CN106377803B - A kind of Mg-Zn-Sr-Ca-Zr medical bone nail and preparation method thereof - Google Patents
A kind of Mg-Zn-Sr-Ca-Zr medical bone nail and preparation method thereof Download PDFInfo
- Publication number
- CN106377803B CN106377803B CN201610789317.7A CN201610789317A CN106377803B CN 106377803 B CN106377803 B CN 106377803B CN 201610789317 A CN201610789317 A CN 201610789317A CN 106377803 B CN106377803 B CN 106377803B
- Authority
- CN
- China
- Prior art keywords
- bone nail
- raw materials
- ball
- medical bone
- preparation
- 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.)
- Expired - Fee Related
Links
- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000005096 rolling process Methods 0.000 claims abstract description 22
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims description 40
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 238000000498 ball milling Methods 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- 229910000831 Steel Inorganic materials 0.000 claims description 10
- 239000010959 steel Substances 0.000 claims description 10
- 238000007731 hot pressing Methods 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 abstract description 23
- 238000005260 corrosion Methods 0.000 abstract description 23
- 229910000861 Mg alloy Inorganic materials 0.000 abstract description 18
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 7
- 238000004663 powder metallurgy Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000007943 implant Substances 0.000 description 6
- 238000005275 alloying Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229910003023 Mg-Al Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 230000035876 healing Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 101001108245 Cavia porcellus Neuronal pentraxin-2 Proteins 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002900 effect on cell Effects 0.000 description 1
- 235000020774 essential nutrients Nutrition 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 210000000963 osteoblast Anatomy 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- A61L31/16—Biologically active materials, e.g. therapeutic substances
-
- 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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0408—Light metal alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
-
- 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
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Vascular Medicine (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Heart & Thoracic Surgery (AREA)
- Surgery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Biomedical Technology (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
本发明涉及一种Mg‑Zn‑Sr‑Ca‑Zr医用骨钉及其制备方法，其组分含量为：Zn：2％～4％、Sr：1％～2％、Ca：0.5％～0.7％、Zr：0.3％～0.5％，其余为镁及其他不可去除杂质；此医用骨钉采用粉末冶金、搓丝工艺制备成型，包括螺钉头、六角扳拧和螺纹杆。本发明Mg‑Zn‑Sr‑Ca‑Zr医用骨钉减少了稀土元素的添加，并且使骨钉在保证要求的力学性能基础上，较原有镁合金有更加良好的生物相容性和耐腐蚀性能，且结构简单，制作方便。
The invention relates to a Mg-Zn-Sr-Ca-Zr medical bone nail and a preparation method thereof. The component contents are: Zn: 2%-4%, Sr: 1%-2%, Ca: 0.5%-0.7 %, Zr: 0.3% to 0.5%, the rest are magnesium and other irremovable impurities; this medical bone nail is prepared by powder metallurgy and wire rolling process, including screw head, hexagonal wrench and threaded rod. The Mg-Zn-Sr-Ca-Zr medical bone nail of the invention reduces the addition of rare earth elements, and on the basis of ensuring the required mechanical properties, the bone nail has better biocompatibility and corrosion resistance than the original magnesium alloy The utility model has the advantages of high performance, simple structure and convenient production.
Description
技术领域technical field
本发明涉及医用生物植入材料领域，具体涉及一种Mg-Zn-Sr-Ca-Zr医用骨钉及其制备方法。The invention relates to the field of medical biological implant materials, in particular to a Mg-Zn-Sr-Ca-Zr medical bone nail and a preparation method thereof.
背景技术Background technique
镁合金具有良好的力学性能和生物相容性及可生物降解的特性，作为可降解医用植入材料有着广泛的应用前景。然而，由于它们在生物环境下易被腐蚀，制约了它们作为医用植入材料的应用。近些年来国内外学者对降低镁合金的腐蚀速率进行了一系列的研究，其中包括合金化、热处理、表面处理等技术，其中合金化技术应用较为广泛。Magnesium alloys have good mechanical properties, biocompatibility and biodegradability, and have broad application prospects as degradable medical implant materials. However, their application as medical implant materials is restricted due to their easy corrosion in biological environment. In recent years, domestic and foreign scholars have carried out a series of researches on reducing the corrosion rate of magnesium alloys, including alloying, heat treatment, surface treatment and other technologies, among which alloying technology is widely used.
