CN118957371A - A biomedical Mn alloy and its preparation method and application - Google Patents
A biomedical Mn alloy and its preparation method and application Download PDFInfo
- Publication number
- CN118957371A CN118957371A CN202410992512.4A CN202410992512A CN118957371A CN 118957371 A CN118957371 A CN 118957371A CN 202410992512 A CN202410992512 A CN 202410992512A CN 118957371 A CN118957371 A CN 118957371A
- Authority
- CN
- China
- Prior art keywords
- alloy
- biomedical
- annealing
- wire
- annealed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910000914 Mn alloy Inorganic materials 0.000 title claims abstract description 166
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000137 annealing Methods 0.000 claims abstract description 86
- 239000013078 crystal Substances 0.000 claims abstract description 63
- 239000000956 alloy Substances 0.000 claims abstract description 44
- 239000007943 implant Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 238000005242 forging Methods 0.000 claims description 37
- 229910045601 alloy Inorganic materials 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 24
- 238000005098 hot rolling Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 17
- 210000000988 bone and bone Anatomy 0.000 claims description 13
- 238000007514 turning Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 238000000265 homogenisation Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 5
- 230000002439 hemostatic effect Effects 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 32
- 238000006731 degradation reaction Methods 0.000 abstract description 32
- 239000000463 material Substances 0.000 abstract description 16
- 229910052748 manganese Inorganic materials 0.000 abstract description 12
- 210000004027 cell Anatomy 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 15
- 229910000640 Fe alloy Inorganic materials 0.000 description 13
- 229910000861 Mg alloy Inorganic materials 0.000 description 12
- 229910001297 Zn alloy Inorganic materials 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000010622 cold drawing Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000002792 vascular Effects 0.000 description 8
- 230000003068 static effect Effects 0.000 description 7
- 238000001000 micrograph Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 239000012981 Hank's balanced salt solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000006698 induction Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- 230000003833 cell viability Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 description 4
- 210000001519 tissue Anatomy 0.000 description 4
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 229910001566 austenite Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000012091 fetal bovine serum Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910000599 Cr alloy Inorganic materials 0.000 description 2
- 206010020751 Hypersensitivity Diseases 0.000 description 2
- 229930182555 Penicillin Natural products 0.000 description 2
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 2
- 210000004204 blood vessel Anatomy 0.000 description 2
- 230000000747 cardiac effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229940049954 penicillin Drugs 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 2
- 229960005322 streptomycin Drugs 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 206010067484 Adverse reaction Diseases 0.000 description 1
- 208000031404 Chromosome Aberrations Diseases 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 208000034827 Neointima Diseases 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- 102000004142 Trypsin Human genes 0.000 description 1
- 108090000631 Trypsin Proteins 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000033115 angiogenesis Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000702 anti-platelet effect Effects 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BQRGNLJZBFXNCZ-UHFFFAOYSA-N calcein am Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(CN(CC(=O)OCOC(C)=O)CC(=O)OCOC(C)=O)=C(OC(C)=O)C=C1OC1=C2C=C(CN(CC(=O)OCOC(C)=O)CC(=O)OCOC(=O)C)C(OC(C)=O)=C1 BQRGNLJZBFXNCZ-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 238000010365 cell imaging technique Methods 0.000 description 1
- 231100000005 chromosome aberration Toxicity 0.000 description 1
- 208000037976 chronic inflammation Diseases 0.000 description 1
- 230000006020 chronic inflammation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002595 magnetic resonance imaging Methods 0.000 description 1
- 230000037353 metabolic pathway Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 208000037803 restenosis Diseases 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 210000000329 smooth muscle myocyte Anatomy 0.000 description 1
- 210000004872 soft tissue Anatomy 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 231100000057 systemic toxicity Toxicity 0.000 description 1
- 239000012588 trypsin Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C22/00—Alloys based on manganese
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L31/00—Materials 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
- A61L31/02—Inorganic materials
- A61L31/022—Metals or alloys
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L31/00—Materials 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
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
- B21C37/047—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire of fine wires
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
- B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/0075—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for rods of limited length
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods
- A61B2017/00831—Material properties
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Surgery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Veterinary Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Heart & Thoracic Surgery (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Epidemiology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Vascular Medicine (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Medical Informatics (AREA)
- Biomedical Technology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses biomedical Mn alloy, a preparation method and application thereof, and relates to the field of biomedical materials. The biomedical Mn alloy comprises 60-75wt.% Mn, 22-37wt.% Fe, 2.75-4.25wt.% Cu and 0.25-0.75wt.% C. The biomedical Mn alloy provided by the invention can be prepared into bars or wires according to different use scenes. The microstructure of the bar material only contains equiaxed crystals, the microstructure of the drawn wire material can be a mixed structure of deformed crystals and equiaxed crystals, and the wire material subjected to the electric annealing only contains equiaxed crystals. The biomedical Mn alloy material provided by the invention has the advantages of excellent mechanical strength, more suitable degradation rate, good biocompatibility, no biotoxicity and the like, and can be widely applied to the field of medical instruments, in particular to the material for preparing medical implants.
Description
Technical Field
The invention relates to the field of biomedical materials, in particular to a preparation method of biomedical Mn alloy.
Background
The biomedical wire is mainly made of non-degradable alloys such as 316L stainless steel, ti alloy, co-Cr alloy and the like, and degradable alloys such as Mg alloy, zn alloy, fe alloy and the like. The preparation process of the 316L stainless steel and Ti alloy wires is mature, the production cost is low, and the mechanical properties are excellent. However, the 316L stainless steel and Ti alloy wires are inferior in corrosion resistance and wear resistance, and after being implanted into a living body, are prone to generating harmful micron-sized metal fragments or metal ions due to corrosion and wear, thereby triggering immune or allergic reactions, generating chronic inflammation, and causing bone dissolution around the implant. The Co-Cr alloy wire has high specific strength, good wear resistance, small pitting tendency and insensitivity to stress corrosion; however, the material is expensive, contains a large amount of elements such as Co and Ni with biotoxicity, and releases a small amount of Co-Cr particles after being implanted into organisms, so that adverse conditions such as chromosome aberration, local soft tissue allergy, systematic Co poisoning and the like are often caused. In addition, the alloy wire is not easy to take out and degrade after being implanted into a body, can be used as a foreign body to be remained in a patient for a long time, can aggravate the negative effects, and can lead to the prolonged treatment time of dual antiplatelet.
