Zirconium-based amorphous alloy and preparation method therefor, structural component, electronic device, and medical device

Abstract

The present application provides a zirconium-based amorphous alloy and a preparation method therefor, a structural component, an electronic device, and a medical device. The atomic percentage expression of the zirconium-based amorphous alloy of the present application is AMYAld, A being ZreTifHfgNbhTai, M being CoxNiyFez, and Y being CumAgn. The zirconium-based amorphous alloy has the characteristics of high strength, high toughness and non-toxicity.

Description

Zirconium-based amorphous alloys and their preparation methods, structural components, electronic devices and medical devices

[0001] Cross-references to related applications

[0002] This application claims priority to Chinese Patent Application No. 202411434427.2, filed on October 14, 2024, entitled "Zirconium-based amorphous alloy and its preparation method, structural parts, electronic devices and medical devices", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This application relates to zirconium-based amorphous alloys and their preparation methods, structural components, electronic devices, and medical devices. Background Technology

[0004] Amorphous alloys, also known as liquid metals or metallic glasses, exhibit short-range order and long-range disorder in their microscopic atomic structure. Therefore, compared to crystalline materials, zirconium-based amorphous alloys possess unique mechanical properties, such as extremely high strength, hardness, elasticity, and corrosion resistance, making them widely used in consumer electronics, sporting goods, smart wearables, medical devices, and automobiles. Furthermore, the excellent formability of existing commercially available zirconium-based amorphous alloy systems makes them the preferred material for complex, irregularly shaped structural components, with broad application prospects. However, most bulk zirconium-based amorphous alloys, such as those with a minimum size greater than 1 mm, contain significant amounts of the precious metal palladium, resulting in high costs and hindering commercial applications. Moreover, existing bulk zirconium-based amorphous alloys with critical glass-forming capabilities exceeding 10 mm, such as vit1, vit105, and vit106, almost all contain large amounts of toxic nickel and beryllium or relatively high levels of copper, and their tensile strength is below 1900 MPa. This results in a scarcity of large-size, high-strength zirconium-based amorphous alloy systems that are non-toxic and harmless to the human body, and these systems cannot meet the requirements for high-strength structural components. Summary of the Invention

[0005] This application provides a zirconium-based amorphous alloy and its preparation method, structural components, electronic devices, and medical devices, to reduce the toxicity of bulk zirconium-based amorphous alloys and improve their strength.

[0006] In a first aspect, this application provides a zirconium-based amorphous alloy, wherein the atomic percentage expression of the zirconium-based amorphous alloy is AMYAl. d A is Zr e Ti f Hf g Nb h Ta i M is Co x Ni y Fez Y is Cu m Ag n ; Among them, e+f+g+h+i=a, 50≤a≤60, 0<f≤5, 0<g≤5, 0<h≤2, 0≤i≤2; x+y+z=b, 1 0≤b≤20, 0≤y≤5, 0≤z≤5; m+n=c, 0<c≤10, 0≤n≤3; a+b+c+d=100, 14≤d≤20.

[0007] The zirconium-based amorphous alloy of this application uses Zr, Co, and Al as the main alloying elements. By adding Ti, Hf, Nb, and Ta—elements with good intermelting properties and biocompatibility with zirconium—as well as Ni and Fe—elements with good intermelting properties and biocompatibility with cobalt—and copper and silver—which have a positive enthalpy of mixing with Co, Ni, and Fe, and a higher proportion of lightweight aluminum, the use of harmful elements such as Be is avoided, and the amount of nickel is reduced. This reduces the toxicity of the zirconium-based amorphous alloy and improves its antibacterial properties. Testing shows that the zirconium-based amorphous alloy of this application can achieve a forming size of 7mm or more and a tensile strength of 2000MPa or more, meeting the strength requirements of structures for various applications. The zirconium-based amorphous alloy of this application can be used in structural and functional products or appearance components in the fields of biomedicine, consumer electronics, and smart wearables.

[0008] In one alternative implementation, 'a' satisfies 54 ≤ a ≤ 60, 'b' satisfies 15 ≤ b ≤ 20, 'c' satisfies 5 ≤ ​​c ≤ 10, and 'd' satisfies 14 ≤ d ≤ 20. By optimizing the content of each component, the formability and mechanical properties of zirconium-based amorphous alloys can be further improved.

