CN116328025A - 一种医用植入体材料、植入体及其制备方法 - Google Patents
一种医用植入体材料、植入体及其制备方法 Download PDFInfo
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- CN116328025A CN116328025A CN202310609103.7A CN202310609103A CN116328025A CN 116328025 A CN116328025 A CN 116328025A CN 202310609103 A CN202310609103 A CN 202310609103A CN 116328025 A CN116328025 A CN 116328025A
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- magnesium alloy
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Abstract
本发明涉及一种医用植入体材料、植入体及其制备方法,该医用植入体材料包括含铜复合合金材料,所述含铜复合合金材料包括镁合金基体和设置于所述镁合金基体的保护层;所述保护层包含稀土氧化物和铜元素;通过对镁合金进行热氧化处理得到位于所述镁合金基体上的所述保护层,向所述保护层中掺入铜元素;所述保护层的厚度为1~5μm;铜元素在保护层中的深度为65~75nm。本发明一实施方式的医用植入体材料,具有较高的抑菌能力、较好的耐腐蚀性和良好的生物相容性,能够满足临床应用要求。
Description
技术领域
本发明涉及镁合金,尤其涉及一种具有抗菌性且耐腐蚀的医用植入体材料、植入体及其制备方法。
背景技术
骨科植入物是骨外科治疗过程中广泛使用的医疗器械,常被用作骨折,韧带和肌腱修复以及全髋关节置换术中的骨填充,固定和稳定装置。
理想中的植入物应当是暂时性的存在于体内,在完成服役任务,协助组织修复之后,逐渐的在体液环境中降解,被人体所吸收。目前以镁合金为代表的可降解金属由于其力学性能上的优异,受到了大量的关注于与研究。
镁及镁合金的密度和弹性模量与自然骨接近,同时具有良好的生物 相容性和可降解性能。因此,镁合金在可降解医用金属领域有望取代传统骨植入材料。
然而,临床上的医用植入体经常面临感染的危险,全球疾病负担2019抗生素耐药合作团队指出细菌感染已经成为紧随缺血性心脏病之后的人类第二大致死因素,控制骨科临床手术中及术后相关的细菌感染具有必要性和紧迫性。目前已有大量研究通过离子注入的方式将铜元素载入植入物表面以解决植入物感染的问题。然而含铜镁合金中的铜会与镁基体之间形成微电偶而加速腐蚀,快速的腐蚀会导致镁合金机械性能过早地降低,也会引起植入体周围组织液pH值的剧烈变化以及炎症反应等。因此,可降解镁合金所需克服的一大困难便是减缓其腐蚀速率,以保证其在植入过程中的力学性能完整性,减缓植入体服役过程中的过早失效。
发明内容
为克服上述现有技术的至少一种缺陷,第一方面,本发明一实施方式提供了一种医用植入体材料,所述医用植入体材料包括含铜复合合金材料,所述含铜复合合金材料包括镁合金基体和设置于所述镁合金基体的保护层;所述保护层包含稀土氧化物和铜元素;
通过对镁合金进行热氧化处理得到位于所述镁合金基体上的所述保护层,向所述保护层中掺入铜元素;所述保护层的厚度为1~5μm;铜元素在保护层中的深度为65~75nm。
根据本发明一实施方式,所述镁合金或所述镁合金基体包含镁和稀土元素。
根据本发明一实施方式,所述稀土元素包括钇和/或锆。
根据本发明一实施方式,所述稀土元素还包括钕和钆中的一种或多种。
第二方面,本发明一实施方式提供了一种医用植入体材料的制备方法,包括如下步骤:
对镁合金进行热氧化处理,在镁合金基体的表面形成保护层;以及
向所述保护层中掺入铜元素;
其中,所述镁合金包含镁和稀土元素。
