CN108411173A - A kind of bio-medical Mg-Sn-Zn-Sr magnesium alloys and preparation method thereof - Google Patents
A kind of bio-medical Mg-Sn-Zn-Sr magnesium alloys and preparation method thereof Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 18
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Abstract
本发明属于镁合金材料技术领域，具体涉及一种生物医用Mg‑Sn‑Zn‑Sr镁合金及其制备方法，所述镁合金包括以下重量百分比组分：Sn 0.5‑1.5％、Zn 0.3‑0.7％、Sr 0.05‑0.15％，杂质元素Si、Fe、Cu和Ni的总量小于0.02％，余量为Mg。其工艺为先对各成分进行混合熔炼，随后进行固溶热处理，最后进行塑性变形。本发明镁合金选择多种人体必需的微量元素，同时控制合金元素总量，材料无毒性、具有良好耐蚀性和高强韧性，可人体降解。The invention belongs to the technical field of magnesium alloy materials, and specifically relates to a biomedical Mg-Sn-Zn-Sr magnesium alloy and a preparation method thereof. The magnesium alloy includes the following components in weight percentage: Sn 0.5-1.5%, Zn 0.3-0.7 %, Sr 0.05‑0.15%, the total amount of impurity elements Si, Fe, Cu and Ni is less than 0.02%, and the balance is Mg. The process is to mix and smelt the various components first, then carry out solid solution heat treatment, and finally carry out plastic deformation. The magnesium alloy of the invention selects a variety of trace elements necessary for the human body and controls the total amount of alloy elements at the same time. The material is non-toxic, has good corrosion resistance and high strength and toughness, and can be degraded by the human body.
Description
技术领域technical field
本发明属于镁合金材料技术领域，具体涉及一种生物医用Mg-Sn-Zn-Sr镁合金及其制备方法。The invention belongs to the technical field of magnesium alloy materials, and in particular relates to a biomedical Mg-Sn-Zn-Sr magnesium alloy and a preparation method thereof.
背景技术Background technique
传统的不锈钢、钛合金等金属生物植入材料在获得广泛临床应用的同时，也暴露出一些弊端：(1)不锈钢、钛合金等材料与人体骨骼在弹性模量上差距很大，植入后产生应力遮挡效应，影响骨愈合过程或导致骨质疏松，甚至引发二次骨折；(2)尽管不锈钢、钛合金等材料的化学性质相对稳定，但在长期植入过程中仍可能释放出部分有害离子，存在引发炎症、过敏的风险；(3)由于不锈钢、钛合金等材料在体内不可降解，在人体组织功能恢复之后需要通过二次手术取出，增加患者的痛苦、二次手术风险和医疗成本。与传统的不锈钢、钛合金等金属材料相比，镁合金作为生物植入材料，具有一系列独特的优势。近年来，镁合金材料已成为生物植入材料领域的研究热点，国内外学者围绕生物镁合金材料开展了大量研究，但目前与临床应用之间仍存在一定的距离，主要障碍在于：(1)部分镁合金中的合金元素存在潜在毒性；(2)在体液环境中，镁合金的降解速率过快，容易发生严重的局部腐蚀。合理的成分设计和加工方法选择，是开发新型生物镁合金材料，改善镁合金在体液环境中耐腐蚀性能，同时提高其力学性能的潜在途径。Traditional metal bioimplantation materials such as stainless steel and titanium alloy have been widely used in clinical practice, but they also have some disadvantages: (1) The elastic modulus of stainless steel, titanium alloy and other materials is very different from that of human bones. Produce stress shielding effect, affect the bone healing process or lead to osteoporosis, and even cause secondary fractures; (2) Although the chemical properties of stainless steel, titanium alloy and other materials are relatively stable, some harmful substances may still be released during long-term implantation. (3) Since stainless steel, titanium alloy and other materials are not degradable in the body, after the function of human tissue is restored, it needs to be removed by a second operation, which increases the pain of the patient, the risk of the second operation and the medical cost. . Compared with traditional metal materials such as stainless steel and titanium alloy, magnesium alloy has a series of unique advantages as a biological implant material. In recent years, magnesium alloy materials have become a research hotspot in the field of bio-implantation materials. Scholars at home and abroad have carried out a lot of research on bio-magnesium alloy materials, but there is still a certain distance between them and clinical applications. The main obstacles are: (1) Alloying elements in some magnesium alloys have potential toxicity; (2) In the body fluid environment, the degradation rate of magnesium alloys is too fast, and severe localized corrosion is prone to occur. Reasonable composition design and processing method selection are potential ways to develop new bio-magnesium alloy materials, improve the corrosion resistance of magnesium alloys in body fluid environment, and improve their mechanical properties at the same time.