[0009] In one optional implementation, f, g, h, and i satisfy: f + g + h + i ≤ 10, y and z satisfy: y + z ≤ 6, and m and n satisfy: m + n ≤ 8. By optimizing the content of each component, the formability and mechanical properties of zirconium-based amorphous alloys can be further improved.

[0010] In one alternative implementation, the critical dimension of the zirconium-based amorphous alloy is ≥7 mm. This zirconium-based amorphous alloy is a large-size zirconium-based amorphous alloy, which facilitates the processing of various structural components.

[0011] In one optional implementation, the compressive strength of the zirconium-based amorphous alloy is ≥2200 MPa. In another optional implementation, the tensile strength of the zirconium-based amorphous alloy is ≥2000 MPa. This zirconium-based amorphous alloy possesses excellent mechanical properties, capable of meeting the strength requirements of most structural components.

[0012] In one optional implementation, the zirconium-based amorphous alloy exhibits a toughness ≥ 80 MPa1 / 2. This zirconium-based amorphous alloy possesses good toughness and a certain degree of room-temperature plastic deformation capability, making it suitable for applications in biomedical and wearable products.

[0013] In one optional implementation, the zirconium-based amorphous alloy has a hardness ≥550 Hv. The high hardness of the zirconium-based amorphous alloy allows it to be used as an encapsulation or support material, improving the reliability and stability of the encapsulation or support material.

[0014] Secondly, this application also provides a method for preparing the zirconium-based amorphous alloy of this application, the method comprising:

[0015] The raw materials of each component are melted and cast into alloy ingots;

[0016] The alloy ingot is melted to obtain a superheated master alloy melt, and the temperature difference between the melting temperature and the melting point of the alloy ingot is greater than 300°C.

[0017] The superheated master alloy melt is cooled to obtain the zirconium-based amorphous alloy.

[0018] The preparation method of this application embodiment obtains zirconium-based amorphous alloys through melt casting. By combining various elements, a non-toxic, harmless, high-strength zirconium-based amorphous alloy can be obtained, exhibiting good formability, good toughness, certain room-temperature plastic deformation capability, and good biocompatibility, making it suitable for applications in biomedicine, consumer electronics, and smart wearables.

[0019] Thirdly, this application also provides a structural component formed using the zirconium-based amorphous alloy of this application.

[0020] Fourthly, this application also provides an electronic device that includes at least one structural component of this application.

[0021] The electronic devices covered by this application include, but are not limited to, mobile phones, computers, tablets, touch screens, and smartwatches, as well as instruments, meters, and mechanical parts used in aerospace electronic equipment. They can be used as housings for the above electronic devices or as components within the above electronic devices.

[0022] Fifthly, this application also provides a medical device, which includes at least one structural component of this application.

[0023] In this application, a medical device refers to a device that can be used in the biomedical field and comes into partial or complete contact with a human or animal. Examples include, but are not limited to, surgical instruments, artificial joints, femoral head supports, bone plates, metal guide wires, or dental screws.

[0024] In this application, the data in the various possible implementations mentioned above, such as the atomic ratio, tensile strength, compressive strength, and toughness of zirconium-based amorphous alloys, should be understood as falling within the range of engineering measurement error when measured, and should be understood as falling within the range defined in this application.

[0025] The technical effects that can be achieved by the second to fifth aspects mentioned above can be referred to the corresponding effect descriptions in the first aspect mentioned above, and will not be repeated here. Attached Figure Description

[0026] Figure 1 shows the XRD comparison of different samples of zirconium-based amorphous alloy provided in this application;

[0027] Figure 2 shows the XRD comparison of different samples of zirconium-based amorphous alloy provided in this application;

[0028] Figure 3 shows the XRD comparison of different samples of zirconium-based amorphous alloy provided in this application;

[0029] Figure 4 shows the tensile strength test results of different embodiments and comparative samples;

[0030] Figure 5 shows the compressive strength test results of different embodiments and comparative samples;

[0031] Figure 6 is a fracture toughness curve of Example 1;

[0032] Figure 7 shows the DSC test curve of the zirconium-based amorphous alloy in Example 1. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of this application clearer, the application will now be described in further detail with reference to the accompanying drawings.

[0034] The terminology used in the following embodiments is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. As used in the specification and appended claims of this application, the singular expressions “a,” “an,” “the,” “the,” and “this” are intended to also include expressions such as “one or more,” unless the context clearly indicates otherwise.