在各种合金元素中，Fe、Cu、Ni、Co等元素因其较低的固溶度限制，作为活跃的阴极将加快镁合金的腐蚀进程。目前，研究热点主要集中在工业上应用比较成熟的Mg-Al系和Mg-RE系镁合金。AM60、AM50、AM20和AZ91E都有较好的机械性能和耐腐蚀性能，但合金中的Al元素在体内吸收很慢，长期积累将对人体健康产生危害。稀土元素是改善镁合金机械性能和腐蚀性能的最有效的元素，但稀土元素在合金中的含量一般在1％～3％之间及3％以上，成本较高，且稀土元素容易在脑中富集，其人体健康特性还有待进一步研究。其中，专利申请号为201310105668.8的发明专利提出一种生物可降解Mg-Gd-Zn-Sr-Zr系镁合金及其制备方法，其合金组分设计为：Gd5～10％；Zn0.5～3％；Sr0.1～1；Zr0.1～1％；余量为Mg，该组分设计中含有重稀土元素Gd，且含量较高，其毒性作用不明确。研究发现低毒性的Mg-Mn-Zn合金对细胞生长无不良影响，细胞毒性评价为0级，但其耐蚀性较差。Among various alloying elements, Fe, Cu, Ni, Co and other elements are limited by their low solid solubility, and will accelerate the corrosion process of magnesium alloys as active cathodes. At present, research hotspots mainly focus on the relatively mature Mg-Al and Mg-RE magnesium alloys used in industry. AM60, AM50, AM20 and AZ91E have good mechanical properties and corrosion resistance, but the Al element in the alloy is absorbed very slowly in the body, and long-term accumulation will cause harm to human health. Rare earth elements are the most effective elements to improve the mechanical properties and corrosion properties of magnesium alloys, but the content of rare earth elements in the alloy is generally between 1% and 3% and above 3%, the cost is high, and rare earth elements are easy to be in the brain. enriched, and its human health properties remain to be further studied. Among them, the invention patent with the patent application number of 201310105668.8 proposes a biodegradable Mg-Gd-Zn-Sr-Zr magnesium alloy and its preparation method. The alloy components are designed as: Gd5～10%; Zn0.5～3 %; Sr0.1～1; Zr0.1～1%; the balance is Mg, the heavy rare earth element Gd is contained in the design of this component, and the content is high, and its toxic effect is not clear. The study found that the low toxicity Mg-Mn-Zn alloy had no adverse effect on cell growth, and the cytotoxicity was rated as 0, but its corrosion resistance was poor.
发明内容SUMMARY OF THE INVENTION
本发明针对上述技术的不足，提出一种具有良好的生物相容性，对人体健康完全无害并具有优异的综合机械性能及耐腐蚀性能的镁合金医用骨钉。Aiming at the deficiencies of the above technologies, the present invention proposes a magnesium alloy medical bone nail which has good biocompatibility, is completely harmless to human health, and has excellent comprehensive mechanical properties and corrosion resistance.
本发明的技术方案是：The technical scheme of the present invention is:
一种Mg-Zn-Sr-Ca-Zr医用骨钉，其特征是，由以下质量百分比的原料制成：A Mg-Zn-Sr-Ca-Zr medical bone nail is characterized in that, it is made from the following raw materials by mass percentage:
Zn：2％～4％、Sr：1％～2％、Ca：0.5％～0.7％、Zr：0.3％～0.5％，余量为镁及其他不可去除杂质。Zn: 2% to 4%, Sr: 1% to 2%, Ca: 0.5% to 0.7%, Zr: 0.3% to 0.5%, and the balance is magnesium and other impurities that cannot be removed.
优选的，由以下质量百分比的原料制成：Preferably, it is made from the following raw materials by mass percentage:
Zn：3％、Sr：1.5％、Ca：0.6％、Zr：0.4％，余量为镁及其他不可去除杂质。Zn: 3%, Sr: 1.5%, Ca: 0.6%, Zr: 0.4%, and the balance is magnesium and other irremovable impurities.
本发明还提供一种Mg-Zn-Sr-Ca-Zr医用骨钉，其特征是，所述医用骨钉结构包括螺钉头、六角扳拧和螺纹杆，所述所述螺纹杆设置于螺钉头上，所述六角扳拧凹陷设置于螺钉头远离螺钉杆的表面上。The present invention also provides a Mg-Zn-Sr-Ca-Zr medical bone nail, characterized in that the medical bone nail structure includes a screw head, a hexagonal wrench and a threaded rod, and the threaded rod is arranged on the screw head On the top, the hexagonal wrench recess is arranged on the surface of the screw head away from the screw rod.
本发明还提供了一种Mg-Zn-Sr-Ca-Zr医用骨钉的制备方法，其特征是，根据根据上述的质量百分比称取原料，然后采用粉末冶金、搓丝工艺制备成型。The present invention also provides a method for preparing a Mg-Zn-Sr-Ca-Zr medical bone nail, which is characterized in that the raw materials are weighed according to the above-mentioned mass percentage, and then prepared and formed by powder metallurgy and wire rolling.
优选的所述Mg-Zn-Sr-Ca-Zr医用骨钉的制备方法，包括以下步骤：The preferred preparation method of the Mg-Zn-Sr-Ca-Zr medical bone nail comprises the following steps:
①称取原料：根据上述的质量百分比称取原料；①Weigh the raw materials: Weigh the raw materials according to the above-mentioned mass percentage;
②粉末制备：将步骤①中称取的原料加入球磨罐中，通入保护气进行球磨；②Powder preparation: add the raw materials weighed in step ① into the ball mill tank, and pass the protective gas into the ball mill;
③成型：将球磨混合好的粉末导入压制磨具模腔内，冷压制得冷压预压坯，后将所述冷压预压坯与模具在真空下热压，得到真空热压坯；3. Forming: introduce the powder mixed by ball milling into the cavity of the pressing mold, and cold-press to obtain a cold-pressed preform, and then hot-press the cold-pressed preform and the mold under vacuum to obtain a vacuum hot-pressed blank;
④烧结：将步骤③得到的真空热压坯放入管式炉中，无氧条件下升温至600℃进行烧结，得到骨钉坯；④ Sintering: put the vacuum hot compact obtained in step ③ into a tube furnace, and heat up to 600° C. under anaerobic conditions for sintering to obtain a bone nail blank;
⑤热处理：将步骤④得到的骨钉坯进行T4热处理；⑤ Heat treatment: perform T4 heat treatment on the bone nail blank obtained in step ④;
⑥搓丝：选择合适的搓丝板，对步骤⑤得到的骨钉坯进行搓丝，制得医用骨钉。⑥ Thread rolling: Select a suitable rolling board, and perform thread rolling on the bone nail blank obtained in step ⑤ to obtain a medical bone nail.
