High-strength medical amorphous alloy and preparation method and application thereof

Abstract

The application discloses a high-strength medical amorphous alloy, and the composition of the amorphous alloy is Zr a Hf b Ti c Nb d Al e Cu f Y g Sb h , a, b, c, d, e, f, g and h are atom percentages of respective alloy elements; the atom percentage ranges of respective elements are 30<=a<=40, 15<=b<=30, 10<=c<=15, 10<=d<=15, 10<=e<=15, 3<=f<=10, 0.5<=g<=1.0 and 0.5<=h<=1.0. The application aims to solve the technical problem of the demand for high-strength precision component materials in the medical instrument field, and also provides a preparation method of the amorphous alloy and specific application fields of the amorphous alloy.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of amorphous alloys, and particularly relates to a high-strength medical amorphous alloy, and a preparation method and application thereof. BACKGROUND

[0002] Multi-component bulk amorphous alloys have been confirmed by the prior art to have excellent glass forming ability and mechanical properties. The development of bulk amorphous alloys (BMG) started from noble metal-based Pd and Pt, and then Mg, Zr, Ti, Ni and Ln-based amorphous alloys, and then to Fe and Cu-based amorphous alloys with cheaper raw materials. In different amorphous alloy systems, a variety of alloy compositions with different glass forming abilities can be formed, and the maximum critical thickness of each alloy composition is different. Compared with traditional crystalline alloy materials, bulk amorphous materials have more excellent mechanical properties, processing properties, resistance to corrosion of various media, magnetic properties, and are expected to be applied to a wider technical field.

[0003] Zr-based bulk amorphous alloys are the most mature amorphous system in commercial industrialization in the prior art, because they have excellent thermal stability, strong glass forming ability and wide supercooled liquid phase region, and can be prepared into high-quality bulk amorphous alloys by using not too complex equipment through a process suitable for batch production. Moreover, Zr-based bulk amorphous alloys exhibit excellent mechanical properties, and thus are increasingly applied in the fields of 3C electronics and precision structural parts.

[0004] In the prior art, there are relatively few studies on the application of amorphous alloys in medical devices, and most of the research and development is concentrated in surgical knives, such as preparing an amorphous thin film on the surface of an existing surgical knife, using an amorphous one-piece forming surgical knife, etc., but there is no successful market case. The factors to be considered for the application of Zr-based bulk amorphous alloys in the field of medical devices include: ① whether the mechanical properties of the alloy can meet the requirements of medical devices; ② whether the biocompatibility of the alloy can meet the requirements of medical devices; ③ whether the forming performance of the alloy can meet the requirements of batch production. Under the premise of ensuring the amorphous alloy forming ability, developing an amorphous alloy product that meets the above three requirements is the key technology for popularizing amorphous alloys in the field of medical devices. SUMMARY

[0005] The commonly used structural materials in existing medical devices include commonly used alloys such as stainless steel, high-carbon steel, titanium alloy, magnesium alloy, etc. The traditional steel materials such as stainless steel and high-carbon steel are needless to say, the material properties are well known in the technical field, the advantages are that the raw materials are easy to obtain and convenient to process, and the improvement can be made on the basis of existing processing technology, the disadvantages are that when applied to high-end medical devices, the composition still needs to be adjusted, and the steel material forming method is limited, and the specific strength is low, and there is no application advantage on the precision components. Although new alloys such as titanium alloy and magnesium alloy have low density and moderate strength, the forming process is complex, and the surface treatment is difficult. With the progress of medical science and technology, the requirements for medical devices are also getting higher and higher, and the precision component materials with low density, high strength and meeting the customization requirements are the development focus of future medical device materials.

[0006] The purpose of the present application is to provide a high-strength medical amorphous alloy, which aims to solve the technical problem of the demand for high-strength precision component materials in the field of medical devices, and also provides a preparation method of the amorphous alloy and its specific application field.

[0007] In order to achieve the above-mentioned purpose of the application, the technical scheme adopted by the present application is as follows:

[0008] The present application provides a high-strength medical amorphous alloy, the composition of the amorphous alloy is

[0009] Zr a Hf b Ti c Nb d Al e Cu f Y g Sb h , a, b, c, d, e, f, g, h are the atomic percentages of each alloying element;

[0010] The atomic percentage range of each element is: 30≤a≤40, 15≤b≤30, 10≤c≤15, 10≤d≤15, 10≤e≤15, 3≤f≤10, 0.5≤g≤1.0, 0.5≤h≤1.0.

