can be, but is not limited to, 0.59, 0.6, 0.61, or 0.62.

[0063] In a specific example, 0.22≤b≤0.28. Specifically, b may be, but is not limited to, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, or 0.28.

[0064] In a specific example, 0.1≤c≤0.14. Specifically, c can be, but is not limited to, 0.1, 0.11, 0.12, 0.13 or 0.14.

[0065] In a specific example, 0.01≤d≤0.04. Specifically, d may be, but is not limited to, 0.01, 0.02, 0.03, or 0.04.

[0066] In a specific example, 0≤x≤2, specifically, x can be but is not limited to 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2.

[0067] In a specific example, the maximum glass-forming capacity of the zirconium-based amorphous alloy material is 1 mm to 10 mm. Specifically, the maximum glass-forming capacity of the zirconium-based amorphous alloy material can be, but is not limited to, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, or 10 mm.

[0068] In a specific example, the maximum compressive strength of the zirconium-based amorphous alloy material at room temperature is 1.3 GPa to 2.3 GPa. Specifically, the compressive strength of the zirconium-based amorphous alloy material at room temperature may be, but is not limited to, 1.3 GPa, 1.4 GPa, 1.5 GPa, 1.6 GPa, 1.7 GPa, 1.8 GPa, 1.9 GPa, 2 GPa, 2.1 GPa, 2.2 GPa, or 2.3 GPa.

[0069] In a specific example, the yield strength of the zirconium-based amorphous alloy material may be, but is not limited to, 1.2 GPa, 1.3 GPa, 1.4 GPa, 1.5 GPa, 1.6 GPa, 1.7 GPa, or 1.8 GPa.

[0070] In a specific example, the plasticity of the zirconium-based amorphous alloy material is 0.2% to 20%. The plasticity of the zirconium-based amorphous alloy material can be, but is not limited to, 0.2%, 0.5%, 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%.

[0071] The present application also provides a method for preparing a zirconium-based amorphous alloy material, comprising the following steps:

[0072] According to the chemical formula (Zr a Cu b Al c M d ) 100-x R x The nominal composition provides each metal element, wherein 0.57≤a≤0.65, 0.20≤b≤0.30, 0.08≤c≤0.16, 0.001≤d≤0.05, 0<x≤2; M includes one or more of Nb, Ti and Hf, and R is a rare earth element;

[0073] The metal elements are mixed and subjected to a first smelting process to prepare an alloy material.

[0074] Furthermore, the vacuum degree of the first smelting process is 10 -3 Pa~10 -4 Pa, the first melting process may be, but is not limited to, induction melting or arc melting, and the first melting process is repeated at least three times. The mold used in the first melting process may be, but is not limited to, a copper mold. Specifically, the temperature of the first melting process is 1800°C to 2200°C, and may be, but is not limited to, 1800°C, 1900°C, 2000°C, 2100°C, or 2200°C. The first melting process lasts for 20 seconds to 60 seconds, and may be, but is not limited to, 20 seconds, 25 seconds, 30 seconds, 35 seconds, 40 seconds, 45 seconds, 50 seconds, 55 seconds, or 60 seconds.

[0075] In a specific example, in order to prevent the alloy material from being oxidized, after preparing the alloy material, the process further includes: mixing the alloy material and the intermediate alloy ingot, and performing a casting process, wherein the casting temperature is greater than the melting point of the intermediate alloy ingot; wherein the chemical formula of the intermediate alloy ingot is Cu m R n , m+n=100 and m is less than n.

[0076] In a specific example, the method for preparing the master alloy ingot includes the following steps:

[0077] According to the chemical formula of the intermediate alloy ingot, Cu m R n Nominal composition, providing each metal element, cleaning, mixing each metal element, performing a second smelting process, and preparing an intermediate alloy ingot.

[0078] Furthermore, the vacuum degree of the second smelting process is 10 -3 Pa~10 -4 Pa, the second melting process can be, but is not limited to, induction melting or arc melting, and the second melting process is repeated at least three times. The mold used in the second melting process can be, but is not limited to, a copper mold.

[0079] In a specific example, the chemical formula of the master alloy ingot is Cu m Y n , 30≤m≤45. Specifically, the chemical formula of the intermediate alloy ingot is Cu 37 R 63 .

[0080] In order to avoid the increase of oxygen content during casting, pure rare earth can be added to reduce the degree of oxidation. However, due to the high melting point of pure rare earth materials (Y is 1500℃), the temperature of casting cannot completely melt the rare earth materials, which will lead to uneven mixing and the rare earth elements cannot fully play their role. m Y n The melting point is lower than the casting molding temperature, and the metal can be completely melted to effectively reduce the oxygen content during the casting molding process.

