Medical amorphous alloy, preparation method thereof and application thereof

Abstract

Medical amorphous alloy, characterized in that the composition of the amorphous alloy is Zr a Al b Ti c Nb d Hf e Ag f Y g Si h , where a, b, c, d, e, f, g, h are the atomic percentages corresponding to each alloy element; the ranges of the atomic percentages corresponding to each element are: 25 ≤ a ≤ 38, 15 ≤ b ≤ 30, 15 ≤ c ≤ 25, 15 ≤ d ≤ 20, 3 ≤ e ≤ 5, 1 ≤ f ≤ 3, 0.5 ≤ g ≤ 1.5, 0.05 ≤ h ≤ 0.1. The amorphous alloy in the present invention has good post-processing performance, good mechanical properties, good biocompatibility, and a forming ability with commercial value, and is suitable for use in the field of medical devices.

Description

Technical Field

[0001] The present invention belongs to the technical field of amorphous alloys, and specifically relates to a medical amorphous alloy, a preparation method of the medical amorphous alloy, and a specific application of the medical amorphous alloy. Background Art

[0002] Due to the special microstructure of long-range disorder and short-range order, amorphous alloys have material properties different from those of traditional crystalline alloys. Amorphous alloys have no crystal defects, and compared with traditional alloys, they have higher hardness, higher strength, better corrosion resistance, and better biocompatibility. Therefore, in recent years, they have been more and more widely used in industries such as the automotive industry, aerospace, and consumer electronics. Currently, the most widely marketed amorphous alloy system is the zirconium-based amorphous. In addition to excellent physical and chemical properties, zirconium-based amorphous alloys also have high formability, making zirconium-based amorphous have manufacturability.

[0003] In the prior art, there is relatively little research on the application of amorphous alloys in the field of medical devices. The more common application is in the field of surgical knives. For example, Tsai et al. coated a zirconium-based amorphous thin film on the surface of a steel surgical knife. However, so far, there has been no marketization of amorphous surgical knives, nor any application in other high-end medical devices. The reason is directly related to the amorphous alloy material system. In the most successful zirconium-based amorphous alloy system in the market, in the early stage, a large amount of beryllium element was added to improve the formability of the amorphous alloy and reduce the forming difficulty. After several material improvements, nickel element was added. Both beryllium element and nickel element are considered to have certain cytotoxicity and may cause physiological effects on the human body if implanted for a long time. However, beryllium element and nickel element are important elements affecting the formability of amorphous alloys. If completely removed, it will lead to a decrease in the formability of the amorphous in this system and thus large-sized parts cannot be made.

[0004] How to develop bulk amorphous suitable for the field of medical devices on the premise of ensuring the formability of amorphous alloys is the key technology to expand the application of amorphous alloys in the field of medical devices. Summary of the Invention

[0005] Commonly used materials in existing medical devices include medical stainless steel, medical high-carbon steel, etc. Iron and materials such as stainless steel are widely used in medical devices because of their mature processing technology and low cost. For example, the most commonly used surgical consumable, the scalpel, is often made of 316L stainless steel. With the gradual improvement of medical technology, the disadvantages of existing steel surgical instruments have gradually emerged. For example, the sharpness of steel knives used for cutting soft tissues will decrease with use, resulting in wound tearing, bleeding, and inflammation. Another example is that as medical devices replace manual operations in the medical field, many devices that rely heavily on doctor operations have been refined to minimize the adverse reactions caused by human factors, which has brought more stringent requirements and challenges to the precision and operability of medical devices. Additionally, commonly used stainless steel materials have low hardness, cannot form a cutting edge with a small arc radius, and have poor wear resistance, making them unsuitable for instruments that require grinding. All of the above have led to the application of new materials in the field of medical devices. The purpose of the present invention is to provide a composition of amorphous alloy suitable for application in the field of medical devices, aiming to solve the technical problem that existing commercial amorphous alloys cannot be applied in the field of medical devices. Further, the present invention also provides a preparation method and application of a medical amorphous alloy.

[0006] In order to achieve the above-mentioned invention purpose, the technical solution adopted by the present invention is as follows:

[0007] The composition of the amorphous alloy provided by the present invention is Zr a Al b Ti c Nb d Hf e Ag f Y g Si h , where a, b, c, d, e, f, g, h are the atomic percentages corresponding to each alloy element;

[0008] The range of the atomic percentages corresponding to each element is: 25 ≤ a ≤ 38, 15 ≤ b ≤ 30, 15 ≤ c ≤ 25, 15 ≤ d ≤ 20, 3 ≤ e ≤ 5, 1 ≤ f ≤ 3, 0.5 ≤ g ≤ 1.5, 0.05 ≤ h ≤ 0.1.

[0009] Further, the range of the atomic percentages corresponding to each element is: 30 ≤ a ≤ 35, 15 ≤ b ≤ 25, 20 ≤ c ≤ 25, 15 ≤ d ≤ 20, 3 ≤ e ≤ 5, 2 ≤ f ≤ 3, 1.0 ≤ g ≤ 1.5, 0.05 ≤ h ≤ 0.1.

[0010] The key problems in the improvement of medical devices can be solved by changing the materials. Amorphous alloys (also known as BMG materials, Bulk Metallic Glass) are alloys formed by the supercooling of molten metals to form amorphous structural blocks, which do not contain crystal defects such as vacancies, grain boundaries, and dislocations. Their macroscopic properties, such as hardness, strength, and corrosion resistance, are superior to those of stainless steel, and the processing difficulty is lower than that of mainstream medical materials such as titanium alloys. The application difficulties of amorphous alloys in existing technologies in medical devices are mainly manifested in the following two aspects:

[0011] 1. The biocompatibility does not meet the requirements of medical devices;

[0012] 2. The surface treatment process after alloy processing and forming is difficult.