[0011] Further, the atomic percentage range of each element is: 35≤a≤38, 20≤b≤25, 10≤c≤12, 10≤d≤12, 10≤e≤12, 3≤f≤5, 0.5≤g≤1.0, 0.5≤h≤1.0.

[0012] Further, the composition of the amorphous alloy is Zr 30.0 Hf 20.0 Ti 15.0 Nb 15.0 Al 15.0 Cu 3.0 Y1.0 Sb 1.0 , Zr 31. OHf 25.0 Ti 12.0 Nb 12.0 Al 13.0 Cu 5.0 Y 1.0 Sb 1.0 , Zr 32.0 Hf 24.0 Ti 10.0 Nb 14.0 Al 15.0 Cu 3.5 Y 0.8 Sb 0.7 , Zr 34.0 Hf 22.0 Ti 11.0 Nb 12.5 Al 15.0 Cu 3.8 Y 0.8 Sb 0.9 , Zr 35.0 Hf 20.0 Ti 15.0 Nb 12.0 Al 12.5 Cu 4.0 Y 1.0 Sb 0.5 , Zr 35.3 Hf 21.8 Ti 12.0 Nb 12.0 Al 12.0 Cu 5.0 Y 0.9 Sb 1.0 , Zr 35.8 Hf 21.4 Ti 12.0 Nb 12.0 Al 12.0 Cu 4.9 Y 0.9 Sb 1.0 , Zr 36.1 Hf 22.4 Ti 11.8 Nb 12.0 Al 11.6 Cu 4.8 Y 0.8 Sb 0.5 , Zr 36.4 Hf 23.6 Ti 12.0 Nb 12.0 Al 11.4 Cu 3.5 Y 0.5 Sb 0.6 , Zr 36.7Hf 24.5 Ti 10.0 Nb 11.0 Al 11.7 Cu 4.6 Y 0.5 Sb 1.0 , Zr 36.9 Hf 23.0 Ti 11.5 Nb 11.5 Al 11.5 Cu 4.0 Y 0.6 Sb 1.0 , Zr 37.0 Hf 22.0 Ti 12.0 Nb 12.0 Al 12.0 Cu 3. 2Y 1.0 Sb 0.8 , Zr 37.2 Hf 23.4 Ti 11.0 Nb 11.0 Al 11.0 Cu 5.0 Y 0.6 Sb 0.8 , Zr 37.5 Hf 21.0 Ti 12.0 Nb 12.0 Al 11.0 Cu 4.5 Y 1.0 Sb 1.0 , Zr 37.8 Hf 22.5 Ti 11.6 Nb 10.0 Al 11.5 Cu 5.0 Y 0.8 Sb 0.8 , Zr 38.0 Hf 22.5 Ti 11.8 Nb 12.0 Al 10.0 Cu 4.0 Y 0.7 Sb 1.0 , Zr 38.6 Hf 21.0 Ti 11.5 Nb 11.9 Al 12.0 Cu 3.5 Y 1.0 Sb 0.5 , Zr 38.9 Hf 22.0 Ti 11.0 Nb12.0 Al 11.6 Cu 3.0 Y 0.5 Sb 1.0 、Zr 39.0 Hf 23.5 Ti 10.0 Nb 11.4 Al 11.8 Cu 3.0 Y 0.5 Sb 0.8 、Zr 40.0 Hf 18.4 Ti 12.0 Nb 12.0 Al 12.0 Cu 4.0 Y 1.0 Sb 0.6 one of the following.

[0013] Further, the amorphous alloy has good formability, and the formability is greater than 8mm.

[0014] Further, the amorphous alloy surface comprises a TiN layer or a TiSiN layer, and the addition of the coating layer makes the amorphous alloy have a smoother surface and obtain a non-reflective surface.

[0015] Further, the amorphous alloy has good biocompatibility, and the amorphous alloy has a skin sensitization rate of 0%; no animal intradermal reaction; the animal stimulation reaction type is extremely slight; the oral mucosa irritation reaction degree is extremely slight; and no acute systemic toxicity.

[0016] Further, the amorphous alloy has the characteristics of high strength, and the bending strength is 2300MPa-3000MPa.

[0017] The application further provides a preparation method of the medical amorphous alloy.