上述制备方法，步骤②中，所述的保护气为现有技术中，球磨步骤所常规采用的保护气，包括但不限于氮气、氩气等等。In the above preparation method, in step (2), the protective gas is the protective gas conventionally used in the ball milling step in the prior art, including but not limited to nitrogen, argon and the like.
优选地，步骤②中，将原料加入球磨罐中时，原料与钢球的质量比为10:1，球磨时加入硬脂酸为控制剂，球磨时间为8-12h。Preferably, in step (2), when the raw materials are added to the ball milling tank, the mass ratio of the raw materials to the steel balls is 10:1, and stearic acid is added as a control agent during ball milling, and the ball milling time is 8-12h.
优选地，步骤③中，冷压压力为250-350MPa，例如250MPa、260MPa、270MPa、280MPa、290MPa、310MPa、330MPa、350MPa等；优选为300MPa。Preferably, in step ③, the cold pressing pressure is 250-350 MPa, such as 250 MPa, 260 MPa, 270 MPa, 280 MPa, 290 MPa, 310 MPa, 330 MPa, 350 MPa, etc.; preferably 300 MPa.
优选地，步骤⑤中所述T4热处理为：先将温度升到350℃保温2h，然后加热到420℃保温14h后随炉冷却。Preferably, the T4 heat treatment in step ⑤ is as follows: first, the temperature is raised to 350° C. for 2 hours, then heated to 420° C. for 14 hours, and then cooled with the furnace.
优选的，步骤②所述保护气为氩气。Preferably, the protective gas in step ② is argon.
更优选地，Mg-Zn-Sr-Ca-Zr医用骨钉的制备方法包括以下步骤：More preferably, the preparation method of Mg-Zn-Sr-Ca-Zr medical bone nail comprises the following steps:
①称取原料：根据上述的质量百分比称取原料；①Weigh the raw materials: Weigh the raw materials according to the above-mentioned mass percentage;
②粉末制备：将步骤①中称取的原料加入球磨罐中，按原料与钢球质量比为10:1的比例加入钢球，加入硬脂酸作为控制剂，密封球磨罐，通入氩气作为保护气，在行星式球磨机上对原料进行球磨混合，设置球磨罐转速为200r/min，球磨10h；②Powder preparation: add the raw materials weighed in step ① into the ball mill tank, add steel balls in a ratio of 10:1 by mass ratio of raw materials to steel balls, add stearic acid as a control agent, seal the ball mill tank, and pass argon gas As a protective gas, the raw materials are ball-milled and mixed on a planetary ball mill, the speed of the ball-milling tank is set to 200r/min, and the ball-milling is performed for 10h;
③成型：将球磨混合好的粉末导入压制磨具模腔内，选择冷压制压力为300MPa，保温时间为5min，冷压制得冷压预压坯；后将所述冷压预压坯与模具在真空且温度为350℃的条件下热压，保温5min，得到真空热压坯；③Molding: introduce the powder mixed by ball milling into the cavity of the pressing mold, select the cold pressing pressure of 300MPa, the holding time of 5min, and cold-press to obtain a cold-pressed preform; then the cold-pressed preform and the mold are placed in Under the condition of vacuum and temperature of 350 ℃, hot pressing, holding for 5 minutes, to obtain vacuum hot pressing;
④烧结：将步骤③得到的真空热压坯放入管式炉中，通氩气排出炉内氧气，90min从室温升温至600℃进行烧结，在烧结温度下保温1h，然后随炉冷却至室温，得到骨钉坯；④Sintering: put the vacuum hot compact obtained in step ③ into a tube furnace, pass argon gas to discharge oxygen in the furnace, raise the temperature from room temperature to 600 ℃ for 90 minutes for sintering, keep at the sintering temperature for 1 hour, and then cool to room temperature with the furnace , get the bone nail blank;
⑤热处理：将步骤④得到的骨钉坯进行T4热处理：先将温度升到350℃保温2h，然后加热到420℃保温14h后随炉冷却。⑤Heat treatment: The bone nail blank obtained in step ④ is subjected to T4 heat treatment: the temperature is first raised to 350°C for 2 hours, then heated to 420°C for 14 hours, and then cooled in the furnace.
⑥搓丝：选择合适的搓丝板，对步骤⑤得到的骨钉坯进行搓丝，制得医用骨钉。⑥ Thread rolling: Select a suitable rolling board, and perform thread rolling on the bone nail blank obtained in step ⑤ to obtain a medical bone nail.