近年来，镁锡(Mg-Sn)系合金作为一类潜在的生物镁合金材料，逐渐引起国内外学者的重视。Sn属于人体必需的微量元素，动物实验证明Sn元素毒性非常低，满足生物相容性要求。从力学性能角度来看，添加Sn元素能够改善镁合金的强度和塑性。Zhen等人将Mg-3Sn-0.5Mn(wt.％)合金与目前生物镁合金中研究最多的WE43合金对比，发现该合金的腐蚀速率低于WE43合金，且腐蚀更加均匀(Zhen Z,Xi T,Zheng Y,et al.In vitro study onMg-Sn-Mn alloy as biodegradable metals[J].Journal of Materials Science&Technology,2014,30(7):675-685.)。J.Kubásek等人对比了不同合金元素含量的Mg-Sn、Mg-Ga和Mg-In三类铸造二元合金，从腐蚀速率、细胞毒性、力学性能和成本等多方面综合考虑，认为Mg-1Sn合金是较为合适的生物镁合金材料(Kubásek J,Vojtěch D,Lipov J,etal.Structure,mechaniSrl properties,corrosion behavior and cytotoxicity ofbiodegradable Mg-X(X＝Sn,Ga,In)alloys[J].Materials Science and Engineering:C,2013,33(4):2421-2432.)。In recent years, magnesium-tin (Mg-Sn) alloys, as a class of potential bio-magnesium alloy materials, have gradually attracted the attention of scholars at home and abroad. Sn is an essential trace element for the human body. Animal experiments have proved that the toxicity of Sn element is very low and meets the requirements of biocompatibility. From the perspective of mechanical properties, the addition of Sn element can improve the strength and plasticity of magnesium alloys. Zhen et al. compared Mg-3Sn-0.5Mn (wt.%) alloy with WE43 alloy, which is the most researched bio-magnesium alloy, and found that the corrosion rate of this alloy is lower than that of WE43 alloy, and the corrosion is more uniform (Zhen Z, Xi T , Zheng Y, et al.In vitro study on Mg-Sn-Mn alloy as biodegradable metals[J].Journal of Materials Science&Technology,2014,30(7):675-685.). J. Kubásek et al. compared Mg-Sn, Mg-Ga and Mg-In three types of cast binary alloys with different alloy element contents, and considered Mg- 1Sn alloy is a more suitable bio-magnesium alloy material (Kubásek J, Vojtěch D, Lipov J, et al. Science and Engineering: C, 2013, 33(4): 2421-2432.).
发明内容Contents of the invention
本发明主要提供了一种生物医用Mg-Sn-Zn-Sr镁合金及其制备方法，该合金材料无毒性、具有良好耐蚀性和高强韧性，可人体降解。其技术方案如下：The invention mainly provides a biomedical Mg-Sn-Zn-Sr magnesium alloy and a preparation method thereof. The alloy material is non-toxic, has good corrosion resistance and high strength and toughness, and can be degraded by human body. Its technical scheme is as follows:
一种生物医用Mg-Sn-Zn-Sr镁合金，其包括以下重量百分比组分：Sn 0.5-1.5％、Zn 0.3-0.7％、Sr 0.05-0.15％，杂质元素Si、Fe、Cu和Ni的总量小于0.02％，余量为Mg。A biomedical Mg-Sn-Zn-Sr magnesium alloy, which includes the following components in weight percent: Sn 0.5-1.5%, Zn 0.3-0.7%, Sr 0.05-0.15%, impurity elements Si, Fe, Cu and Ni The total amount is less than 0.02%, and the balance is Mg.