[0018] 01: ingredient preparation;

[0019] According to the composition of the amorphous alloy, Zr a Hf b Ti c Nb d Al e Cu f Y g Sb h , a, b, c, d, e, f, g, and h are the atomic percentages of each alloy element;

[0020] The atomic percentage of each element ranges from 30 to 40, 15 to 30, 10 to 15, 10 to 15, 10 to 15, 3 to 10, 0.5 to 1.0, and 0.5 to 1.0.

[0021] S02: Master alloy melt;

[0022] The symmetrical raw materials are smelted in a crucible by a vacuum arc furnace;

[0023] The raw materials are placed in the crucible as follows: half of the mixed Zr and Hf is placed at the bottom of the crucible, then the mixed Ti, Nb, Al and Cu is placed, and finally the other half of the mixed Zr, Hf and Y and Sb is placed at the top;

[0024] The smelting furnace is smelted by argon as a protective gas until the metal raw materials are uniformly melted to form a master alloy ingot with uniform composition;

[0025] S03: Amorphous alloy forming;

[0026] The obtained master alloy ingot is used as raw material to manufacture an amorphous alloy product by a vacuum die casting machine and a vacuum die casting process.

[0027] Further, the above amorphous alloy preparation process further comprises the following steps:

[0028] S04: Surface treatment;

[0029] A TiN layer or a TiSiN layer with a thickness of 6-10 microns is deposited on the surface of the obtained amorphous alloy product by PVD.

[0030] The medical amorphous alloy provided in the application can be used to manufacture metal parts in medical anastomat, surgical robot and medical suture.

[0031] The application has the following advantages:

[0032] 1. The medical amorphous alloy in the application has high strength and excellent biocompatibility, and high specific strength, and under the same strength, the volume of the amorphous product is smaller than that of ordinary stainless steel, which is more in line with the research and development trend of light weight and miniaturization of medical devices.

[0033] 2. The medical amorphous alloy in the application has high forming ability and good forming performance, and can form various small-size precision structural parts with a forming precision as low as 0.01 mm, and is suitable for manufacturing precision metal parts in medical anastomat, surgical robot and medical suture.

[0034] 3、The medical amorphous alloy in the application can obtain a surface deposition layer with strong adhesion by simple PVD process, can form a non-reflective outer surface, and meets the special application environment of medical devices. DETAILED DESCRIPTION

[0035] In order to make the purpose, technical scheme and technical effect of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application is described clearly and completely, and the following described embodiments are part of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by those skilled in the art without creative labor on the basis of the embodiments in the present application belong to the protection scope of the present application. The specific conditions not mentioned in the embodiments are carried out according to the conventional conditions or the conditions suggested by the manufacturer; the reagents or instruments not mentioned by the manufacturer are all conventional products that can be obtained by market purchase.

[0036] It should be understood that the weight of the related components mentioned in the embodiments of the present application can not only refer to the specific content of each component, but also represent the weight ratio relationship between each component, therefore, as long as the content of the related components in the embodiments of the present application is enlarged or reduced in proportion, it is within the scope disclosed by the present application. Specifically, the weight in the embodiments of the present application can be μg, mg, g, kg and other mass units known in the chemical field.

[0037] In addition, the expression of the singular form of the word should be understood as including the plural form of the word, unless the context clearly uses the singular form. The term "includes" or "has" is intended to specify the existence of the characteristics, quantities, steps, operations, elements, parts or combinations thereof, but is not used to exclude the existence or possible addition of one or more other characteristics, quantities, steps, operations, elements, parts or combinations thereof.

[0038] The embodiments of the present application provide a high-strength medical amorphous alloy, and the composition of the amorphous alloy is Zr a Hf b Ti c Nb d Al e Cu f Y g Sb h, a, b, c, d, e, f, g, h are the atomic percentages of each alloying element; the atomic percentage of each element ranges from: 30≤a≤40, 15≤b≤30, 10≤c≤15, 10≤d≤15, 10≤e≤15, 3≤f≤10, 0.5≤g≤1.0, 0.5≤h≤1.0. Preferably, the atomic percentage of each element ranges from: 35≤a≤38, 20≤b≤25, 10≤c≤12, 10≤d≤12, 10≤e≤12, 3≤f≤5, 0.5≤g≤1.0, 0.5≤h≤1.0.

