WO2016145956A1 - 一种人体可降解的耐蚀高强韧Zn‐Fe‐X系锌合金及其应用 - Google Patents

一种人体可降解的耐蚀高强韧Zn‐Fe‐X系锌合金及其应用 Download PDF

Info

Publication number
WO2016145956A1
WO2016145956A1 PCT/CN2016/073437 CN2016073437W WO2016145956A1 WO 2016145956 A1 WO2016145956 A1 WO 2016145956A1 CN 2016073437 W CN2016073437 W CN 2016073437W WO 2016145956 A1 WO2016145956 A1 WO 2016145956A1
Authority
WO
WIPO (PCT)
Prior art keywords
zinc alloy
human body
stent
degradable
mass percentage
Prior art date
Application number
PCT/CN2016/073437
Other languages
English (en)
French (fr)
Inventor
周功耀
宫海波
屈功奇
Original Assignee
西安爱德万思医疗科技有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 西安爱德万思医疗科技有限公司 filed Critical 西安爱德万思医疗科技有限公司
Publication of WO2016145956A1 publication Critical patent/WO2016145956A1/zh

Links

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
    • A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • 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
    • 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
    • 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
    • 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
    • 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 present invention relates to a human body degradable corrosion-resistant high-strength Zn-Fe-X-based zinc alloy, which belongs to the technical field of medical implant materials.
  • Zinc ions are essential nutrients for the human body and participate in many metabolic activities of the human body.
  • the American Clinical Innovation Agency (ACI) recommends that the body must consume 2.5 to 6.4 mg of zinc per day, and adults who consume about 300 mg of zinc per day may have some toxic effects.
  • a zinc-based degradable bone nail releases about 0.3 to 0.3 mg of zinc per day. Even if all of these zinc ions are released into the blood vessels, they are far below the necessary intake. That is to say, the zinc ions released by the degradation of the zinc-based degradable orthopedic implant device do not cause systemic toxicity. Studies have also found that zinc ions are transported very quickly in human tissues, so zinc enrichment, cytotoxicity or necrosis does not occur near zinc-based degradable orthopedic implant devices.
  • Zinc ions have many functions in the human body and are very important to the human body. One of the most important functions is to promote bone tissue growth. The researchers found that zinc ions can activate the aminoacyl tRNA synthetase in osteoblasts and effectively inhibit the differentiation and growth of osteoclasts. Therefore, the presence of zinc ions not only promotes the increase of bone calcium content, but also facilitates bone. The increase in collagen content suggests that zinc ions have a direct osteogenesis. In addition, studies have found that zinc ions promote the binding of cartilage oligomeric matrix proteins to collagen and are catalytic elements for soft bone growth and regeneration.
  • Conventional vascular stents are generally made of non-degradable metal.
  • the disadvantage is that the metal is not degradable and cannot be removed, and retention in the blood vessel tends to cause late thrombosis.
  • a large number of clinical cases have confirmed that the thrombosis rate of patients with such stents is as high as 3% ⁇ 9 ⁇ 3 ⁇ 4 after 1 ⁇ 5 years, and the mortality after thrombosis is as high as 30%.
  • Bone nails and bone plates are commonly used medical implants for fixation of fractures and ligament injuries. Traditional bone nails and bone plates cannot be removed by non-degradable metals. Secondary surgery is required, which causes great trauma to patients. At the same time, the strength of traditional metal materials is too high, which tends to cause stress shielding, which makes it difficult for injured bone tissue to regenerate and heal.
  • Degradable medical materials in human body are becoming the focus of research and development, among which degradable polymer materials, Pure iron and iron-based alloys, pure magnesium and magnesium-based alloys are the most in-depth materials studied in recent years.
  • Degradable polymer materials are too low in strength, and breakage accidents often occur during clinical use, and clinical applicability is greatly limited.
  • the strength and toughness of pure iron and iron-based alloys are much higher than those of polymer materials, but the degradation rate of iron is too slow, and the complete degradation of the day may last for several years. More seriously, the volume of rust-like substances generated during the degradation of iron has expanded several times and has a significant migration tendency.
  • the degradation products of pure magnesium and magnesium-based alloys are non-toxic and degradable, but their corrosion resistance is very poor, and they are quickly degraded in the human body, which cannot provide sufficient mechanical support.
  • the object of the present invention is to address the deficiencies of the existing medical implant materials, and provide a low cost, high strength, good plasticity, controllable degradation rate, no degradation or migration of degradation products, and the same can be Human body degraded Zn-Fe-X zinc alloy and its application.