[0013] The composition of the amorphous alloy provided in the present invention can overcome the above two application difficulties.

[0014] First of all, the amorphous alloy provided in the present invention still selects a zirconium-based system to endow the amorphous alloy system with certain basic properties. Then, aluminum, titanium, and niobium elements adapted to the zirconium-based are selected as the main element components, and then the composition is finely adjusted. Hafnium, silver, yttrium, and silicon are added to adjust the alloy structure and properties. This not only avoids the use of component elements that affect biocompatibility but also improves the alloy processing and forming ability, increases the surface energy of the amorphous alloy, and makes the surface treatment process after forming easier. The composition of the amorphous alloy in the present invention is obtained through the research on the zirconium-based amorphous system, considering the requirements for alloy properties, the difficulty of alloy melting, and the difficulty of alloy processing, so as to select the alloy composition in the present invention.

[0015] In the main component of the alloy in the present invention, the atomic percentages of zirconium, aluminum, titanium, and niobium in the alloy are similar, having a "high-entropy effect". After adding other trace elements, the chemical compatibility between various components is good, and the microscopic phase of the alloy is more inclined to directly form an amorphous phase body, and it is not easy to form brittle intermetallic compounds, thus ensuring the macroscopic mechanical properties of the alloy.

[0016] Further preferably, the composition of the amorphous alloy is Zr 25.00 Al 26.00 Ti 25.00 Nb 18.00 Hf 3.00 Ag 1.40 Y 1.55 Si 0.05 、Zr 25.60 Al 30.00 Ti 22.00 Nb 15.00 Hf 3.00 Ag 2.80 Y 1.50 Si 0.10 、Zr26.30 Aluminum 28.00 Titanium 21.40 Niobium 15.00 Hafnium 5.00 Silver 3.0 0 Yttrium 1.20 Silicon 0.10 and Zirconium 26.70 Aluminum 29.00 Titanium 19.90 Niobium 15.00 Hafnium 5.00 Silver 3.00 Yttrium 1.30 Silicon 0.10 and Zirconium 27.00 Aluminum 25.60 Titanium 24.00 Niobium 16.00 Hafnium 4.00 Silver 2.10 Yttrium 1.20 Silicon 0.10 and Zirconium 27.40 Aluminum 25.00 Titanium 24.00 Niobium 16.60 Hafnium 4.00 Silver 1.50 Yttrium 1.45 Silicon 0.05 and Zirconium 28.00 Aluminum 26.00 Titanium 24.00 Niobium 15.00 Hafnium 4.50 Silver 1.00 Yttrium 1.40 Silicon 0.10 and Zirconium 28.60 Aluminum 27.00 Titanium 21.00 Niobium 17.00 Hafnium 3.50 Silver 1.30 Yttrium 1.50 Silicon 0.10 and Zirconium 29.00 Aluminum 27.00 Titanium 21.50 Niobium 16.00 Hafnium 3.00 Silver 2.00 Yttrium 1.45 Silicon 0.05 and Zirconium 29.50 Aluminum 25.00 Titanium 21.00 Niobium 18.00 Hafnium 3.00 Silver 2.00 Yttrium 1.40 Silicon 0.10 and Zirconium 30.00 Aluminum 22.00 Titanium22.00 Nb 16.40 Hf 5.00 Ag 3.00 Y 1.50 Si 0.10 、Zr 30.60 Al 21.00 Ti 22.60 Nb 17.00 Hf 4.30 Ag 3.00 Y 1.45 Si 0.05 、Zr 30.90 Al 24.00 Ti 21.00 Nb 17.00 Hf 3.50 Ag 2.00 Y 1.50 Si 0.10 、Zr 31.00 Al 25.00 Ti 21.00 Nb 15.00 Hf 4.50 Ag 2.50 Y 0.90 Si 0.10 、Zr 31.50 Al 22.00 Ti 21.00 Nb 18.30 Hf 3.60 Ag 2.20 Y 1.33 Si 0.07 、Zr 32.00 Al 23.00 Ti 22.00 Nb 15.00 Hf 4.00 Ag 2.50 Y 1.42 Si 0.08 、Zr 32.50 Al 20.00 Ti 25.00 Nb 15.00 Hf 4.00 Ag 2.00 Y 1.40 Si 0.10 、Zr 33.00 Al 22.00 Ti 22.00 Nb 15.40 Hf 4.00 Ag 2.2 0 Y 1.30 Si 0.10 、Zr 33.50 Al 20.00 Ti 23.00 Nb 15.20 Hf5.00 Ag 2.00 Y 1.20 Si 0.10 、Zr 34.00 Al 18.00 Ti 22.00 Nb 19.70 Hf 3.00 Ag 2.00 Y 1.25 Si 0.05 、Zr 34.50 Al 23.30 Ti 20.00 Nb 15.00 Hf 4.00 Ag 2.00 Y 1.10 Si 0.10 、Zr 35.00 Al 21.00 Ti 20.00 Nb 16.70 Hf 4.00 Ag 2.20 Y 1.00 Si 0.10 、Zr 35.00 Al 22.00 Ti 20.00 Nb 15.80 Hf 4.00 Ag 2.10 Y 1.00 Si 0.10 、Zr 35.50 Al 20.00 Ti 21.00 Nb 17.40 Hf 3.00 Ag 2.00 Y 1.00 Si 0.10 、Zr 36.00 Al 16.00 Ti 20.00 Nb 20.90 Hf 4.00 Ag 2.00 Y 1.00 Si 0.10 、Zr 36.50 Al 20.00 Ti 20.00 Nb 15.00 Hf 4.60 Ag 3.00 Y 0.85 Si 0.05 、Zr 37.00 Al 20.00 Ti 15.00 Nb 19.90 Hf 4.00 Ag 3.00 Y 1.00Si 0.10 、Zr 37.50 Al 19.00 Ti 20.00 Nb 15.00 Hf 5.00 Ag 2.50 Y 0.90 Si 0.10 、Zr 38.00 Al 17.00 Ti 16.00 Nb 22.50 Hf 3.00 Ag 2.50 Y 0.90 Si 0.10 One of them.