[0039] Example 1

[0040] The present embodiment provides an amorphous alloy, which is composed of Zr 30.0 Hf 20.0 Ti 15.0 Nb 15.0 Al 15.0 Cu 3.0 Y 1.0 Sb 1.0 .

[0041] The amorphous alloy is prepared as follows:

[0042] According to the composition of the amorphous alloy, the corresponding elemental raw materials are weighed, and the purity is greater than 99.95%;

[0043] The weighed raw materials are subjected to high-temperature smelting in a smelting crucible by using a vacuum arc furnace. The raw materials are placed in the crucible as follows: half of the mixed Zr and Hf is placed at the bottom of the crucible, then the mixed Ti, Nb, Al, and Cu is placed, and finally the other half of the mixed Zr, Hf, Y, and Sb is placed at the top to cover the relatively difficult-to-melt components, thereby wrapping the relatively difficult-to-melt components with the easy-to-melt components and improving the smelting efficiency.

[0044] The smelting furnace is vacuumed to below 500 Pa, then argon gas is introduced, and smelting is carried out with argon gas as the protective gas. The temperature is raised and repeated smelting is carried out 5-6 times until the metal raw materials are uniformly melted. The mother alloy ingot with uniform composition is prepared by using the casting process.

[0045] The obtained mother alloy ingot is used as raw material to prepare 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, by using a vacuum die casting machine and a vacuum die casting process. The length of the round bar samples is 80 mm.

[0046] The obtained mother alloy ingot is used as raw material to prepare long strip samples with thicknesses of 1 mm, 2 mm, 3 mm, 4 mm, and 5 mm, respectively, by using a vacuum die casting machine and a vacuum die casting process. The length of the long strip samples is 100 mm, and the width is 15 mm.

[0047] The amorphous alloy testing process is as follows:

[0048] (1) Amorphous forming ability test

[0049] The prepared round bar samples are subjected to metallographic testing to observe whether there is crystallization phenomenon, thereby determining the forming ability of the alloy composition.

[0050] In Example 1, the round bar samples are up to 8 mm, and the microstructure is amorphous, which can confirm that the forming ability is ≥8 mm.

[0051] (2) Amorphous bending strength test

[0052] The long strip-shaped samples are subjected to bending strength test, and the test method is YB / T 5349-2014 Metal Materials Bending Mechanical Property Test Method.

[0053] In Example 1, the bending strength of the amorphous alloy is 2760 MPa.

[0054] (3) Amorphous hardness test

[0055] The long strip-shaped samples are subjected to Vickers hardness test, and the test method is GB / T 4340.1-2009 Metal Materials Vickers Hardness Test Part 1: Test Method.

[0056] In Example 1, the Vickers hardness test value of the amorphous alloy is 526 Hv.

[0057] Example 2

[0058] This example provides an amorphous alloy, which is composed of Zr 31.0 Hf 25.0 Ti 12.0 Nb 12.0 Al 13.0 Cu 5.0 Y 1.0 Sb 1.0 .

[0059] The preparation process and the testing process are the same as those of Example 1.

[0060] In Example 2, the amorphous forming ability is ≥8 mm, the bending strength of the amorphous alloy is 2840 MPa, and the Vickers hardness test value of the amorphous alloy is 533 Hv.

[0061] Example 3

[0062] This example provides an amorphous alloy, which is composed of Zr 32.0 Hf 24.0 Ti 10.0 Nb 14.0 Al 15.0 Cu 3.5Y 0.8 Sb 0.7 .

[0063] The preparation process and the testing process are the same as those of Example 1.

[0064] The amorphous alloy in Example 3 has an amorphous forming ability of ≥8mm, a bending strength of 2680MPa, and a Vickers hardness of 511Hv.

[0065] Example 4

[0066] This example provides an amorphous alloy with a composition of Zr 34.0 Hf 22.0 Ti 11.0 Nb 12.5 Al 15.0 Cu 3.8 Y 0.8 Sb 0.9 .

[0067] The preparation process and the testing process are the same as those of Example 1.

[0068] The amorphous alloy in Example 4 has an amorphous forming ability of ≥8mm, a bending strength of 2640MPa, and a Vickers hardness of 520Hv.

[0069] Example 5

[0070] This example provides an amorphous alloy with a composition of Zr 35.0 Hf 20.0 Ti 15.0 Nb 12.0 Al 12.5 Cu 4.0 Y 1.0 Sb 0.5 .