根据本发明一实施方式,所述热氧化处理的温度为510~530℃;和/或,
所述热氧化处理的工艺过程包括:将所述镁合金在氧化气氛中进行加热处理,所述加热处理过程包括升温处理和保温处理,所述升温处理包括以8~10℃/min的加热速度对所述镁合金进行加热,待温度升至510~530℃时进行保温处理;所述保温处理的时间为4~12h。
根据本发明一实施方式,通过离子注入的方式将所述铜元素掺入所述保护层。
第三方面,本发明一实施方式提供了一种医用植入体,由上述的医用植入体材料制备得到。
本发明一实施方式的医用植入体材料,具有较高的抑菌能力、较好的耐腐蚀性和良好的生物相容性,能够满足临床应用要求。
本发明中,上述各技术方案之间还可以相互组合,以实现更多的优选组合方案。本发明的其他特征和优点将在随后的说明书中阐述,并且,部分优点可从说明书中变得显而易见,或者通过实施本发明而了解。本发明的目的和其他优点可通过说明书以及附图中所特别指出的内容中来实现和获得。
附图说明
附图仅用于示出具体实施例的目的,而并不认为是对本发明的限制。其中:
图1a为对比例1的合金D的表面形貌图;
图1b为对比例2的合金Z的表面形貌图;
图1c为实施例1的合金S的表面形貌图;
图2为实施例1的合金S横截面的扫描电镜图;
图3为实施例1的合金S的基体表面元素沿深度的变化图;
图4为合金S、合金Z与钛合金试样的体外细胞毒性测试;
图5为合金S、合金Z与钛合金试样的抑菌圈测试结果。
具体实施方式
下面对本发明的优选实施方式进行具体描述,其中,附图构成本发明一部分,并与本发明的实施方式一起用于阐释本发明的原理,并非用于限定本发明的范围。
本发明一实施方式提供了一种医用植入体材料,该医用植入体材料包括含铜复合合金材料,该含铜复合合金材料包括镁合金基体和设置于所述镁合金基体的保护层,所述保护层包含稀土氧化物和铜元素。铜元素可以为铜离子。
本发明一实施方式的含铜复合合金材料,铜元素的掺入使得合金材料具有更高的抑菌能力;同时,将铜元素设置于保护层中可以避免铜与镁合金基体之间形成微电偶,相较于现有的未设置保护层的包含铜元素的镁合金,降低了镁合金的腐蚀电位,降低了镁合金的腐蚀速率,能够满足临床应用要求。
于一实施方式中,保护层为包括稀土元素的氧化物层,通过将含稀土元素的镁合金进行热氧化处理制得。在热氧化处理的过程中,稀土元素会优先于镁元素发生氧化反应,生成氧化物层。
于一实施方式中,铜元素位于保护层中,进一步地,铜元素位于稀土氧化物层中。
于一实施方式中,保护层的厚度为1~5μm,例如2μm、3 μm、4 μm。
于一实施方式中,稀土元素钇和锆在镁合金中比 Mg 更具活性,并能在表面形成致密的钝化层来阻止镁基体的进一步氧化和腐蚀,因此,稀土元素包括钇和/或锆。
于一实施方式中,稀土元素还包括钕和钆中的一种或多种。
于一实施方式中,镁合金基体包括镁和稀土元素。
于一实施方式中,铜元素在保护层中呈高斯分布。
于一实施方式中,铜元素在保护层中深度为65~75nm。
于一实施方式中,保护层中铜元素的含量为:铜元素注入样本浸提液中的铜元素浓度为0.01~0.20mg/L。
本发明一实施方式提供了一种上述含铜复合合金材料的制备方法,包括如下步骤:
对镁合金进行热氧化处理,在镁合金基体的表面形成保护层;以及
向保护层中掺入铜元素;
其中,镁合金包含镁和稀土元素。
于一实施方式中,镁合金中,各元素的质量百分比可以为4.21%~4.27% Y、2.42%~2.47% Nd、1.23%~1.29% Gd、0.40%~0.43% Zr,剩余为Mg。
于一实施方式中,镁合金可以为WE43镁合金。WE43镁合金的各元素的质量百分比为4.26% Y、2.46% Nd、1.28% Gd、0.43% Zr,剩余为Mg。
于一实施方式中,在进行热氧化处理之前,可先对镁合金进行表面处理,以提高表面的品质。其中,表面处理可以包括振动除粉、机械研磨、化学抛光和超声清洗中的一种或多种。