Mg alloy, zn alloy and Fe alloy wires generally do not contain bio-toxic elements, can provide sufficient mechanical support within a prescribed treatment time after implantation in vivo, and then are discharged outside the body through normal physiological metabolic pathways, so that occurrence of various adverse reactions as described above due to non-degradability of the wires can be avoided. However, mg alloy wires have low strength and plasticity, and the degradation rate is too fast, so that the fabricated vascular stent can only maintain mechanical integrity in the blood vessel for 1-3 months. Premature degradation and collapse of the stent often results in vascular recoil, restenosis within the stent, and thrombosis within the stent. The Zn alloy wire has good biocompatibility and moderate degradation rate, but has lower tensile strength. Fe alloy wires have excellent mechanical and processing properties, little change to local microenvironment of tissues after being implanted into a body, and corrosion byproducts generally do not generate systemic toxicity. However, the degradation rate of the Fe alloy wire is too slow, the vascular stent is almost intact after being implanted into a blood vessel for 4 years, and a firm corrosion product generated by degradation is always left in situ and is easily wrapped by a neointima, so that the regeneration of vascular tissues is hindered.
Therefore, how to prepare an alloy material can prepare wires for the fields of medical instruments and medical implants, has good mechanical strength, moderate degradation rate, good biocompatibility and no biotoxicity, and is a difficult problem to be solved in the fields of medical instruments and biomedical materials.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides biomedical Mn alloy, and a preparation method and application thereof. The Mn alloy material is prepared from four elements of Mn, fe, cu and C by adopting a specific composition ratio, and the Mn alloy has the advantages of excellent mechanical strength, moderate degradation rate, good biocompatibility, no biotoxicity and the like; can be processed into bars or wires with different sizes, and is widely applied to the field of medical appliances, in particular to the materials for preparing medical implants. Specifically, the method is realized by the following technology.
In a first aspect of the invention, a biomedical Mn alloy is provided, wherein the composition of the biomedical Mn alloy comprises 60-75wt.% of Mn, 22-37wt.% of Fe, 2.75-4.25wt.% of Cu and 0.25-0.75wt.% of C; the microstructure of the bar of biomedical Mn alloy only contains equiaxed crystals, and the size of the equiaxed crystals is 12-25 mu m;
In the microstructure of the biomedical Mn alloy wire, the number of deformed crystals and equiaxed crystals is (0.5-1.5): 1, and the size of the equiaxed crystals is 0.15-0.65 mu m; or the microstructure of the biomedical Mn alloy wire material only contains equiaxed crystals, and the size of the equiaxed crystals is 2.2-2.8 mu m.
It is to be understood that the biomedical Mn alloy provided by the invention is divided into two material forms of a bar and a wire according to the difference of practical application scenes. The two material forms each have the corresponding microstructure described above. The microstructure of the Mn alloy bar only contains equiaxed crystals. The microstructure of the Mn alloy wire may be a mixed structure containing both deformed crystals and equiaxed crystals and having a number of (0.5-1.5): 1, or may be a structure containing only equiaxed crystals, depending on the difference in processing technique.
The Mn alloy provided by the invention takes Mn as a main element component, and when the potential of an Mn electrode is lower than Fe and the Mn content is 60-75 wt%, the alloy is an austenite phase with lower magnetic susceptibility. The invention adds Fe, cu and C elements into Mn alloy material. The inventors of the present invention have intensively studied and found that the microstructure of the bar and wire of the above Mn alloy exhibits a structure containing only equiaxed crystals or a mixed structure of deformed crystals and equiaxed crystals.
It is easy to know that the Mn alloy provided by the invention, regardless of the preparation method, is within the protection scope of the invention as long as the element composition and the microstructure requirement are met.
In the Mn alloy, the content of C is 0.25-0.75wt.% and can play a role in solid solution strengthening, and fine carbides distributed in a dispersed manner can be generated in a microstructure during smelting, so that the grain nucleation is promoted, the grain growth is limited, and the effect of refining the grains is achieved. During subsequent processing and heat treatment, the fine dispersed carbide is oxidized to form dispersed black oxide, which has the second phase strengthening effect and forms micro-couple corrosion pair with the matrix to accelerate the corrosion degradation of Mn alloy.
The grain refinement not only can play a role in strengthening fine grains, but also can increase the grain boundary density to play a role in accelerating the inter-crystal corrosion of the alloy, and finally, the mechanical and degradation properties of the Mn alloy are obviously improved.
When the Cu content is 2.75 to 4.25wt.%, the alloy is completely solid-dissolved without forming precipitates, and the solid-solution strengthening effect is exerted together with C. Cu 2+ released during Cu degradation has a strong antibacterial effect, and can promote the growth of smooth muscle cells to help the recovery of angiogenesis and blood transport reconstruction.
The Mn alloy provided by the invention takes Mn as a base, the electrode potential of Mn is lower than Fe, and an austenite phase can be stabilized; the theoretical degradation rate of the corresponding wire is higher than that of the Fe wire, and the Fe wire only contains an austenite phase with lower magnetic susceptibility, has excellent magnetic resonance imaging performance, and is suitable for the preparation of medical instruments such as degradable vascular stents and the like.
In terms of degradation rate of Mn alloy wire: according to the invention, mn with lower electrode potential than Fe is used as a base, the drawn state wire (the equiaxial crystal size is 0.15-0.65 mu m) and the electrified annealed state wire (the equiaxial crystal size is 2.2-2.8 mu m) are fine in crystal grains, the grain boundary density is high, the intergranular corrosion effect is strong, and a large amount of black oxides which can form micro-couple corrosion pairs with a matrix are dispersed and distributed in a tissue. The prepared phi 3 rotary forging annealed Mn alloy round rod is statically soaked in Hank solution for 1-14 days, and the degradation rate reaches 0.16-0.25 mm-year -1. The same method is adopted to test the Mn alloy wire in the phi 0.1 drawing state, the degradation rate is higher than that of a round bar, and the degradation rate can reach 0.20-0.30 mm-year -1. Therefore, the Mn alloy material of the invention basically meets the service requirement of degradable vascular stent degradation rate of 0.20 mm-year -1 no matter the Mn alloy material is a wire or a bar.