[0035] References to "one embodiment" or "some embodiments" as described in this specification mean that one or more embodiments of this application include a specific feature, structure, or characteristic described in connection with that embodiment. Therefore, the phrases "in one embodiment," "in some embodiments," "in other embodiments," "in still other embodiments," etc., appearing in different parts of this specification do not necessarily refer to the same embodiment, but rather mean "one or more, but not all, embodiments," unless otherwise specifically emphasized. The terms "comprising," "including," "having," and variations thereof mean "including but not limited to," unless otherwise specifically emphasized.

[0036] Amorphous alloys are a new type of alloy material composed of atoms exhibiting long-range disorder and short-range order. Due to their unique microstructure, they possess superior mechanical, physical, and chemical properties compared to conventional crystalline metals. Currently, zirconium-based bulk amorphous alloys have become a research hotspot in amorphous materials due to their excellent amorphous forming ability, mechanical properties, and thermal stability. The excellent formability of zirconium-based amorphous alloys makes their industrial applications possible. Bulk zirconium-based amorphous alloys are typically produced using vacuum die casting technology, and their products can be used in high-strength structural components for consumer electronics such as hinges for folding phones, and smart wearables such as watches and headphones. However, most of the existing zirconium-based amorphous alloys with application potential contain beryllium (Be) and a high content of nickel. The addition of beryllium and nickel can significantly improve the amorphous forming ability of zirconium-based amorphous alloys, but they have toxic side effects on cells, thus limiting the application of this material in product components that come into direct and close contact with the human body. Furthermore, the currently developed zirconium-based amorphous alloys with high amorphous forming ability have low mechanical strength, especially low tensile strength and fracture toughness, which means they cannot yet meet the requirements of high-strength structural components.

[0037] This application provides a high-strength, high-toughness zirconium-based amorphous alloy to improve the strength and toughness of existing zirconium-based amorphous alloys. Furthermore, this zirconium-based amorphous alloy is free of Be and contains a low Ni content, thereby significantly reducing its toxicity. This zirconium-based amorphous alloy can be used in biomedical products, consumer electronics, and end products, specifically in structural or appearance components for mobile phones, PCs, and smart wearables.

[0038] The zirconium-based amorphous alloys in this application are bulk zirconium-based amorphous alloys, such as bulk zirconium-based amorphous alloys with a minimum size greater than 1 mm. The atomic percentage expression formula of the zirconium-based amorphous alloys in this application is AMYAl. d Where A is Zr e Ti f Hf g Nb h Tai M is Co x Ni y Fe z Y is Cu m Ag n .

[0039] In this model, A is the main constituent element. e+f+g+h+i=a, 50≤a≤60. The elements Ti, Hf, Nb, and Ta in A have high compatibility with Zr, can form alloys with Zr, lower the forming temperature of Zr, and improve the forming ability of Zr.

[0040] In the M component unit, Co x Ni y Fe z In this context, x + y + z = b, and 10 ≤ b ≤ 20. Ni and Fe have high compatibility with Co, which can improve the formability of Co. In zirconium-based amorphous alloys, Zr and Co are the main elements used to form the primary amorphous structure. The addition of Fe can reduce the amount of Ni added, thereby reducing the toxicity of zirconium-based amorphous alloys.

[0041] In the Y-component unit, m+n=c, 0<c≤10. The enthalpy of mixing of Cu and Ag with the elements in the M-structure unit is positive. The components in the Y-structure unit are relatively miscible with the components in the M-structure unit, which is conducive to the formation of amorphous alloys.

[0042] The amount of Al added, d, satisfies 14 ≤ d ≤ 20. The addition of Al can improve the strength of amorphous alloys and reduce the density of zirconium-based amorphous alloys.

[0043] In the embodiments of this application, a, b, c, and d satisfy the following relationship: a + b + c + d = 100.

[0044] In one embodiment, 'a' satisfies 52 ≤ a ≤ 60, or 54 ≤ a ≤ 60, or 54 ≤ a ≤ 58. For example, the value of 'a' can be any two values ​​between 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60 or higher, and all of these values ​​can be used as the maximum or minimum value of 'a'.

[0045] In one embodiment, b satisfies 12≤b≤20, or b satisfies 15≤b≤20, or b satisfies 15≤b≤18. For example, the value of b can be any two values ​​between 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 or more, and all of these values ​​can be used as the maximum or minimum value of b.

