WO2015139355A1 - 一种人体可吸收的耐蚀高强韧锌镁合金植入材料 - Google Patents

一种人体可吸收的耐蚀高强韧锌镁合金植入材料 Download PDF

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WO2015139355A1
WO2015139355A1 PCT/CN2014/076275 CN2014076275W WO2015139355A1 WO 2015139355 A1 WO2015139355 A1 WO 2015139355A1 CN 2014076275 W CN2014076275 W CN 2014076275W WO 2015139355 A1 WO2015139355 A1 WO 2015139355A1
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human body
absorbable
implant material
magnesium alloy
alloy
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PCT/CN2014/076275
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French (fr)
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周功耀
屈功奇
宫海波
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西安爱德万思医疗科技有限公司
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Priority to US15/126,728 priority Critical patent/US20170035942A1/en
Publication of WO2015139355A1 publication Critical patent/WO2015139355A1/zh

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    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/58—Materials at least partially resorbable by the body
    • 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
    • A61L31/148—Materials at least partially resorbable by the body
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc

Definitions

  • the invention relates to a corrosion-resistant high-strength tough zinc-magnesium alloy implant material which can be completely degraded, and belongs to the technical field of medical materials.
  • An vascular stent is an implantable mesh-like instrument for the treatment of vascular diseases such as coronary heart disease, with a length of about 8 to 23 mm and a diameter of about 2.5. ⁇ 5 mm.
  • Current mainstream drug-eluting stents Drug Eluting Stent, DES
  • the expandable cobalt-chromium mesh provides mechanical support for the stenotic vessels, and the drug coating on the surface of the stent can release the drug continuously for about one month, inhibiting the growth of smooth muscle and lymphocytes, and reducing the inflammatory response and immune response.
  • Chinese patients have not understood the stent product because the incidence of coronary heart disease in China has been extremely low in the past.
  • Conventional vascular stents are generally made of non-absorbable metal.
  • the preparation technique of the stent is divided into two steps. First, the metal ingot is prepared into a tube by extrusion molding, and then the tube is precisely processed into a mesh stent by laser cutting technology.
  • the disadvantage is that the metal is not degradable and cannot be taken out, and it is easy to cause late thrombus in the blood vessel.
  • the laser cutting technique has low efficiency and high cost.
  • a large number of clinical cases have proven that traditional stents are very effective in reducing the rate of stenosis reconstruction, but patients are implanted with such stents.
  • the clinically frequent late thrombosis problem is the technical bottleneck that traditional stents are difficult to break through.
  • the fundamental reason is that The material used in the DES stent cannot be absorbed by the body and can only remain permanently in the blood vessels of the lesion.
  • the diseased blood vessels only need 1 to 3 months of mechanical support to reconstruct the vascular function, 3 After a month, the blood vessels have basically recovered their functions, and the stents that are retained in the blood vessels may cause numerous side effects to the patient.
  • bone nails and bone plates are commonly used medical implants for fixation of fractures and ligament injuries.
  • the fractures near the joints and extending into the joints are especially fixed with bone nails and bone plates.
  • the ageing of contemporary society is severe, and patients with osteoporosis are increasing year by year.
  • Accidents such as car accidents or falls often cause comminuted fractures.
  • Athletes may also have fractures or ligament tears during intense confrontational activities.
  • magnesium alloy is the most in-depth research material in recent years. The material can be safely absorbed by the human body, its strength and toughness are much higher than that of the polymer, and the elastic modulus is closer to human bone.
  • magnesium alloys have very poor corrosion resistance and are quickly degraded and absorbed in the human body, failing to provide sufficient mechanical support time (service period).
  • the present invention provides a zinc-magnesium alloy implant material that can be absorbed and degraded by the human body, and can be used to make an absorbable medical implant, particularly a blood vessel stent, a bone nail or a bone plate.