[0017] Furthermore, the amorphous alloy in the present invention has practical value, and the amorphous alloy has a forming capacity greater than 6 mm and has market value.

[0018] Furthermore, the amorphous alloy in the present invention can be surface treated before use, so that the surface of the amorphous alloy contains a TiN layer, a TiSiN layer or a CrN layer, which helps to improve the surface properties of the alloy product, making the surface energy of the product lower and making it more difficult for matrix ions to diffuse and escape during use.

[0019] Furthermore, the amorphous alloy in the present invention has good biocompatibility, which is specifically manifested as follows: the cell survival rate in the MTT cytotoxicity test of the amorphous alloy is 97.8%; the skin sensitization rate is 0%; there is no animal intradermal reaction; the animal irritation reaction type is extremely mild; the degree of oral mucosal irritation reaction is extremely mild; and there is no acute systemic toxicity.

[0020] The present invention also provides a method for preparing a medical amorphous alloy, comprising the following steps:

[0021] S01: ingredients;

[0022] According to the composition of amorphous alloy, Zr a Al b Ti c Nb d Hf e Ag f Y g Si h , a, b, c, d, e, f, g, h are the atomic percentages of the alloying elements, and the metal raw materials are weighed respectively; the atomic percentage range of each element is: 25≤a≤38, 15≤b≤30, 15≤c≤25, 15≤d≤20, 3≤e≤5, 1≤f≤3, 0.5≤g≤1.5, 0.05≤h≤0.1

[0023] S02: master alloy melt;

[0024] The symmetrically good raw materials are melted in a crucible by a vacuum arc furnace;

[0025] The placement position of the raw materials in the crucible is as follows: After mixing Zr and Hf, half of them are laid on the bottom of the crucible, then the mixed Al, Ti, Nb, and Ag are laid, and finally the other half of the raw materials mixed with Zr, Hf, Y, and Si are covered on the top;

[0026] The melting is carried out in the melting furnace with argon as the protective gas until the metal raw materials are uniformly melted to form a master alloy ingot with uniform composition;

[0027] S03: Amorphous alloy forming;

[0028] The obtained master alloy ingot is used as raw material, and an amorphous alloy product is made by a vacuum die-casting machine and a vacuum die-casting process.

[0029] Furthermore, the following steps are also included:

[0030] S04: Surface treatment;

[0031] A TiN layer or a TiSiN layer is deposited on the surface of the obtained amorphous alloy product by PVD, and the thickness of the TiN layer or the TiSiN layer is 3 - 8 μm.

[0032] Furthermore, the following steps are also included:

[0033] S04: Surface treatment;

[0034] A CrN layer is deposited on the surface of the obtained amorphous alloy product by PVD, and the thickness of the CrN layer is 6 - 10 μm.

[0035] Finally, the present invention provides an application of a medical amorphous alloy, which is used to make fixed components or micro-elastic components on medical staplers;

[0036] For clamping components or movable assembly components in surgical robots;

[0037] For metal components in medical sutures, such as curved needles and angular needles.

[0038] The amorphous alloy in the present invention has good post-processing performance, good mechanical properties, good biocompatibility, and a forming ability with commercial value, and is suitable for use in the field of medical devices. Specific embodiments

[0039] To make the objectives, technical solutions, and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below. The embodiments described below are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art in combination with the embodiments of the present invention without creative efforts fall within the scope of protection of the present invention. For those conditions not specified in the embodiments, they are carried out according to conventional conditions or the conditions recommended by the manufacturer; for the reagents or instruments whose manufacturers are not specified, they are all conventional products that can be obtained through commercial purchase.

[0040] It should be understood that the weights of the relevant components mentioned in the embodiments of the present invention not only can refer to the specific contents of each component, but also can represent the proportional relationship of the weights between the components. Therefore, as long as the contents of the relevant components in the embodiments of the present invention are enlarged or reduced in proportion, they are within the scope disclosed by the present invention. Specifically, the weights described in the embodiments of the present invention can be mass units well-known in the chemical industry such as μg, mg, g, kg, etc.

[0041] In addition, unless otherwise explicitly stated in the context, the singular form of a word should be understood to include its plural form. The terms "comprising" or "having" are intended to specify the presence of features, quantities, steps, operations, elements, parts, or combinations thereof, but are not used to exclude the presence or possible addition of one or more other features, quantities, steps, operations, elements, parts, or combinations thereof.

[0042] A series of amorphous alloys provided in this embodiment have a composition of Zr a Al b Ti c Nb d Hf e Ag f Y g Si h , where a, b, c, d, e, f, g, h are the atomic percentages corresponding to each alloy element, and the ranges of the atomic percentages corresponding to each element are: 25 ≤ a ≤ 38, 15 ≤ b ≤ 30, 15 ≤ c ≤ 25, 15 ≤ d ≤ 20, 3 ≤ e ≤ 5, 1 ≤ f ≤ 3, 0.5 ≤ g ≤ 1.5, 0.05 ≤ h ≤ 0.1. Preferably, 30 ≤ a ≤ 35, 15 ≤ b ≤ 25, 20 ≤ c ≤ 25, 15 ≤ d ≤ 20, 3 ≤ e ≤ 5, 2 ≤ f ≤ 3, 1.0 ≤ g ≤ 1.5, 0.05 ≤ h ≤ 0.1.

