CN111676390A - 一种Zn-Ga系合金及其制备方法与应用 - Google Patents
一种Zn-Ga系合金及其制备方法与应用 Download PDFInfo
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- CN111676390A CN111676390A CN202010765449.2A CN202010765449A CN111676390A CN 111676390 A CN111676390 A CN 111676390A CN 202010765449 A CN202010765449 A CN 202010765449A CN 111676390 A CN111676390 A CN 111676390A
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/165—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon of zinc or cadmium or alloys based thereon
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Abstract
本发明公开了一种Zn‑Ga系合金及其制备方法与应用,属于医用合金技术领域,所述Zn‑Ga系合金包括Zn和Ga,所述Zn‑Ga系合金中Ga占0~30wt%,但不包括0,所述制备方法为将Zn和Ga或Zn、Ga和微量元素混合,进行熔炼或烧结或者熔炼或烧结之后涂覆涂层得到Zn‑Ga系合金。制备的Zn‑Ga系合金的力学性质符合医用植入体材料的强度和韧性的要求,同时又可体内降解,具有可生物腐蚀降解特性和适宜的腐蚀速率保证提供长期有效的力学支撑双重特性。
Description
技术领域
本发明涉及医用合金技术领域,特别是涉及一种Zn-Ga系合金及其制备方法与应用。
背景技术
目前用于临床的生物医用材料主要有生物医用金属材料、无机材料、高分子材料、复合材料及仿生材料等。医用金属材料与高分子材料和陶瓷材料相比,具有较高的强度、韧性和加工性能,因此应用最为广泛。如:316L、317L、304V不锈钢、Co-Cr-Mo合金、纯钛、Ti-6Al-4V、TiNi合金等。这些材料在人体内不可降解,为永久性植入,当植入体在人体内的服役期满后,必须通过二次手术取出,从而给患者带来不必要的生理痛苦及经济负担。
随着医学和材料科学的发展,对于一些需要临时服役的材料,如缝合线、骨折固定板,血管支架、胆道支架等,人们希望植入体内的材料只是起到暂时替代的作用,并随着组织或器官的再生而逐渐降解吸收,以最大的限度地减少材料对机体的长期影响。由于生物降解性材料容易在生物体内与体液等介质相互作用逐渐降解,其分解产物可以代谢,并最终排出体外,无需二次手术取出,因而越来越受到人们的重视,已成为当前国际生物材料领域的前沿与研究热点。
目前临床常用的可生物降解材料主要为可生物降解高分子材料和可生物降解陶瓷。可生物降解高分子材料虽能够完全被人体吸收,但强度低,很难提供结构支撑的功能;可生物降解陶瓷的缺点是韧性差,无法协调变形。
近年来,可降解生物医用镁合金材料成为研究热点之一,开发了一系列的生物医用可降解镁合金,如AZ31、WE43、Mg-Ca等,尽管镁合金作为生物材料有着诱人的应用前景,然而研究发现镁合金存在腐蚀速度过快,在组织器官没有充分愈合之前,植入物便很快会丧失它的机械完整性,因而有必要开发新型可降解合金以满足临床需求。
与镁及镁合金相同,金属锌及其合金由于化学性质活泼、易于腐蚀常常被用作腐蚀保护中被牺牲的阳极材料。但与镁相比,金属锌及其合金具有更高的腐蚀电位,因而相比镁合金来说金属锌及其合金腐蚀速率减慢,因而更加符合临床需求,有望发展成为新型生物医用可降解植入材料及器件。