  • the present invention provides a human body degradable corrosion-resistant high-strength Zn-Fe-X-based zinc alloy, wherein the zinc alloy includes Zn, Fe and X elements, and the X element is Mg, Ca, Sr At least one of them; wherein the mass percentage of the Zn element is: 89.92 ⁇ 99.997 ⁇ 3 ⁇ 4, the mass percentage of the Fe element is 0.002 ⁇ 10 ⁇ 3 ⁇ 4, and the mass percentage of the X element is 0.001 ⁇ 0.08%.
  • the alloy material in order to optimize the mechanical properties and the biocorrosion properties, we optimize the alloy material to have a mass percentage of Zn element in the zinc alloy: 91.95 to 99.993%, the mass of the Fe element. The percentage is 0.005 to 8%, and the mass percentage of X element is 0.002 to 0.05%.
  • the elemental composition of the alloy material further includes a trace element, wherein the trace element is at least one of Li, Si, Mn, and a rare earth element, and the mass ratio of the trace element to Zn is 0 to 0.056. : 1.
  • the material is optimized to have a mass ratio of trace elements to Zn elements in the zinc alloy of 0 to 0.023:1.
  • the human body degradable high-strength and tough Zn-Fe-X-based zinc alloy prepared by the above invention is prepared into a degradable medical implant by a conventional method in the art.
  • the present invention also provides a human body degradable corrosion-resistant high-strength Zn-Fe-X-based zinc alloy for use in preparing a degradable medical device material.
  • the degradable medical device is an implanted stent, an orthopedic implant device, a dental implant device, a surgical suture or an anastomat.
  • the implanted stent comprises a vascular stent, a tracheal stent, a urethral stent, an esophageal stent, an intestinal stent or a biliary stent;
  • the orthopedic implant device comprises a fixing screw, a fixed rivet, a bone plate, a bone sleeve, an intramedullary nail or a bone tissue repairing stent;
  • the stapler includes an intestinal stapler, a vascular anastomat or a nerve stapler.
  • the added material is low in cost, and the degradation products of the prepared alloy materials can be metabolized by the human body; [0016] 2.
  • the corrosion resistance is much higher than that of the magnesium alloy, the degradation rate is controllable, and the degradation products are not expanded or migrated. ;
  • the strength and toughness of the alloy material are good.
  • the iron element has the dual functions of solid solution strengthening and precipitation strengthening at room temperature and high temperature, and can form a plurality of stable intermetallic compounds with Zn to strengthen the X element. It has obvious solid solution strengthening effect, and has the effect of refining crystal grains and improving plasticity, and improves the strength and toughness of the alloy material.
  • FIG. 1 is a schematic view showing the microstructure of an alloy of the present invention degraded in an animal.
  • the corrosion potential of zinc is -0.76V
  • the corrosion potential of iron is -0.44V. Therefore, the addition of iron as an alloying element to zinc can produce two opposite effects.
  • the first effect is that iron is dissolved in the matrix zinc. , the corrosion potential of zinc decreases, the corrosion resistance increases, and the degradation rate decreases; the second effect is iron and
  • the zinc element forms a particulate compound, forms a microbattery with the matrix zinc, has reduced corrosion resistance, and has an increased degradation rate.
  • a human body degradable corrosion-resistant high-strength Zn-Fe-X-based zinc alloy of the present invention has an elemental composition and mass percentage of: Zn 90 ⁇ 3 ⁇ 4, Fe 9.92%, and Sr 0.08 ⁇ 3 ⁇ 4.
  • a human body degradable corrosion-resistant high-strength Zn-Fe-X-based zinc alloy of the present invention has an elemental composition and mass percentage of: Zn 99.997%, Fe 0.002%, and Ca 0.001%.
  • a human body degradable corrosion-resistant high-strength Zn-Fe-X-based zinc alloy of the present invention has an elemental composition and mass percentage of: Zn 99.975%, Fe O.01%, Mg0.015 ⁇ 3 ⁇ 4.
  • a human body degradable corrosion-resistant high-strength Zn-Fe-X-based zinc alloy of the invention has an elemental composition and mass percentage: Zn 97.45%, Fe 2%, Mg 0.05%, Ce 0.5 ⁇ 3 ⁇ 4.
  • This embodiment studies the in vitro degradation mechanism and degradation performance of a zinc-based Zn-Fe-X alloy according to the ASTM-G31-72 standard test method, and simulates a human body fluid environment at 37 degrees Celsius to simulate a human body fluid environment. In the environment, the degradation rate of Zn-Fe-X zinc alloy is slow and controllable.
  • the in vivo implantation test was carried out using the zinc alloy prepared by the conventional techniques in the art using the elemental composition in Example 1.
  • the zinc alloy prepared in Example 1 was made into filaments and implanted into the abdominal aorta of New Zealand white rabbit for 12 months.
  • the bright area in the figure is the cross section of the alloy wire, and the gray area close to the alloy wire is The degradation product, the black area is a resin material for fixing the sample. It was found that the alloy wire did not show any swelling and migration after degradation, and its degradation products remained in the original shape, and no phenomenon of falling particles or fragments was found.
  • the zinc alloy prepared in the other examples was also subjected to in vivo implantation test, and the obtained microscopic image was similar to that of the zinc alloy of Example 1.