[0071] The preparation process and the testing process are the same as those of Example 1.

[0072] The amorphous alloy in Example 5 has an amorphous forming ability of ≥8mm, a bending strength of 2390MPa, and a Vickers hardness of 504Hv.

[0073] Example 6

[0074] This example provides an amorphous alloy with a composition of Zr 35.3 Hf 21.8 Ti 12.0 Nb 12.0 Al 12.0 Cu 5.0 Y 0.9 Sb 1.0 .

[0075] The preparation process and the testing process are the same as those of Example 1.

[0076] The amorphous alloy in Example 6 has an amorphous forming ability of ≥8 mm, a bending strength of 2460 MPa, and a Vickers hardness of 502 Hv.

[0077] Example 7

[0078] This example provides an amorphous alloy with a composition of Zr 35.8 Hf 21.4 Ti 12.0 Nb 12.0 Al 12.0 Cu 4.9 Y 0.9 Sb 1.0 .

[0079] The preparation process and the testing process are the same as those of Example 1.

[0080] The amorphous alloy in Example 7 has an amorphous forming ability of ≥8 mm, a bending strength of 2840 MPa, and a Vickers hardness of 505 Hv.

[0081] Example 8

[0082] This example provides an amorphous alloy with a composition of Zr 36.1 Hf 22.4 Ti 11.8 Nb 12.0 Al 11.6 Cu 4.8 Y 0.8 Sb 0.5 .

[0083] The preparation process and the testing process are the same as those of Example 1.

[0084] The amorphous alloy in Example 8 has an amorphous forming ability of ≥8 mm, a bending strength of 2720 MPa, and a Vickers hardness of 489 Hv.

[0085] Example 9

[0086] This example provides an amorphous alloy with a composition of Zr 36.4 Hf 23.6 Ti 12.0 Nb 12.0 Al 11.4 Cu 3.5 Y 0.5 Sb 0.6 .

[0087] The preparation process and the testing process are the same as those of Example 1.

[0088] The amorphous alloy of Example 9 has an amorphous forming ability of ≥8mm, a bending strength of 2850MPa, and a Vickers hardness of 514Hv.

[0089] Example 10

[0090] This example provides an amorphous alloy with a composition of Zr 36.7 Hf 24.5 Ti 10.0 Nb 11.0 Al 11.7 Cu 4.6 Y 0.5 Sb 1.0 .

[0091] The preparation process and the testing process are the same as those of Example 1.

[0092] The amorphous alloy of Example 10 has an amorphous forming ability of ≥8mm, a bending strength of 2870MPa, and a Vickers hardness of 501Hv.

[0093] Example 11

[0094] This example provides an amorphous alloy with a composition of Zr 36.9 Hf 23.0 Ti 11.5 Nb 11.5 Al 11.5 Cu 4.0 Y 0.6 Sb 1.0 .

[0095] The preparation process and the testing process are the same as those of Example 1.

[0096] The amorphous alloy of Example 11 has an amorphous forming ability of ≥8mm, a bending strength of 2870MPa, and a Vickers hardness of 501Hv.

[0097] Example 12

[0098] This example provides an amorphous alloy with a composition of Zr 37.0 Hf 22.0 Ti 12.0 Nb 12.0 Al 12.0 Cu 3.2 Y 1.0 Sb 0.8 .

[0099] The preparation process and the testing process are the same as those of Example 1.

[0100] The amorphous alloy of Example 12 has an amorphous forming ability of ≥8mm, a bending strength of 2930MPa, and a Vickers hardness of 488Hv.

[0101] Example 13

[0102] This example provides an amorphous alloy, composition Zr 37.2 Hf 23.4 Ti 11.0 Nb 11.0 Al 11.0 Cu 5.0 Y 0.6 Sb 0.8 .

[0103] The preparation process and the testing process are the same as those of Example 1.

[0104] In Example 13, the amorphous forming ability is ≥8mm, the bending strength of the amorphous alloy is 2940MPa, and the Vickers hardness test value of the amorphous alloy is 476Hv.

[0105] Example 14

[0106] This example provides an amorphous alloy, composition Zr 37.5 Hf 21.0 Ti 12.0 Nb 12.0 Al 11.0 Cu 4.5 Y 1.0 Sb 1.0 .

[0107] The preparation process and the testing process are the same as those of Example 1.