人体正常含锌量为2-3克。锌是体内数十种酶的主要成分。锌分布于绝大部分器官与组织中,其中肝脏、肌肉和骨骼中含量较高。锌在人体中虽为微量元素,但作用却非常之大。有“生命的火花塞”之称。(1)锌与各种骨基质合成酶有关,它能够参与骨形成与骨重建。当锌缺乏时,骨中多种含锌酶的活性下降,骨的生长受到抑制;(2)锌是生物膜的关键组成部分,其在维持2000多种转录因子和300多种酶的结构和功能中具有重要作用;(3)锌能够迅速进入内皮细胞,维持内皮细胞的完整性,降低血管对动脉粥样硬化的易感性;(4)锌可以保护心肌细胞避免急性氧化应激以及心肌损伤引起的炎性反应;(5)锌能够积极参与核酸蛋白合成,加速创伤愈合;(6)此外,锌还与体内各种细胞代谢作用密切相关,如糖代谢、脂类代谢和抗衰老等。锌缺乏会导致动脉硬化、心率失常与衰竭、脑功能畸形、免疫力低下、下痢、食欲不振、生长减缓、掉发、夜盲、前列腺肥大、男性生殖功能减退、贫血等。成人每日需补充15-25mg锌。
镓(Ga)是人体强骨固钙剂,可用于治疗癌症相关高钙血症及变形性骨炎。镓因为能与细菌蛋白结合而具有较强的杀菌作用。镓及其化合物具有抗炎、抗骨质疏松的作用。镓能够抑制破骨细胞再吸收,抑制骨溶解,阻止骨钙释放,改变骨中Ⅰ型胶原和纤维蛋白的基因表达,有利于新骨的形成,还能增加骨骼中钙和磷的含量,直接作用于人体骨的形成。
目前国内外还没有文献和专利报道Zn-Ga系合金的合成及性能,也没有相关文献和专利提出将Zn-Ga系合金用作可降解生物医用材料使用。
发明内容
本发明的目的是提供一种Zn-Ga系锌合金及其制备方法与应用,具体涉及一种Zn-Ga系锌合金及其制备方法与在制备可体液降解医用植入体中的应用。本发明制备的锌合金力学性能优异,能够在体内提供长期有效的支撑力,具有优异的细胞相容性、血液相容性和组织、器官相容性,可用于生物医用植入材料。
为实现上述目的,本发明提供了如下方案:
本发明提供一种Zn-Ga系合金,包括Zn和Ga,所述Zn-Ga系合金中Ga占0~30wt%,但不包括0。
作为本发明的进一步改进,所述Zn-Ga系合金还包括微量元素,所述微量元素为镁、钙、锶、锰、钛、锆、锗、铜、硅、磷、锂、银、锡和稀土元素中的至少一种,所述微量元素占比0~10wt%。
作为本发明的进一步改进,所述Zn-Ga系合金的表面还涂覆有可降解高分子涂层、可降解陶瓷涂层或可降解药物涂层。
作为本发明的进一步改进,所述可降解高分子涂层、所述可降解陶瓷涂层和所述可降解药物涂层的厚度均为0.001~5mm。
作为本发明的进一步改进,所述可降解高分子涂层的制备材料为下述1)和2)中至少一种:
1)聚己酸内酯(PCL)、聚乳酸(PLA)、聚羟基乙酸(PGA)、L-聚乳酸(PLLA)、聚氰基丙烯酸酯(PACA)、聚酸酐、聚膦腈、聚对二氧杂环己烷酮、聚-羟基丁酸酯和聚羟基戊酸酯中任一种;
2)聚乳酸(PLA)、聚己酸内酯(PCL)、聚羟基乙酸(PGA)、L-聚乳酸(PLLA)、聚氰基丙烯酸酯(PACA)和聚对二氧杂环己烷酮中的任意两种或两种以上的共聚物;
所述可降解陶瓷涂层的制备材料为羟基磷灰石、磷酸三钙或磷酸氧四钙中的至少一种;
所述可降解药物涂层为雷帕霉素及其衍生物涂层、紫杉醇涂层、依维莫司涂层、西罗莫司涂层、丝裂霉素涂层和抗菌涂层中的至少一种。
作为本发明的进一步改进,所述的Zn-Ga系锌合金具体为下述1)-4)中任一种,为质量百分比:
1)由95~99%的Zn和1%~5%的Ga组成;
2)由99%的Zn和1%的Ga组成;
3)由98%的Zn和2%的Ga组成;
4)由98.5%的Zn、1%的Ga和0.5%的Y组成。