Abstract

一种人体可降解的耐蚀高强韧Zn-Fe-X系锌合金及其在医用植入材料中的应用，所述的锌合金中包括Zn、Fe和X元素，所述的X元素为Mg、Ca、Sr中至少一种；其中Zn元素的质量百分含量为：89.92～99.997％，Fe元素的质量百分含量为：0.002～10％，X元素的质量百分含量为：0.001～0.08％。

Description

一种人体可降解的耐蚀高强韧 Zn-Fe-X系锌合金及其应 用
技术领域
[0001] 本发明涉及一种人体可降解的耐蚀高强韧 Zn-Fe-X系锌合金， 属于医用植入材 料技术领域。
背景技术
[0002] 锌离子是人体必需的营养元素， 参与人体很多的新陈代谢活动。 美国临床创新 机构 （ACI) 推荐人体每天必需摄入 2.5到 6.4毫克的锌， 成年人每天摄入大约 300 毫克锌才可能会有一定毒性反应。 一枚锌基可降解骨钉每天释放的锌大约为 0.2~ 0.3毫克， 即使这些锌离子全部释放到血管里， 也远远低于人体必需的摄入量。 也就是说， 锌基可降解骨科植入器械降解释放的锌离子不会引起全身毒性。 研 究还发现， 锌离子在人体组织中的运输非常迅速， 因此锌基可降解骨科植入器 械附近不会出现锌富集、 细胞毒性或坏死。
[0003] 锌离子在人体内的功能很多， 对人体非常重要， 其中很重要的一个功能就是促 进骨组织生长。 研究人员发现由于锌离子可以激活成骨细胞中的氨酰 tRNA合成 酶， 并可有效抑制破骨细胞的分化与生长， 因此锌离子的存在不仅促进了骨钙 盐含量的增加， 还有利于骨胶原蛋白含量的提高， 这说明锌离子有直接的促成 骨功能。 另外， 研究还发现锌离子促进软骨低聚基质蛋白与胶原的结合， 是软 骨成长与再生的催化元素。
[0004] 传统的血管支架一般采用不可降解的金属制成， 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。 大量的临床病例证实病人植入这类支 架 1〜5年后血栓形成率高达 3%〜9<¾， 血栓形成后死亡率高达 30%。 骨钉和骨板 是常用的固定骨折和韧带损伤的医疗植入器械， 传统骨钉和骨板由不可降解的 金属无法取出， 必须进行二次手术， 对患者带来极大的创伤。 同吋， 传统金属 材料强度过高， 容易带来应力屏蔽， 导致受伤的骨组织难以再生和愈合。
[0005] 人体内可降解医用材料正在成为研究和幵发的重点， 其中可降解高分子材料、 纯铁及铁基合金、 纯镁及镁基合金是近年研究最为深入的材料。 可降解高分子 材料强度过低， 在临床使用过程中经常会发生断裂事故， 临床适用性收到极大 限制。 纯铁及铁基合金的强度和韧性远高于高分子材料， 但铁的降解速度太慢 ， 完全降解吋间可能长达数年。 更为严重的是， 铁降解过程中生成的铁锈状物 质体积膨胀了数倍， 并有明显的迁移趋势。 纯镁及镁基合金的降解产物无毒、 可降解， 但其耐蚀性非常差， 在人体内很快就会被降解， 无法提供足够的力学 支撑吋间。
[0006] 纯锌及其合金也是一种人体环境下可降解的材料， 但应用在医用材料方面仍然 存在力学强度低、 降解速率不可控的缺点， 目前都是通过向其添加其它物质来 达到改善力学性能和调控降解速率， 如申请号 201310756776.1公幵的锌中添加 Ce 、 Mg、 Cu、 Ca， 但该申请制备的锌合金材料塑性较低， 而目前还未发现将价格 低廉的铁作为锌的添加材料， 作为生物医用材料来使用。
技术问题
[0007] 本发明的目的是针对现有医用植入材料存在的不足， 提供一种添加材料成本低 ， 强度高、 塑性好， 降解速率可控， 降解产物不膨胀、 不迁移， 同吋可被人体 降解的 Zn-Fe-X系锌合金及其应用。