In terms of biocompatibility and biotoxicity: mn, fe, cu and C are all major elements in the human body or elements capable of playing important physiological functions, and the elements have very good biocompatibility and lower biotoxicity.
Further, the biomedical Mn alloy provided by the invention comprises, by mass, 60wt.% of Mn, 35-37wt.% of Fe, 2.75-4.25wt.% of Cu and 0.25-0.75wt.% of C.
Still further, the biomedical Mn alloy provided by the invention consists of Mn 60wt.%, fe 36wt.%, cu 3.5wt.%, C0.5 wt.%.
Further, the biomedical Mn alloy provided by the invention comprises, by mass, 75wt.% of Mn, 20-22wt.% of Fe, 2.75-4.25wt.% of Cu and 0.25-0.75wt.% of C.
Still further, the biomedical Mn alloy provided by the invention consists of 75wt.% Mn, 21wt.% Fe, 3.5wt.% Cu, and 0.5wt.% C.
The second aspect of the invention also provides a preparation method of the biomedical Mn alloy wire, which comprises the following steps: uniformly mixing pure Mn, fe, cu and C particles, and vacuum smelting to obtain an as-cast alloy round bar;
And sequentially homogenizing, turning, hot rolling, primary annealing, rotary forging, secondary annealing and grinding the as-cast alloy round bar to obtain the rotary forging annealed Mn alloy bar meeting the size requirement. The Mn alloy bar has microstructure containing only equiaxed crystal with the size of 12-25 μm.
Or on the basis of the preparation method, further carrying out drawing treatment on the Mn alloy bar to obtain the drawn Mn alloy wire meeting the size requirement. In the microstructure of the drawn Mn alloy wire, the number of deformed crystals and equiaxed crystals is (0.5-1.5): 1, and the size of the equiaxed crystals is 0.15-0.65 μm.
It should be appreciated by those skilled in the art that in the above-described method for preparing Mn alloy of the present invention, pure Mn, fe, cu and C particles may be selected from commercially available materials satisfying medical grade requirements.
Generally, the purity of pure Mn, fe, cu and C particles is not less than 99.99% of the commercially pure Mn, fe, cu and C particles.
The Mn alloy bar in the rotary forging annealed state is prepared by sequentially carrying out vacuum melting, homogenization, turning, hot rolling, primary annealing, rotary forging, secondary annealing and grinding on pure Mn, fe, cu and C particles in a specific proportion.
When the rotary forging annealed Mn alloy bar is used for further preparing the wire, drawing (single-pass drawing/multi-pass drawing) treatment is further carried out after grinding, so that the drawn Mn alloy wire is obtained.
It will also be appreciated by those skilled in the art that each of the above-described processing stages may be accomplished using techniques commonly used in the industry, and that the process parameters for each processing stage may be conventional or readily known.
Optionally, in the preparation method of the invention, the homogenization treatment temperature is 1050-1150 ℃ and the treatment time is 4-8h.
Alternatively, in the above preparation method of the present invention, the hot rolling temperature is 850 to 950 ℃ and the deformation amount is 85 to 95%.
Optionally, in the preparation method of the invention, the temperature of the first annealing is 950-1050 ℃, and the annealing time is 0.5-1.5h.
Optionally, in the preparation method of the invention, the temperature of the rotary forging is 400-500 ℃ and the deformation is 85-95%.
Optionally, in the preparation method of the invention, the temperature of the second annealing is 800-1000 ℃ and the annealing time is 0.2-0.8h.
Alternatively, in the above-described production method of the present invention, when multi-pass drawing is employed, the cold drawing deformation amount per pass is 40 to 90%, and the total drawing deformation amount is 99.7 to 99.9%.
Further, carrying out electrifying annealing treatment on the drawn Mn alloy wire to obtain an electrifying annealed Mn alloy wire; the conditions of the electrical annealing treatment were: annealing for 3-30s under the current of 0.65-0.85A.
The inventor of the invention researches and discovers that on the basis of the preparation method, the drawn Mn alloy wire is subjected to the electrifying annealing treatment in the mode, so that the drawn Mn alloy wire is completely recrystallized during electrifying annealing, and the drawing residual stress is eliminated; so that the deformed crystal grains are equiaxed, the equiaxed crystal grows (the size is 2.2-2.8 mu m), and the plasticity is recovered, thereby further improving the comprehensive mechanical properties of the Mn alloy wire. The microstructure of the Mn alloy wire after the electric annealing only contains equiaxed crystals, and the size of the equiaxed crystals is 2.2-2.8 mu m.
Further, the conditions of the electrical annealing treatment are: annealing for 30s at a current of 0.7A.
Optionally, the first annealing treatment mode is: annealing at 950-1050 deg.c for 0.5-1.5 hr.
Optionally, the second annealing treatment mode is: annealing at 800-1000 deg.c for 0.2-0.8 hr.
Further, the rotary forging annealed round bar is subjected to single-pass drawing treatment, and the drawing deformation is 99.7-99.9%.
In a third aspect of the invention, the invention also provides application of the biomedical Mn alloy in preparing medical equipment.
Further, in the above application method of biomedical Mn alloy, the medical devices include, but are not limited to, sutures, implant scaffolds, bone nails, bone needles, hemostatic clips, threaded anchors, screws, bone plates, bone covers, intramedullary needles, staplers, orthodontic archwires, cardiac pacemaker leads, and venous filters.
It will be readily appreciated by those skilled in the art that Mn alloy rods or wires of different sizes (diameters) may be selected for the different applications described above.
Further, for example, mn alloy bars may be used as human or animal body implant materials common in surgery for bone nails, bone pins, hemostatic clips, threaded anchors, screws, bone plates, bone covers, and the like. The specific size of the Mn alloy bar can be properly adjusted according to actual needs.
Further, for example, mn alloy wires may be used as implant materials for orthodontic archwires, cardiac pacemaker leads, and venous filters. The specific size of the Mn alloy wire can be properly adjusted according to actual needs.