[0046] In one embodiment, c satisfies 3≤c≤10, or 5≤c≤10, or 5≤c≤8. For example, the value of c can be any two values ​​between 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 or higher, and all of these values ​​can be used as the maximum or minimum value of c.

[0047] In one embodiment, d satisfies 15≤d≤20, or 15≤d≤19, or 15≤d≤18. For example, the value of d can be any two values ​​between 14, 15, 16, 17, 18, 19, or 20, and all of the above values ​​can be used as the maximum or minimum value of d.

[0048] Zirconium-based amorphous alloys with the above general formula are characterized by high strength, high toughness, and lightweight. This zirconium-based amorphous alloy avoids the use of Be and reduces the Ni content, making it non-toxic, harmless, and possessing good forming ability, good toughness, certain room-temperature plastic deformation capability, and good biocompatibility. It can be used in biomedical, consumer electronics, and smart wearable fields.

[0049] In the zirconium-based amorphous alloy of this application embodiment, in component unit A, e + f + g + h + i = a, 0 < f ≤ 5, 0 < g ≤ 5, 0 < h ≤ 2, 0 ≤ i ≤ 2, and e is the remaining value of a. The value of f can also be 1 ≤ f ≤ 5, 1 ≤ f ≤ 4, etc. The value of g can also be 1 ≤ g ≤ 5, 1 ≤ g ≤ 4, etc. The value of h can also be 0.5 ≤ h ≤ 2, 0.5 ≤ f ≤ 1.5, etc. The value of i can also be 0.5 ≤ i ≤ 2, 0.5 ≤ i ≤ 1.5, etc. In one embodiment, f, g, h, and i satisfy: f + g + h + i ≤ 10.

[0050] For example, the value of f can be any value between two values, such as 0.1, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2.0, 2.2, 2.5, 3.0, 3.2, 3.5, 3.8, 4.0, 4.2, 4.5, 4.8, or 5.0. All of these values ​​can be considered as the maximum or minimum value of f. Similarly, the value of g can be any value between two values, such as 0.1, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2.0, 2.2, 2.5, 3.0, 3.2, 3.5, 3.8, 4.0, 4.2, 4.5, 4.8, or 5.0. All of these values ​​can be considered as the maximum or minimum value of g. For example, the value of h can be any value between two values, such as 0.1, 0.2, 0.5, 0.8, 1, 1.2, 1.5, 1.8, or 2.0, and any of these values ​​can be used as the maximum or minimum value of h. For example, the value of i can be any value between two values, such as 0.1, 0.2, 0.5, 0.8, 1, 1.2, 1.5, 1.8, or 2.0, and any of these values ​​can be used as the maximum or minimum value of i.

[0051] In unit M, x + y + z = b, 0 ≤ y ≤ 5, 0 ≤ z ≤ 5. x is the remaining value among the possible values ​​of b. In one embodiment, y and z satisfy: y + z ≤ 6.

[0052] The range of values ​​for y can also be 0 ≤ y ≤ 5, or 1 ≤ y ≤ 4, etc. The range of values ​​for z can also be 0 ≤ z ≤ 5, or 1 ≤ z ≤ 4, etc. For example, the value of y can be any value between two of the following: 0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5. All of these values ​​can be considered as the maximum or minimum value of y. Similarly, the value of z can be any value between two of the following: 0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5. All of these values ​​can be considered as the maximum or minimum value of z.

[0053] In the Y-component unit, m + n = c, 0 ≤ n ≤ 3, and m is the remaining value among the possible values ​​of c. In one embodiment, m and n satisfy: m + n ≤ 8. The value of n can also be 1 ≤ n ≤ 3. For example, the value of n can be any two values ​​between 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, or 3, and all of these values ​​can be used as the maximum or minimum value of n.

[0054] In one embodiment, in a zirconium-based amorphous alloy (Zr e Ti f Hf gNb h Ta i (Co) x Ni y Fe z (Cu) m Ag n Al d In the case where 54≤a≤60, 15≤b≤20, 5<c≤8, 14≤d≤20, f+g+h+i≤10, y+z≤6, and m+n≤8, the critical size of the zirconium-based amorphous alloy is not less than Φ7mm, the compressive strength is not less than 2200MPa, the tensile strength is not less than 2000MPa, the toughness is not less than 80MPam1 / 2, and the hardness is not less than 550Hv.