本发明Mg-Zn-Sr-Ca-Zr医用骨钉中各种元素的作用如下：Zn、Ca是人体必需元素，Zn能促进细胞的更新，可以有效改善镁合金的力学性能和在一定程度上改善镁合金的耐蚀性能；Ca可以改善镁合金的力学性能，这两种合金元素随降解作为营养元素被人体吸收，不会产生负面影响，是镁合金生物材料的良好候选合金元素；Sr是人体所需元素，人体中的99％的Sr在骨骼中，能够促进成骨细胞的增长，Sr能细化镁合金晶粒，提高机械性能；Zr是一种强大的细晶元素，它与Zn元素添加到镁合金中，在T4热处理下可以显著提高合金的耐腐蚀性能。本发明通过粉末冶金法法制备的一种Mg-Zn-Sr-Ca-Zr医用骨钉，具有优异的致密度和良好的机械性能，该镁合金密度约1.83g/cm3，与人骨密度(1.75g/cm3)非常接近，弹性模量约为45GPa，能够有效消除植入物与人体骨骼之间产生的“应力屏蔽效应”，且经热处理后，该医用骨钉的室温抗拉强度能够达到180GPa，拉伸强度达到273GPa，能够满足植入物的力学相容性要求。该镁合金在腐蚀降解的过程中，不会产生任何对人体健康有潜在危险的元素，并且还会产生人体必需的营养元素。更加优异的是，该镁合金具有良好的耐腐蚀性能，使骨钉溶解速率与骨愈合速率相匹配，且腐蚀产物还能诱导骨的生长。The functions of various elements in the Mg-Zn-Sr-Ca-Zr medical bone nail of the present invention are as follows: Zn and Ca are essential elements of the human body, Zn can promote cell renewal, can effectively improve the mechanical properties of magnesium alloys and to a certain extent Improve the corrosion resistance of magnesium alloys; Ca can improve the mechanical properties of magnesium alloys. These two alloying elements are absorbed by the human body as nutrients with degradation without negative effects. They are good candidate alloying elements for magnesium alloy biomaterials; Sr is a Elements needed by the human body, 99% of Sr in the human body is in the bones, which can promote the growth of osteoblasts. Sr can refine magnesium alloy grains and improve mechanical properties; Zr is a powerful fine-grained element, which is closely related to Zn Elements added to magnesium alloys can significantly improve the corrosion resistance of alloys under T4 heat treatment. A Mg-Zn-Sr - Ca-Zr medical bone nail prepared by powder metallurgy method in the present invention has excellent density and good mechanical properties. 1.75g/cm 3 ) is very close, and the elastic modulus is about 45GPa, which can effectively eliminate the "stress shielding effect" between the implant and the human bone, and after heat treatment, the room temperature tensile strength of the medical bone nail can be It reaches 180GPa and the tensile strength reaches 273GPa, which can meet the mechanical compatibility requirements of implants. In the process of corrosion and degradation, the magnesium alloy does not produce any elements that are potentially dangerous to human health, and also produces essential nutrients for the human body. More excellently, the magnesium alloy has good corrosion resistance, so that the dissolution rate of the bone nail matches the bone healing rate, and the corrosion products can also induce bone growth.
本发明的有益效果在于：The beneficial effects of the present invention are:
(1)本发明的Mg-Zn-Sr-Ca-Zr医用骨钉具有良好的力学相容性且满足植入的力学要求，并且在腐蚀过程中，骨钉的腐蚀速率与骨的愈合速率相匹配，达到了植入物材料支撑的良好效果；(1) The Mg-Zn-Sr-Ca-Zr medical bone nail of the present invention has good mechanical compatibility and meets the mechanical requirements of implantation, and during the corrosion process, the corrosion rate of the bone nail is related to the healing rate of the bone Matching, to achieve a good effect of implant material support;
(2)本发明的Mg-Zn-Sr-Ca-Zr医用骨钉与现有的Mg-Al系镁合金相比，去除了对人体有害的Al元素，具有良好的生物相容性；(2) Compared with the existing Mg-Al series magnesium alloy, the Mg-Zn-Sr-Ca-Zr medical bone nail of the present invention has removed the Al element that is harmful to the human body, and has good biocompatibility;
(3)本发明的Mg-Zn-Sr-Ca-Zr医用骨钉与现有的Mg-RE系镁合金相比，保证稀土机械性能和腐蚀性能的前提下，减少稀土元素的使用，降低成本，且避免稀土元素对人体健康负面影响的风险性，同时保证了骨钉。(3) Compared with the existing Mg-RE series magnesium alloy, the Mg-Zn-Sr-Ca-Zr medical bone nail of the present invention reduces the use of rare earth elements and reduces the cost under the premise of ensuring the mechanical properties and corrosion properties of rare earths , and avoid the risk of the negative impact of rare earth elements on human health, while ensuring the bone nail.
(4)本发明的Mg-Zn-Sr-Ca-Zr医用骨钉添加Sr元素、Ca元素、Zr元素，Sr元素不仅是人体必需元素，且能刺激新骨形成且无毒副作用，Ca、Zr元素的添加将显著提高合金的耐腐蚀性能，提高了骨钉的应用性。(4) The Mg-Zn-Sr-Ca-Zr medical bone nail of the present invention adds Sr element, Ca element, and Zr element. Sr element is not only an essential element of the human body, but also can stimulate the formation of new bone without toxic and side effects. Ca, Zr The addition of elements will significantly improve the corrosion resistance of the alloy and improve the applicability of bone nails.