[0043] Example 1

[0044] This embodiment provides an amorphous alloy with a composition of Zr 25.00 Al 26.00 Ti 25.00 Nb 18.00 Hf3.00 Ag 1.40 Y 1.55 Si 0.05 。

[0045] The preparation process of the amorphous alloy is as follows:

[0046] Weigh the metal elemental raw materials respectively according to the composition of the amorphous alloy;

[0047] Use a vacuum arc furnace to melt the weighed raw materials in a crucible;

[0048] Feed the materials according to the melting points of different raw materials and the difficulty of alloying. The placement positions of the raw materials in the crucible are as follows: After mixing Zr and Hf, lay half of them on the bottom of the crucible (Zr and Hf are easy to mix and are also easy to be compatible with other components), then lay the mixed Al, Ti, Nb, Ag (relatively refractory components), and finally cover the top with the other half of the mixed raw materials of Zr, Hf, Y, and Si, wrapping the relatively refractory components with easily fusible components to improve the melting efficiency;

[0049] Vacuumize the melting furnace to below 500 Pa, then introduce argon gas, and use argon gas as the protective gas for melting. Heat up and melt repeatedly for 5 - 6 times until the metal raw materials are uniformly melted, and use the casting process to make an ingot of the master alloy with uniform composition;

[0050] Use the obtained ingot of the master alloy as the raw material, and use a vacuum die-casting machine and the vacuum die-casting process to make round bar samples with diameters of 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, and 10 mm respectively. The lengths of the round bar samples are all 80 mm;

[0051] Use the obtained ingot of the master alloy as the raw material, and use a vacuum die-casting machine and the vacuum die-casting process to make strip-shaped samples with thicknesses of 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, and 6 mm respectively. The lengths of the strip-shaped samples are all 100 mm and the widths are all 15 mm.

[0052] The testing process of the amorphous alloy is as follows:

[0053] (1) Test of the ability to form amorphous

[0054] Conduct a metallographic test on the prepared round bar samples to observe whether there is crystallization phenomenon, so as to determine the formation ability of the alloy composition.

[0055] In Example 1, the microstructure of the round bar samples up to 8 mm is all in the amorphous state, and it can be confirmed that its formation ability ≥ 8 mm.

[0056] (2) Test of the hardness of amorphous

[0057] Vickers hardness test was carried out on the strip-shaped samples, and the test method was "GB / T 4340.1-2009 Metallic materials - Vickers hardness test - Part 1: Test method".

[0058] The Vickers hardness test value of the amorphous alloy in Example 1 was 535 Hv.

[0059] (3)Flexural strength test of amorphous

[0060] Flexural strength test was carried out on the strip-shaped samples, and the test method was "YB / T 5349-2014 Metallic materials - Test method for flexural mechanical properties".

[0061] The flexural strength of the amorphous alloy in Example 1 was 2420 MPa.

[0062] Example 2

[0063] This example provides an amorphous alloy with a composition of Zr 25.60 Al 30.00 Ti 22.00 Nb 15.00 Hf 3.00 Ag 2.80 Y 1.50 Si 0.10 。

[0064] Its preparation process and test process were the same as those in Example 1.

[0065] In Example 2, the amorphous forming ability was ≥6 mm, the Vickers hardness test value of the amorphous alloy was 526 Hv, and the flexural strength of the amorphous alloy was 2640 MPa.

[0066] Example 3

[0067] This example provides an amorphous alloy with a composition of Zr 26.30 Al 28.00 Ti 21.40 Nb 15.00 Hf 5.00 Ag 3.00 Y 1.20 Si 0.10 。

[0068] Its preparation process and test process were the same as those in Example 1.

[0069] In Example 3, the amorphous forming ability was ≥6 mm, the Vickers hardness test value of the amorphous alloy was 542 Hv, and the flexural strength of the amorphous alloy was 2530 MPa.

[0070] Example 4

[0071] This example provides an amorphous alloy with a composition of Zr 26.70 Al29.00 Ti 19.90 Nb 15.00 Hf 5.00 Ag 3.00 Y 1.30 Si 0.10 。

[0072] The preparation process and the testing process are the same as those in Example 1.

[0073] In Example 4, the amorphous forming ability is ≥ 8 mm, the Vickers hardness test value of the amorphous alloy is 532 Hv, and the bending strength of the amorphous alloy is 2610 MPa.

[0074] Example 5

[0075] This example provides an amorphous alloy with a composition of Zr 27.00 Al 25.60 Ti 24.00 Nb 16.00 Hf 4.00 Ag 2.10 Y 1.20 Si 0.10 。

[0076] The preparation process and the testing process are the same as those in Example 1.

[0077] In Example 5, the amorphous forming ability is ≥ 8 mm, the Vickers hardness test value of the amorphous alloy is 535 Hv, and the bending strength of the amorphous alloy is 2450 MPa.

[0078] Example 6

[0079] This example provides an amorphous alloy with a composition of Zr 27.40 Al 25.00 Ti 24.00 Nb 16.60 Hf 4.00 Ag 1.50 Y 1.45 Si 0.05 。

[0080] The preparation process and the testing process are the same as those in Example 1.

[0081] In Example 6, the amorphous forming ability is ≥ 8 mm, the Vickers hardness test value of the amorphous alloy is 550 Hv, and the bending strength of the amorphous alloy is 2380 MPa.