问题的解决方案
技术解决方案
[0008] 本发明提供一种人体可降解的耐蚀高强韧 Zn-Fe-X系锌合金， 所述的锌合金中 包括 Zn、 Fe和 X元素， 所述的 X元素为 Mg、 Ca、 Sr中至少一种； 其中 Zn元素的 质量百分含量为： 89.92〜99.997<¾， Fe元素的质量百分含量为： 0.002〜10<¾， X 元素的质量百分含量为： 0.001〜0.08%。
[0009] 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 料进优化为， 所述锌合金中 Zn元素的质量百分含量为： 91.95〜99.993%， Fe元素 的质量百分含量为： 0.005〜8%， X元素的质量百分含量为： 0.002〜0.05%。
[0010] 更优选地， 所述合金材料的元素组成还包括微量元素， 所述微量元素为 Li、 Si 、 Mn、 稀土元素中至少一种， 所述微量元素与 Zn的质量比为 0〜0.056： 1。
[0011] 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 料优化为， 所述锌合金中微量元素与 Zn元素的质量比为 0〜0.023： 1。
[0012] 上述发明所制备的人体可降解的耐蚀高强韧 Zn-Fe-X系锌合金， 使用本领域常 规的方法制备成可降解医疗植入体。
[0013] 因此， 本发明还提供一种人体可降解的耐蚀高强韧 Zn-Fe-X系锌合金在制备可 降解医疗器械材料中的应用。
[0014] 所述可降解医疗器械为植入支架、 骨科植入器械、 齿科植入器械、 手术缝合线 或吻合器。 其中植入支架包括血管支架、 气管支架、 尿道支架、 食道支架、 肠 道支架或胆道支架； 骨科植入器械包括固定螺丝、 固定铆钉、 骨板、 骨套、 髓 内针或骨组织修复支架； 吻合器包括肠道吻合器、 血管吻合器或神经吻合器。 发明的有益效果
有益效果
[0015] 1、 添加材料成本低廉， 制备的合金材料各成分降解产物可被人体代谢降解； [0016] 2、 耐蚀性远高于镁合金， 降解速率可控， 降解产物不膨胀、 不迁移；
[0017] 3、 合金材料强度和韧性好， 铁元素在室温和高温下具有固溶强化和沉淀强化 的双重作用， 能与 Zn形成多种稳定的金属间化合物、 起到强化作用， X元素有明 显的固溶强化作用， 并有细化晶粒、 提高塑性的效果， 提高了合金材料强度和 韧性。
对附图的简要说明
附图说明
[0018] 图 1为本发明合金在动物体内降解显微结构示意图。
本发明的实施方式
[0019] 下面结合具体实施例对本发明做进一步说明。
[0020] 由于生物环境和功能需求的差异， 不同的可降解植入器械对降解速度的要求是 不一样的。 锌的的腐蚀电位是 -0.76V, 铁的腐蚀电位是 -0.44V, 因此铁作为合金 元素加入锌中可同吋产生两种相反的效果， 第一种效果是铁元素固溶到基体锌 中， 锌的腐蚀电位降低、 耐蚀性增强、 降解速度降低； 第二种效果是铁元素与 锌元素生成颗粒状化合物， 与基体锌形成微电池、 耐蚀性下降、 降解速度升高 。 通过调节铁的含量， 可以达到控制锌合金的降解速度使其适于医用植入材料 的要求。
[0021] 实施例 1
[0022] 本发明的一种人体可降解的耐蚀高强韧 Zn-Fe-X系锌合金， 其元素组成及质量 百分比为： Zn 90<¾， Fe 9.92% , Sr 0.08<¾。
[0023] 实施例 2