[0081] In a specific example, a mixed alloy material and an intermediate alloy ingot are subjected to a casting molding process, and the steps of preparing a zirconium-based amorphous alloy material specifically include: placing the alloy material and the intermediate alloy ingot in a graphite or corundum crucible, evacuating the vacuum, and using coil induction melting for die casting at a vacuum degree between 10Pa and 30Pa; when the temperature and time of the induction melting reach the program set values, the crucible automatically rotates to pour the molten alloy material and the intermediate alloy ingot into the runner, and the plunger quickly presses the molten alloy material and the intermediate alloy ingot into the mold.

[0082] It can be understood that the casting molding process includes one of a suction casting molding process, a spray casting molding process, a pouring molding process and a die casting molding process. Furthermore, the casting molding process is a die casting molding process. In order to avoid severe oxidation, the temperature during the die casting molding process should not be too high, and is generally 50°C to 100°C higher than the melting point of the zirconium-based amorphous alloy material to be prepared. Furthermore, the temperature during the die casting molding process can be higher than the melting point of the zirconium-based amorphous alloy material, but is not limited to, 50°C, 60°C, 70°C, 80°C, 90°C or 100°C.

[0083] In a specific example, the mass ratio of the alloy material to the intermediate alloy ingot is (90-99.9):(0.01-0.6).

[0084] The melting point of the intermediate alloy used in this application is lower than the casting molding process temperature. During the die-casting smelting, the intermediate alloy forms a diaphragm on the surface of the alloy material to inhibit the direct reaction of the alloy material with external oxygen. At the same time, the rare earth elements will not be completely dissolved in the alloy material. While ensuring that the obtained zirconium-based amorphous alloy material has sufficient amorphous forming ability, its mechanical properties will not be reduced. It can be understood that the temperature of the above-mentioned casting molding process is 850℃~1050℃. Specifically, the temperature of the casting molding process can be but not limited to 850℃, 900℃, 950℃, 1000℃ or 1050℃. The time of the above-mentioned casting molding process is 30s~70s. Specifically, the time of the casting molding process can be but not limited to 30s, 40s, 50s, 60s or 70s.

[0085] In industrial die-casting, mold temperatures typically need to be kept high, typically around 200°C, to reduce internal stress in the casting. This reduces the glass-forming ability (GFA), a fundamental difference from the copper molds used in laboratories. Therefore, lowering the master alloy melt temperature allows for lower mold temperatures, which improves the GFA of zirconium-based amorphous alloys and enhances the performance of castings made from them.

[0086] In a specific example, the vacuum degree of the casting is 30Pa~100Pa.

[0087] It can be understood that the zirconium-based amorphous alloy material provided in the present application can be used to produce amorphous alloy plates with a thickness of 2 mm through industrial die-casting, which can be used to prepare small structural parts and thin-walled processed parts.

[0088] It can be understood that the zirconium-based amorphous alloy material provided in the present application does not contain Be and Ni elements, has high amorphous forming ability and also has high strength and plasticity. It can be die-cast under low vacuum conditions to form large-sized amorphous alloys of different thicknesses, and can therefore be used in the biomedical field.

[0089] Furthermore, the present application provides a structural component, wherein the material of the structural component includes the aforementioned zirconium-based amorphous alloy material or the aforementioned zirconium-based amorphous alloy material. It is understood that the structural component is a small structural component, and further, the small structural component can be, but is not limited to, one or both of a flexspline and a gear.

[0090] Furthermore, the present application provides a thin-walled workpiece, the material of which includes the aforementioned zirconium-based amorphous alloy material or the aforementioned zirconium-based amorphous alloy material. It is understood that the thin-walled workpiece herein specifically refers to a workpiece having a thickness of 1 mm to 2 mm. The thin-walled workpiece may be, but is not limited to, one or more of a smartwatch case, a mobile phone case, and a nose pad.

[0091] The present application will be further described in detail below with reference to specific examples. It should be understood that these examples are intended to illustrate the present application only and are not intended to limit the scope of the present application. For experimental methods in the following examples where specific conditions are not specified, reference should be made to the instructions provided in this application, or to experimental manuals or conventional conditions in the art, or to conditions recommended by the manufacturer, or to experimental methods known in the art.