[0082] Example 7

[0083] This example provides an amorphous alloy with a composition of Zr 28.00 Al 26.00 Ti 24.00 Nb 15.00 Hf 4.50 Ag1.00 Y 1.40 Si 0.10 。

[0084] The preparation process and the testing process are the same as those in Example 1.

[0085] In Example 7, the amorphous forming ability is ≥8 mm, the Vickers hardness test value of the amorphous alloy is 535 Hv, and the flexural strength of the amorphous alloy is 2470 MPa.

[0086] Example 8

[0087] This example provides an amorphous alloy with a composition of Zr 28.60 Al 27.00 Ti 21.00 Nb 17.00 Hf 3.50 Ag 1.30 Y 1.50 Si 0.10 。

[0088] The preparation process and the testing process are the same as those in Example 1.

[0089] In Example 8, the amorphous forming ability is ≥8 mm, the Vickers hardness test value of the amorphous alloy is 527 Hv, and the flexural strength of the amorphous alloy is 2670 MPa.

[0090] Example 9

[0091] This example provides an amorphous alloy with a composition of Zr 29.00 Al 27.00 Ti 21.50 Nb 16.00 Hf 3.00 Ag 2.00 Y 1.45 Si 0.05 。

[0092] The preparation process and the testing process are the same as those in Example 1.

[0093] In Example 9, the amorphous forming ability is ≥8 mm, the Vickers hardness test value of the amorphous alloy is 548 Hv, and the flexural strength of the amorphous alloy is 2580 MPa.

[0094] Example 10

[0095] This example provides an amorphous alloy with a composition of Zr 29.50 Al 25.00 Ti 21.00 Nb 18.00 Hf 3.00 Ag 2.00 Y 1.40 Si 0.10 。

[0096] The preparation process and the testing process are the same as those in Example 1.

[0097] In Example 10, the amorphous formation ability is ≥8 mm, the Vickers hardness test value of the amorphous alloy is 511 Hv, and the flexural strength of the amorphous alloy is 2610 MPa.

[0098] Example 11

[0099] This example provides an amorphous alloy with a composition of Zr 30.00 Al 22.00 Ti 22.00 Nb 16.40 Hf 5.00 Ag 3.00 Y 1.50 Si 0.10 .

[0100] The preparation process and the testing process are the same as those in Example 1.

[0101] In Example 11, the amorphous formation ability is ≥8 mm, the Vickers hardness test value of the amorphous alloy is 540 Hv, and the flexural strength of the amorphous alloy is 2570 MPa.

[0102] Example 12

[0103] This example provides an amorphous alloy with a composition of Zr 30.60 Al 21.00 Ti 22.60 Nb 17.00 Hf 4.30 Ag 3.00 Y 1.45 Si 0.05 .

[0104] The preparation process and the testing process are the same as those in Example 1.

[0105] In Example 12, the amorphous formation ability is ≥8 mm, the Vickers hardness test value of the amorphous alloy is 511 Hv, and the flexural strength of the amorphous alloy is 2270 MPa.

[0106] Example 13

[0107] This example provides an amorphous alloy with a composition of Zr 30.90 Al 24.00 Ti 21.00 Nb 17.00 Hf 3.50 Ag 2.00 Y 1.50 Si 0.10 .

[0108] The preparation process and the testing process are the same as those in Example 1.

[0109] In Example 13, the amorphous forming ability is ≥6 mm, the measured Vickers hardness of the amorphous alloy is 528 Hv, and the flexural strength of the amorphous alloy is 2710 MPa.

[0110] Example 14

[0111] This example provides an amorphous alloy with a composition of Zr 31.00 Al 25.00 Ti 21.00 Nb 15.00 Hf 4.50 Ag 2.50 Y 0.90 Si 0.10 。

[0112] Its preparation process and testing process are the same as those in Example 1.

[0113] In Example 14, the amorphous forming ability is ≥6 mm, the measured Vickers hardness of the amorphous alloy is 520 Hv, and the flexural strength of the amorphous alloy is 2640 MPa.

[0114] Example 15

[0115] This example provides an amorphous alloy with a composition of Zr 31.50 Al 22.00 Ti 21.00 Nb 18.30 Hf 3.60 Ag 2.20 Y 1.33 Si 0.07 。

[0116] Its preparation process and testing process are the same as those in Example 1.

[0117] In Example 15, the amorphous forming ability is ≥8 mm, the measured Vickers hardness of the amorphous alloy is 511 Hv, and the flexural strength of the amorphous alloy is 2380 MPa.

[0118] Example 16

[0119] This example provides an amorphous alloy with a composition of Zr 32.00 Al 23.00 Ti 22.00 Nb 15.00 Hf 4.00 Ag 2.50 Y 1.42 Si 0.08 。

[0120] Its preparation process and testing process are the same as those in Example 1.

[0121] In Example 16, the amorphous forming ability is ≥8 mm, the measured Vickers hardness of the amorphous alloy is 527 Hv, and the flexural strength of the amorphous alloy is 2460 MPa.

[0122] Example 17

[0123] This example provides an amorphous alloy with a composition of Zr 32.50 Al 20.00 Ti 25.00 Nb 15.00 Hf 4.00 Ag 2.00 Y 1.40 Si 0.10 .

[0124] Its preparation process and testing process are the same as those in Example 1

[0125] In Example 17, the amorphous forming ability is ≥8 mm, the Vickers hardness test value of the amorphous alloy is 528 Hv, and the flexural strength of the amorphous alloy is 2870 MPa

[0126] Example 18

[0127] This example provides an amorphous alloy with a composition of Zr 33.00 Al 22.00 Ti 22.00 Nb 15.40 Hf 4.00 Ag 2.20 Y 1.30 Si 0.10 .