[0108] In Example 14, the amorphous forming ability is ≥8mm, the bending strength of the amorphous alloy is 2750MPa, and the Vickers hardness test value of the amorphous alloy is 496Hv.

[0109] Example 15

[0110] This example provides an amorphous alloy, composition Zr 37.8 Hf 22.5 Ti 11.6 Nb 10.0 Al 11.5 Cu 5.0 Y 0.8 Sb 0.8 .

[0111] The preparation process and the testing process are the same as those of Example 1.

[0112] In Example 15, the amorphous forming ability is ≥8mm, the bending strength of the amorphous alloy is 2810MPa, and the Vickers hardness test value of the amorphous alloy is 501Hv.

[0113] Example 16

[0114] The embodiment provides an amorphous alloy, and the composition of the amorphous alloy is Zr 38.0 Hf 22.5 Ti 11.8 Nb 12.0 Al 10.0 Cu 4.0 Y 0.7 Sb 1.0 .

[0115] The preparation process and the test process are the same as those in Embodiment 1.

[0116] In the embodiment 16, the amorphous forming ability is greater than or equal to 8 mm, the bending strength of the amorphous alloy is 2850 MPa, and the Vickers hardness test value of the amorphous alloy is 504 Hv.

[0117] Embodiment 17

[0118] The embodiment provides an amorphous alloy, and the composition of the amorphous alloy is Zr 38.6 Hf 21.0 Ti 11.5 Nb 11.9 Al 12.0 Cu 3.5 Y 1.0 Sb 0.5 .

[0119] The preparation process and the test process are the same as those in Embodiment 1.

[0120] In the embodiment 17, the amorphous forming ability is greater than or equal to 8 mm, the bending strength of the amorphous alloy is 2590 MPa, and the Vickers hardness test value of the amorphous alloy is 511 Hv.

[0121] Embodiment 18

[0122] The embodiment provides an amorphous alloy, and the composition of the amorphous alloy is Zr 38.9 Hf 22.0 Ti 11.0 Nb 12.0 Al 11.6 Cu 3.0 Y 0.5 Sb 1.0 .

[0123] The preparation process and the test process are the same as those in Embodiment 1.

[0124] In the embodiment 18, the amorphous forming ability is greater than or equal to 8 mm, the bending strength of the amorphous alloy is 2580 MPa, and the Vickers hardness test value of the amorphous alloy is 501 Hv.

[0125] Embodiment 19

[0126] The embodiment provides an amorphous alloy, and the composition of the amorphous alloy is Zr 39.0 Hf 23.5 Ti10.0 Nb 11.4 Al 11.8 Cu 3.0 Y 0.5 Sb 0.8 .

[0127] The preparation process and the testing process are the same as those of Example 1.

[0128] The amorphous alloy in Example 19 has an amorphous forming ability of ≥8 mm, a bending strength of 2460 MPa, and a Vickers hardness of 521 Hv.

[0129] Example 20

[0130] The amorphous alloy provided in this example has a composition of Zr 40.0 Hf 18.4 Ti 12.0 Nb 12.0 Al 12.0 Cu 4.0 Y 1.0 Sb 0.6 .

[0131] The preparation process and the testing process are the same as those of Example 1.

[0132] The amorphous alloy in Example 20 has an amorphous forming ability of ≥8 mm, a bending strength of 2660 MPa, and a Vickers hardness of 511 Hv.

[0133] Example 21

[0134] The long strip-shaped amorphous sample prepared in Example 16 is coated with a TiN layer on the surface by using a PVD process, and the thickness of the TiN layer is 8 μm.

[0135] It is found by testing that the mechanical properties of the amorphous sample in Example 21 are not obviously different from those of the amorphous sample in Example 16, and the surface of the amorphous sample in Example 21 is gray-black and has no reflection. It is confirmed that the corrosion resistance of the amorphous sample in Example 21 is stronger than that of the amorphous sample in Example 16 which is not surface treated after the neutral salt spray test.

[0136] Example 22

[0137] The long strip-shaped amorphous sample prepared in Example 16 is coated with a TiSiN layer on the surface by using a PVD process, and the thickness of the TiSiN layer is 8 μm.

[0138] The test results show that the mechanical properties of the amorphous sample in Example 22 have no obvious difference with those of the amorphous sample in Example 16, and the surface is gray-black without reflection. After the neutral salt spray test, it is verified that the corrosion resistance of the amorphous sample in Example 22 is better than that of the amorphous sample without surface treatment in Example 16, as in the comparative method in Example 21.