[0092] In the following specific examples, the measured parameters of raw material components may have slight deviations within the range of weighing accuracy unless otherwise specified. For temperature and time parameters, acceptable deviations due to instrument testing accuracy or operational accuracy are allowed. "Normal temperature" refers to 25°C; "normal pressure" refers to 100 kPa or 101 kPa.

[0093] The raw materials used in the following examples and comparative examples are zirconium particles, copper particles, aluminum particles, titanium particles and yttrium particles, which were purchased from Zhongnuo New Materials Technology Co., Ltd.

[0094] Example 1

[0095] This embodiment provides a zirconium-based amorphous alloy material, the chemical formula of which is (Zr 0.61 Cu 0.25 Al 0.12 Ti 0.02 ) 99.9 Y 0.1 , the preparation method of this material is as follows:

[0096] According to the chemical formula (Zr 0.61 Cu 0.25 Al 0.12 Ti 0.2 ) 99.9 Y 0.1 Prepare zirconium particles, copper particles, aluminum particles, titanium particles, and yttrium particles in corresponding mass proportions according to the nominal composition, and wash the particles;

[0097] Evacuate to a vacuum degree of 10-3 Pa to 10 -4 Pa, an inert gas is introduced; under the conditions of inert gas protection and electromagnetic stirring, arc melting at 2000 ° C for 30 seconds is repeated at least three times, the molten metal liquid is cast into a copper mold, and a rapid cooling treatment is performed to prepare an alloy material.

[0098] Example 2

[0099] This embodiment provides a chemical formula (Zr 61 Cu 25 Al 12 Ti2) 99.7 Y 0.3 The zirconium-based amorphous alloy material, the preparation method thereof is different from that of Example 1 in that the proportions of the corresponding raw materials are changed according to the chemical formula.

[0100] Example 3

[0101] This embodiment provides a chemical formula (Zr 61 Cu 25 Al 12 Ti2) 99.6 Y 0.4 The zirconium-based amorphous alloy material, the preparation method thereof is different from that of Example 1 in that the proportions of the corresponding raw materials are changed according to the chemical formula.

[0102] Example 4

[0103] This embodiment provides a chemical formula (Zr 61 Cu 25 Al 12 Ti2) 99.5 Y 0.5 The zirconium-based amorphous alloy material, the preparation method thereof is different from that of Example 1 in that the proportions of the corresponding raw materials are changed according to the chemical formula.

[0104] Example 5

[0105] This embodiment provides a chemical formula (Zr 61 Cu 25 Al 12 Ti2) 99 The preparation method of the zirconium-based amorphous alloy material Y1 is different from that of Example 1 in that the proportions of the corresponding raw materials are changed according to the chemical formula.

[0106] Example 6

[0107] This embodiment provides a chemical formula (Zr 0.6 Cu 0.25 Al 0.12 Ti 0.03 ) 99.7 Y 0.3The zirconium-based amorphous alloy material, the preparation method thereof is different from that of Example 2 in that the proportions of the corresponding raw materials are changed according to the chemical formula.

[0108] Example 7

[0109] This embodiment provides a chemical formula (Zr 0.61 Cu 0.24 Al 0.12 Ti 0.03 ) 99.7 Y 0.3 The zirconium-based amorphous alloy material, the preparation method thereof is different from that of Example 2 in that the proportions of the corresponding raw materials are changed according to the chemical formula.

[0110] Example 8

[0111] This embodiment provides a chemical formula (Zr 0.61 Cu 0.25 Al 0.11 Ti 0.03 ) 99.7 Y 0.3 The zirconium-based amorphous alloy material, the preparation method thereof is different from that of Example 2 in that the proportions of the corresponding raw materials are changed according to the chemical formula.

[0112] Example 9

[0113] This embodiment provides a chemical formula (Zr 0.61 Cu 0.25 Al 0.1 Ti 0.04 ) 99.7 Y 0.3 The zirconium-based amorphous alloy material, the preparation method thereof is different from that of Example 2 in that the proportions of the corresponding raw materials are changed according to the chemical formula.

[0114] Comparative Example 1

[0115] This comparative example provides a chemical formula of Zr 61 Cu 25 Al 12 The preparation method of the Ti2 zirconium-based amorphous alloy material is different from that of Example 1 in that no rare earth metal is added during preparation, and the proportion of the corresponding raw materials is changed according to the chemical formula.

[0116] Test methods and results:

[0117] Yield strength: The strength at which yielding occurs in the elastic stage.

[0118] Compression plasticity: The diameter of the compression specimen is 2 mm, the height-to-diameter ratio is 2:1, and the compression rate is 1x10 -4 s -1 .