[0128] Its preparation process and testing process are the same as those in Example 1

[0129] In Example 18, the amorphous forming ability is ≥10 mm, the Vickers hardness test value of the amorphous alloy is 504 Hv, and the flexural strength of the amorphous alloy is 2800 MPa

[0130] Example 19

[0131] This example provides an amorphous alloy with a composition of Zr 33.50 Al 20.00 Ti 23.00 Nb 15.20 Hf 5.00 Ag 2.00 Y 1.20 Si 0.10 .

[0132] Its preparation process and testing process are the same as those in Example 1

[0133] In Example 19, the amorphous forming ability is ≥10 mm, the Vickers hardness test value of the amorphous alloy is 529 Hv, and the flexural strength of the amorphous alloy is 2670 MPa

[0134] Example 20

[0135] This embodiment provides an amorphous alloy with a composition of Zr 34.00 Al 18.00 Ti 22.00 Nb 19.70 Hf 3.00 Ag 2.00 Y 1.25 Si 0.05 .

[0136] Its preparation process and testing process are the same as those in Embodiment 1.

[0137] In Embodiment 20, the amorphous formation ability is ≥8 mm, the Vickers hardness test value of the amorphous alloy is 550 Hv, and the flexural strength of the amorphous alloy is 2750 MPa.

[0138] Embodiment 21

[0139] This embodiment provides an amorphous alloy with a composition of Zr 34.50 Al 23.30 Ti 20.00 Nb 15.00 Hf 4.00 Ag 2.00 Y 1.10 Si 0.10 .

[0140] Its preparation process and testing process are the same as those in Embodiment 1.

[0141] In Embodiment 21, the amorphous formation ability is ≥10 mm, the Vickers hardness test value of the amorphous alloy is 525 Hv, and the flexural strength of the amorphous alloy is 2930 MPa.

[0142] Embodiment 22

[0143] This embodiment provides an amorphous alloy with a composition of Zr 35.00 Al 21.00 Ti 20.00 Nb 16.70 Hf 4.00 Ag 2.20 Y 1.00 Si 0.10 .

[0144] Its preparation process and testing process are the same as those in Embodiment 1.

[0145] In Embodiment 22, the amorphous formation ability is ≥10 mm, the Vickers hardness test value of the amorphous alloy is 521 Hv, and the flexural strength of the amorphous alloy is 2840 MPa.

[0146] Embodiment 23

[0147] This embodiment provides an amorphous alloy with a composition of Zr 35.00 Al22.00 Ti 20.00 Nb 15.80 Hf 4.00 Ag 2.10 Y 1.00 Si 0.10 。

[0148] The preparation process and the testing process are the same as those in Example 1.

[0149] In Example 23, the amorphous formation ability is ≥8 mm, the Vickers hardness test value of the amorphous alloy is 527 Hv, and the bending strength of the amorphous alloy is 2800 MPa.

[0150] Example 24

[0151] This example provides an amorphous alloy with a composition of Zr 35.50 Al 20.00 Ti 21.00 Nb 17.40 Hf 3.00 Ag 2.00 Y 1.00 Si 0.10 。

[0152] The preparation process and the testing process are the same as those in Example 1.

[0153] In Example 24, the amorphous formation ability is ≥8 mm, the Vickers hardness test value of the amorphous alloy is 526 Hv, and the bending strength of the amorphous alloy is 2770 MPa.

[0154] Example 25

[0155] This example provides an amorphous alloy with a composition of Zr 36.00 Al 16.00 Ti 20.00 Nb 20.90 Hf 4.00 Ag 2.00 Y 1.00 Si 0.10 。

[0156] The preparation process and the testing process are the same as those in Example 1.

[0157] In Example 25, the amorphous formation ability is ≥6 mm, the Vickers hardness test value of the amorphous alloy is 511 Hv, and the bending strength of the amorphous alloy is 2840 MPa.

[0158] Example 26

[0159] This example provides an amorphous alloy with a composition of Zr 36.50 Al 20.00 Ti 20.00 Nb 15.00 Hf4.60 Ag 3.00 Y 0.85 Si 0.05 。

[0160] The preparation process and the testing process are the same as those in Example 1.

[0161] In Example 26, the amorphous forming ability is ≥6 mm, the Vickers hardness test value of the amorphous alloy is 509 Hv, and the bending strength of the amorphous alloy is 2930 MPa.

[0162] Example 27

[0163] This example provides an amorphous alloy with a composition of Zr 37.00 Al 20.00 Ti 15.00 Nb 19.90 Hf 4.00 Ag 3.00 Y 1.00 Si 0.10 。

[0164] The preparation process and the testing process are the same as those in Example 1.

[0165] In Example 27, the amorphous forming ability is ≥8 mm, the Vickers hardness test value of the amorphous alloy is 540 Hv, and the bending strength of the amorphous alloy is 2350 MPa.

[0166] Example 28

[0167] This example provides an amorphous alloy with a composition of Zr 37.50 Al 19.00 Ti 20.00 Nb 15.00 Hf 5.00 Ag 2.50 Y 0.90 Si 0.10 。

[0168] The preparation process and the testing process are the same as those in Example 1.

[0169] In Example 28, the amorphous forming ability is ≥8 mm, the Vickers hardness test value of the amorphous alloy is 522 Hv, and the bending strength of the amorphous alloy is 2650 MPa.

[0170] Example 29

[0171] This example provides an amorphous alloy with a composition of Zr 38.00 Al 17.00 Ti 16.00 Nb 22.50 Hf 3.00 Ag 2.50 Y 0.90 Si 0.10。

[0172] Its preparation process and testing process are the same as those in Example 1.