[0055] The zirconium-based amorphous alloy of this application is obtained by simultaneously adding multiple metal elements such as Ti, Hf, Nb, Ta, Ni, Fe, Cu, and Ag to a Zr-Co-Al ternary amorphous alloy. Ti, Hf, Nb, and Ta have similar crystal structures to Zr, and their binary phase diagrams can intermesh, occupying or replacing zirconium positions, increasing the complexity of the alloy system and improving amorphous formation capability and mechanical properties. Furthermore, Ti, Hf, Nb, Ta, and Zr exhibit good biocompatibility, facilitating their application in biomedical devices. The addition of Nb and Ta improves the corrosion resistance of the zirconium-based amorphous alloy. Similarly, Co, Ni, and Fe are also intermesh elements, further enhancing amorphous formation capability. By introducing Cu and Ag elements into Zr-based amorphous alloys, where Cu and Ag are immiscible components with positive enthalpy of mixing compared to Co, Ni, and Fe, the complexity of the immiscible components in the alloy system can be further increased. The mutual repulsion between these immiscible components increases the inhomogeneity of the Zr-based amorphous as-cast microstructure, improving the room-temperature plasticity of the amorphous alloy. Simultaneously, the addition of silver also enhances the alloy's antibacterial properties. Furthermore, in this embodiment, the Al content is increased, which further improves the material strength, while the use of lightweight Al reduces the overall material strength.

[0056] The zirconium-based amorphous alloys of the present application embodiments can be prepared using the following methods.

[0057] In one embodiment, the method for preparing the zirconium-based amorphous alloy according to this application includes the following steps:

[0058] Step S1: The raw materials of each component are melted and cast into an alloy ingot; the proportion of each component raw material satisfies the general formula of the zirconium-based amorphous alloy in the embodiments of this application.

[0059] Step S2: The alloy ingot is melted to obtain a superheated master alloy melt, wherein the temperature difference between the melting temperature and the melting point of the alloy ingot is greater than 300°C.

[0060] Step S3: The superheated master alloy melt is cooled to obtain the zirconium-based amorphous alloy.

[0061] Exemplarily, in step S1, according to the general formula (Zr) of the embodiments of this application... e Ti f Hf g Nb h Ta i (Co) x Ni y Fe z (Cu) m Ag n Al d The raw materials are weighed according to their composition and proportions. The purity of the weighed raw materials is greater than 99.9%, and the source materials can be pure metallic substances. The weighed raw materials can be melted uniformly in an electric arc furnace protected by oxygen absorption and high-purity inert gas, such as argon, and then cooled to obtain the required alloy ingot.

[0062] For example, in step S2, the alloy ingot is melted at a temperature 300°C higher than the melting point of the alloy ingot to obtain an overheated master alloy melt, which is then drawn into a water-cooled copper mold of different apertures or a copper mold cooled by liquid nitrogen to obtain an amorphous zirconium-based amorphous alloy.

[0063] In step S2, when the melting point of the material used is greater than that of zirconium, elements such as Ti, Hf, Nb, Ta, Ni, Fe, Cu and Ag can be first melted and mixed evenly with Al, and then mixed and melted with Zr and Co.

[0064] To protect the raw materials for zirconium-based amorphous alloys during the melting process and prevent oxidation that could affect the alloy's formation, the melting process can be carried out under a protective gas atmosphere or vacuum. As an example, the protective gas can be one or more of the following: Group 0 element gases from the periodic table, helium, or preferably, inexpensive high-purity argon. The melting method can be any conventional melting method in the art, as long as the raw materials for the amorphous alloy are sufficiently melted; for example, melting can be carried out in a melting apparatus. The melting apparatus can be conventional melting equipment, including but not limited to electric arc furnaces or induction furnaces.

[0065] In the preparation method of this application embodiment, all raw materials are metallic raw materials with a purity greater than 99.95 wt.%, including some raw materials that are easily oxidized. Therefore, during the preparation process, it is necessary to pre-treat the easily oxidized raw materials to remove the oxide layer.

[0066] In one embodiment, the method for preparing a zirconium-based amorphous alloy includes the following steps:

[0067] Step S1: Prepare raw materials

[0068] Ultrasonic cleaners and grinders are used to remove oxide scale and impurities from the surface of raw materials. High-precision electronic balances are used for weighing to prepare raw materials that conform to the chemical formula ratio. The weighing accuracy is guaranteed to be ±0.003g during the weighing process of each raw material.