Alternatively, the common alloy bar has the common size of phi 3. Alternatively, common Mn alloy wire sizes include diameter (mm) parameters of Φ0.1, Φ0.125, Φ0.15, Φ0.175, Φ0.2, and Φ0.25. Regardless of the size adjustment, these Mn alloy wires and rods are within the scope of the present invention.
Compared with the prior art, the invention has the following advantages:
1. The invention provides a biomedical Mn alloy which has excellent mechanical properties through the synergistic combination of four elements of Mn, fe, cu and C in a specific proportion;
The yield strength of the prepared rotary forging annealed round bar of phi 3 reaches 262MPa at most, the tensile strength reaches 617MPa at most, the elongation reaches 47% at most, and the elastic modulus reaches 172GPa at most; completely meets the requirements of the degradable vascular stent that the tensile yield strength is more than 200MPa, the tensile strength is more than 300MPa and the elongation is more than 18 percent;
The tensile strength of the prepared drawn Mn alloy wire with phi 0.1 reaches 682MPa at most, and the elongation is generally 18-24%.
2. The degradation rate of the Mn alloy provided by the invention is moderate, after static soaking in Hank solution for 1-14 days, the degradation rate of the prepared rotary forging annealed Mn alloy round bar of phi 3 reaches 0.16-0.25 mm-year -1, and the degradation rate of the prepared drawn Mn alloy of phi 0.1 reaches 0.20-0.30 mm-year -1, and the rotary forging annealed Mn alloy round bar has good biocompatibility and no biotoxicity. After the treatment is finished, the Mn alloy wire can be gradually and uniformly degraded in a controllable time and can be completely absorbed by a human body, so that long-term rejection and secondary operation caused by nondegradable wire can be avoided, and the physical and economic burden of a patient can be reduced.
3. The invention provides a preparation method of biomedical Mn alloy wire, which comprises the steps of vacuum melting, homogenizing, turning, hot rolling, primary annealing, rotary forging, secondary annealing and grinding to prepare a rotary forging annealed Mn alloy bar; and further preparing the drawn Mn alloy wire by single-pass/multi-pass drawing.
On the basis, the invention also carries out electrifying annealing again after drawing, can eliminate residual drawing stress and further improves the comprehensive mechanical property of the wire.
4. In the preparation method of the Mn alloy wire, the alloy round bar subjected to rotary forging annealing can be drawn by multiple passes; the method can also directly adopt single-pass drawing one-step molding, is simple to process, and saves production time and instruments. The preparation method has the advantages that all the processes are simple in equipment, and the preparation method is suitable for large-scale production, popularization and application.
Drawings
FIG. 1 is a scanning electron microscope image of the microstructure of a Phi 0.1 Mn alloy wire (not annealed) of example 1 at 50000 (left) and 100000 (right) magnifications;
FIG. 2 is a scanning electron microscope image of the microstructure of the Mn alloy wire of Φ0.1 of example 2 (0.7A electrical annealing 30 s) at magnifications of 10000 (left panel) and 30000 (right panel); ;
FIG. 3 is a scanning electron microscope image of the microstructure of the Mn alloy wire of Φ0.1 of example 3 (0.75A electrical anneal 15 s) at a magnification of 5000 (left) and 10000 (right);
FIG. 4 is a scanning electron microscope image of the microstructure of the phi 0.1 Mn alloy wire of example 4 (0.75A electrical anneal 30 s) at 5000 (left) and 10000 (right) magnifications;
FIG. 5 is a scanning electron microscope image of the microstructure of the Mn alloy wire of Φ0.1 of example 5 (0.8A electrical annealing 5 s) at a magnification of 5000 (left) and 10000 (right);
FIG. 6 is a scanning electron microscope image of the microstructure of the Mn alloy wire of Φ0.1 of example 6 (0.8A electrical annealing 10 s) at magnifications of 10000 (left panel) and 30000 (right panel);
FIG. 7 is a drawing curve of a rotary swaging annealed round bar of example 1 (left graph) and a comparison of mechanical properties with a portion of the conventional degradable Mg alloy, zn alloy, and Fe alloy of comparative example 3 (right graph); in the right graph, RF-800℃means that the second annealing of example 1 was 800℃for 0.4 hours, and RF-1-1000℃means that the second annealing of example 1 was 1000℃for 0.6 hours;
FIG. 8 is a graph showing degradation weight loss and degradation rate change per unit area of Mn alloy wire prepared in example 1 (left graph) after static immersion in Hank solution for 1-14 days, in comparison with degradation rates of conventional degradable Mg alloy wire, zn alloy wire and Fe alloy wire in the literature (right graph);
FIGS. 9-10 are the results of a cell compatibility test for Mn alloy wire of Φ0.1 prepared in example 2.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are only some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by one of ordinary skill in the art without undue burden on the person of ordinary skill in the art based on embodiments of the present invention, are within the scope of the present invention.
In some embodiments of the invention, the composition of the Mn alloy, in mass fraction, consists of Mn 60-75 wt.%, fe 22-37wt.%, cu 2.75-4.25wt.%, C0.25-0.75 wt.%.
Further, in some embodiments of the invention, the composition of the Mn alloy consists of Mn 60wt.%, fe 35-37wt.%, cu 2.75-4.25wt.%, C0.25-0.75 wt.%.
Further, in other embodiments of the present invention, the composition of the Mn alloy consists of 75wt.% Mn, 20-22wt.% Fe, 2.75-4.25wt.% Cu, 0.25-0.75wt.% C.
Further, the composition of the Mn alloy consists of Mn 60wt.%, fe 36wt.%, cu 3.5wt.%, C0.5 wt.%.
Further, the composition of the Mn alloy consists of 75wt.% Mn, 21wt.% Fe, 3.5wt.% Cu, 0.5wt.% C.
In some specific embodiments of the present invention, the biomedical Mn alloy wire (drawn state) provided by the present invention has a microstructure of mixed deformed crystals and equiaxed crystals, the number of deformed crystals and equiaxed crystals is (0.5-1.5): 1, and the grain size is 0.15-0.65 μm.