附图说明Description of drawings
附图1为本发明实施例中粉末冶金成型骨钉示意图；Accompanying drawing 1 is the schematic diagram of powder metallurgy forming bone nail in the embodiment of the present invention;
附图2为本发明实施例中骨钉搓丝成型后示意图；Accompanying drawing 2 is the schematic diagram after the bone nail rolling thread is formed in the embodiment of the present invention;
其中，1为螺钉头，2为六角扳拧，3为螺纹杆。Among them, 1 is the screw head, 2 is the hexagonal wrench, and 3 is the threaded rod.
具体实施方式Detailed ways
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例，实施例不应视作对本发明保护范围的限定。In order to better understand the present invention, the content of the present invention is further illustrated below in conjunction with the examples, but the content of the present invention is not limited to the following examples, and the examples should not be regarded as limiting the protection scope of the present invention.
一种Mg-Zn-Sr-Ca-Zr医用骨钉，由以下质量百分比的原料制成：A Mg-Zn-Sr-Ca-Zr medical bone nail is made from the following raw materials by mass percentage:
Zn：2％～4％、Sr：1％～2％、Ca：0.5％～0.7％、Zr：0.3％～0.5％，余量为镁及其他不可去除杂质。优选的，由以下质量百分比的原料制成：Zn：3％、Sr：1.5％、Ca：0.6％、Zr：0.4％，余量为镁及其他不可去除杂质。Zn: 2% to 4%, Sr: 1% to 2%, Ca: 0.5% to 0.7%, Zr: 0.3% to 0.5%, and the balance is magnesium and other impurities that cannot be removed. Preferably, it is made from the following raw materials by mass percentage: Zn: 3%, Sr: 1.5%, Ca: 0.6%, Zr: 0.4%, and the balance is magnesium and other irremovable impurities.
本发明还提供一种Mg-Zn-Sr-Ca-Zr医用骨钉，所述医用骨钉结构包括螺钉头、六角扳拧和螺纹杆。The present invention also provides a Mg-Zn-Sr-Ca-Zr medical bone nail. The medical bone nail structure includes a screw head, a hexagonal wrench and a threaded rod.
本发明还提供了一种Mg-Zn-Sr-Ca-Zr医用骨钉的制备方法，根据根据上述的质量百分比称取原料，然后采用粉末冶金、搓丝工艺制备成型。The present invention also provides a method for preparing a Mg-Zn-Sr-Ca-Zr medical bone nail. The raw materials are weighed according to the above-mentioned mass percentage, and then prepared and formed by powder metallurgy and wire rolling.
优选的所述Mg-Zn-Sr-Ca-Zr医用骨钉的制备方法，包括以下步骤：The preferred preparation method of the Mg-Zn-Sr-Ca-Zr medical bone nail comprises the following steps:
①称取原料：根据上述的质量百分比称取原料；①Weigh the raw materials: Weigh the raw materials according to the above-mentioned mass percentage;
②粉末制备：将步骤①中称取的原料加入球磨罐中，通入保护气进行球磨；原料通过球磨混合；②Powder preparation: add the raw materials weighed in step ① into the ball mill tank, and pass in protective gas for ball milling; the raw materials are mixed by ball milling;
③成型：将球磨混合好的粉末导入压制磨具模腔内，冷压制得冷压预压坯，后将所述冷压预压坯与模具在真空下热压，得到真空热压坯；3. Forming: introduce the powder mixed by ball milling into the cavity of the pressing mold, and cold-press to obtain a cold-pressed preform, and then hot-press the cold-pressed preform and the mold under vacuum to obtain a vacuum hot-pressed blank;
④烧结：将步骤③得到的真空热压坯放入管式炉中，无氧条件下升温至600℃进行烧结，得到骨钉坯；④ Sintering: put the vacuum hot compact obtained in step ③ into a tube furnace, and heat up to 600° C. under anaerobic conditions for sintering to obtain a bone nail blank;
⑤热处理：将步骤④得到的骨钉坯进行T4热处理；⑤ Heat treatment: perform T4 heat treatment on the bone nail blank obtained in step ④;
⑥搓丝：选择合适的搓丝板，对步骤⑤得到的骨钉坯进行搓丝，制得医用骨钉。⑥ Thread rolling: Select a suitable rolling board, and perform thread rolling on the bone nail blank obtained in step ⑤ to obtain a medical bone nail.
上述制备方法，步骤②中，所述的保护气为现有技术中，球磨步骤所常规采用的保护气，包括但不限于氮气、氩气等等。作为优选的，步骤②所述保护气为氩气。In the above preparation method, in step (2), the protective gas is the protective gas conventionally used in the ball milling step in the prior art, including but not limited to nitrogen, argon and the like. Preferably, the protective gas in step ② is argon.