一种上述生物医用Mg-Sn-Zn-Sr镁合金的制备方法，包括以下步骤：A preparation method of the above biomedical Mg-Sn-Zn-Sr magnesium alloy, comprising the following steps:
(1)按照配方量采用纯镁锭、纯锡锭、纯锌锭和Mg-Sr中间合金在气体保护下进行熔炼，得到Mg-Sn-Zn-Sr系镁合金铸锭；(1) adopting pure magnesium ingot, pure tin ingot, pure zinc ingot and Mg-Sr master alloy to carry out smelting under gas protection according to formula quantity, obtain Mg-Sn-Zn-Sr series magnesium alloy ingot;
(2)对Mg-Sn-Zn-Sr系镁合金铸锭进行固溶热处理，固溶处理温度为350-450℃，时间为12-24h，固溶结束后水淬至室温；(2) Carrying out solution heat treatment to Mg-Sn-Zn-Sr series magnesium alloy ingot, solution treatment temperature is 350-450 ℃, time is 12-24h, water quenching to room temperature after solution;
(3)对固溶热处理后的Mg-Sn-Zn-Sr系镁合金进行塑性变形，采用搅拌摩擦加工技术，搅拌头转速为400-1600r/min，进给速度为40-200mm/min。(3) Perform plastic deformation on the Mg-Sn-Zn-Sr series magnesium alloy after solution heat treatment, adopt friction stir processing technology, the stirring head speed is 400-1600r/min, and the feed speed is 40-200mm/min.
优选的，步骤(1)中保护气体为SF6与CO2的混合气体。Preferably, the protective gas in step (1) is a mixed gas of SF 6 and CO 2 .
优选的，步骤(1)中熔炼方法为：先将纯镁熔化，当温度升至720-740℃时加入纯锡和纯锌，待其熔化后搅拌8-12min；随后加入Mg-10Sr中间合金，继续搅拌8-12min使合金元素分布均匀，降温至710-720℃保温10min，去除表面浮渣，浇注到预热至180-220℃的金属型模具中。Preferably, the smelting method in step (1) is as follows: first melt pure magnesium, add pure tin and pure zinc when the temperature rises to 720-740°C, and stir for 8-12 minutes after melting; then add Mg-10Sr master alloy , continue to stir for 8-12 minutes to distribute the alloying elements evenly, cool down to 710-720°C and hold for 10 minutes, remove surface scum, and pour into a metal mold preheated to 180-220°C.
镁合金中各合金元素的作用如下：The role of each alloy element in magnesium alloy is as follows:
Sn是人体必需的微量元素之一，毒性极小，体重70kg的成年人每天需摄入约7.0mg的Sn。Sn能够提高镁合金的室温塑性和强度。Sn is one of the essential trace elements for the human body, with minimal toxicity, and an adult with a body weight of 70kg needs to consume about 7.0mg of Sn per day. Sn can improve the room temperature ductility and strength of magnesium alloys.
Zn是人体必需的微量元素之一，参与形成促卵泡激素和黄体化荷尔蒙(LH)，同时参与形成DNA组成元素锌指蛋白的合成，参与多种酶的形成。Zn也会提升镁合金的抗拉强度和屈服强度。Zn is one of the essential trace elements for the human body. It participates in the formation of follicle-stimulating hormone and luteinizing hormone (LH), and at the same time participates in the synthesis of zinc finger protein, a constituent element of DNA, and the formation of various enzymes. Zn also increases the tensile strength and yield strength of magnesium alloys.