In some specific embodiments of the present invention, biomedical Mn alloy wires (electrical annealed state) provided by the present invention have microstructures containing only equiaxed crystals, the equiaxed crystals having a size of 2.2-2.8 μm.
In some specific embodiments of the present invention, biomedical Mn alloy bars (as in the as-swaged annealed state) provided by the present invention have microstructures comprising only equiaxed crystals, the equiaxed crystals having a size of 12-25 μm.
In some embodiments of the invention, the Mn alloy wire is prepared by:
Uniformly mixing pure Mn, fe, cu and C particles, and then placing the mixture into a crucible of a vacuum induction melting furnace for vacuum melting to obtain an as-cast Mn alloy round bar;
Homogenizing, turning, hot rolling, first annealing, rotary forging, second annealing and grinding (fine grinding) are sequentially carried out on the cast alloy round bar, so that the rotary forging annealed Mn alloy bar meeting the size requirement is obtained. The Mn alloy bar has microstructure containing only equiaxed crystal with the size of 12-25 μm.
On the basis, drawing treatment is also carried out on the rotary forging annealed Mn alloy bar, so that the drawn Mn alloy wire meeting the size requirement is obtained. In the microstructure of the drawn Mn alloy wire, the number of deformed crystals and equiaxed crystals is (0.5-1.5): 1, and the size of the equiaxed crystals is 0.15-0.65 μm.
As will be appreciated by those skilled in the art, the raw materials for preparing Mn alloy wire are generally selected from the group consisting of industrially pure Mn, pure Fe, pure Cu and pure C particles having a purity of not less than 99.99%.
In other specific embodiments of the present invention, based on the above-mentioned method for producing Mn alloy wire, the Mn alloy wire in a drawn state is subjected to an electric annealing treatment, the electric current is 0.65 to 0.85A, and the annealing time is 3 to 30 seconds, to produce a final Mn alloy wire in an electric annealed state.
In other embodiments of the invention, the energizing current for the energizing annealing treatment is 0.7A and the annealing time is 30 seconds.
It should be further appreciated by those skilled in the art that in the method for preparing Mn alloy wires according to some embodiments of the present invention, the steps of vacuum melting, homogenizing, turning, hot rolling, first annealing, rotary forging, second annealing, grinding, drawing (single drawing/multi drawing) and the like may be implemented by conventional techniques commonly used in the industry, and the process parameters of each processing stage may be conventional or easily known.
In some embodiments of the present invention, the conditions for the homogenization treatment in the preparation method of the Mn alloy wire rod may be selected as follows: the temperature is 1050-1150 ℃, and the treatment time is 4-8h.
In some embodiments of the present invention, the conditions for hot rolling in the above-mentioned method for producing Mn alloy wire rods may be selected as follows: the temperature is 850-950 ℃ and the deformation is 85-95%.
In some embodiments of the present invention, the conditions for the first annealing in the preparation method of the Mn alloy wire may be selected as follows: the temperature is 950-1050 ℃, and the annealing time is 0.5-1.5h.
In some embodiments of the present invention, the conditions for swaging in the above-mentioned method for producing Mn alloy wire material may be selected as follows: the temperature is 400-500 ℃ and the deformation is 85-95%.
In some embodiments of the present invention, the conditions for the second annealing in the above-mentioned method for producing Mn alloy wire may be selected as follows: the temperature is 800-1000 ℃, and the annealing time is 0.2-0.8h.
In some embodiments of the present invention, in the method for preparing a Mn alloy wire, when multi-pass drawing is used, the cold drawing deformation per pass is 40 to 90%, and the total drawing deformation is 99.7 to 99.9%.
It should also be known to those skilled in the art that in the Mn alloy wire production method, the homogenization treatment is to redissolve and disperse precipitates in the tissue; the turning is to remove an oxide layer on the surface of the alloy round bar; the first anneal is to promote recrystallization of the round alloy rod.
It will be appreciated by those skilled in the art that the size of the Mn alloy wire is tailored to the specific requirements of different medical devices. Common Mn alloy wire sizes include diameter parameters of Φ0.1, Φ0.125, Φ0.15, Φ0.175, Φ0.2, and Φ0.25. Mn alloy wires of these dimensions are within the scope of the present invention.
Hot rolling, rotary forging and drawing are used for reducing the diameter of the round alloy rod; grinding is used for removing oxide layers and smooth surfaces on the surfaces of the round alloy rods, and the second annealing is used for promoting the recrystallization of the round alloy rods. The equipment selected for preparing the Mn alloy wire comprises a vacuum induction melting furnace, a box-type resistance furnace, a precision lathe, a grinding machine, a small rolling mill, a direct current power supply, a metal drawing machine and the like. These devices, which are common in the art, are readily available and are widely used.
Example 1
The Mn alloy wire provided by the embodiment is prepared by the following method:
(1) Uniformly mixing industrial pure Mn, pure Fe, pure Cu and pure C particles with the purity of 99.9 percent according to the mass proportion of 60wt.%, 36wt.%, 3.5wt.% and 0.5wt.%, and then loading the mixture into a vacuum induction smelting furnace crucible (the vacuum degree is 1X 10 - 4 Pa) for smelting to obtain an alloy cast round bar with phi 40, namely Mn-36Fe-3.5Cu-0.5C;
(2) Homogenizing, turning, hot rolling and first annealing treatment are carried out on the closed Jin Zhutai round bar, and a hot rolling annealed round bar with phi 10 is obtained. Wherein the homogenization treatment temperature and time are 1100 ℃ and 6 hours, the turning depth is 2.5mm, the hot rolling temperature and deformation are 900 ℃ and 90%, and the first annealing temperature and time are 1000 ℃ and 1 hour;
(3) And (3) performing rotary swaging, secondary annealing and grinding on the hot rolled annealed round bar to obtain the rotary swaging annealed round bar with phi 3. Wherein the rotary forging temperature and the deformation are 450 ℃ and 90%;
the second annealing temperature and time are 800 ℃ annealing for 0.4h or 1000 ℃ annealing for 0.6h, and the grinding depth is 0.1mm;
(4) Carrying out multi-pass cold drawing treatment on a rotary forging annealed round bar with smooth and flawless surface, wherein the diameter of the round bar after cold drawing of each pass is changed into:
Phi 3- & gt phi 2- & gt phi 1.5- & gt phi 1- & gt phi 0.75- & gt phi 0.5- & gt phi 0.25- & gt phi 0.1, wherein the total deformation is 99.9%, and the Mn alloy wire is obtained.