[0024] 本发明的一种人体可降解的耐蚀高强韧 Zn-Fe-X系锌合金， 其元素组成及质量 百分比为： Zn 99.997%， Fe 0.002% , Ca 0.001%。
[0025] 实施例 3
[0026] 本发明的一种人体可降解的耐蚀高强韧 Zn-Fe-X系锌合金， 其元素组成及质量 百分比为： Zn 99.975%， Fe O.01% , Mg0.015<¾。
[0027] 实施例 4
[0028] 本发明的一种人体可降解的耐蚀高强韧 Zn-Fe-X系锌合金， 其元素组成及质量 百分比为： Zn 97.45% , Fe 2% , Mg 0.05% , Ce 0.5<¾。
[0029] 实施例 5
[0030] 以实施例 1〜4中元素组成使用本领域常规技术制得的锌合金， 进行模拟人体体 液浸泡试验， 测试 Zn-Fe-X系锌合金降解速率实验测试结果如表一：
[0031] 表一
Figure imgf000005_0001
[0032] 本实施例依据 ASTM-G31-72标准测试方法对锌基 Zn-Fe-X系合金的体外降解机 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， 发现 在这种环境中， Zn-Fe-X系锌合金的降解速度缓慢且可控。
[0033] 实施例 6
[0034] 以实施例 1〜4中元素组成使用本领域常规技术制得的锌合金， 进行拉伸强度试 验结果如表二所示。
[0035] 表二
Figure imgf000006_0001
[0036] 本实施例根据 GB/T228.1-2010测试标准， 对 Zn-Fe-X系锌合金实施例 1〜4进行 拉伸力学性能测试， 结果如表二所示。 发现 Zn-Fe-X系锌合金屈服强度最高可达 380MPa, 断裂延伸率高达 24.5%， 这是由于铁与锌生成弥散分布的细小化合物 颗粒， 达到细化晶粒的效果， 而镁 ^丐 /锶固溶于 α相锌中， 只需要加入极少量的 镁 / /锶就可达到极高的强度， 还可增加抗蠕变性能,加入的微量元素则进一步改 善材料力学性能。
[0037] 实施例 7
[0038] 以实施例 1〜4中元素组成使用本领域常规技术制得的锌合金， 进行体外细胞毒 性测试。
[0039] 本实施例根据 GB/T 16886.5-2003对锌合金进行了体外细胞毒性测试， 将成纤维 细胞 L-929培养在锌合金降解产物的提取液里， 测量 24小吋和 72小吋的细胞活性 ， 并与培养在常规培养液的细胞活性作对比， 发现培养在锌合金降解产物提取 液里的细胞活性均高于 90%， 且细胞形貌非常健康， 因此可以认为锌合金降解产 物对细胞活性没有影响， 细胞对锌合金降解产物没有毒性反应。 [0040] 实施例 8
[0041] 以实施例 1中元素组成使用本领域常规技术制得的锌合金， 进行体内植入测试 。 将实施例 1制备的锌合金制成细丝植入新西兰白兔腹主动脉中 12个月， 如图 1 所示， 图中亮区为合金丝横截面， 紧贴合金丝的灰色区域即为降解产物， 黑色 区域为固定样品用的树脂材料。 研究发现合金丝在降解后没有发现任何膨胀和 迁移的情况， 其降解产物仍维持原来的形状， 没有发现掉落颗粒、 碎片的现象 。 同吋对其它实施例制备的锌合金同样进行体内植入测试， 得到的显微图像与 以实施例 1的锌合金相似。
[0042] 以上内容是结合具体的实施方式对本发明所做的进一步详细说明， 不能认定本 发明的具体实施只局限于这些说明。 对于本发明所属技术领域的普通技术人员 来说， 在不脱离本发明构思的前提下， 还可以做出若干简单推演或替换， 都应 当视为属于本发明的保护范围。