  • the corrosion-resistant high-strength tough zinc-magnesium alloy implant material of the invention can realize three technical indexes: the human body can be safely absorbed, the appropriate mechanical strength and sufficient mechanical support time.
  • the absorbable stent made of the alloy material of the invention can effectively restore the normal function of the blood vessel while effectively treating the coronary heart disease, which is impossible for the conventional metal stent.
  • the blood vessels of patients treated with absorbable stents may eventually have the ability to move, flex and beat, just like untreated blood vessels.
  • the absorbable bone nail and the bone plate made of the alloy material of the invention can match the regenerative healing of the bone tissue, and the mechanical strength matches the human bone tissue, no stress shielding occurs, and no fracture accident occurs.
  • the human body absorbable corrosion-resistant high-strength tough zinc-magnesium alloy implant material has a composition and a weight percentage of: Zn 96 ⁇ 99.998 wt%, Mg 0.002 to 4 wt%.
  • the present invention strictly controls the content of impurities such as Fe, Al, Mn: Zn
  • impurities such as Fe, Al, Mn: Zn
  • the purity is greater than or equal to 99.95%, preferably greater than or equal to 99.999%; the purity of Mg is greater than or equal to 99.9%, preferably greater than or equal to 99.99%; except for Zn, Mg
  • the total amount of inclusion elements other than is not more than 0.5%, preferably not more than 0.01%.
  • the alloy material prepared by the present invention described above can be prepared into an absorbable medical implant using methods conventional in the art.
  • the absorbable medical implant is preferably a vascular stent and an orthopedic implant (such as a nail or a bone plate).
  • Corrosion resistance is much higher than that of magnesium alloy, and the degradation rate is greatly reduced, which can provide longer mechanical support and avoid premature failure of implants such as vascular stents and bone nails.
  • the alloy material obtained has a zinc content of 99.5 wt% and a magnesium content of 0.5 wt%.
  • the other steps are the same as in the first embodiment.
  • the alloy material obtained was zinc-containing 98 wt% and magnesium 2 wt%.
  • the other steps are the same as in the first embodiment.
  • the body fluid immersion test was simulated by the alloy materials prepared in Examples 1 to 3.
  • the in vitro degradation mechanism and degradation performance of zinc-magnesium alloy were studied according to the ASTM-G31-72 standard test method.
  • the 37-degree Celsius simulated human body fluid simulates the human body fluid environment.
  • the degradation rate of zinc-magnesium alloy is slow and controllable.
  • Simulated human body fluid immersion test proves that the degradation rate of zinc-magnesium alloy is much lower than that of pure magnesium and magnesium alloy. WE43.
  • the surface of the zinc-magnesium alloy forms a low-solubility protective layer, so the degradation rate is much lower than that of the magnesium alloy, and the minimum is only 0.14 mm / year, which can ensure that the vascular stent provides the blood vessel for the lesion. More than a month of radial support, fixation and bone plate mechanical support time of at least half a year.
  • the slow, uniform degradation process allows the blood vessels to gradually regenerate and eventually regain expansion and pulsation, just like healthy blood vessels.
  • This embodiment is based on ASTM-E8-04
  • the tensile strength of the zinc-magnesium alloy bar was evaluated by the test standard. It was found that the elastic modulus of the zinc-magnesium alloy is about 80 GPa, the tensile strength is at least 220 MPa, and the highest is 340 MPa. . The highest strength zinc-magnesium alloy has an elongation of 11%, and the lowest strength zinc-magnesium alloy has an elongation of 29%. That is to say, the strength of zinc-magnesium alloy is inversely proportional to the toughness. This shows that the strength and toughness of zinc-magnesium alloy can be adjusted to meet the requirements of different stent patterns and orthopedic implant structure design. The study found that the elastic modulus of human cortical bone is 3 ⁇ 20GPa, the yield strength is 35 ⁇ 280MPa, the alloy prepared by the invention has very good matching with the mechanical properties of the human cortical bone.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Public Health (AREA)
  • Epidemiology (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Transplantation (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Surgery (AREA)
  • Dermatology (AREA)
  • Vascular Medicine (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Prostheses (AREA)