Examples 2 to 6
The Mn alloy wire rods provided in examples 2 to 6 were prepared by carrying out the electrical annealing treatment after drawing based on the method of example 1 (the second annealing method was 1000 ℃ C. Annealing for 0.6 hours), and then the final Mn alloy wire rod product was obtained. That is, the drawn Mn alloy wire having a diameter of 0.1 is annealed.
The method of the current-carrying annealing of this example 2-6 was 0.7A current annealing 30s,0.75A current annealing 15s,0.75A current annealing 30s,0.8A current annealing 5s and 0.8A current annealing 10s in this order.
Examples 7 to 11
The Mn alloy wires provided in this example 7-11 were prepared in substantially the same manner as in example 2 (i.e., the current annealing method was 0.7A current annealing for 30 s), except that the composition of the elemental composition was changed in each example. The contents of the respective elemental components in the Mn alloy wires of examples 7 to 11 in terms of mass fraction are shown in Table 1 below, respectively.
Table 1 Mn alloy wire comprises the following components in percentage by mass
Comparative example 1
The alloy wire provided in this comparative example comprises, in mass fraction, mn 60wt.%, fe 36wt.%, cu 4wt.%, i.e., contains no C.
The preparation method of the alloy wire comprises the following steps:
(1) Mixing industrial pure Mn, pure Fe and pure Cu particles with the purity of 99.9 percent uniformly according to the mass proportion of 60wt.%, 36wt.% and 4wt.%, and then loading the mixture into a vacuum induction melting furnace crucible (the vacuum degree is 1X 10 -4 Pa) for melting to obtain an alloy cast round bar with phi 40, namely Mn-36Fe-4Cu;
(2) Homogenizing, turning, hot rolling and first annealing treatment are carried out on the closed Jin Zhutai round bar, and a hot rolling annealed round bar with phi 10 is obtained. Wherein the homogenization treatment temperature and time are 1100 ℃ and 6 hours, the turning depth is 2.5mm, the hot rolling temperature and deformation are 900 ℃ and 90%, and the first annealing temperature and time are 1000 ℃ and 1 hour;
(3) And (3) performing rotary swaging, secondary annealing and grinding on the hot rolled annealed round bar to obtain the rotary swaging annealed round bar with phi 3. Wherein the rotary forging temperature and the deformation amount are 450 ℃ and 90%, the second annealing temperature and the second annealing time are 1000 ℃ and 0.6h, and the grinding depth is 0.1mm;
(4) Carrying out multi-pass cold drawing treatment on the rotary forging annealed round bar with smooth and defect-free surface, wherein the diameter of the rotary forging annealed round bar after cold drawing of each pass is changed into:
Phi 3- & gt phi 2- & gt phi 1.5- & gt phi 1- & gt phi 0.75- & gt phi 0.5- & gt phi 0.25- & gt phi 0.1, wherein the total deformation is 99.9%, and the Mn alloy wire is obtained.
Comparative example 2
The alloy wire provided in this comparative example comprises, in mass fraction, mn 60wt.%, fe 36wt.%, cu 4wt.%, i.e., contains no C. The alloy wire of this comparative example was produced by conducting an electrical annealing treatment after drawing. The specific method comprises the following steps:
(1) Mixing industrial pure Mn, pure Fe and pure Cu particles with the purity of 99.9 percent uniformly according to the mass proportion of 60wt.%, 36wt.% and 4wt.%, and then loading the mixture into a vacuum induction melting furnace crucible (the vacuum degree is 1X 10 -4 Pa) for melting to obtain an alloy cast round bar with phi 40, namely Mn-36Fe-4Cu;
(2) Homogenizing, turning, hot rolling and first annealing treatment are carried out on the closed Jin Zhutai round bar, and a hot rolling annealed round bar with phi 10 is obtained. Wherein the homogenization treatment temperature and time are 1100 ℃ and 6 hours, the turning depth is 2.5mm, the hot rolling temperature and deformation are 900 ℃ and 90%, and the first annealing temperature and time are 1000 ℃ and 1 hour;
(3) And (3) performing rotary swaging, secondary annealing and grinding on the hot rolled annealed round bar to obtain the rotary swaging annealed round bar with phi 3. Wherein the rotary forging temperature and the deformation amount are 450 ℃ and 90%, the second annealing temperature and the second annealing time are 1000 ℃ and 0.6h, and the grinding depth is 0.1mm;
(4) Carrying out multi-pass cold drawing treatment on the rotary forging annealed round bar with smooth and defect-free surface, wherein the diameter of the rotary forging annealed round bar after cold drawing of each pass is changed into:
phi 3-phi 2-phi 1.5 → phi 1 → phi 0.75- & gt phi 0.5- & gt phi 0.25- & gt phi 0.1, the total deformation is 99.9%;
(5) Carrying out electrifying annealing, specifically 0.7A current annealing for 30s, on the drawn Mn alloy wire in the step (4); obtaining the finished product of the final electrified annealed alloy wire.
Comparative example 3: traditional degradable Mg alloy, zn alloy and Fe alloy
The comparative example separately prepared conventional degradable Mg alloy, zn alloy and Fe alloy rods having a size of Φ3, their constituent compositions, and their mechanical properties and elongation are shown in table 2 below. Carrying out static soaking test on traditional degradable Mg alloy, zn alloy and Fe alloy bar with phi 3 in Hank solution, carrying out static soaking for 1-14 days, and testing degradation rate.
In the table, taking "Fe-20Mn-3Cu" as an example, it is indicated that the alloy is based on Fe, wherein (in mass fraction) the Mn element content is 20wt.%, and the Cu element content is 3wt.%.