本发明制备的Zn-Ga系锌合金为致密结构或多孔结构,具备良好的组织相容性,是一种可靠的生物医用植入材料。
本发明还提供一种所述的Zn-Ga系合金的制备方法,包括以下步骤:
将Zn、Ga和所述微量元素按照下述1)和2)中任一种方式进行混合得到混合物:
1)Zn和Ga;
2)Zn、Ga和微量元素;
按照下述a)或b)的步骤即得到所述锌合金:
a)在CO2和SF6气氛保护下,将所述混合物进行熔炼或烧结,经冷却后即得所述锌合金;
b)在CO2和SF6气氛保护下,将所述混合物进行熔炼或烧结,经冷却后涂覆所述可降解高分子涂层、所述可降解陶瓷涂层或所述可降解药物涂层即得所述锌合金。制备锌合金的方法还包括涂覆涂层的步骤是为了适应不同临床需求。
作为本发明的进一步改进,制备方法中所述熔炼的温度为500~700℃。
作为本发明的进一步改进,制备方法中还包括将所述锌合金进行机械加工的步骤。
作为本发明的进一步改进,所述机械加工为轧制、锻造、快速凝固和挤压中至少一种。
作为本发明的进一步改进,返式轧机中反复轧制,热轧温度在250℃,最后在精轧机中,在250℃下将其轧制到1.5mm厚度。
作为本发明的进一步改进,所述锻造包括将所述Zn-Ga系合金在150~200℃的条件下进行保温以及在200~300℃的条件下进行锻造的步骤,所述保温的时间为3~50h,所述锻造的速率不小于350mm/s。
作为本发明的进一步改进,所述挤压的温度为150~250℃,具体为200~220℃;挤压比为10~70,具体为20~25。
作为本发明的进一步改进,所述快速凝固包括如下步骤:在Ar气保护下,采用高真空快淬系统制备快速凝固薄带,然后将所述薄带破碎成粉末状,然后在200~350℃的条件下,真空热压1~24h。
作为本发明的进一步改进,所述高真空快淬系统的设置如下:加料量2~8g、感应加热功率为3~7kW、喷嘴与辊间距为0.80mm、喷射压力为0.05~0.2MPa、辊轮转速为500~3000r/min及喷嘴狭缝尺寸为1film×8mm×6mm。
作为本发明的进一步改进,所述烧结为下述任一种方法:元素粉末混合烧结法、预合金粉烧结法和自蔓延高温合成法。
作为本发明的进一步改进,所述元素粉末混合烧结法是将所述制备多孔结构Zn-Ga系合金的原料混合均匀,压制成坯,然后在真空烧结炉中,以2~4℃/min慢速升温至100~200℃后接着以30℃/min快速升温至200~300℃烧结,然后降温,得到成多孔结构的Zn-Ga系合金;
作为本发明的进一步改进,所述预合金粉烧结法是将所述制备多孔结构Zn-Ga系合金的原料混合后进行高能球磨,然后压制成型,在250~350℃进行热处理10-20小时,得到多孔结构的Zn-Ga系合金;
作为本发明的进一步改进,所述自蔓延高温合成法是将制备多孔结构Zn-Ga系合金的原料混合后压制成坯,在惰性气体保护下,压力为1×103~1×105Pa,温度为250~350℃下,然后将Zn-Ga系合金坯料点燃进行自蔓延高温合成,得到多孔结构的Zn-Ga系合金。
作为本发明的进一步改进,涂覆可生物降解高分子涂层的方法是将所述锌合金进行酸洗,然后将其在所述生物降解高分子涂层的制备材料溶于三氯乙烷制备的胶体中浸涂10~30min后,匀速拉出进行离心处理得到涂覆有可生物降解高分子涂层的锌合金。
作为本发明的进一步改进,涂覆可降解陶瓷涂层的方法可为等离子喷涂、电泳沉积、阳极氧化和水热合成中任一种;
作为本发明的进一步改进,等离子体喷涂所用的等离子气体主气为Ar,流量为30~100scfh,等离子气体次气为H2,流量为5~20scfh,喷涂电流为400~800A,喷涂电压为40~80V,喷涂距离为100~500mm;