Sr也有助于提高骨强度和骨矿物质密度，可以用于治疗骨质缩松症。此外，Sr也被证明能降低破骨细胞活性并且促进成骨细胞的繁殖，在刺激骨质形成的同时减少骨质的吸收。Sr在镁合金众有强烈的晶粒细化作用。Sr also helps to improve bone strength and bone mineral density, which can be used to treat osteoporosis. In addition, Sr has also been shown to reduce the activity of osteoclasts and promote the proliferation of osteoblasts, while stimulating bone formation and reducing bone resorption. Sr has a strong grain refinement effect in magnesium alloys.
塑性变形能够诱发镁合金的再结晶，细化晶粒，实现细晶强化，晶粒细化对提高镁合金的耐腐蚀性能也有很大帮助。Plastic deformation can induce recrystallization of magnesium alloys, refine grains, and achieve fine grain strengthening. Grain refinement is also very helpful to improve the corrosion resistance of magnesium alloys.
采用上述方案，本发明具有以下优点：Adopt above-mentioned scheme, the present invention has the following advantages:
(1)本发明所述的一种兼具无毒性、良好耐蚀性和高强韧性的可降解生物医用Mg-Sn-Zn-Sr系镁合金及其制备方法，采用无毒的成分设计，所涉及的Sn、Zn和Sr元素都是人体必需的微量元素；(1) A kind of degradable biomedical Mg-Sn-Zn-Sr series magnesium alloy and its preparation method with non-toxicity, good corrosion resistance and high toughness of the present invention, adopts non-toxic component design, so The Sn, Zn and Sr elements involved are all trace elements necessary for the human body;
(2)本发明所述的Mg-Sn-Zn-Sr系镁合金，采用多元微合金化设计，能够比较好地发挥各合金元素在合金中的作用，改善合金的耐腐蚀性能，并提高其力学性能；(2) The Mg-Sn-Zn-Sr series magnesium alloy described in the present invention adopts multi-element microalloying design, which can bring into play the effect of each alloy element in the alloy better, improve the corrosion resistance of the alloy, and increase its mechanical properties;
(3)本发明所述的Mg-Sn-Zn-Sr系镁合金，控制合金元素总量，经铸造、固溶和塑性变形后获得单相镁合金，基本消除第二相，大幅度抑制了电偶腐蚀的发生，改善合金的耐腐蚀性能，同时确保合金的植入生物体内后能够完全降解；(3) In the Mg-Sn-Zn-Sr series magnesium alloy described in the present invention, the total amount of alloying elements is controlled, and a single-phase magnesium alloy is obtained after casting, solid solution and plastic deformation, and the second phase is basically eliminated, and the The occurrence of galvanic corrosion improves the corrosion resistance of the alloy, and at the same time ensures that the alloy can be completely degraded after being implanted in the organism;
(4)本发明所述的Mg-Sn-Zn-Sr系镁合金，经塑性变形后，晶粒得到细化，合金的耐腐蚀性能和力学性能均得到提高。(4) In the Mg-Sn-Zn-Sr series magnesium alloy of the present invention, after plastic deformation, the crystal grains are refined, and the corrosion resistance and mechanical properties of the alloy are improved.
具体实施方式Detailed ways
以下实施例中的实验方法如无特殊规定，均为常规方法，所涉及的实验试剂及材料如无特殊规定均为常规生化试剂和材料。The experimental methods in the following examples are conventional methods unless otherwise specified, and the involved experimental reagents and materials are conventional biochemical reagents and materials unless otherwise specified.