Abstract

一种人体可吸收的耐蚀高强韧锌镁合金植入材料，所述合金植入材料包括：Zn 96-99.98wt%，Mg 0.002-4wt%。该合金植入材料应用于可吸收的医疗植入体，特别是血管支架、骨科植入体。该合金植入材料可在人体环境下吸收，避免二次手术给患者带来的痛苦，且耐蚀性远高于镁合金，可同时实现高耐蚀性和高强韧这两个指标。

Description

一种人体可吸收的耐蚀高强韧锌镁合金植入材料 技术领域
本发明涉及一种可完全降解的耐蚀高强韧锌镁合金植入材料，属于医用材料技术领域。
背景技术
血管支架是用于治疗冠心病等血管性疾病的植入式丝网状器械，长度约为 8 ～ 23 毫米 ，直径约为 2.5 ～ 5 毫米 。目前主流的药物洗脱支架（ Drug Eluting Stent, DES ）由可扩张的钴铬合金丝网为狭窄病灶血管提供机械支撑，支架表面的药物涂层可在约一个月内持续释放药物，抑制平滑肌和淋巴细胞生长，降低炎症反应和免疫反应。长期以来 , 我国病人一直不了解支架这一产品 , 因为过去我国的冠心病发病率极低。随着国民收入的逐年上升和人民生活水平的改善及饮食结构的变化 , 近年冠心病在我国上升势头较快，男性增加了 42.2% ，女性增加了 12.5% ，而且趋于年轻化。据国外医学界报道，冠心病发展到一定程度就必须安装血管支架 , 以此预防发生心肌梗死。进入 21 世纪后 , 随着国产支架的问世 , 国内做血管支架植入手术的病人数量剧增，极个别症状严重的冠心病人 , 其血管中竟先后植入 7 ～ 8 个支架。据来自北京阜外医院的一位心血管病专家说 , 过去几年来 , 我国每年死于冠心病急性发作的病人总数超过 100 万人，这些人如若及早安装血管支架 , 至少可降低 50% 的死亡率，由此可见，全面推广应用血管支架迫在眉睫。
传统的血管支架一般采用不可吸收的金属制成，支架的制备技术分为两步，首先是通过挤出成型将金属铸块制备成管材，然后利用激光切割技术将管材精确加工成网状支架。其缺点是金属不可降解、无法取出，滞留在血管内容易引发晚期血栓，另外激光切割技术效率较低，成本较高。大量的临床病例证实传统支架在降低狭窄重建率方面十分有效，但病人植入这类支架 1 ～ 5 年后血栓形成率高达 3% ～ 9% ，血栓形成后死亡率高达 30% 。临床频繁出现的晚期血栓问题正是传统支架难以突破的技术瓶颈，其根本原因在于 DES 支架使用的材料不能被人体降解吸收，只能永久性留在病灶血管。而病灶血管仅需要 1 ～ 3 个月的机械支撑来重建血管机能， 3 个月后血管已基本恢复其机能，滞留在血管内的支架反而可能会给病人带来众多副作用。
同时，骨钉和骨板是常用的固定骨折和韧带损伤的医疗植入体，靠近关节和延伸至关节内的骨折尤其常用骨钉和骨板进行固定。当代社会老龄化严重，骨质疏松患者逐年增加，车祸或跌倒等意外经常会造成粉碎性骨折。运动员在激烈的对抗性活动中，也有可能发生骨折或者韧带撕裂的状况。
类似血管支架的问题同样出现在传统骨钉和骨板行业，不可降解的金属无法取出，必须进行二次手术，对患者带来极大的创伤。同时，传统金属骨钉和骨板强度过高，容易带来应力屏蔽，导致受伤的骨组织难以再生和愈合。传统多聚物可吸收骨钉和骨板则强度过低，在临床使用过程中经常会发生断裂事故。
正是因为传统医用植入材料的各种问题，人体内可吸收医用材料正在成为上述领域（血管内支架、骨科植入物）研究和开发的重点。其中，镁合金是近年研究最为深入的材料，该材料可被人体安全吸收，强度和韧性远高于多聚物，且弹性模量更接近人骨。但是，镁合金耐蚀性非常差，在人体内很快就会被降解、吸收，无法提供足够的力学支撑时间（服役期）。
 技术问题
针对上述问题，本发明提供了一种可被人体吸收降解的锌镁合金植入材料，并可利用该材料制成可吸收性的医疗植入体，特别是血管支架、骨钉或骨板。 本发明的耐蚀高强韧锌镁合金植入材料可以实现三个技术指标分别是：人体可安全吸收、适当的机械强度和足够的力学支撑时间。采用本发明合金材料制成的可吸收支架，在有效治疗冠心病的同时，让血管恢复正常功能的可能，这是传统金属支架不可能做得到的。由于没有永久金属植入物留在体内，经可吸收支架治疗的患者的血管可能最终有能力运动，伸缩和搏动，如同未进行过治疗的血管一样。而采用本发明合金材料制成的可吸收骨钉和骨板能够匹配骨组织的再生愈合，其力学强度与人体骨组织匹配，不会产生应力屏蔽，也不会发生断裂事故。