于一实施方式中,表面处理包括:将镁合金进行机械振动去粉后,在无水乙醇内进行超声清洗;然后使用5%硝酸和5%盐酸混合的酒精溶液进行酸洗,或者采用磷酸酸洗进行酸洗,完全去除表面粘黏的粉末并产生适度的表面抛光。
于一实施方式中,热氧化处理的温度可以为510~530℃,例如515℃、520℃、525℃。
于一实施方式中,热氧化处理的工艺过程包括将镁合金在氧化气氛中进行加热处理;其中,加热处理过程包括升温阶段和保温阶段,升温阶段的加热速度为8~10℃/min,待温度升至510~530℃时进行保温;保温阶段的时间为4~12h;保温处理结束后,可将镁合金进行淬火处理。
于一实施方式中,保温阶段每过一小时对试样进行翻转。
于一实施方式中,保温处理结束后,将镁合金试样快速置入冷水中进行淬火处理。
于一实施方式中,可通过离子注入的方式将铜元素掺入保护层,离子注入可以采用现有的工艺进行。
于一实施方式中,考虑到所使用的铜元素剂量过大,会有毒性;铜元素剂量过小,抗菌效果差,经过深入研究,控制所使用的铜元素剂量为(3.5~4.5)× 1017 个/cm2。
于一实施方式中,可通过3D打印的方式制得镁合金。
于一实施方式中,可根据所需镁合金的形状,绘制生成相应的三维几何结构数据文件,使用粉末床激光熔融3D打印机自带的剖分软件进行剖分,将剖分完成的数据文件导入打印机进行打印。
于一实施方式中,将粒径为20~63μm的镁合金粉末预置在3D 打印机的粉仓中,将刮刀预置于设备的焦平面上,使用氩气作为保护气进行洗气,并将氧含量控制在100ppm以下,开启150~250℃的预热;打印过程中使用循环送风系统将烟尘吹除。
于一实施方式中,在打印过程中,激光光斑直径取50~120μm,激光功率50~200W,扫描速度取400~1600mm/s,扫描间距取50~120μm,粉末层厚度取10~40μm,采用逐层偏转的“之”字形内部填充及外轮廓塑形扫描策略,打印得到镁合金。
本发明一实施方式提供了一种医用植入体,由上述医用植入体材料制得。
于一实施方式中,可根据所需医用植入体的形状通过3D打印制得相应形状的镁合金,再针对镁合金进行热氧化处理及离子注入处理。
本发明一实施方式的医用植入体材料,相较于未将铜元素设置于保护层中的镁合金,腐蚀电位降低了70~80mV,腐蚀电流降低至1/20~1/30。
本发明一实施方式的医用植入体材料,包含铜元素的保护层与镁合金基体之间的结合强度良好,纳米压痕试验显示保护层的纳米结合强度为64GPa以上,例如 64.56GPa。
本发明一实施方式的医用植入体材料,具有抗菌性,腐蚀电流大大降低。
本发明一实施方式的医用植入体材料,具有较高的抑菌能力、良好的生物相容性以及全降解的特点,能够满足临床应用要求,可以用作医用植入体。
以下,结合附图及具体实施例对本发明一实施方式的医用植入体材料的制备及其应用进行进一步说明。
实施例1
本实施例提供了一种医用植入体材料,该医用植入体材料包括含铜复合合金材料,含铜复合合金材料包括镁合金基体和设置于镁合金基体的保护层,保护层包含稀土氧化物和铜元素。含铜复合合金材料的制备方法包括如下步骤:
S1:镁合金前处理
通过3D打印得到特定形状的WE43镁合金试样,将镁合金试样经进行机械振动去粉后,在无水乙醇内进行超声清洗,然后使用5%硝酸和5%盐酸混合的酒精溶液进行酸洗,完全去除表面粘黏的粉末并产生适度的表面抛光;酸洗抛光处理结束后,再次用无水乙醇超声清洗,洗去表面残留酸液,用吹风机将表面残留的酒精吹干。
S2:热氧化处理
将步骤S1处理后的镁合金试样放入热处理炉中,在氧化气氛中进行热处理,热处理条件为:以10 ℃/min的加热速度进行升温,至525 ℃时保温8小时,保温阶段每过一小时对试样进行翻转;保温结束后将试样快速置入冷水中进行淬火处理,后用吹风机将试样表面残留的水分吹干。
S3:铜元素注入
通过离子注入机将镁合金试样进行铜元素掺杂处理,制得含铜复合合金材料(简称“合金S”);离子注入机选择靶材为铜靶,掺杂铜元素所需参数为:真空度,铜元素剂量为4×1017个/cm2,电压为45keV,电流为2mA。