[0069] Step S2: Melting the master alloy ingot

[0070] When the melting point of the raw materials used is greater than that of zirconium, elements such as Ti, Hf, Nb, Ta, Ni, Fe, Cu, and Ag can be first melted and mixed evenly with Al, and then mixed and melted with Zr and Co. Specifically, the prepared raw materials are placed in a high-vacuum electric arc melting furnace, and the vacuum degree is maintained at 3 × 10⁻⁶. -3 After Pa, the gas is repeatedly purged with argon gas at least once, and then argon gas is introduced to ignite an arc on Ti to melt the raw material. After complete melting, electromagnetic stirring is started, and then the material is cooled to obtain the desired alloy ingot. During the cooling process, each alloy ingot is repeatedly turned over 4-6 times.

[0071] Step S3: Divide the alloy ingot prepared in step S2 into small pieces, grind off the oxide scale and grease and other impurities on the surface of the alloy ingot, and then perform vacuum arc melting again. The melting temperature is more than 300°C higher than the melting point of the alloy ingot to obtain an overheated master alloy melt. Then, it is sucked into a water-cooled copper mold with different apertures or into a copper mold cooled by liquid nitrogen to obtain the above-mentioned amorphous zirconium-based amorphous alloy.

[0072] The properties of the zirconium-based amorphous alloy of this application will be explained and described below with reference to specific embodiments. Unless otherwise specified, the operations and processing methods involved in the following preparation methods are conventional methods in the art. Unless otherwise specified, the instruments used in this application are conventional instruments in the art.

[0073] Example 1

[0074] This embodiment is a zirconium-based amorphous alloy with the chemical formula (Zr) 53 Ti1Hf1Nb1Ta1)(Co 14 Ni4Fe1)(Cu7Ag1)Al 16 .

[0075] The preparation process of the zirconium-based amorphous alloy in this embodiment is as follows:

[0076] High-purity raw materials with a purity greater than 99.95 wt.% were used, and the mixture was prepared and weighed according to the chemical formula. The melting sequence was as follows: first, Ti, Hf, Nb, Ta, Ni, Fe, Cu, and Ag were melted and mixed evenly with Al, and then Zr and Co were mixed and melted. The prepared raw materials were placed in a high-vacuum electric arc melting furnace, and the furnace was melted until the vacuum degree reached 3 × 10⁻⁶. -3After Pa, the ingot is repeatedly purged with argon gas at least twice. Then, argon gas is introduced to ignite an arc on the Ti ingot to melt the raw material. After complete melting, electromagnetic stirring is started, followed by cooling to obtain the desired alloy ingot. During the cooling process, each alloy ingot is repeatedly turned over 4-6 times to obtain the desired alloy. The alloy ingots are then divided and remelted, and the bulk amorphous alloy is prepared using a copper mold suction casting method. The prepared zirconium-based amorphous alloy is in the form of rods with diameters of 1 mm and 2 mm, and rods with 3-5-7-9 mm steps.

[0077] Example 2

[0078] This embodiment is a zirconium-based amorphous alloy with the chemical formula (Zr) 53 Ti 1.5 Hf 0.5 Nb1Ta1)(Co 15 Ni4)(Cu8)Al 16 .

[0079] Example 3

[0080] This embodiment is a zirconium-based amorphous alloy with the chemical formula (Zr) 53.5 Ti1Hf1Nb1Ta 0.5 (Co) 15 Fe4)(Cu7Ag1)Al 16 .

[0081] Example 4

[0082] This embodiment is a zirconium-based amorphous alloy with the chemical formula (Zr) 53 Ti2Hf1Nb1Ta1)(Co 14 Ni4Fe1)(Cu6Ag2)Al 15 .

[0083] Example 5

[0084] This embodiment is a zirconium-based amorphous alloy with the chemical formula (Zr) 53 Ti1Hf1Nb1Ta1)(Co 20 Ni4Fe1)Cu2Al 16 .

[0085] Comparative Example 1

[0086] The comparative example is a zirconium-based amorphous alloy with the chemical formula (Zr₂)₃. 58 Ti1Hf1Nb1Ta1)(Co 12 Ni4Fe1)(Cu7Ag1)Al 13 .