实施例1Example 1
本实施例所述镁合金由Mg、Sn、Zn和Sr元素组成，其各组分质量百分含量为：0.5％Sn、0.3％Zn、0.15％Sr，杂质元素Si、Fe、Cu和Ni的总量小于0.02％，余量为Mg。The magnesium alloy described in this embodiment is composed of Mg, Sn, Zn and Sr elements, and the mass percent content of each component is: 0.5% Sn, 0.3% Zn, 0.15% Sr, the impurity elements Si, Fe, Cu and Ni The total amount is less than 0.02%, and the balance is Mg.
该合金的制备方法包括熔炼、固溶热处理和塑性变形三个工艺工序。The preparation method of the alloy includes three process steps of smelting, solution heat treatment and plastic deformation.
其中，在前的熔炼工艺工序在SF6和CO2混合气体保护条件下进行，步骤如下：将纯镁在坩埚电阻炉中熔化，当温度升至730℃时加入纯锡和纯锌，待其熔化后搅拌10min；随后加入Mg-10Sr中间合金，继续搅拌10min使合金元素分布均匀。降温至720℃保温10min，捞去表面浮渣，浇注到预热至200℃的金属型模具中。Among them, the previous smelting process is carried out under the protection condition of mixed gas of SF 6 and CO 2 , and the steps are as follows: melt pure magnesium in a crucible resistance furnace, add pure tin and pure zinc when the temperature rises to 730°C, and wait until Stir for 10 minutes after melting; then add Mg-10Sr master alloy and continue stirring for 10 minutes to make the alloy elements evenly distributed. Cool down to 720°C and keep it warm for 10 minutes, remove the scum on the surface, and pour it into a metal mold preheated to 200°C.
随后的固溶热处理工艺工序为：将熔炼得到的合金铸锭在350℃保温24h，随后水淬至室温。The subsequent solution heat treatment process is as follows: the smelted alloy ingot is kept at 350° C. for 24 hours, and then water quenched to room temperature.
随后的塑性变形工艺工序为：对固溶处理后的Mg-Sn-Zn-Sr合金进行塑性变形，采用搅拌摩擦加工技术，搅拌头转速为400r/min，进给速度为200mm/min。The subsequent plastic deformation process is: plastic deformation of the solution-treated Mg-Sn-Zn-Sr alloy, using friction stir processing technology, the stirring head speed is 400r/min, and the feed speed is 200mm/min.
所得到合金的室温抗拉强度为257MPa，延伸率为21％。The room temperature tensile strength of the obtained alloy is 257MPa, and the elongation is 21%.
实施例2Example 2
本实施例所述镁合金由Mg、Sn、Zn和Sr元素组成，其各组分质量百分含量为：1.0％Sn，0.5％Zn，0.1％Sr，杂质元素Si、Fe、Cu和Ni的总量小于0.02％，余量为Mg。The magnesium alloy described in this embodiment is composed of Mg, Sn, Zn and Sr elements, and the mass percent content of each component is: 1.0% Sn, 0.5% Zn, 0.1% Sr, impurity elements Si, Fe, Cu and Ni The total amount is less than 0.02%, and the balance is Mg.
该合金的制备方法包括熔炼、固溶热处理和塑性变形三个工艺工序。The preparation method of the alloy includes three process steps of smelting, solution heat treatment and plastic deformation.
其中，在前的熔炼工艺工序在SF6和CO2混合气体保护条件下进行，步骤如下：将纯镁在坩埚电阻炉中熔化，当温度升至730℃时加入纯锡和纯锌，待其熔化后搅拌10min；随后加入Mg-10Sr中间合金，继续搅拌10min使合金元素分布均匀。降温至720℃保温10min，捞去表面浮渣，浇注到预热至200℃的金属型模具中。Among them, the previous smelting process is carried out under the protection condition of mixed gas of SF 6 and CO 2 , and the steps are as follows: melt pure magnesium in a crucible resistance furnace, add pure tin and pure zinc when the temperature rises to 730°C, and wait until Stir for 10 minutes after melting; then add Mg-10Sr master alloy and continue stirring for 10 minutes to make the alloy elements evenly distributed. Cool down to 720°C and keep it warm for 10 minutes, remove the scum on the surface, and pour it into a metal mold preheated to 200°C.