实施例2
本实施例提供了一种医用植入体材料,该医用植入体材料包括含铜复合合金材料,含铜复合合金材料的制备方法与实施例1整体步骤相同,不同之处在于:
S2中,热处理条件为:以9 ℃/min的加热速度进行升温,至530 ℃时保温7.5小时,保温阶段每过一小时对试样进行翻转;保温结束后将试样快速置入冷水中进行淬火处理,后用吹风机将试样表面残留的水分吹干。
对比例1
本例采用与实施例1基本相同的原料、工艺制备合金材料(简称“合金D”),区别仅在于:缺少步骤S2。
对比例2
本例采用与实施例1基本相同的原料、工艺制备合金材料(简称“合金Z”),区别仅在于:缺少步骤S3。
将实施例1、对比例1和对比例2的合金进行相关表征,其中,图1a为对比例1的合金D的表面形貌图,图1b为对比例2的合金Z的表面形貌图,图1c为实施例1的合金S的表面形貌图。相比较可以看出,铜元素注入处理对镁合金表面粗糙度影响不大。
图2为实施例1的合金S横截面的扫描电镜图,在较低倍率图像显示出稀土氧化物层和基体的梯度结构,而且在稀土氧化物层和镁合金基体之间形成析出相较少的中间层。稀土氧化物层的厚度约为2~5μm。采用俄歇电子能谱仪(AES,AESULVAC-PHI 700)对铜元素注入后试样表面改性层的元素含量进行深度剖析,Ar离子枪连续剥离表面并实时采集不同深度处各个元素的信号,得到元素浓度沿深度方向的变化曲线。测试在超高真空环境下进行,Ar离子枪束斑直径为50μm。
图3显示了实施例1的合金S的基体表面元素沿深度的变化,通过图3可以看出,位于表面的稀土氧化物层主要由Mg、O、Y、Zr和Cu元素构成,各元素浓度沿深度方向发生明显变化,注入的Cu元素深度约为70nm,Cu元素在稀土氧化物层中呈高斯分布。保护层中铜元素的含量为:铜元素注入样本浸提液中的铜元素浓度为0.01~0.20mg/L。
通过电化学性能测试评价了合金S、合金Z与合金D的耐腐蚀性能。将实施例1制得的合金S在37±1℃,模拟体液SBF溶液中进行电化学测试,采用三电极体系,铂极作为辅助电极,饱和甘汞作为参比电极,电位扫描速度为 0.001V /s,腐蚀电压和腐蚀电流密度由PDP曲线的Tafel外推计算,相关结果参见下表1。从表1中可以看出,实施例1制备的合金S腐蚀电位与合金D相比降低了70~80mV,合金S的腐蚀电流降低至合金D的1/27左右,表明合金S的耐蚀性最好。对比可知,合金S的耐蚀性与合金Z相比也有明显的提高。
表1 不同合金的腐蚀性能数据
图4为合金S、合金Z与钛合金试样的体外细胞毒性测试。在不同提取物中培养3天的骨髓间充质干细胞用磷酸盐缓冲盐水洗涤,并在培养箱中用 2 mM 钙黄绿素和 4 mM 碘化丙啶染色 10 分钟。温和冲洗后,使用荧光显微镜检查细胞。从图中可以看出,健康纺锤形细胞在所有组中分布广泛,细胞培养实验结果表明,合金S和合金Z均具有良好的生物相容性。
图5为合金S、合金Z与钛合金试样的抑菌圈测试结果。100μL MRSA悬浮液(1×107CFU/mL)均匀涂覆在色氨酸大豆琼脂板上,将合金S、合金Z与钛合金试样金属圆盘轻轻放置在板的中心。抗菌效率取决于琼脂扩散的抗菌环的直径。从图中可以看出,钛合金片没有抗菌能力,没有形成抑菌圈。合金Z合金具有一定的抗菌性能。三种合金中,合金S的抗菌性能最好。
合金D由于耐腐蚀较差,过快的腐蚀速率导致其植入实验动物体内7天后失去了结构完整性,不具有临床应用的可能,故未将其与合金S与合金D的抗菌性能进行比较。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种医用植入体材料,所述医用植入体材料包括含铜复合合金材料,所述含铜复合合金材料包括镁合金基体和设置于所述镁合金基体的保护层;所述保护层包含稀土氧化物和铜元素;
通过对镁合金进行热氧化处理得到位于所述镁合金基体上的所述保护层,向所述保护层中掺入铜元素;