[0173] In Example 29, the amorphous formation ability ≥ 8 mm, the measured Vickers hardness of the amorphous alloy is 539 Hv, and the flexural strength of the amorphous alloy is 2780 MPa.

[0174] Example 30

[0175] Using the strip-shaped amorphous sample prepared in Example 26, a TiN layer with a thickness of 5 μm was deposited on the surface of the amorphous sample by PVD process.

[0176] It was tested and found that the mechanical properties of the amorphous sample in Example 30 had no obvious difference from those of the amorphous sample in Example 26. After the neutral salt spray test, it was confirmed that the corrosion resistance of the amorphous sample in Example 30 was stronger than that of the non-surface-treated amorphous sample in Example 26. Example

[0177] Using the strip-shaped amorphous sample prepared in Example 26, a TiSiN layer with a thickness of 5 μm was deposited on the surface of the amorphous sample by PVD process.

[0178] Similarly, in the same comparison method as in Example 30, after the neutral salt spray test, it was confirmed that the corrosion resistance of the amorphous sample in Example 31 was stronger than that of the non-surface-treated amorphous sample in Example 26. Example

[0179] Using the strip-shaped amorphous sample prepared in Example 26, a CrN layer with a thickness of 8 μm was deposited on the surface of the amorphous sample by PVD process.

[0180] Similarly, in the same comparison method as in Example 30, after the neutral salt spray test, it was confirmed that the corrosion resistance of the amorphous sample in Example 32 was stronger than that of the non-surface-treated amorphous sample in Example 26.

[0181] Examples 30 - 32 illustrate that depositing a TiN layer, a TiSiN layer or a CrN layer on the surface of the amorphous alloy helps to improve the surface properties of the alloy product, making the surface energy of the product lower and the matrix ions more difficult to diffuse and escape during use. Through the analysis of the three different PVD coatings, the thickness of the TiN layer or the TiSiN layer is preferably 3 - 8 μm, while the CrN coating needs to be thicker than the above two coatings to achieve the ideal effect, preferably 6 - 10 μm.

[0182] Biocompatibility test:

[0183] In the present invention, the components in Example 26 were selected and die-cast into amorphous thin sheets with a length of 20 mm, a width of 20 mm, and a thickness of 0.3 mm for biocompatibility testing.

[0184] The testing methods are as follows:

[0185] Cytotoxicity: Conducted in accordance with Appendix C of GB / T 16886.5-2017 (MTT method);

[0186] Sensitization reaction: Conducted in accordance with the method specified in 7.5 of GB / T 16886.10-2017 (maximum dose method);

[0187] Intradermal reaction: Conducted in accordance with the test method specified in 6.4 of GB / T16886.10-2017;

[0188] Skin irritation: Conducted in accordance with the test method specified in 6.3 of GB / T16886.10-2017;

[0189] Mucosal irritation: Conducted in accordance with the test method specified in GB / T 16886.10-2017;

[0190] Acute systemic toxicity: Conducted in accordance with the test method specified in GB / T16886.11-2011.

[0191] After being tested by a third-party testing agency, the following conclusions were obtained:

[0192] The cell survival rate in the MTT cytotoxicity experiment was 97.8%;

[0193] The skin sensitization rate was 0%;

[0194] There was no animal intradermal reaction;

[0195] The animal irritation reaction type was extremely mild;

[0196] The degree of oral mucosal irritation reaction was extremely mild;

[0197] There was no acute systemic toxicity.

[0198] From the test results, it can be seen that the amorphous alloy in this example has excellent biocompatibility and is suitable for use in the medical device field.

[0199] From the above examples, it can be seen that the amorphous alloy in the present invention has good mechanical properties and biocompatibility, and its forming ability has commercial value, making it suitable for use in the medical device field.

[0200] The above-described embodiments merely represent several implementation manners of the present invention. The description thereof is relatively specific and detailed, but it should not be construed as a limitation to the scope of the patent for the present invention. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all fall within the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention shall be subject to the appended claims.