Claims

权利要求书
[权利要求 1] 一种人体可降解的耐蚀高强韧 Zn-Fe-X系锌合金， 其特征在于： 所述 的锌合金中包括 Zn、 Fe和 X元素， 所述的 X元素为 Mg、 Ca、 Sr中至少 一种； 其中 Zn元素的质量百分含量为： 89.92〜99.997<¾， Fe元素的质 量百分含量为： 0.002〜10%， X元素的质量百分含量为： 0.001〜0.08 。
[权利要求 2] 如权利要求 1所述的人体可降解的耐蚀高强韧 Zn-Fe-X系锌合金， 其特 征在于： 所述锌合金中 Zn元素的质量百分含量为： 91.95〜99.993%， Fe元素的质量百分含量为： 0.005〜8%， X元素的质量百分含量为： 0. 002〜0.05<¾。
[权利要求 3] 如权利要求 1或 2所述的人体可降解的耐蚀高强韧 Zn-Fe-X系锌合金， 其特征在于： 所述的锌合金中还包括微量元素， 所述微量元素为 Li、 Si、 Mn和稀土元素中至少一种， 所述微量元素与 Zn元素的质量比为 0 〜0.056： 1。
[权利要求 4] 如权利要求 3所述的人体可降解的耐蚀高强韧 Zn-Fe-X系锌合金， 其特 征在于： 所述锌合金中微量元素与 Zn元素的质量比为 0〜0.023： 1。
[权利要求 5] —种如权利要求 1〜4中任一项所述的人体可降解的耐蚀高强韧 Zn-Fe-
X系锌合金在制备可降解医疗器械材料中的应用。
[权利要求 6] 如权利要求 5所述的人体可降解的耐蚀高强韧 Zn-Fe-X系锌合金在制备 可降解医疗器械材料中的应用， 其特征在于： 所述可降解医疗器械为 植入支架、 骨科植入器械、 齿科植入器械、 手术缝合线或吻合器， 其 中植入支架包括血管支架、 气管支架、 尿道支架、 食道支架、 肠道支 架或胆道支架； 骨科植入器械包括固定螺丝、 固定铆钉、 骨板、 骨套 、 髓内针或骨组织修复支架； 吻合器包括肠道吻合器、 血管吻合器或 神经吻合器。
PCT/CN2016/073437 2015-03-13 2016-02-04 一种人体可降解的耐蚀高强韧Zn‐Fe‐X系锌合金及其应用 WO2016145956A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510111213.6 2015-03-13
CN201510111213.6A CN104689378B (zh) 2015-03-13 2015-03-13 一种人体可降解的耐蚀高强韧Zn‐Fe‐X系锌合金及其应用