技术解决方案
本发明技术方案所述的人体可吸收的耐蚀高强韧锌镁合金植入材料，其组分及重量百分比为： Zn 96 ～ 99.998wt%, Mg 0.002 ～ 4wt% 。
基于以上合金材料的组成，为了优化力学性能和生物腐蚀性能，我们对合金材料进一步优化为： Zn 97 ～ 99.995wt%, Mg 0.005 ～ 3wt% 。
为获得最佳的力学性能和生物腐蚀性能，本发明严格控制 Fe 、 Al 、 Mn 等杂质的含量： Zn 的纯净度大于等于 99.95% ，优选为大于等于 99.999% ； Mg 的纯净度大于等于 99.9% ，优选为大于等于 99.99% ；除 Zn 、 Mg 以外的夹杂元素总量不大于 0.5% ，优选为不大于 0.01% 。
上述本发明所制备的合金材料，可使用本领域常规的方法制备成可吸收性医疗植入体。其中，可吸收性医疗植入体优选为血管支架和骨科植入体（如骨钉或骨板）。
 有益效果
相对于现有技术，本发明的合金材料优点有：
1 ）可在人体环境下吸收，避免二次手术给患者带来的痛苦。
2 ）耐蚀性远高于镁合金，降解速度大幅度降低，可提供更长时间的力学支撑，避免血管支架、骨钉等植入体提前失效。
3 ）机械强度远高于多聚物，韧性高、易于制造，弹性模量与人体匹配好。
4 ） 可以同时实现高耐蚀性和高强韧这两个指标。
本发明的实施方式
以下是本发明内容的具体实施例，用于阐述本申请文件中所要解决技术问题的技术方案，有助于本领域技术人员理解本发明内容，但本发明技术方案的实现并不限于这些实施例。
实施例 1
采用先进的冶炼与加工工艺，利用高真空电磁熔铸炉熔炼，使炉料在被加热的同时产生悬浮，这样既可以避免坩埚污染，又可以实现合金元素的均匀混合；在真空条件下完成浇铸，避免合金的氧化；制得合金材料含量为锌 99wt% ，镁 1wt% 。随后对铸件进行多道次变形加工和热处理，大幅度提高其韧性和强度。
实施例 2
制得合金材料含锌 99.5wt% ，镁 0.5wt% 。其它步骤与实施例 1 相同。
实施例 3
制得合金材料含锌 98wt% ，镁 2wt% 。其它步骤与实施例 1 相同。
实施例 4
以实施例 1 ～ 3 中制得的合金材料，进行模拟人体体液浸泡试验。
实验结果见表 1 。
表 1 模拟人体体液浸泡实验测试结果
序号 实验材料 降解速度（毫米 / 年）
1 实施例 1 0.19
2 实施例 2 0.14
3 实施例 3 0.27
4 纯镁 3.53
5 WE43 镁合金 3.89
本实施例 依据 ASTM-G31-72 标准测试方法对锌镁合金的体外降解机理与降解性能进行了研究， 37 摄氏度的模拟人体体液模拟人体体液环境，我们发现在这种环境中，锌镁合金的降解速度缓慢且可控。模拟人体体液浸泡试验证明，锌镁合金的降解速度远低于纯镁和镁合金 WE43 。锌镁合金表面形成低溶保护层，因此降解速度远低于镁合金，最低仅为 0.14 毫米 / 每年，可以保证血管支架为病灶血管提供 6 个月以上的径向支撑，固定和骨板的力学支撑时间达到至少半年。缓慢、均匀的降解过程允许血管逐步再生，最终恢复伸缩和搏动，如同健康的血管一样。
实施例 5
以实施例 1 ～ 3 中制得的合金材料，进行拉伸强度试验。
本实施例根据 ASTM-E8-04 测试标准对锌镁合金棒材的拉伸力学性能进行了评价，发现锌镁合金的弹性模量约为 80GPa, 拉伸强度最低为 220 MPa ，最高可达 340 MPa 。强度最高的锌镁合金的延伸率为 11 % ，强度最低的锌镁合金延伸率高达 29% ，也就是说锌镁合金的强度与韧性成反比。这说明锌镁合金的强度和韧性是可以调控的，可满足不同支架花型和骨科植入体结构设计的要求。研究发现人体皮质骨的弹性模量为 3 ～ 20GPa ，屈服强度为 35 ～ 280MPa ，本发明制备的合金与人体皮质骨的力学性能匹配非常好。
最后应说明的是：以上实施例仅用以说明本实用新型的技术方案，而非对其限制；尽管参照前述实施例对本实用新型进行了详细的说明，本领域的普通技术人员应当理解，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本实用新型各实施例技术方案的精神和范围。