Claims

1. Medical amorphous alloys, It is characterized in that The composition of the amorphous alloy is Zr a Al b Ti c Nb d Hf e Ag f Y g Si h , where a, b, c, d, e, f, g, h are the atomic percentages corresponding to the respective alloying elements; The atomic percentage range of each element is: 25≤a≤38, 15≤b≤30, 15≤c≤25, 15≤d≤20, 3≤e≤5, 1≤f≤3, 0.5≤g≤1.5, 0.05≤h≤0.1; The composition of the amorphous alloy is Zr 25.60 Al 30.00 Ti 22.00 Nb 15.00 Hf 3.00 Ag 2.80 Y 1.50 Si 0.10 、Zr 26.30 Al 28.00 Ti 21.40 Nb 15.00 Hf 5.00 Ag 3.00 Y 1.20 Si 0.10 、Zr 26.70 Al 29.00 Ti 19.90 Nb 15.00 Hf 5.00 Ag 3.00 Y 1.30 Si 0.10 、Zr 27.00 Al 25.60 Ti 24.00 Nb 16.00 Hf 4.00 Ag 2.10 Y 1.20 Si 0.10 、Zr 27.40 Al 25.00 Ti 24.00 Nb 16.60 Hf 4.00 Ag 1.50 Y 1.45 Si 0.05 、Zr 28.00 Al 26.00 Ti 24.00 Nb 15.00 Hf 4.50 Ag 1.00 Y 1.40 Si 0.10 、Zr 28.60 Al 27.00 Ti 21.00 Nb 17.00 Hf 3.50 Ag 1.30 Y 1.50 Si 0.10 、Zr 29.00 Al 27.00 Ti 21.50 Nb 16.00 Hf 3.00 Ag 2.00 Y 1.45 Si 0.05 、Zr 29.50 Al 25.00 Ti 21.00 Nb 18.00 Hf 3.00 Ag 2.0 0 Y 1.40 Si 0.10 、Zr 30.00 Al 22.00 Ti 22.00 Nb 16.40 Hf 5.00 Ag 3.00 Y 1.50 Si 0.10 、Zr 30.60 Al 21.00 Ti 22.60 Nb 17.00 Hf 4.30 Ag 3.00 Y 1.45 Si 0.05 、Zr 30.90 Al 24.00 Ti 21.00 Nb 17.00 Hf 3.50 Ag 2.00 Y 1.50 Si 0.10 、Zr 31.00 Al 25.00 Ti 21.00 Nb 15.00 Hf 4.50 Ag 2.50 Y 0.90 Si 0.10 、Zr 31.50 Al 22.00 Ti 21.00 Nb 18.30 Hf 3.60 Ag 2.20 Y 1.33 Si 0.07 、Zr 32.00 Al 23.00 Ti 22.00 Nb 15.00 Hf 4.00 Ag 2.50 Y 1.42 Si 0.08 、Zr 32.50 Al 20.00 Ti 25.00 Nb 15.00 Hf 4.00 Ag 2.00 Y 1.40 Si 0.10 、Zr 33.00 Al 22.00 Ti 22.00 Nb 15.40 Hf 4.00 Ag 2.20 Y 1.30 Si 0.10 、Zr 33.50 Al 20.00 Ti 23.00 Nb 15.20 Hf 5.00 Ag 2.00 Y 1.20 Si 0.10 、Zr 34.00 Al 18.00 Ti 22.00 Nb 19.70 Hf 3.00 Ag 2.00 Y 1.25 Si 0.05 、Zr 34.50 Al 23.30 Ti 20.00 Nb 15.00 Hf 4.00 Ag 2.00 Y 1.10 Si 0.10 、Zr 35.00 Al 21.00 Ti 20.00 Nb 16.70 Hf 4.00 Ag 2.20 Y 1.00 Si 0.10 、Zr 35.00 Al 22.00 Ti 20.00 Nb 15.80 Hf 4.00 Ag 2.10 Y 1.00 Si 0.10 、Zr 35.50 Al 20.00 Ti 21.00 Nb 17.40 Hf 3.00 Ag 2.00 Y 1.00 Si 0.10 、Zr 36.50 Al 20.00 Ti 20.00 Nb 15.00 Hf 4.60 Ag 3.0 0 Y 0.85 Si 0.05 、Zr 37.00 Al 20.00 Ti 15.00 Nb 19.90 Hf 4.00 Ag 3.00 Y 1.00 Si 0.10 , Zr 37.50 Al 19.00 Ti 20.00 Nb 15.00 Hf 5.00 Ag 2.50 Y 0.90 Si 0.10 or one of the following 2. The medical amorphous alloy according to claim 1, It is characterized in that The amorphous alloy has a forming capacity greater than 6 mm.

3. The medical amorphous alloy according to claim 1, It is characterized in that The amorphous alloy surface includes a TiN layer, a TiSiN layer or a CrN layer.

4. The medical amorphous alloy according to claim 3, It is characterized in that In the MTT cytotoxicity test of the amorphous alloy, the cell survival rate was 97.8%; the skin sensitization rate was 0%; there was no intradermal reaction in animals; the animal irritation reaction type was extremely mild; the degree of oral mucosal irritation reaction was extremely mild; and there was no acute systemic toxicity.

5. A method for preparing the medical amorphous alloy as claimed in claim 1, comprising the following steps: S01: ingredients; According to the composition of the amorphous alloy being Zr a Al b Ti c Nb d Hf e Ag f Y g Si h , where a, b, c, d, e, f, g, h are the atomic percentages corresponding to each alloying element, and the metallic elemental raw materials are weighed respectively; the ranges of the atomic percentages corresponding to each element are: 25 ≤ a ≤ 38, 15 ≤ b ≤ 30, 15 ≤ c ≤ 25, 15 ≤ d ≤ 20, 3 ≤ e ≤ 5, 1 ≤ f ≤ 3, 0.5 ≤ g ≤ 1.5, 0.05 ≤ h ≤ 0.1 S02: master alloy melt; The symmetrical raw materials are melted in a crucible using a vacuum arc furnace; The raw materials are placed in the crucible in the following positions: half of the mixed Zr and Hf is laid on the bottom of the crucible, followed by the mixed Al, Ti, Nb, and Ag, and finally the other half of the mixed Zr, Hf, Y, and Si is placed on the top; Argon is used as a protective gas in the smelting furnace to melt the metal raw materials uniformly to form a master alloy ingot with uniform composition; S03: Amorphous alloy forming; The obtained master alloy ingot is used as a raw material to manufacture an amorphous alloy product by using a vacuum die-casting machine and a vacuum die-casting process.

6. The method for preparing the medical amorphous alloy according to claim 5, It is characterized in that The following steps are also included: S04: surface treatment; A TiN layer or a TiSiN layer is deposited on the surface of the obtained amorphous alloy product by using PVD, and the thickness of the TiN layer or the TiSiN layer is 3-8 μm.

7. The method for preparing the medical amorphous alloy according to claim 5, It is characterized in that The following steps are also included: S04: surface treatment; A CrN layer is deposited on the surface of the obtained amorphous alloy product by using PVD, and the thickness of the CrN layer is 6-10 μm.