作为本发明的进一步改进,所述电沉积可降解陶瓷涂层的方法为以锌合金为阴极在含钙、磷盐的电解液中,电流密度为2~10mA/cm2,处理10~60min后,清洗干燥得到所述锌合金;
作为本发明的进一步改进,所述阳极氧化和水热合成结合的方法为将所述锌合金在含有0.01~0.5mol/Lβ-甘油磷酸钠和0.1~2mol/L醋酸钙的电解液中,在200~500V下氧化10~30min,然后将所述锌合金在200~400℃下处理1~4h。
作为本发明的进一步改进,所述涂覆可降解药物涂层的方法为物理和化学方法;
所述物理方法涂层工艺主要采用浸泡、喷涂方法;所述化学方法主要运用电化学原理进行电镀;
所述浸泡方法为将活性药物与控释载体(或单独的活性药物)配制成溶液,具体浓度可因溶液粘度和所需药物剂量不同而不同,然后将所述医用植入体浸泡入溶液中,然后经过必要的后处理过程,如交联、干燥、固化等步骤,制成药物涂层;
所述喷涂方法为将活性药物与控释载体(或单独的活性药物)配制成溶液,然后通过喷洒工具或特制的喷涂设备将溶液均匀涂布于所述医用植入体表面,经干燥、固化等后处理步骤之后即制成药物涂层;
所述化学方法是利用活性药物和(或)控释载体在由所述医用植入制作的电极上发生电氧化还原反应,使所述医用植入表面形成稳定的由化学键连接的药物涂层。
本发明利用Zn及Zn合金易于腐蚀的特点,选择了Zn-Ga系合金作为降解性材料应用于医用植入体。本发明的Zn-Ga系合金的力学性质符合医用植入体材料的强度和韧性的要求,同时又可体内降解,即可以克服医用高分子材料强度低和316L不锈钢、钛及钛合金等传统医用金属材料不可降解的弱点,又可以克服镁及镁合金降解速率过快导致植入体内力学性能丧失的缺陷,作到兼具有“可生物腐蚀降解特性”和“适宜的腐蚀速率保证提供长期有效的力学支撑”双重特性。
本发明还提供所述的Zn-Ga系合金的应用,所述Zn-Ga系合金用于制备可体液降解医用植入体。所述可体液降解医用植入体包括:治疗用植入支架、骨修复器械、颅颌面修复器械;
作为本发明的进一步改进,所述治疗用植入支架可为血管支架、食道支架、肠道支架、气管支架、胆道支架或尿道支架;
所述骨修复器械可为骨组织修复支架、接骨器、固定线、固定螺丝、固定铆钉、固定针、夹骨板、髓内针或接骨套;
所述颅颌面修复器械可为颅骨修复网、颌面骨缺损修复支架等。
本发明公开了以下技术效果:
(1)本发明制备的Zn-Ga系合金的力学性质符合医用植入体材料的强度和韧性的要求,同时又可体内降解,具有“可生物腐蚀降解特性”和“适宜的腐蚀速率保证提供长期有效的力学支撑”双重特性。
(2)本发明Zn-Ga系合金用于可降解医用植入体时,在植入一段时间内既能发挥其金属材料的高强度特点,完成植入体的功能(如诱导新骨组织形成或者支撑狭窄的血管),又能在人体病变部位进行自身修复的同时作为“异体”逐渐被人体腐蚀降解,数量和体积逐渐减少,溶出的金属离子能被生物体吸收利用促进骨生长或代谢排除体外,最终在人体结束自身修复时金属材料植入体完全降解消失。
(3)本发明提供的可体液降解的医用植入体无毒,具备良好的组织相容性和血液相容性。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其他的附图。
图1为细胞在Zn-Ga合金细胞相容性测试结果。
具体实施方式
现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时,以本说明书的内容为准。
在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本申请说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等,均为开放性的用语,即意指包含但不限于。