[0087] Comparative Example 2

[0088] The comparative example is a zirconium-based amorphous alloy with the chemical formula (Zr₂)₃. 50 Ti1Hf1Nb1Ta1)(Co 17 Ni4Fe1)(Cu7Ag1)Al 16 .

[0089] Comparative Example 3

[0090] The comparative example is a zirconium-based amorphous alloy with the chemical formula (Zr₂)₃. 50 Ti1Hf1Nb1Ta1)(Co 12 Ni4Fe1)(Cu 10 Ag3)Al 16 .

[0091] Comparative Example 4

[0092] The comparative example is a zirconium-based amorphous alloy with the chemical formula (Zr₂)₃. 56 Ti1Hf1Nb1Ta1)(Co 15 Ni4Fe1)(Cu8Ag2)Al 10 .

[0093] Comparative Example 5

[0094] The comparative example is a zirconium-based amorphous alloy with the chemical formula Zr. 58 Cu 19 Ni9Al 10 Hf2Ti2.

[0095] The properties of the zirconium-based amorphous alloys in each embodiment and comparative example were tested. The test items and methods are as follows:

[0096] 1. Use XRD to test the phase structure of the prepared sample. The test angle is selected from 10° to 90° and the test speed is selected from 5° to 10° / min.

[0097] 2. DSC curve tests were performed on 5-15 mg zirconium-based amorphous alloys at a heating rate of 20 K / min to obtain thermodynamic information of the zirconium-based amorphous alloys.

[0098] 3. Take a sample with a diameter of 2 mm and a height of 4 mm, and conduct a compression test at room temperature using a 100 kN universal testing machine with a strain rate of 2 × 10⁻⁶. -4 s -1 The compressive stress-strain curves of the examples and comparative examples were obtained. The tensile strength and fracture toughness of each zirconium-based amorphous alloy sample were tested.

[0099] Table 1

[0100] The zirconium-based amorphous alloys of Examples 1-5 of this application do not contain Be, and the Ni content in these alloys is also low, with an atomic percentage of 5% or less. As shown in the test data in Table 1, the zirconium-based amorphous alloys of the embodiments of this application, without the addition of Be or with only a small amount of Ni, achieve tensile and compressive strengths exceeding 1900 MPa, thus obtaining high-strength and non-toxic zirconium-based amorphous alloys. Compared with Comparative Examples 1 and 2, Examples 1-5 show improved tensile and compressive strengths.

[0101] Comparative data from Examples 1, 3, and 4 with Examples 2 and 5 show that the presence of Ag in the zirconium-based amorphous alloy improves its plasticity. Furthermore, the addition of Ag also enhances the alloy's antibacterial properties. In this application's examples, the higher Al content helps improve the strength of the zirconium-based amorphous alloy, while the use of lightweight Al reduces the material's density.

[0102] Figure 1 shows a comparison of XRD patterns for different samples with a diameter of 3 mm. Figure 2 shows a comparison of XRD patterns for different samples with a diameter of 5 mm. Figure 3 shows a comparison of XRD patterns for different samples with a diameter of 7 mm. As shown in Figures 1-3, the zirconium-based amorphous alloys of the embodiments of this application can all be made into bulk amorphous alloys with a diameter of 5 mm. The amorphous alloys of Examples 1-4 can achieve a diameter of 7 mm.

[0103] As shown in Figure 1, the alloys corresponding to Comparative Examples 1-5 are all zirconium-based amorphous alloys, indicating that the alloy compositions of Comparative Examples 1-5 can yield zirconium-based amorphous alloys with a diameter of 3 mm. As shown in Figure 2, when the sample size reaches 5 mm, the alloys of Comparative Examples 1-3 exhibit crystallization. As shown in Figure 3, when the sample size reaches 7 mm, the alloy of Comparative Example 4 exhibits crystallization. This indicates that bulk zirconium-based amorphous alloys cannot be obtained when the total content (a) of Zr, Ti, Hf, Nb, and Ta exceeds the range defined in this application; when the total content (b) of Co, Ni, and Fe exceeds the range defined in this application; when the total content (c) of Cu and Ag exceeds the range defined in this application; or when the content (d) of Al exceeds the range defined in this application.