优选地，步骤②中，将原料加入球磨罐中时，原料与钢球的质量比为10:1，球磨时加入硬脂酸为控制剂，球磨时间为8-12h。Preferably, in step (2), when the raw materials are added to the ball milling tank, the mass ratio of the raw materials to the steel balls is 10:1, and stearic acid is added as a control agent during ball milling, and the ball milling time is 8-12h.
优选地，步骤③中，冷压压力为250-350MPa；优选为300MPa。Preferably, in step ③, the cold pressing pressure is 250-350 MPa; preferably 300 MPa.
优选地，步骤⑤中所述T4热处理为：先将温度升到350℃保温2h，然后加热到420℃保温14h后随炉冷却。Preferably, the T4 heat treatment in step ⑤ is as follows: first, the temperature is raised to 350° C. for 2 hours, then heated to 420° C. for 14 hours, and then cooled with the furnace.
更优选地，Mg-Zn-Sr-Ca-Zr医用骨钉的制备方法包括以下步骤：More preferably, the preparation method of Mg-Zn-Sr-Ca-Zr medical bone nail comprises the following steps:
①称取原料：根据上述的质量百分比称取原料；①Weigh the raw materials: Weigh the raw materials according to the above-mentioned mass percentage;
②粉末制备：将步骤①中称取的原料加入球磨罐中，按原料与钢球质量比为10:1的比例加入钢球，加入硬脂酸作为控制剂，密封球磨罐，通入氩气作为保护气，在行星式球磨机上对原料进行球磨混合，设置球磨罐转速为200r/min，球磨10h；②Powder preparation: add the raw materials weighed in step ① into the ball mill tank, add steel balls in a ratio of 10:1 by mass ratio of raw materials to steel balls, add stearic acid as a control agent, seal the ball mill tank, and pass argon gas As a protective gas, the raw materials are ball-milled and mixed on a planetary ball mill, the speed of the ball-milling tank is set to 200r/min, and the ball-milling is performed for 10h;
③成型：将球磨混合好的粉末导入压制磨具模腔内，选择冷压制压力为300MPa，保温时间为5min，冷压制得冷压预压坯；后将所述冷压预压坯与模具在真空且温度为350℃的条件下热压，保温5min，得到真空热压坯；③Molding: introduce the powder mixed by ball milling into the cavity of the pressing mold, select the cold pressing pressure of 300MPa, the holding time of 5min, and cold-press to obtain a cold-pressed preform; then the cold-pressed preform and the mold are placed in Under the condition of vacuum and temperature of 350 ℃, hot pressing, holding for 5 minutes, to obtain vacuum hot pressing;
④烧结：将步骤③得到的真空热压坯放入管式炉中，通氩气排出炉内氧气，90min从室温升温至600℃进行烧结，在烧结温度下保温1h，然后随炉冷却至室温，得到骨钉坯；④Sintering: put the vacuum hot compact obtained in step ③ into a tube furnace, pass argon gas to discharge oxygen in the furnace, raise the temperature from room temperature to 600 ℃ for 90 minutes for sintering, keep at the sintering temperature for 1 hour, and then cool to room temperature with the furnace , get the bone nail blank;
⑤热处理：将步骤④得到的骨钉坯进行T4热处理：先将温度升到350℃保温2h，然后加热到420℃保温14h后随炉冷却。⑤Heat treatment: The bone nail blank obtained in step ④ is subjected to T4 heat treatment: the temperature is first raised to 350°C for 2 hours, then heated to 420°C for 14 hours, and then cooled in the furnace.
⑥搓丝：选择合适的搓丝板，对步骤⑤得到的骨钉坯进行搓丝，制得医用骨钉。⑥ Thread rolling: Select a suitable rolling board, and perform thread rolling on the bone nail blank obtained in step ⑤ to obtain a medical bone nail.
下面结合具体实施例对本发明进行说明，但本发明不仅限于这些例子。The present invention will be described below with reference to specific embodiments, but the present invention is not limited to these examples.
实施例1Example 1
一种Mg-Zn-Sr-Ca-Zr医用骨钉，由以下质量百分比的原料制成：A Mg-Zn-Sr-Ca-Zr medical bone nail is made from the following raw materials by mass percentage:
Zn：3％、Sr：1.5％、Ca：0.6％、Zr：0.4％，余量为镁及其他不可去除杂质。Zn: 3%, Sr: 1.5%, Ca: 0.6%, Zr: 0.4%, and the balance is magnesium and other irremovable impurities.