[0139] Examples 21-22 show that coating a TiN layer or a TiSiN layer on the surface of an amorphous alloy helps to improve the surface properties of the alloy product, not only obtaining a non-reflective surface, but also making the surface of the product lower and the matrix ions more difficult to diffuse and escape during use, which is very suitable as a material for medical suture needles.

[0140] Biocompatibility test:

[0141] In the present application, the composition in Example 16 is selected, and an amorphous sheet with a length of 20 mm, a width of 20 mm, and a thickness of 0.5 mm is prepared by die casting for biocompatibility test.

[0142] The test method is as follows:

[0143] Sensitization reaction: according to the method specified in GB / T 16886.10-2017 (maximum dose method);

[0144] Intracutaneous reaction: according to the test method specified in GB / T 16886.10-2017;

[0145] Skin irritation: according to the test method specified in GB / T 16886.10-2017;

[0146] Mucous membrane irritation: according to the test method specified in GB / T 16886.10-2017;

[0147] Acute systemic toxicity: according to the test method specified in GB / T 16886.11-2011.

[0148] After detection by a third-party testing institution, the following conclusions are obtained:

[0149] The skin sensitization rate is 0%;

[0150] There is no intracutaneous reaction in animals;

[0151] The animal irritation reaction type is very slight;

[0152] The oral mucous membrane irritation reaction degree is very slight;

[0153] There is no acute systemic toxicity.

[0154] From the test results, it can be seen that the amorphous alloy in the embodiment has excellent biocompatibility, and is suitable for use in the field of medical devices.

[0155] As can be seen from the above embodiments, the medical amorphous alloy in the application has high strength and excellent biocompatibility, and high specific strength, which meets the research and development trend of lightweight and miniaturization of medical devices. The medical amorphous alloy in the application has high forming ability and good forming performance, and can form various small-size precision structural parts, and the forming precision is as low as 0.01 mm. The medical amorphous alloy in the application can obtain a surface deposition layer with strong adhesion by a simple PVD process, can form a non-reflective outer surface, and meets the special application environment of medical devices.

[0156] The above embodiments only express several embodiments of the application, and the description is relatively specific and detailed, but it should not be understood as a limitation on the scope of the patent of the application. It should be pointed out that, for ordinary skilled persons in the art, several modifications and improvements can be made without departing from the concept of the application, and these all belong to the protection scope of the application. Therefore, the protection scope of the patent of the application should be subject to the appended claims.

Claims

1. A high-strength medical amorphous alloy, characterized by, The non-crystalline alloy has a composition Zr a Hf b Ti c Nb d Al e Cu f Y g Sb h a, b, c, d, e, f, g, h are the atomic percentages of the respective alloying elements; The atomic percentage of each element ranges from 30 to 40, 15 to 30, 10 to 15, 10 to 15, 10 to 15, 3 to 10, 0.5 to 1.0, and 0.5 to 1.0; and the non-crystalline alloy has a forming capacity greater than 8 mm.

2. The medical amorphous alloy according to claim 1, characterized by The atomic percentage of each element ranges from 35 to 38, 20 to 25, 10 to 12, 10 to 12, 10 to 12, 3 to 5, 0.5 to 1.0, and 0.5 to 1.

0.