Table 2 relevant properties of alloy bars
As can be seen from table 2 above, the above conventional degradable Mg alloys, zn alloys and Fe alloys are either good in mechanical properties but generally in extensibility or degradability; or good extensibility but insufficient mechanical properties. None of these alloy bars can give consideration to excellent mechanical properties, biocompatibility, and good elongation and degradation rate.
Test example 1: microstructure comparison of Mn alloys prepared in examples 1-6.
The microstructure of the round bar with a rotary forging annealed state of Φ3, the drawn state Mn alloy wire with Φ0.1 and the energized annealed state Mn alloy wire with Φ0.1 prepared in examples 1 to 6 was observed after hot-setting, grinding and polishing.
As can be seen from FIG. 1, in example 1, the Mn alloy wire was subjected to incomplete dynamic recrystallization during multi-pass cold drawing, and the deformed crystal and equiaxed crystal were in the microstructure in the drawn state in an equivalent amount, and the grain size was smaller than 1 μm (about 0.65 μm).
As is clear from fig. 2 to 6, the drawn and electrically annealed Mn alloy wires of examples 2 to 6 were completely recrystallized during the electrically annealing, and deformed crystals in the structure were gradually equiaxed and the equiaxed crystals were grown. The wire is oxidized during the energization annealing, and a small amount of black oxide which is dispersed and distributed in the microstructure is generated.
Mn alloy wires of examples 2-6 were subjected to 0.7A current anneal 30s,0.75A current anneal 15s,0.75A current anneal 30s,0.8A current anneal 5s and 0.8A current anneal 10s, and the equiaxed crystal sizes in the microstructure of the wires were 2.2 μm, 2.7 μm, 2.8 μm, 2.6 μm and 2.8 μm, respectively. It can be seen that in general, the equiaxed grain size increases with increasing power-on time and current density.
Finally, through observation and statistics, the microstructure of the round bar in the rotary forging annealed state of phi 3 prepared in examples 1-6 only contains equiaxed crystals, and the size is 12-25 mu m. The microstructure of the drawn Mn alloy wire of phi 0.1 prepared in examples 1 to 6 contains both deformed crystals and equiaxed crystals, the number of deformed crystals and equiaxed crystals is (0.5-1.5): 1, and the grain size is 0.15-0.65 μm. The microstructure of the Mn alloy wire in the electric annealed state of Φ0.1 prepared in examples 1 to 6 contains only equiaxed crystals, and the size of the equiaxed crystals is 2.2 to 2.8. Mu.m.
Through analysis, the smaller the equiaxed crystal size is, the more uniform the size is, and the better the mechanical properties of the Mn alloy wire are. Along with the increase of the energizing current, the energizing time is prolonged, the equiaxed crystal size is gradually increased, and the strength of the Mn alloy wire is gradually reduced. As the equiaxed grain size of the Mn alloy wire increases, the equiaxed grain size becomes more uniform, and the plasticity of the Mn alloy wire gradually improves. As the current continues to increase, the time continues to extend, a loose oxide layer is generated on the surface of the Mn alloy wire, and the plasticity of the Mn alloy wire is reduced.
Test example 2: mechanical property test of Mn alloy wires prepared in examples 1 to 11 and comparative examples 1 to 2.
Mn alloy wires of Φ0.1 prepared in examples 1 to 11 and comparative examples 1 to 2 were subjected to tensile test, and the resulting tensile strength (UTS) and Elongation (EL) are shown in Table 3 below.
Table 3 mechanical Properties of Mn alloy wire of phi 0.1
From table 3 above, the tensile strength and elongation of the alloy wire of example 1 are significantly improved compared with those of comparative example 1, which indicates that the mechanical properties of the alloy material are significantly improved by adopting the alloy composition of the present invention. After 0.7A current annealing 30s,0.75a current annealing 15s and 30s, and 0.8a current annealing 5s and 10s, the tensile strength of the prepared phi 0.1 current annealed state Mn alloy wire was 682MPa, 614MPa, 598MPa, 557MPa and 514MPa, and the corresponding elongation was 22%, 18%, 23%, 20% and 21%. From this, it was found that the tensile strength of the Mn alloy wire decreases with an increase in current density and energization time, but the elongation does not change much. This may be related to the presence of a small amount of diffusion-distributed black oxide in the microstructure of the Mn alloy wire, and the presence of a loose oxide layer of about 3.2 μm on the surface, as analyzed.
Test example 3: mechanical properties of Mn alloy bars prepared in examples 1 and 7-11, comparative example 1 were tested.
This test example was a tensile test of the round bar in the as-swaged annealed form of Φ3 prepared in examples 1 and 7-11, and the Mn alloy bar (without C) of Φ3 prepared in comparative example 1, respectively.
The tensile curve of the alloy bar of example 1 is shown in the left graph of fig. 7, and the mechanical properties of the alloy bar of example 1 versus the conventional degradable Mg alloy, zn alloy and Fe alloy of comparative example 3 are shown in the right graph of fig. 7. The RF-800℃in FIG. 7 represents the second anneal of example 1 at 800℃for 0.4h and the RF-1-1000℃represents the second anneal of example 1 at 1000℃for 0.6h. The right-hand diagram of fig. 7 is derived from the prior art.
The results of the mechanical properties (yield strength YS, tensile strength UTS, elongation EL and elastic modulus E) of examples 1 and 7-11 and comparative example 1 are shown in Table 4 below.
Table 4 Mn comparison of mechanical properties of alloy bars
As can be seen from FIG. 6 and Table 4 above, the Mn alloy rods prepared in examples 1-11 were excellent in plasticity and had high strength. Wherein, the Mn alloy bar of example 1 has a yield strength of 262MPa or more, a tensile strength of 617MPa or more, an elongation of 47% or more, and an elastic modulus of 172GPa or more. After rotary forging annealing, the comprehensive performance of the alloy is obviously superior to that of the traditional degradable Mg alloy, zn alloy and Fe alloy, and the requirements of the degradable vascular stent that the tensile yield strength is more than 200 MPa, the tensile strength is more than 300 MPa and the elongation is more than 18% are completely met.
Test example 4: degradation performance test of phi 3 rotary forging annealed Mn alloy bars prepared in example 1 and comparative example 1.