本实施例中，Mg-Zn-Sr-Ca-Zr医用骨钉的制备方法包括以下步骤：In this embodiment, the preparation method of the Mg-Zn-Sr-Ca-Zr medical bone nail includes the following steps:
①称取原料：根据上述的质量百分比称取原料；①Weigh the raw materials: Weigh the raw materials according to the above-mentioned mass percentage;
②粉末制备：将步骤①中称取的原料加入球磨罐中，按原料与钢球质量比为10:1的比例加入钢球，加入硬脂酸作为控制剂，密封球磨罐，通入氩气作为保护气，在行星式球磨机上对原料进行球磨混合，设置球磨罐转速为200r/min，球磨10h；②Powder preparation: add the raw materials weighed in step ① into the ball mill tank, add steel balls in a ratio of 10:1 by mass ratio of raw materials to steel balls, add stearic acid as a control agent, seal the ball mill tank, and pass argon gas As a protective gas, the raw materials are ball-milled and mixed on a planetary ball mill, the speed of the ball-milling tank is set to 200r/min, and the ball-milling is performed for 10h;
③成型：将球磨混合好的粉末导入压制磨具模腔内，选择冷压制压力为300MPa，保温时间为5min，冷压制得冷压预压坯；后将所述冷压预压坯与模具在真空且温度为350℃的条件下热压，保温5min，得到真空热压坯；③Molding: introduce the powder mixed by ball milling into the cavity of the pressing mold, select the cold pressing pressure of 300MPa, the holding time of 5min, and cold-press to obtain a cold-pressed preform; then the cold-pressed preform and the mold are placed in Under the condition of vacuum and temperature of 350 ℃, hot pressing, holding for 5 minutes, to obtain vacuum hot pressing;
④烧结：将步骤③得到的真空热压坯放入管式炉中，通氩气排出炉内氧气，90min从室温升温至600℃进行烧结，在烧结温度下保温1h，然后随炉冷却至室温，得到骨钉坯；结构如图1所示。④Sintering: put the vacuum hot compact obtained in step ③ into a tube furnace, pass argon gas to discharge oxygen in the furnace, raise the temperature from room temperature to 600 ℃ for 90 minutes for sintering, keep at the sintering temperature for 1 hour, and then cool to room temperature with the furnace , to obtain a bone nail blank; the structure is shown in Figure 1.
⑤热处理：将步骤④得到的骨钉坯进行T4热处理：先将温度升到350℃保温2h，然后加热到420℃保温14h后随炉冷却。⑤Heat treatment: The bone nail blank obtained in step ④ is subjected to T4 heat treatment: the temperature is first raised to 350°C for 2 hours, then heated to 420°C for 14 hours, and then cooled in the furnace.
⑥搓丝：选择合适的搓丝板，对步骤⑤得到的骨钉坯进行搓丝，制得医用骨钉；结构如图2所示。⑥ Thread rolling: Select a suitable rolling plate, and perform thread rolling on the bone nail blank obtained in step ⑤ to obtain a medical bone nail; the structure is shown in Figure 2.
实施例2Example 2
一种Mg-Zn-Sr-Ca-Zr医用骨钉，由以下质量百分比的原料制成：A Mg-Zn-Sr-Ca-Zr medical bone nail is made from the following raw materials by mass percentage:
Zn：2％、Sr：1％、Ca：0.5％、Zr：0.5％，余量为镁及其他不可去除杂质。Zn: 2%, Sr: 1%, Ca: 0.5%, Zr: 0.5%, and the balance is magnesium and other irremovable impurities.
制备方法同实施例1。The preparation method is the same as in Example 1.
实施例3Example 3
一种Mg-Zn-Sr-Ca-Zr医用骨钉，由以下质量百分比的原料制成：A Mg-Zn-Sr-Ca-Zr medical bone nail is made from the following raw materials by mass percentage:
Zn：4％、Sr：2％、Ca：0.7％、Zr：0.3％，余量为镁及其他不可去除杂质。Zn: 4%, Sr: 2%, Ca: 0.7%, Zr: 0.3%, and the balance is magnesium and other irremovable impurities.
制备方法同实施例1。The preparation method is the same as in Example 1.
具体见下表1。See Table 1 below for details.
表1实施例所用合金的成分(质量百分含量wt％)The composition of the alloy used in the embodiment of Table 1 (mass percentage wt%)
对以上实施例1-3中制得的骨钉进行耐腐蚀性能测试：根据国标GB/T10125-1997对上述制成的实施例1、实施例2、实施例3的医用骨钉进行标准中性盐雾试验，得出性能数据见表2。Corrosion resistance test was carried out on the bone nails prepared in the above Examples 1-3: according to the national standard GB/T10125-1997, the medical bone nails of Example 1, Example 2 and Example 3 prepared above were subjected to standard neutrality The performance data obtained from the salt spray test are shown in Table 2.