3. The medical amorphous alloy according to claim 1, wherein The non-crystalline alloy has a composition of Zr 30.0 Hf 20.0 Ti 15.0 Nb 15.0 Al 15.0 Cu 3.0 Y 1.0 Sb 1.0 , Zr 31.0 Hf 25.0 Ti 12.0 Nb 12.0 Al 13.0 Cu 5.0 Y 1.0 Sb 1.0 , Zr 32.0 Hf 24.0 Ti 10.0 Nb 14.0 Al 15.0 Cu 3.5 Y 0.8 Sb 0.7 , Zr 34.0 Hf 22.0 Ti 11.0 Nb 12.5 Al 15.0 Cu 3.8 Y 0.8 Sb 0.9 , Zr 35.0 Hf 20.0 Ti 15.0 Nb 12.0 Al 12.5 Cu 4.0 Y 1.0 Sb 0.5 , Zr 35.3 Hf 21.8 Ti 12.0 Nb 12.0 Al 12.0 Cu 5.0 Y 0.9 Sb 1.0 , Zr 35.8 Hf 21.4 Ti 12.0 Nb 12.0 Al 12.0 Cu 4.9 Y 0.9 Sb 1.0 , Zr 36.1 Hf 22.4 Ti 11.8 Nb 12.0 Al 11.6 Cu 4.8 Y 0.8 Sb 0.5 , Zr 36.4 Hf 23.6 Ti 12.0 Nb 12.0 Al 11.4 Cu 3.5 Y 0.5 Sb 0.6 , Zr 36.7 Hf 24.5 Ti 10.0 Nb 11.0 Al 11.7 Cu 4.6 Y 0.5 Sb 1.0 , Zr 36.9 Hf 23.0 Ti 11.5 Nb 11.5 Al 11.5 Cu 4. 0Y 0.6 Sb 1.0 , Zr 37.0 Hf 22.0 Ti 12.0 Nb 12.0 Al 12.0 Cu 3.2 Y 1.0 Sb 0.8 , Zr 37.2 Hf 23.4 Ti 11.0 Nb 11.0 Al 11.0 Cu 5.0 Y 0.6 Sb 0.8 , Zr 37.5 Hf 21.0 Ti 12.0 Nb 12.0 Al 11.0 Cu 4.5 Y 1.0 Sb 1.0 , Zr 37.8 Hf 22.5 Ti 11.6 Nb 10.0 Al 11.5 Cu 5.0 Y 0.8 Sb 0.8 , Zr 38.0 Hf 22.5 Ti 11.8 Nb 12.0 Al 10.0 Cu 4.0 Y 0.7 Sb 1.0 , Zr 38.6 Hf 21.0 Ti 11.5 Nb 11.9 Al 12.0 Cu 3.5 Y 1.0 Sb 0.5 , Zr 38.9 Hf 22.0 Ti 11.0 Nb 12.0 Al 11.6 Cu 3.0 Y 0.5 Sb 1.0 , Zr 39.0 Hf 23.5 Ti 10.0 Nb 11.4 Al 11.8 Cu 3.0 Y 0.5 Sb 0.8 , Zr 40.0 Hf 18.4 Ti 12.0 Nb 12.0 Al 12.0 Cu 4.0 Y 1.0 Sb 0.6 one of 4. The medical amorphous alloy according to any one of claims 1 to 3, characterized by, The surface of the non-crystalline alloy comprises a TiN layer or a TiSiN layer.

5. The medical amorphous alloy according to any one of claims 1 to 3, characterized by The non-crystalline alloy has a skin sensitization rate of 0%, no intradermal reaction in animals, a very slight animal irritation reaction type, a very slight oral mucosa irritation reaction degree, and no acute systemic toxicity.

6. The medical amorphous alloy according to any one of claims 1 to 3, characterized by The non-crystalline alloy has a bending strength of 2300 MPa to 3000 MPa.

7. A method for preparing a medical non-crystalline alloy, comprising the following steps, S01: batching; According to the composition of the amorphous alloy being Zr a Hf b Ti c Nb d Al e Cu f Y g Sb h a, b, c, d, e, f, g, h are the atomic percentages of each alloying element; The atomic percentage of each element ranges from 30 to 40, 15 to 30, 10 to 15, 10 to 15, 10 to 15, 3 to 10, 0.5 to 1.0, and 0.5 to 1.0; and the non-crystalline alloy has a forming capacity greater than 8 mm. S02: master alloy melting material; The symmetrical raw materials are melted in a crucible using a vacuum arc furnace; The raw materials are placed in the crucible as follows: half of the mixed Zr and Hf is placed at the bottom of the crucible, then the mixed Ti, Nb, Al, and Cu is placed, and finally the other half of the mixed Zr and Hf with Y and Sb is placed at the top; The melting furnace is used to melt the raw materials with argon as the protective gas until the raw materials are uniformly melted to form a master alloy ingot with uniform composition; S03: non-crystalline alloy forming; The obtained master alloy ingot is used as the raw material to produce a non-crystalline alloy product using a vacuum die casting machine and a vacuum die casting process.

8. The method of claim 7, wherein the medical non-crystalline alloy is prepared by a method comprising: Further comprising the following steps: S04: surface treatment; A TiN layer or a TiSiN layer is deposited on the surface of the obtained non-crystalline alloy product using PVD, and the thickness of the TiN layer or the TiSiN layer is 6 to 10 μm.