[0104] Figure 4 shows the tensile strength test results of different embodiments and comparative examples. Figure 5 shows the compressive strength test results of different embodiments and comparative examples. As shown in Figures 4 and 5, high tensile and compressive strengths can be obtained with all embodiments 1-5. The zirconium-based amorphous alloys of this application have high strength and good toughness, which can improve the processing performance of amorphous alloys. However, the tensile and compressive strengths of comparative example 5 are low, indicating that although existing high-Ni zirconium-based amorphous alloys can produce large-volume samples, their compressive and tensile strengths are low, which cannot meet the requirements for high-strength structures.

[0105] Figure 6 shows the fracture toughness curve of Example 1. As shown in Figure 6, the zirconium-based amorphous alloy of this embodiment exhibits relatively low toughness, which meets the support requirements of the structural components. Figure 7 shows the DSC test curve of the zirconium-based amorphous alloy of Example 1. As shown in Figure 7, the zirconium-based amorphous alloy of this embodiment can have a high melting point.

[0106] In summary, the zirconium-based amorphous alloy of this application embodiment is a highly complex, high-strength, high-toughness, lightweight, non-toxic, and harmless zirconium-based amorphous alloy, which can improve the problems of low strength, low toughness, insufficient amorphous forming ability, poor biocompatibility, and high cytotoxicity of existing zirconium-based amorphous alloys.

[0107] The zirconium-based amorphous alloy of this application possesses certain room-temperature plastic deformation capability and biocompatibility, making it suitable for use in medical devices and electronic products. Electronic products may include consumer electronics and smart wearable devices. Medical devices include, but are not limited to, surgical instruments, artificial joints, femoral head supports, bone plates, metal guide wires, or dental screws. Consumer electronics and smart wearable devices include, but are not limited to, smartwatches, mobile phones, headphones, and electronic skin. The physical state of these medical devices or electronic products is not limited to bulk, thin film, filament, powder, or porous structures.

[0108] The above are merely specific embodiments of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A zirconium-based amorphous alloy, characterized by, The zirconium-based amorphous alloy has an atomic percentage expression of AMYAl d , A is Zr e Ti f Hf g Nb h Ta i , M is Co x Ni y Fe z , Y is Cu m Ag n ; Where, e+f+g+h+i=a, 50≤a≤60, 0<f≤5, 0<g≤5, 0<h≤2, 0≤i≤2; x+y+z=b, 10≤b≤20, 0≤y≤5, 0≤z≤5; m+n=c, 0<c≤10, 0≤n≤3; a+b+c+d=100, 14≤d≤20.

2. The zirconium-based amorphous alloy of claim 1, wherein, The condition 'a' satisfies 54≤a≤60, the condition 'b' satisfies 15≤b≤20, the condition 'c' satisfies 5≤c≤10, and the condition 'd' satisfies 14≤d≤20.

3. The zirconium-based amorphous alloy according to claim 1 or 2, characterized by The following conditions are met: f, g, h, and i satisfy f+g+h+i≤10; y and z satisfy y+z≤6; and m and n satisfy m+n≤8.

4. The zirconium-based amorphous alloy according to any one of claims 1 to 3, characterized in that, The critical dimension of the zirconium-based amorphous alloy is ≥7 mm.

5. The zirconium-based amorphous alloy according to any one of claims 1 to 4, characterized in that, The compressive strength of the zirconium-based amorphous alloy is ≥2200MPa.

6. The zirconium-based amorphous alloy according to any one of claims 1 to 5, wherein The tensile strength of the zirconium-based amorphous alloy is ≥2000MPa.

7. The zirconium-based amorphous alloy according to any one of claims 1 to 6, wherein The zirconium-based amorphous alloy has a toughness ≥80 MPaam1 / 2.

8. The zirconium-based amorphous alloy according to any one of claims 1 to 7, characterized in that, The zirconium-based amorphous alloy has a hardness ≥550Hv.

9. A method of making a zirconium-based amorphous alloy as claimed in any one of claims 1 to 8, characterised in that, include: The raw materials of each component are melted and cast into alloy ingots; The alloy ingot is melted to obtain a superheated master alloy melt, and the temperature difference between the melting temperature and the melting point of the alloy ingot is greater than 300°C. The superheated master alloy melt is cooled to obtain the zirconium-based amorphous alloy.

10. A structural member, characterized by It is formed using a zirconium-based amorphous alloy as described in any one of claims 1-8.

11. An electronic device, comprising: It includes at least one structural component as described in claim 10.

12. A medical device, characterized by It includes at least one structural component as described in claim 10.

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