表2实施例1-3中的医用骨钉的耐腐蚀性能Corrosion resistance of medical bone nails in Table 2 Examples 1-3
由表2可以看出，当合金成分按照本发明配比且在本发明所规定的范围内时，医用骨钉具有较好的耐腐蚀性能，其中，Mg-2％Zn-1％Sr-0.5％Ca-0.5％Zr医用骨钉的耐腐蚀性能最好。It can be seen from Table 2 that when the alloy components are proportioned according to the present invention and within the range specified by the present invention, the medical bone nail has better corrosion resistance, wherein Mg-2%Zn-1%Sr-0.5 %Ca-0.5%Zr medical bone nails have the best corrosion resistance.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610789317.7A CN106377803B (en) | 2016-08-31 | 2016-08-31 | A kind of Mg-Zn-Sr-Ca-Zr medical bone nail and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610789317.7A CN106377803B (en) | 2016-08-31 | 2016-08-31 | A kind of Mg-Zn-Sr-Ca-Zr medical bone nail and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106377803A CN106377803A (en) | 2017-02-08 |
| CN106377803B true CN106377803B (en) | 2019-09-03 |
Family
ID=57937796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610789317.7A Expired - Fee Related CN106377803B (en) | 2016-08-31 | 2016-08-31 | A kind of Mg-Zn-Sr-Ca-Zr medical bone nail and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106377803B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107447122A (en) * | 2017-08-04 | 2017-12-08 | 江苏中科亚美新材料有限公司 | The preparation method of magnesium alloy |
| CN113263298A (en) * | 2021-06-09 | 2021-08-17 | 苏州英德力电子科技有限公司 | Processing technology of high-strength bolt for steel mesh frame bolt ball joint |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102552973A (en) * | 2012-02-17 | 2012-07-11 | 浙江海圣医疗器械有限公司 | Medical degradable and absorbable Mg-Sr-Ca series magnesium alloy implant and preparation method thereof |
| CN103180473A (en) * | 2010-10-12 | 2013-06-26 | 住友电气工业株式会社 | Threads, bolts, nuts and washers made of magnesium alloy |
| CN103725942A (en) * | 2013-12-31 | 2014-04-16 | 重庆大学 | Mg-Zn-Sr-Ca system magnesium alloy and preparation method thereof |
| CN104630587A (en) * | 2015-02-28 | 2015-05-20 | 天津理工大学 | Degradable magnesium alloy plate and bar for fracture internal fixation and preparation methods thereof |
| CN105087980A (en) * | 2015-09-06 | 2015-11-25 | 天津理工大学 | Method for preparing hemostatic clips through surface-passivated degradable magnesium alloy |
-
2016
- 2016-08-31 CN CN201610789317.7A patent/CN106377803B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103180473A (en) * | 2010-10-12 | 2013-06-26 | 住友电气工业株式会社 | Threads, bolts, nuts and washers made of magnesium alloy |
| CN102552973A (en) * | 2012-02-17 | 2012-07-11 | 浙江海圣医疗器械有限公司 | Medical degradable and absorbable Mg-Sr-Ca series magnesium alloy implant and preparation method thereof |
| CN103725942A (en) * | 2013-12-31 | 2014-04-16 | 重庆大学 | Mg-Zn-Sr-Ca system magnesium alloy and preparation method thereof |
| CN104630587A (en) * | 2015-02-28 | 2015-05-20 | 天津理工大学 | Degradable magnesium alloy plate and bar for fracture internal fixation and preparation methods thereof |
| CN105087980A (en) * | 2015-09-06 | 2015-11-25 | 天津理工大学 | Method for preparing hemostatic clips through surface-passivated degradable magnesium alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106377803A (en) | 2017-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108754232B (en) | A high-strength and high-plastic biodegradable Zn-Mn-Li series zinc alloy and use thereof | |
| KR102253200B1 (en) | Magnesium alloy with adjustable degradation rate | |
| CN109680195B (en) | A kind of Mg-RE series magnesium alloy and its preparation method and application | |
| AU2020102567A4 (en) | A high plasticity degradable LiZn4-X intermetallic compound and its preparation method | |
| CN103184379B (en) | Biodegradable Mg-Gd-Zn-Ag-Zr series magnesium alloy and preparation method thereof | |
| CN105349858B (en) | The bone fixation magnesium alloy implant material of degradable and preparation method | |
| CN105986146B (en) | A kind of degradable medical is metal material embedded and preparation method thereof | |
| WO2011160533A1 (en) | Magnesium alloy used for degradable implant material of bone in vivo and preparation method thereof | |
| CN103014465B (en) | A uniformly degradable magnesium alloy material for orthopedic implants | |
| CN103184380B (en) | Biodegradable Mg-Gd-Zn-Sr-Zr series magnesium alloy and preparation method thereof | |
| CN101015711A (en) | Medical implantation material capable of by degraded by body fluid and its preparing process | |
| CN109439986B (en) | A magnesium alloy with high medical performance | |
| CN104342583A (en) | Ti-Ta alloy as well as preparation method and application thereof | |
| CN103343273B (en) | biomedical degradable corrosion-resistant Mg-Zn-Zr alloy and preparation method | |
| CN115029584B (en) | A kind of biodegradable medical zinc alloy and its preparation method and application | |
| CN110317973B (en) | Biodegradable LiZn4-Zn complex phase material and preparation method thereof | |
| CN105925848A (en) | Biomedical degradable zinc alloy inner implantation material and preparation method of sheet material of biomedical degradable zinc alloy inner implantation material | |
| CN106377803B (en) | A kind of Mg-Zn-Sr-Ca-Zr medical bone nail and preparation method thereof | |
| CN103882274B (en) | Biological medical degradable Mg-Zn-Zr-Sc Alloy And Preparation Method | |
| CN110106413B (en) | Mg-Si-Ca-Zn magnesium alloy and its preparation method and application | |
| CN111331128A (en) | Method for preparing zinc alloy degradable material by sintering metal powder | |
| CN104694848B (en) | A kind of biodegradable quaternary ferrous alloy material and preparation method thereof | |
| CN108165782B (en) | A kind of medical zinc-based alloy strip and preparation method thereof | |
| CN106180193B (en) | A kind of rolling processing method of medical beta titanium alloy light sheet | |
| CN108330367B (en) | Absorbable orthopedic implant magnesium alloy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190903 Termination date: 20210831 |