Claims (9)

  1. 一种人体可吸收的耐蚀高强韧锌镁合金植入材料，其特征在于所述合金材料包括：Zn 96～99.998wt%, Mg 0.002～4wt%。
  2. 如权利要求1所述的人体可吸收的耐蚀高强韧锌镁合金植入材料，其特征在于所述合金材料包括：Zn 97～99.995wt%, Mg 0.005～3wt%。
  3. 如权利要求1或2所述的人体可吸收的耐蚀高强韧锌镁合金植入材料，其特征在于：Zn的纯净度大于等于99.95%。
  4. 如权利要求3所述的人体可吸收的耐蚀高强韧锌镁合金植入材料，其特征在于：Zn的纯净度大于等于99.999%。
  5. 如权利要求1或2所述的人体可吸收的耐蚀高强韧锌镁合金植入材料，其特征在于：Mg的纯净度大于等于99.9%。
  6. 如权利要求5所述的人体可吸收的耐蚀高强韧锌镁合金植入材料，其特征在于：Mg的纯净度大于等于99.99%。
  7. 如权利要求1或2所述的人体可吸收的耐蚀高强韧锌镁合金植入材料，其特征在于：除Zn、Mg以外的夹杂元素总量小于0.5%。
  8. 如权利要求1或2所述的合金材料用于制备可吸收性医疗植入体的用途。
  9. 如权利要求8所述的用途，其特征在于：所述可吸收性医疗植入体为血管内支架、骨科植入体。
PCT/CN2014/076275 2014-03-19 2014-04-25 一种人体可吸收的耐蚀高强韧锌镁合金植入材料 WO2015139355A1 (zh)

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