Publications (1)

Publication Number Publication Date
WO2016145956A1 true WO2016145956A1 (zh) 2016-09-22

Family

ID=53337188

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/073437 WO2016145956A1 (zh) 2015-03-13 2016-02-04 一种人体可降解的耐蚀高强韧Zn‐Fe‐X系锌合金及其应用

Country Status (2)

Country Link
CN (1) CN104689378B (zh)
WO (1) WO2016145956A1 (zh)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104689378B (zh) * 2015-03-13 2017-04-05 西安爱德万思医疗科技有限公司 一种人体可降解的耐蚀高强韧Zn‐Fe‐X系锌合金及其应用
CN106974718A (zh) * 2016-01-15 2017-07-25 西安爱德万思医疗科技有限公司 一种接骨螺钉
CN106890356B (zh) * 2016-03-10 2020-07-24 山东瑞安泰医疗技术有限公司 一种可降解的锌基合金植入材料及其制备方法与应用
CN106319287A (zh) * 2016-08-25 2017-01-11 上海交通大学 生物可降解医用Zn‑Li‑X系合金材料及制备与应用
CN109200342A (zh) * 2017-07-06 2019-01-15 先健科技(深圳)有限公司 植入式器械
CN108165782B (zh) * 2017-12-28 2020-01-07 东南大学 一种医用锌基合金带材及其制备方法
CN110029240A (zh) * 2019-03-07 2019-07-19 袁婉荣 一种生物可降解的Zn-Cu-Sr-Ti合金制备方法及应用
CN110512117B (zh) * 2019-09-27 2022-05-13 石家庄新日锌业有限公司 一种医用锌合金材料及制备方法
US11351290B1 (en) 2020-04-08 2022-06-07 Admtech, Llc Absorbable high-strength zinc alloy for medical implants
CN113304326A (zh) * 2021-05-27 2021-08-27 深圳雅施达科技有限公司 一种可吸收的高强度锌合金植入物材料

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19856983A1 (de) * 1998-06-25 1999-12-30 Biotronik Mess & Therapieg Implantierbare, bioresorbierbare Gefäßwandstütze, insbesondere Koronarstent
CN102634725A (zh) * 2012-03-31 2012-08-15 大连理工大学 一种生物医用可腐蚀降解的二元Fe-Zn合金材料
CN104195369A (zh) * 2014-08-21 2014-12-10 北京大学 一种Zn-Ca系锌合金及其制备方法与应用
CN104689378A (zh) * 2015-03-13 2015-06-10 周功耀 一种人体可降解的耐蚀高强韧Zn‐Fe‐X系锌合金及其应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100340308C (zh) * 2005-12-22 2007-10-03 上海交通大学 生物体内可吸收的Mg－Zn－Fe三元镁合金材料
CN100372574C (zh) * 2005-12-22 2008-03-05 上海交通大学 生物体内可吸收的Mg-Zn-Ca-Fe多元镁合金材料
CN101516292B (zh) * 2006-09-22 2013-08-21 友和安股份公司 由生物可降解金属构成的植入物及其制造方法
CN103736152B (zh) * 2013-12-26 2016-12-07 西安爱德万思医疗科技有限公司 一种人体可吸收的耐蚀高强韧锌合金植入材料
CN104313439B (zh) * 2014-11-04 2016-05-11 哈尔滨理工大学 一种可降解镁合金接骨板的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19856983A1 (de) * 1998-06-25 1999-12-30 Biotronik Mess & Therapieg Implantierbare, bioresorbierbare Gefäßwandstütze, insbesondere Koronarstent
CN102634725A (zh) * 2012-03-31 2012-08-15 大连理工大学 一种生物医用可腐蚀降解的二元Fe-Zn合金材料
CN104195369A (zh) * 2014-08-21 2014-12-10 北京大学 一种Zn-Ca系锌合金及其制备方法与应用
CN104689378A (zh) * 2015-03-13 2015-06-10 周功耀 一种人体可降解的耐蚀高强韧Zn‐Fe‐X系锌合金及其应用

Also Published As

Publication number Publication date
CN104689378B (zh) 2017-04-05
CN104689378A (zh) 2015-06-10

Similar Documents

Publication Publication Date Title
WO2016145956A1 (zh) 一种人体可降解的耐蚀高强韧Zn‐Fe‐X系锌合金及其应用
WO2016145957A1 (zh) 一种人体可降解的耐蚀高强韧Zn‐Fe 系锌合金及其应用
WO2016145958A1 (zh) 一种人体可降解的耐蚀高强韧Zn‐Fe‐Li 系锌合金及其应用
WO2016145955A1 (zh) 一种人体可降解的耐蚀高强韧Zn‐Fe‐RE系锌合金及其应用
CN109680195B (zh) 一种Mg-RE系镁合金及其制备方法与应用
CN109972007B (zh) 一种生物体内可降解Mg-Zn-Ca-M的吻合钉材料及其制备方法
CN106319287A (zh) 生物可降解医用Zn‑Li‑X系合金材料及制备与应用
Wang et al. Research progress of biodegradable magnesium-based biomedical materials: A review
WO2017084363A1 (zh) 医用可降解Zn-Cu-X合金材料及其制备方法
CN100368028C (zh) 生物体内可吸收的Mg-Zn两元镁合金材料
CN1792383A (zh) 生物体内可吸收的Mg－Zn－Ca三元镁合金材料
WO2020042745A1 (zh) 降解速率可控的Mg-Zn-Sn系镁合金及其制备方法和应用
CN108754232A (zh) 一种高强高塑可生物降解Zn-Mn-Li系锌合金及其用途
CN100372574C (zh) 生物体内可吸收的Mg-Zn-Ca-Fe多元镁合金材料
CN106282664A (zh) 生物可降解医用锌锂二元合金材料及其制备方法与应用
CN108165782B (zh) 一种医用锌基合金带材及其制备方法
Huang et al. The design, development, and in vivo performance of intestinal anastomosis ring fabricated by magnesium‑zinc‑strontium alloy
Du et al. Systematic in vitro and in vivo study on biodegradable binary Zn-0.2 at% Rare Earth alloys (Zn-RE: Sc, Y, La–Nd, Sm–Lu)
CN108815589A (zh) 一种医用可降解锌基合金血管支架制品
CN109280827A (zh) 吻合钉及其制备方法和应用
Bao et al. β duplex phase Ti–Zr–Nb–Ag alloys with impressive mechanical properties, excellent antibacterial and good biocompatibility
WO2017107858A1 (zh) 一种合金材料及其应用
CN112426570A (zh) 体内可降解高强韧医用Zn-Cu-Ag-Zr合金材料
CN100340308C (zh) 生物体内可吸收的Mg－Zn－Fe三元镁合金材料
CN112430764B (zh) 生物体内可降解高强韧医用Zn-Cu-Mn-Zr合金

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16764137

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205 DATED 21/11/2018)

122 Ep: pct application non-entry in european phase

Ref document number: 16764137

Country of ref document: EP

Kind code of ref document: A1