随后的固溶热处理工艺工序为：将熔炼得到的合金铸锭在400℃保温16h，随后水淬至室温。The subsequent solution heat treatment process is as follows: the smelted alloy ingot is kept at 400° C. for 16 hours, and then water quenched to room temperature.
随后的塑性变形工艺工序为：对固溶处理后的Mg-Sn-Zn-Sr合金进行塑性变形，采用搅拌摩擦加工技术，搅拌头转速为1000r/min，进给速度为120mm/min。The subsequent plastic deformation process is: plastic deformation of the solution-treated Mg-Sn-Zn-Sr alloy, using friction stir processing technology, the stirring head speed is 1000r/min, and the feed speed is 120mm/min.
所得到合金的室温抗拉强度为289MPa，延伸率为19％。The room temperature tensile strength of the obtained alloy is 289MPa, and the elongation is 19%.
实施例3Example 3
本实施例所述镁合金由Mg、Sn、Zn和Sr元素组成，其各组分质量百分含量为：1.5％Sn，0.7％Zn，0.05％Sr，杂质元素Si、Fe、Cu和Ni的总量小于0.02％，余量为Mg。The magnesium alloy described in this embodiment is composed of Mg, Sn, Zn and Sr elements, and the mass percent content of each component is: 1.5% Sn, 0.7% Zn, 0.05% Sr, impurity elements Si, Fe, Cu and Ni The total amount is less than 0.02%, and the balance is Mg.
该合金的制备方法包括熔炼、固溶热处理和塑性变形三个工艺工序。The preparation method of the alloy includes three process steps of smelting, solution heat treatment and plastic deformation.
其中，在前的熔炼工艺工序在SF6和CO2混合气体保护条件下进行，步骤如下：将纯镁在坩埚电阻炉中熔化，当温度升至730℃时加入纯锡和纯锌，待其熔化后搅拌10min；随后加入纯钙，继续搅拌10min使合金元素分布均匀。降温至720℃保温10min，捞去表面浮渣，浇注到预热至200℃的金属型模具中。Among them, the previous smelting process is carried out under the protection condition of mixed gas of SF 6 and CO 2 , and the steps are as follows: melt pure magnesium in a crucible resistance furnace, add pure tin and pure zinc when the temperature rises to 730°C, and wait until Stir for 10 minutes after melting; then add pure calcium and continue stirring for 10 minutes to make the alloy elements evenly distributed. Cool down to 720°C and keep it warm for 10 minutes, remove the scum on the surface, and pour it into a metal mold preheated to 200°C.
随后的固溶热处理工艺工序为：将熔炼得到的合金铸锭在450℃保温12h，随后水淬至室温。The subsequent solution heat treatment process is as follows: the smelted alloy ingot is kept at 450° C. for 12 hours, and then water quenched to room temperature.
随后的塑性变形工艺工序为：对固溶处理后的Mg-Sn-Zn-Sr合金进行塑性变形，采用搅拌摩擦加工技术，搅拌头转速为1600r/min，进给速度为40mm/min。The subsequent plastic deformation process is: plastic deformation of the solution-treated Mg-Sn-Zn-Sr alloy, using friction stir processing technology, the stirring head speed is 1600r/min, and the feed speed is 40mm/min.
所得到合金的室温抗拉强度为299MPa，延伸率为22％。The room temperature tensile strength of the obtained alloy is 299MPa, and the elongation is 22%.
对本领域的技术人员来说，可根据以上描述的技术方案以及构思，做出其它各种相应的改变以及形变，而所有的这些改变以及形变都应该属于本发明权利要求的保护范围之内。Those skilled in the art can make various other corresponding changes and deformations according to the above-described technical solutions and concepts, and all these changes and deformations should fall within the protection scope of the claims of the present invention.
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