[0119] Highest compressive strength: The highest strength corresponding to the entire stress-strain process at room temperature.

[0120] Maximum amorphous formation ability: The zirconium-based amorphous alloy materials prepared in all examples and all comparative examples are columnar castings. The XRD patterns of the diameters of these columnar castings are tested. Denote the diameter of the columnar casting as D (unit: mm). If crystallization peaks appear in its XRD pattern, the amorphous formation ability < D; otherwise, the amorphous formation ability ≥ D, and D is denoted as the maximum amorphous formation ability of this zirconium-based amorphous alloy material. As Figure 1 Shown are the XRD patterns of the zirconium-based amorphous alloy materials with a diameter of 2 mm in Examples 1 to 5 and Comparative Example 1. As Figure 2 Shown in (a) are the XRD patterns of the zirconium-based amorphous alloy materials with a diameter of 10 mm in Examples 1 to 5 and (b) Comparative Example 1. As Figure 3 Shown are the differential scanning calorimetry test diagrams of the zirconium-based amorphous alloy materials with a diameter of 2 mm in Examples 1 to 5 and Comparative Example 1, where T x is the crystallization temperature and T g is the glass transition temperature. As Figure 4 Shown are the stress-strain curves of the zirconium-based amorphous alloy materials in Examples 1 to 5 and Comparative Example 1. As Figure 5 Shown in (a) is the scanning electron microscope image of the fracture morphology of the zirconium-based amorphous alloy material in Comparative Example 1 and (b) to (f) correspond to Examples 1 to 5 in sequence.

[0121] Table 1

[0122]

[0123] It can be seen from Table 1 above that as the content of the rare earth metal Y in the alloy increases, the O content decreases, the number of atomic clusters increases, which is beneficial to the improvement of the plasticity of the alloy material. However, the further increase of the rare earth metal Y leads to an increase in the volume fraction of the Y-containing compound, resulting in a decrease in the mechanical properties of the alloy material.

[0124] Furthermore, in order to prevent the alloy from being oxidized, the following steps are further included based on the alloy material in Example 1:

[0125] Preparation of the master alloy ingot

[0126] (1) Based on the chemical formula of the master alloy Cu 37 Y 63 , prepare copper particles and yttrium particles with the corresponding mass ratios according to the nominal composition, and clean the above particles;

[0127] (2) Evacuate the air, and the vacuum degree during melting is between 10 -4 Pa and 10​​​​(3) Arc melting, wherein the melting temperature is about 2000°C, each melting time is 30 seconds, and it is repeated at least three times to prepare a rare earth intermediate alloy ingot.

[0129] Industrial die casting and melting

[0130] (1) The alloy material obtained in Example 1 and the above-mentioned intermediate alloy ingot were placed in a graphite or corundum crucible at a mass ratio of 99.6:0.4;

[0131] (2) Vacuuming: the vacuum degree during smelting should be between 30Pa and 10Pa;

[0132] (3) Induction melting;

[0133] (4) When the melting temperature reaches 950°C and the time reaches the program setting value of 50s, the crucible rotates to pour the molten alloy into the runner, and the plunger quickly presses the alloy melt into the mold to prepare the zirconium-based amorphous alloy material specimen.

[0134] As shown in Table 2 below, the changes in oxygen and nitrogen content before and after the addition of the master alloy Cu-Y in Example 1.

[0135] Table 2

[0136]

[0137] The alloy materials of Examples 1 to 5 and Comparative Example 1 were further subjected to industrial die casting by adding intermediate alloys to obtain the above-mentioned Figure 6 The following are the industrial die-casting pictures of the zirconium-based amorphous alloy materials of Examples 1 to 5. Figure 7 The figure shows the industrial die-casting of the zirconium-based amorphous alloy material in comparative example 1. Figure 8 The XRD pattern of the industrial die-cast sample of the zirconium-based amorphous alloy material in Example 2 is shown. Figure 9 The figure shows the phase diagram of Al-Y binary alloy. The melting point of Al-Y alloy is about 1300K (1027℃). The die casting temperature is 950℃, but Al-Y alloy still cannot be completely melted. As the number of die casting cycles increases, the high melting point Al-containing crystal phase precipitates, and the amorphous forming ability of the casting decreases. Figure 10 As shown in the figure, the micromorphology of the alloy after Al-Y alloy was recycled three times as an intermediate alloy. Specifically, during the third cycle of die-casting, Al-rich crystal phase precipitated, and the amorphous forming ability of the die-casting was reduced. Analysis showed that the main component of the crystal phase was Zr2Al, which has a melting point of 1500℃ and is difficult to dissolve during die-casting and melting. It requires additional process treatment, which increases the cost.