The intermediate product "rotary forging annealed round bar of Φ3" prepared in example 1 and comparative example 1 was subjected to a static soaking test in a hank solution for 14 days, and the degradation weight loss per unit area (mg·cm -2) and degradation rate (mm·year -1) were recorded for soaking 1, 3, 7 and 14 days, respectively. The test results are shown in fig. 8 and table 5 below.
Table 5 comparison of degradation Properties of alloy materials
As can be seen from FIG. 8 and Table 5 above, the degradation weight per unit area of the round bar in the rotary forging annealed state of example 1 after static immersion for 14 days was 3.46 mg/cm -2, and the degradation rate was 0.12 mm/year -1; the degradation rate after 14 days of static soaking is lower than that of part of Mg alloy and higher than that of most of Fe alloy and Zn alloy.
Test example 5: cell compatibility test of Mn alloy wire of example 2.
The Mn alloy wire prepared in example 2 was subjected to a cell compatibility test using an indirect extraction method with reference to ISO10993-5:2009 standard. Wherein L929 cells were cultured in MEM medium supplemented with 10% fetal bovine serum and 1% (v/v) penicillin/streptomycin in a culture environment of 5% CO 2, 95% humidity and 37 ℃. The medium was changed every 2 to 3 days and when the cells reached 90% confluence, the cells were exposed to 0.25% trypsin with 1mM EDTA solution for 3-5min for passaging. After washing and sterilization of Mn alloy wire, the wire was incubated in MEM medium supplemented with 10% fetal bovine serum and 1% (v/v) penicillin/streptomycin for 24 hours to prepare a leaching solution having a volume to surface area ratio of 1.25ml/cm 2.
After culturing L-929 cells in the broth medium for 24, 48 and 72 hours, cell viability was examined using live/dead cell imaging techniques. Cells were rinsed with 10% fetal bovine serum and then stained with CALCEIN AM/EthD-I solution. After staining, the cells were incubated at room temperature in the dark for 20min, and then photographed using a fluorescence microscope, and the results are shown in fig. 9.
After quantifying the number of living and dead cells in the image, the cell viability was calculated as follows:
In the above formula, cell AO represents a living Cell, and Cell EB represents a dead Cell.
L929 cell cultures 24, 48 and 72h survived are shown in FIGS. 9-10, where cell density is shown in the left panel of FIG. 10 and cell viability is shown in the right panel of FIG. 10. As can be seen from FIGS. 9-10, the cell densities for culture 4, 24 and 72 hours were 28%, 49% and 90%, and the cell viability was 99.2%, 99.1% and 96.5%. This shows that the Mn-36Fe-3.5Cu-0.5C alloy wire prepared by the invention has better cell compatibility, the L-929 cells grow well in the culture time of 72 hours, and the cell number is continuously increased.
The above detailed description describes in detail the practice of the invention, but the invention is not limited to the specific details of the above embodiments. Many simple modifications and variations of the technical solution of the present invention are possible within the scope of the claims and technical idea of the present invention, which simple modifications are all within the scope of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410992512.4A CN118957371A (en) | 2024-07-23 | 2024-07-23 | A biomedical Mn alloy and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410992512.4A CN118957371A (en) | 2024-07-23 | 2024-07-23 | A biomedical Mn alloy and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118957371A true CN118957371A (en) | 2024-11-15 |
Family
ID=93395463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410992512.4A Pending CN118957371A (en) | 2024-07-23 | 2024-07-23 | A biomedical Mn alloy and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118957371A (en) |
-
2024
- 2024-07-23 CN CN202410992512.4A patent/CN118957371A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2087915B1 (en) | Implant with a base body made of a biocorrodible iron alloy | |
| KR102246887B1 (en) | Magnesium-aluminum-zinc alloy, method for the production thereof and use thereof | |
| RU2647951C2 (en) | Magnesium alloy, method for production thereof and use thereof | |
| CN108754232B (en) | A high-strength and high-plastic biodegradable Zn-Mn-Li series zinc alloy and use thereof | |
| CN101215655B (en) | Metastable beta type ti-nb-ta-zr-o alloy and preparation method thereof | |
| CN101921929B (en) | Medicinal oxygen-containing beta titanium alloy for orthopedic implantation and preparation method thereof | |
| KR20150032934A (en) | Magnesium-zinc-calcium alloy, method for production thereof, and use thereof | |
| JPH02107734A (en) | Titanium alloy having a high strength, a low elastic modulus, ductility and organism-compatibility | |
| JP2003293058A (en) | Biological superelastic titanium alloy | |
| CN113088652B (en) | Preparation method of dispersion-strengthened high-stability medical high-nitrogen nickel-free austenitic stainless steel | |
| CN101003873A (en) | Beta type Ti Nb Zr alloy with low modulus of elasticity, preparation method and application | |
| CN109602960B (en) | Preparation method of medical zinc alloy bar with superplasticity | |
| CN111020295A (en) | A high-performance biodegradable Zn-Cu-Li-X alloy and its preparation and application methods | |
| CN107190191B (en) | A kind of biological medical magnesium alloy and preparation method thereof | |
| CN110106413B (en) | Mg-Si-Ca-Zn magnesium alloy and its preparation method and application | |
| CN1490421A (en) | A kind of β-type titanium alloy for vascular stent | |
| CN115029584A (en) | Biodegradable medical zinc alloy and preparation method and application thereof | |
| CN101225489A (en) | Ti-Mo-Sn-Al series titanium alloy and preparation method thereof | |
| ZHANG | Achieving high strength and antibacterial Zn− 4Ag− Mn alloy with homogenous corrosion behavior via high-pressure solid solution | |
| CN111809090A (en) | A kind of medical degradable Mg-Pr series magnesium alloy and its preparation method and application | |
| CN116103539B (en) | High-strength low-modulus biomedical zirconium alloy and preparation method thereof | |
| CN118957371A (en) | A biomedical Mn alloy and its preparation method and application | |
| CN118256790A (en) | Medical high-strength and high-toughness tantalum-containing medium-entropy alloy and preparation method thereof | |
| KR100888679B1 (en) | Titanium alloy with excellent biocompatibility and biostability | |
| CN110042289A (en) | A kind of magnesium alloy containing Sr |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |