CN113249661A - Biomedical amorphous alloy and application thereof - Google Patents

Biomedical amorphous alloy and application thereof Download PDF

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CN113249661A
CN113249661A CN202110650495.2A CN202110650495A CN113249661A CN 113249661 A CN113249661 A CN 113249661A CN 202110650495 A CN202110650495 A CN 202110650495A CN 113249661 A CN113249661 A CN 113249661A
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amorphous alloy
medical
ltoreq
amorphous
equal
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孙玉春
王霏斐
周永胜
王勇
陈虎
翟文茹
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Peking University School of Stomatology
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Peking University School of Stomatology
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Priority to PCT/CN2022/097351 priority patent/WO2022257915A1/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C45/00Amorphous alloys
    • C22C45/10Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00Preparations for dentistry
    • A61K6/15Compositions characterised by their physical properties
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00Preparations for dentistry
    • A61K6/80Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/84Preparations for artificial teeth, for filling teeth or for capping teeth comprising metals or alloys
    • A61K6/844Noble metals
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/047Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/06Titanium or titanium alloys
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54Biologically active materials, e.g. therapeutic substances
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/02Inorganic materials
    • A61L31/022Metals or alloys
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/16Biologically active materials, e.g. therapeutic substances
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C45/00Amorphous alloys
    • C22C45/001Amorphous alloys with Cu as the major constituent
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A61L2300/104Silver, e.g. silver sulfadiazine
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404Biocides, antimicrobial agents, antiseptic agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/12Materials or treatment for tissue regeneration for dental implants or prostheses
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/24Materials or treatment for tissue regeneration for joint reconstruction

Abstract

The invention provides an amorphous alloy and application thereof. Wherein the amorphous alloy has ZraCubAlcAgdTieNbfWherein a, b, c, d, e and f respectively represent the mass percent of each element, 45-72 of a, 8-50 of b, 3-15 of c, 0-8 of d, 0-4 of e, 0-5 of f, and a + b + c + d + e + f = 100. The nickel-free and beryllium-free zirconium-based amorphous alloy provided by the invention avoids toxic and side effects on cells, improves the biocompatibility of the amorphous alloy, has the effects of actively sterilizing and reducing stress barriers between products and biological tissues, and can be applied to preparation of medical implants, medical intervention bodies or other medical instruments.

Description

Biomedical amorphous alloy and application thereof
Technical Field
The application relates to the field of metal materials, in particular to a biomedical amorphous alloy and application thereof.
Background
Amorphous alloys (also known as metallic glasses) have excellent physical and chemical properties, such as low elastic modulus, high biocompatibility, high strength, high hardness, high elastic limit, high wear resistance, high corrosion resistance, superplasticity, etc. Therefore, the amorphous alloy has wide application prospect in the aspects of structural materials, miniature precision devices, sports equipment, consumer electronics and the like.
The currently developed zirconium-based amorphous alloys with strong glass forming ability almost contain nickel or beryllium, and simultaneously, the content of copper is high. Although the nickel element and the beryllium element play an important role in improving the forming capability of the zirconium-based amorphous alloy glass, the nickel element and the beryllium element are both high-cytotoxicity and biocompatible elements, and if the beryllium element and the nickel element are simply removed from the alloy, the amorphous forming capability of the system is often greatly reduced, so that the nickel element and the beryllium element become barriers for the application of the zirconium-based amorphous alloy in the field of biomedicine.
Disclosure of Invention
The invention provides an amorphous alloy which can be applied to the field of biological medical treatment and a medical implant comprising the amorphous alloy.
The invention provides an amorphous alloy, wherein the composition of the amorphous alloy is ZraCubAlcAgdTieNbfWherein a, b, c, d, e and f respectively represent the mass percent of each element, 45-72 of a, 8-50 of b, 3-15 of c, 0-8 of d, 0-4 of e, 0-5 of f, and a + b + c + d + e + f = 100.
According to an embodiment of the present invention, d, e and f in the amorphous alloy are not 0 at the same time.
According to another embodiment of the present invention, d and e in the amorphous alloy are both greater than 0.
According to another embodiment of the invention, d is more than or equal to 2 and less than or equal to 8 in the amorphous alloy.
According to another embodiment of the invention, e is more than or equal to 2 and less than or equal to 4 in the amorphous alloy.
According to another embodiment of the invention, c is more than or equal to 5 and less than or equal to 8 in the amorphous alloy.
According to another embodiment of the invention, b is more than or equal to 8 and less than or equal to 10 in the amorphous alloy.
According to another embodiment of the present invention, the amorphous alloy has a composition of Zr72Cu8Al12Ag8、Zr70Cu10Al15Ag5、Zr70Cu15Al10Nb5、Zr65Cu25Al10、Zr65Cu13Al14Ag8、Zr65Cu29Al12Ti2Ag2、Zr65Cu27Al3Ti2Ag3、Zr64Cu20Al12Ti2Ag2、Zr61Cu23Al12Ti2Ag2、Zr61Cu31Al14Ti2Ag2、Zr61Cu25Al12Ti2、Zr60Cu20Al12Ag8、Zr46Cu38Al8Ag8、Zr46Cu46Al6Ti2、Zr46Cu40Al4Ti2Ag8、Zr45Cu45Al8Nb2、Zr45Cu40Al6Ti4Ag5Or Zr40Cu50Al5Nb5
The invention also provides a biomedical material comprising the amorphous alloy.
The invention also provides an application of the biomedical material in the fields of medical implants, medical intervention bodies or other medical apparatuses and instruments; preferably, the medical implant comprises an artificial bone block, an artificial joint, a femoral head support, a bone fracture plate, a dental implant and a base station; the medical intervention body comprises an adjacent surface forming sheet, a dental support and a false tooth; the medical instrument comprises a metal needle and a root canal file.
The nickel-free and beryllium-free zirconium-based amorphous alloy provided by the invention avoids toxic and side effects on cells, improves the biocompatibility of the amorphous alloy, has the effects of actively sterilizing and reducing stress barriers between products and biological tissues, and can be applied to preparation of medical implants, medical intervention bodies or other medical instruments.
Drawings
Fig. 1 is an XRD spectrum of the amorphous alloy prepared in example 1.
Fig. 2 is an XRD spectrum of the amorphous alloy prepared in example 2.
Fig. 3 is an XRD pattern of the amorphous alloy prepared in example 3.
Fig. 4 is an XRD pattern of the amorphous alloy prepared in example 4.
Fig. 5 is an XRD pattern of the amorphous alloy prepared in example 5.
Fig. 6 is an XRD pattern of the amorphous alloy prepared in example 6.
Fig. 7 is an XRD pattern of the amorphous alloy prepared in example 7.
Fig. 8 is an XRD pattern of the amorphous alloy prepared in example 8.
Fig. 9 is an XRD pattern of the amorphous alloy prepared in example 9.
Fig. 10 is an XRD pattern of the amorphous alloy prepared in example 10.
Fig. 11 is an XRD pattern of the amorphous alloy prepared in example 11.
Fig. 12 is an XRD pattern of the amorphous alloy prepared in example 12.
Fig. 13 is an XRD pattern of the amorphous alloy prepared in example 13.
Fig. 14 is an XRD pattern of the amorphous alloy prepared in example 14.
Fig. 15 is an XRD pattern of the amorphous alloy prepared in example 15.
Fig. 16 is an XRD pattern of the amorphous alloy prepared in example 16.
Fig. 17 is an XRD pattern of the amorphous alloy prepared in example 17.
Fig. 18 is an XRD pattern of the amorphous alloy prepared in example 18.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention provides an amorphous alloy, wherein the amorphous alloy comprises an amorphous alloy component of ZraCubAlcAgdTieNbfWherein a, b, c, d, e and f respectively represent the mass percent (%) of each element, 45-72 of a, 8-50 of b, 3-15 of c, 0-8 of d, 0-4 of e, 0-5 of f, and a + b + c + d + e + f = 100. The nickel-free and beryllium-free amorphous alloy avoids toxic and side effects on cells, improves the biocompatibility of the zirconium-based amorphous alloy, has the effects of actively sterilizing and reducing stress barriers of products and biological tissues, and can be applied to preparation of medical implants, medical intervention bodies or other medical apparatuses.
The amorphous alloy comprises any combination of values of a, b, c, d, e and f in the composition range. For example, a can be, but is not limited to, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, etc.; b can be, but is not limited to, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, etc.; c may be, but is not limited to, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, etc.; d can be, but is not limited to, 0, 1, 2, 3, 4, 5, 6, 7, 8, etc.; e can be, but is not limited to, 0, 1, 2, 3, 4, etc.; f can be, but is not limited to, 0, 1, 2, 3, 4, 5, etc.
In an alternative embodiment, d, e and f are not 0 at the same time in the amorphous alloy. The Ti in the amorphous alloy can reduce the elastic modulus of the amorphous alloy. Ag in the amorphous alloy has a sterilization effect, and the sterilization performance of the amorphous alloy can be provided by adding the Ag. The Nb in the amorphous alloy can improve the forming capability of the amorphous alloy. Those skilled in the art can select appropriate values for the ranges of Ti, Ag and Nb defined in the present invention according to actual needs to meet the requirements as medical implants, medical implants or medical devices.
According to another embodiment of the present invention, d in the amorphous alloy is greater than 0 to improve the sterilization effect. More preferably, d is more than or equal to 2 and less than or equal to 8 in the amorphous alloy.
According to another embodiment of the present invention, e in the amorphous alloy is greater than 0, so as to reduce the elastic modulus and reduce the possibility of stress complications such as stress concentration and fracture caused by the stress shielding effect. More preferably, e is more than or equal to 2 and less than or equal to 4 in the amorphous alloy.
According to another embodiment of the invention, c is more than or equal to 5 and less than or equal to 8 in the amorphous alloy. It is known that Al has some toxicity to human body, and the content of Al in the amorphous alloy should be reduced, preferably, the content of Al in the amorphous alloy is between 5 and 8.
According to another embodiment of the invention, b is more than or equal to 8 and less than or equal to 10 in the amorphous alloy. The amorphous alloy can also separate out copper ions with certain concentration in the using process, and the copper ions have potential biological toxicity. Preferably, the Cu content of the non-via alloy is between 8 and 10.
According to another embodiment of the present invention, a specific example of the composition of the amorphous alloy may be Zr72Cu8Al12Ag8、Zr70Cu10Al15Ag5、Zr70Cu15Al10Nb5、Zr65Cu25Al10、Zr65Cu13Al14Ag8、Zr65Cu29Al12Ti2Ag2、Zr65Cu27Al3Ti2Ag3、Zr64Cu20Al12Ti2Ag2、Zr61Cu23Al12Ti2Ag2、Zr61Cu31Al14Ti2Ag2、Zr61Cu25Al12Ti2、Zr60Cu20Al12Ag8、Zr46Cu38Al8Ag8、Zr46Cu46Al6Ti2、Zr46Cu40Al4Ti2Ag8、Zr45Cu45Al8Nb2、Zr45Cu40Al6Ti4Ag5Or Zr40Cu50Al5Nb5
The invention also provides a biomedical material comprising the amorphous alloy.
The invention also provides application of the biomedical material in the fields of medical implants, medical intervention bodies or medical apparatuses and instruments. The medical implant may be, but is not limited to, an artificial bone block, an artificial joint, a femoral head support, a bone plate, a dental implant, an abutment, and the like. The medical intervention body may be, but is not limited to, an abutment, a dental brace, a denture, and the like. The medical instrument may be, but is not limited to, a metal needle, an endodontic file, and the like.
The present invention is further described below by way of specific examples. However, these examples are only illustrative and do not set any limit to the scope of the present invention.
In the following examples and comparative examples, reagents, materials and instruments used therefor were commercially available unless otherwise specified.
The purities of the raw materials such as Zr, Cu, Al, Ag, Ti, Nb and the like adopted in the experiment are all more than 99.9 percent. Before blending, the surface of the raw material is polished by sand paper to remove an oxide film and other impurities on the surface. Then the experimental material is put into alcohol and oscillated by an ultrasonic cleaner and dried by a hair drier. And (3) during batching, taking zirconium as a reference, predicting the total mass of the alloy ingot, calculating the mass of each component through a component calculation program, and accurately weighing by using an electronic balance (the mass error is not more than 0.0005 g). The prepared raw materials are put into a copper crucible which can be used for smelting, and a furnace door is closed. Respectively vacuumizing to 3X 10 by using a mechanical pump and a molecular pump-3Pa, washing gas, and then filling high-purity argon to 0.005 MPa. When smelting is started, firstly, a titanium ingot at a middle station is melted to remove residual air in the furnace chamber, then, the metal is placed from top to bottom according to the melting point, the smelting is repeated for more than 4 times, the unoxidized alloy ingot with proper size is heated and re-melted, the alloy melt is quickly sucked into a die by utilizing the air pressure difference between a smelting chamber and a copper die cavity, the quick cooling is realized, and the alloy rod with the diameter of 1mm, 2mm, 4mm or 5mm is prepared.
Amorphous alloys of examples 1 to 18 were prepared in the above manner, and the compositions of the amorphous alloys of the respective examples are shown in table 1.
XRD testing was performed on the amorphous alloys prepared in examples 1-18. XRD detection results are shown in figures 1-18. As can be seen from fig. 1-18, the alloys prepared in examples 1-18 were all amorphous.
The performance tests were performed on the amorphous alloys prepared in examples 1 to 11. The instrument used was an INSTRON-5982 universal tester. The stress-strain curve is obtained by applying a continuous and gradual axial compressive load to the sample and controlling the loading speed. Before the experiment, the amorphous rod is cut into the length-diameter ratio of about 2 along the cross section direction: 1, and polishing the two ends of the sample smoothly and flatly by using a self-made clamp on the sand paper so as to ensure that the two ends are parallel and vertical to the column body. As the amorphous rod with the diameter of 2mm is selected in the compression experiment, the height of the polished sample is 4mm in order to ensure the height-diameter ratio of 2: 1. After the sample is prepared, a universal testing machine and computer testing software are utilized to obtain a relevant pressure-strain curve. At least 3 specimens per component alloy were selected for repeated experiments to improve the reliability of the experimental data. The test results are shown in table 1.
TABLE 1
Figure DEST_PATH_IMAGE001
The alloy compositions of examples 12-18 and the diameters of the resulting alloy rods are shown in Table 2.
TABLE 2
Figure DEST_PATH_IMAGE002
From the data shown in table 1, it can be seen that the elastic modulus of the amorphous alloy prepared in examples 1 to 11 is significantly lower than that of the crystalline alloy, and is closer to that of human skeleton or tooth, thereby reducing the possibility of fracture caused by stress shielding effect during the use of the implant and the denture framework. Thus being suitable for medical implants. In addition, the amorphous alloys of examples 1 to 11 have high compressive strength, are not easily fractured when used as medical implants, and can be made smaller in diameter, so that they are more suitable for the thinner alveolar bone of asian and the elderly when used as dental implants, and reduce the possibility of bone grafting to shorten the treatment period. And can be made thinner for use as a dental shaping sheet, reducing discomfort during treatment of a patient. As can be seen from the data in tables 1 and 2, the amorphous alloys prepared in examples 1-18 have better forming ability and can be formed during actual use.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (11)