[0138] In industrial die casting, in order to reduce the internal stress of the casting, the mold temperature is usually required to be 200℃, which reduces the amorphous forming ability. This is completely different from the copper mold used in the laboratory. Therefore, the lower the melt temperature, the lower the mold temperature setting, which is conducive to improving the amorphous forming ability and the performance of the casting. Figure 11 The phase diagram of Cu-Y binary alloy is shown. 37 Y 63 The melting point of the master alloy is as low as 1100K (827℃), which is suitable for low melting point alloy components. At the same time, it can reduce the melting temperature and mold temperature, and improve the amorphous forming ability, such as Figure 12 The micromorphology of a Cu-Y alloy used as an intermediate alloy after three cycles is shown. No crystalline phase precipitates after the third cycle, indicating uniform distribution of elements. The casting remains amorphous, allowing for multiple die-casting cycles, high raw material utilization, and cost savings. Large-scale amorphous alloys of varying thicknesses can be die-cast under low vacuum conditions, finding applications in biomedicine.

[0139] The technical features of the above embodiments can be combined arbitrarily. To make the description concise, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0140] The above embodiments merely represent several implementation methods of the present application, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the invention patent. It should be noted that a person of ordinary skill in the art can make a number of variations and improvements without departing from the concept of the present application, and these are all within the scope of protection of the present application. Therefore, the scope of protection of the patent application of this application shall be based on the attached claims, and the description and drawings shall be used to interpret the scope of the claims.

Claims

1. A zirconium-based amorphous alloy material, characterized in that: The chemical formula of the zirconium-based amorphous alloy material is (Zr a Cu b Al c M d ) 100-x R x ; Among them, 0.57≤a≤0.65, 0.20≤b≤0.30, 0.08≤c≤0.16, 0.001≤d≤0.05, 0<x≤2; M includes one or more of Nb, Ti and Hf, and R is a rare earth element.

2. The zirconium-based amorphous alloy material according to claim 1, wherein R includes one or more of Y, Er, Ga, and Dy.

3. The zirconium-based amorphous alloy material according to claim 2, wherein: R is Y.

4. The zirconium-based amorphous alloy material according to claim 1, wherein One or more of the following conditions are met: （1）0.59≤a≤0.62； （2）0.22≤b≤0.28； （3）0.1≤c≤0.14； （4）0.001≤d≤0.04； （5）0＜x≤2。 5. The zirconium-based amorphous alloy material according to any one of claims 1 to 4, characterized in that: The zirconium-based amorphous alloy material meets one or more of the following conditions: (1) The maximum amorphous forming capacity is 1mm~10mm; (2) The maximum compressive strength at room temperature is 1.3 GPa~2.3 GPa; (3) Yield strength is 1.2 GPa~1.8 GPa; (4) Plasticity is 0.2%~20%.

6. A method for preparing a zirconium-based amorphous alloy material, characterized in that: The following steps are involved: According to the chemical formula (Zr a Cu b Al c M d ) 100-x R x The nominal composition provides each metal element, wherein 0.57≤a≤0.65, 0.20≤b≤0.30, 0.08≤c≤0.16, 0.001≤d≤0.05, 0<x≤2; M includes one or more of Nb, Ti and Hf, and R is a rare earth element; The metal elements are mixed and subjected to a first smelting process to prepare an alloy material.

7. The preparation method according to claim 6, wherein After preparing the alloy material, the method further comprises: Mixing the alloy material and the master alloy ingot, and performing a casting process, wherein the casting temperature is greater than the melting point of the master alloy ingot; Wherein, the chemical formula of the intermediate alloy ingot is Cu m R n , m+n=100 and m is less than n.

8. The preparation method according to claim 7, wherein One or both of the following conditions are met: (1) The chemical formula of the intermediate alloy ingot is Cu 37 R 63 ; (2) The mass ratio of the alloy material to the intermediate alloy ingot is (90-99.9):(0.01-0.6).

9. A structural member, characterized in that: The material of the structural component includes the zirconium-based amorphous alloy material according to any one of claims 1 to 5 or the zirconium-based amorphous alloy material prepared by the preparation method according to any one of claims 6 to 8.

10. A thin-walled workpiece, characterized in that: The material of the thin-walled workpiece includes the zirconium-based amorphous alloy material according to any one of claims 1 to 5 or the zirconium-based amorphous alloy material prepared by the preparation method according to any one of claims 6 to 8.

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