下述实施例中所用的百分含量,如无特别说明,均为质量百分含量。
实施例1、制备铸态Zn-Ga系合金
以纯Zn(99.99wt.%)、纯Ga(99.95wt.%)(购自北京翠柏林有色金属技术开发中心)作为原料,按不同的质量比(Zn与Ga及其他微量元素Y(Gd,Nd)的质量比为99:1;98.5:1.5;98:2;97:3;95:5)混合,在CO2+SF6气氛保护下,550℃熔炼,待原料充分熔解后,保温10min后,循环水快速冷却,制得Zn-Ga合金锭。
实施例2、制备轧态Zn-Ga系合金
首先按照实施例1中的步骤制备得到铸态的Zn-Ga系合金铸锭;然后对上述得到Zn-Ga合金锭进行热轧,先250℃预热铸锭,然后采用热轧方式,在往返式轧机中反复轧制,温轧温度在250℃,最后在精轧机中,在250℃下将其轧制到1.5mm厚度。
实施例3、制备挤压态Zn-Ga系合金
按照下述1)或2)的步骤进行制备:
1)首先按照实施例1中的步骤制备得到铸态的Zn-Ga系合金铸锭,采用挤压的方式制备Zn-Ga系合金棒材,采用径向挤压,挤压温度为200℃,挤压比为20,制备出直径为10mm的Zn-Ga系合金棒材。
2)首先按照实施例1中的步骤制备得到铸态的Zn-Ga系合金铸锭,采用高真空快淬系统制备快速凝固Zn-Ga系合金薄带,具体方法是:将原料按所述比例混合后采用高真空快淬系统制备快速凝固Zn-Ga系薄带(温度550℃,没有热压时间),参数为加料量2~8g、感应加热功率3~7kW、喷嘴与辊间距0.80mm、喷射压力0.1MPa、辊轮转速2000r/mln及喷嘴狭缝尺寸1film×8mm×6mm。然后将薄带粉碎后压制成坯,采用挤压的方式制备Zn-Ga系合金棒材,采用径向挤压,挤压温度为200℃,挤压比为20,制备出直径为10mm的Zn-Ga系合金棒材。
实施例4、Zn-Ga系合金力学性能
将按照实施例1-3的方法制备的Zn-Ga系合金,分别按照ASTM-E8-04拉伸测试标准制备拉伸样品,依次经400#、800#、1200#和2000#SiC砂纸系列打磨抛光。在丙酮、无水乙醇和去离子水中分别超声清洗15min后,采用万能材料力学试验机在室温下进行拉伸试验,拉伸速度为1mm/min。
Zn-Ga系合金各试样的室温拉伸性能如表1所示,由表1可知,相对于铸态合金,轧制态合金和挤压态合金的屈服强度和拉伸强度均得到了明显提高,同时,延伸率得到大幅度增加,表明材料经过变形加工过程后力学性能得到进一步优化。
表1.Zn-Ga合金抗拉力学性能数据
实施例5、Zn-Ga合金血液相容性
将实施例2经轧制的Zn-Ga合金,通过线切割制备10×10×1.5mm Zn-Ga合金试样片,经400#、800#、1200#和2000#SiC砂纸系列打磨抛光。在丙酮、无水乙醇和去离子水中分别超声清洗15min后,25℃下干燥。采集健康志愿者身上新鲜血液,置于内含3.8wt.%柠檬酸钠作为抗凝剂的抗凝管保存。用0.9%生理盐水按4:5的比例稀释制成稀释血液样本。将试样浸泡在10mL生理盐水,37±0.5℃保温30min,加入0.2mL稀释血液样本,37±0.5℃保温60min。采用10mL生理盐水作为阴性对照组,10mL去离子水作为阳性对照组。经3000rpm离心5分钟,取上清液用Unic-7200紫外可见分光光度计545nm测量吸光度OD值,设置三组平行样以进行统计学分析。
用以下公式计算溶血率:
溶血率=(实验组OD值-阴性组OD值)/(阳性组OD值-阴性组OD值)×100%。
实验结果表明,Zn-Ga系合金的溶血率在0.2%-0.5%之间,远远小于临床使用要求的安全阈值5%,表现出良好的红细胞和血红蛋白相容性。
实施例7、可体液降解医用Zn-Ga植入体的制备及其细胞相容性实验