1. An amorphous alloy, characterized in that the composition of the amorphous alloy is ZraCubAlcAgdTieNbfWherein a, b, c, d, e and f respectively represent the mass percent of each element, 45-72 of a, 8-50 of b, 3-15 of c, 0-8 of d, 0-4 of e, 0-5 of f, and a + b + c + d + e + f = 100.
2. The amorphous alloy according to claim 1, wherein d, e and f are not simultaneously 0.
3. The amorphous alloy of claim 1, wherein both d and e are greater than 0.
4. The amorphous alloy of claim 1, wherein d is 2. ltoreq. d.ltoreq.8.
5. The amorphous alloy of claim 1, wherein 2. ltoreq. e.ltoreq.4 in the amorphous alloy.
6. The amorphous alloy of claim 1, wherein c is 5. ltoreq. c.ltoreq.8 in the amorphous alloy.
7. The amorphous alloy of claim 1, wherein b is greater than or equal to 8 and less than or equal to 10.
8. The amorphous alloy according to claim 1, wherein the composition of the amorphous alloy is Zr72Cu8Al12Ag8、Zr70Cu10Al15Ag5、Zr70Cu15Al10Nb5、Zr65Cu25Al10、Zr65Cu13Al14Ag8、Zr65Cu29Al12Ti2Ag2、Zr65Cu27Al3Ti2Ag3、Zr64Cu20Al12Ti2Ag2、Zr61Cu23Al12Ti2Ag2、Zr61Cu31Al14Ti2Ag2、Zr61Cu25Al12Ti2、Zr60Cu20Al12Ag8、Zr46Cu38Al8Ag8、Zr46Cu46Al6Ti2、Zr46Cu40Al4Ti2Ag8、Zr45Cu45Al8Nb2、Zr45Cu40Al6Ti4Ag5Or Zr40Cu50Al5Nb5
9. Biomedical material, characterized in that it comprises the amorphous alloy according to any of claims 1 to 8.
10. Use of the biomedical material according to claim 9 in the field of medical implants, medical interventions or other medical devices.
11. The use of claim 10, wherein the medical implant comprises an artificial bone block, an artificial joint, a femoral head support, a bone plate, a dental implant, an abutment; the medical intervention body comprises an adjacent surface forming sheet, a dental support and a false tooth; the medical instrument comprises a metal needle and a root canal file.
CN202110650495.2A 2021-06-11 2021-06-11 Biomedical amorphous alloy and application thereof Pending CN113249661A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115255390A (en) * 2022-09-26 2022-11-01 中国人民解放军北部战区总医院 Preparation method of zirconium-based amorphous alloy self-expansion aorta covered stent based on SLM
WO2022257915A1 (en) * 2021-06-11 2022-12-15 北京大学口腔医学院 Biomedical amorphous alloy and use thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113528883B (en) * 2021-07-13 2022-05-20 上海理工大学 Copper-niobium alloy for medical biopsy puncture needle