按实施例1-3的方法制备Zn-Ga合金,将6枚长、宽、厚度分别为10、10、1.5mm的上述制备的Zn-Ga合金块经γ射线消毒灭菌,置于无菌培养瓶中,按试样表面积与MEM细胞培养基体积之比为1.25cm2/mL的比例加入MEM细胞培养基,置于37℃、95%相对湿度、5%CO2培养箱中72h,得到Zn-Ga合金浸提液原液,密封,4℃冰箱保存备用。
浸提液与细胞接种培养及结果观察:将MG63细胞(购自于广州吉妮欧生物科技有限公司)复苏、传代后,悬浮于MEM细胞培养基中,接种于96孔培养板上,阴性对照组加入MEM细胞培养基,Zn-Ga合金浸提液组加入上述得到的稀释4倍的Zn-Ga合金浸提液,使最终细胞浓度为5×104/mL。置于37℃、5%CO2培养箱中培养,5天后取出培养板,在倒置相差显微镜下观察活细胞的形态(如图1所示)。结果表明:细胞形貌呈现为健康伸展的梭形汇聚生长,说明Zn-Ga合金具有优异的细胞相容性。
以上所述的实施例仅是对本发明的优选方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
Claims (10)
1.一种Zn-Ga系合金,其特征在于,包括Zn和Ga,所述Zn-Ga系合金中Ga占0~30wt%,但不包括0。
2.根据权利要求1所述的一种Zn-Ga系合金,其特征在于,所述Zn-Ga系合金还包括微量元素,所述微量元素为镁、钙、锶、锰、钛、锆、锗、铜、硅、磷、锂、银、锡和稀土元素中的至少一种。
3.根据权利要求2所述的一种Zn-Ga系合金,其特征在于,所述微量元素占比0~10wt%。
4.根据权利要求1所述的一种Zn-Ga系合金,其特征在于,所述Zn-Ga系合金的表面还涂覆有可降解高分子涂层、可降解陶瓷涂层或可降解药物涂层。
5.根据权利要求1所述的一种Zn-Ga系合金,其特征在于,所述可降解的高分子涂层的制备材料为下述1)和2)中至少一种:
1)聚己酸内酯、聚乳酸、聚羟基乙酸、L-聚乳酸、聚氰基丙烯酸酯、聚酸酐、聚膦腈、聚对二氧杂环己烷酮、聚-羟基丁酸酯和聚羟基戊酸酯中任一种;
2)聚乳酸、聚己酸内酯、聚羟基乙酸、L-聚乳酸、聚氰基丙烯酸酯和聚对二氧杂环己烷酮中的任意两种或两种以上的共聚物;
所述陶瓷涂层的制备材料为羟基磷灰石、磷酸三钙或磷酸氧四钙中的至少一种;
所述药物涂层为雷帕霉素及其衍生物涂层、紫杉醇涂层、依维莫司涂层、西罗莫司涂层、丝裂霉素涂层和抗菌涂层中的至少一种。
6.一种如权利要求1~5任一项所述的Zn-Ga系合金的制备方法,其特征在于,包括以下步骤:
将Zn、Ga和所述微量元素按照下述1)和2)中任一种方式进行混合得到混合物:
1)Zn和Ga;
2)Zn、Ga和微量元素;
按照下述a)或b)的步骤即得到所述锌合金:
a)在CO2和SF6气氛保护下,将所述混合物进行熔炼或烧结,经冷却后即得所述锌合金;
b)在CO2和SF6气氛保护下,将所述混合物进行熔炼或烧结,经冷却后涂覆所述可降解高分子涂层、所述可降解陶瓷涂层或所述可降解药物涂层即得所述Zn-Ga系合金。
7.根据权利要求6所述的Zn-Ga系合金的制备方法,其特征在于,还包括将所述Zn-Ga系合金进行机械加工的步骤。
8.根据权利要求7所述的Zn-Ga系合金的制备方法,其特征在于,所述机械加工为轧制、锻造、快速凝固和挤压中至少一种。
9.根据权利要求6所述的Zn-Ga系合金的制备方法,其特征在于,所述烧结为下述任一种方法:元素粉末混合烧结法、预合金粉烧结法和自蔓延高温合成法。
10.一种根据权利要求1~5任一项所述的Zn-Ga系合金的应用,其特征在于,所述Zn-Ga系合金在制备可体液降解医用植入体中的应用。
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