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1990896A (en) * 2005-12-28 2007-07-04 中国科学院金属研究所 Zirconium base massive nano-amorphous alloy with larger plastic strain
CN101020991A (en) * 2007-03-26 2007-08-22 浙江大学 Lumpy noncrystal Zr-Cu-Ag-Al alloy
CN102146550A (en) * 2010-02-05 2011-08-10 中国科学院金属研究所 Nickel-free zirconium alloy with amorphous structure easily formed by pouring melt copper mould
US20130255837A1 (en) * 2012-03-29 2013-10-03 Atakan Peker Zirconium based bulk metallic glasses
CN105714216A (en) * 2016-02-29 2016-06-29 宋佳 High-tenacity and high-plasticity amorphous alloy and preparation method and application thereof
CN105779910A (en) * 2014-12-16 2016-07-20 辽宁工业大学 Copper, zirconium and aluminum based metal glass composite with large elastic deformability
CN105886966A (en) * 2016-06-06 2016-08-24 天津大学 Zirconium-based multi-component amorphous alloy with high thermal stability and preparation method thereof
CN106413948A (en) * 2014-05-15 2017-02-15 德国贺利氏有限两合公司 Method for producing a component from an amorphous-phase metal alloy
CN109504925A (en) * 2019-01-15 2019-03-22 燕山大学 A kind of zirconium-based bulk amorphous alloy and the preparation method and application thereof
US20190177826A1 (en) * 2012-09-28 2019-06-13 California Institute Of Technology Systems and Methods Implementing Wear-Resistant Copper-Based Materials
CN111922318A (en) * 2020-08-05 2020-11-13 兰州理工大学 Near-net forming die for zirconium-based amorphous flexible gear and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113249661A (en) * 2021-06-11 2021-08-13 北京大学口腔医学院 Biomedical amorphous alloy and application thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1990896A (en) * 2005-12-28 2007-07-04 中国科学院金属研究所 Zirconium base massive nano-amorphous alloy with larger plastic strain
CN101020991A (en) * 2007-03-26 2007-08-22 浙江大学 Lumpy noncrystal Zr-Cu-Ag-Al alloy
CN102146550A (en) * 2010-02-05 2011-08-10 中国科学院金属研究所 Nickel-free zirconium alloy with amorphous structure easily formed by pouring melt copper mould
US20130255837A1 (en) * 2012-03-29 2013-10-03 Atakan Peker Zirconium based bulk metallic glasses
US20190177826A1 (en) * 2012-09-28 2019-06-13 California Institute Of Technology Systems and Methods Implementing Wear-Resistant Copper-Based Materials
CN106413948A (en) * 2014-05-15 2017-02-15 德国贺利氏有限两合公司 Method for producing a component from an amorphous-phase metal alloy
CN105779910A (en) * 2014-12-16 2016-07-20 辽宁工业大学 Copper, zirconium and aluminum based metal glass composite with large elastic deformability
CN105714216A (en) * 2016-02-29 2016-06-29 宋佳 High-tenacity and high-plasticity amorphous alloy and preparation method and application thereof
CN105886966A (en) * 2016-06-06 2016-08-24 天津大学 Zirconium-based multi-component amorphous alloy with high thermal stability and preparation method thereof
CN109504925A (en) * 2019-01-15 2019-03-22 燕山大学 A kind of zirconium-based bulk amorphous alloy and the preparation method and application thereof
CN111922318A (en) * 2020-08-05 2020-11-13 兰州理工大学 Near-net forming die for zirconium-based amorphous flexible gear and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
S. VINCENT ET AL.: "Thermodynamic prediction of bulk metallic glass forming alloys in ternary Zr–Cu–X(X=Ag, Al, Ti, Ga) systems", 《JOURNAL OF NON-CRYSTALLINE SOLIDS》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022257915A1 (en) * 2021-06-11 2022-12-15 北京大学口腔医学院 Biomedical amorphous alloy and use thereof
CN115255390A (en) * 2022-09-26 2022-11-01 中国人民解放军北部战区总医院 Preparation method of zirconium-based amorphous alloy self-expansion aorta covered stent based on SLM

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