所述保护层的厚度为1~5μm;铜元素在保护层中的深度为65~75nm。
2.根据权利要求1所述的医用植入体材料,其中,所述镁合金或所述镁合金基体包含镁和稀土元素。
3.根据权利要求2所述的医用植入体材料,其中,所述稀土元素包括钇和/或锆。
4.根据权利要求3所述的医用植入体材料,其中,所述稀土元素还包括钕和钆中的一种或多种。
5.一种医用植入体材料的制备方法,包括如下步骤:
对镁合金进行热氧化处理,在镁合金基体的表面形成保护层;以及
向所述保护层中掺入铜元素;
其中,所述镁合金包含镁和稀土元素。
6.根据权利要求5所述的方法,其中,所述热氧化处理的温度为510~530℃;和/或,
所述热氧化处理的工艺过程包括:将所述镁合金在氧化气氛中进行加热处理,所述加热处理过程包括升温处理和保温处理,所述升温处理包括以8~10℃/min的加热速度对所述镁合金进行加热,待温度升至510~530℃时进行保温处理;所述保温处理的时间为4~12h。
7.根据权利要求5所述的方法,其中,通过离子注入的方式将所述铜元素掺入所述保护层。
9.根据权利要求7所述的方法,其中,在所述离子注入工艺中,电压为43~45 keV,电流为1.8~2mA。
10.一种医用植入体,由权利要求1至4任一项所述的医用植入体材料制备得到。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160339144A1 (en) * | 2012-05-09 | 2016-11-24 | Amedica Corporation | Ceramic and/or glass materials and related methods |
CN107304472A (zh) * | 2016-04-18 | 2017-10-31 | 中国科学院上海硅酸盐研究所 | 兼具骨修复功能和抗菌性能的医用钛基复合涂层及其制备方法 |
US20220016315A1 (en) * | 2018-11-23 | 2022-01-20 | Meotec Gmbh | Biodegradeable implant comprising coated metal alloy product |
CN114288471A (zh) * | 2021-12-31 | 2022-04-08 | 清华大学 | 镁合金医用植入物及其制备方法 |
CN114340689A (zh) * | 2019-08-21 | 2022-04-12 | 百优瑞泰克有限公司 | 复合材料、包括其的植入物、复合材料的用途以及制备复合材料和医疗装置的方法 |
CN114369808A (zh) * | 2021-12-20 | 2022-04-19 | 中国兵器科学研究院宁波分院 | 一种镁及镁合金表面制备抗菌涂层的方法 |
CN115522175A (zh) * | 2022-05-07 | 2022-12-27 | 东莞宜安科技股份有限公司 | 一种可降解纯镁或镁合金表面改性方法及纯镁或镁合金材料 |
-
2023
- 2023-05-29 CN CN202310609103.7A patent/CN116328025B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160339144A1 (en) * | 2012-05-09 | 2016-11-24 | Amedica Corporation | Ceramic and/or glass materials and related methods |
CN107304472A (zh) * | 2016-04-18 | 2017-10-31 | 中国科学院上海硅酸盐研究所 | 兼具骨修复功能和抗菌性能的医用钛基复合涂层及其制备方法 |
US20220016315A1 (en) * | 2018-11-23 | 2022-01-20 | Meotec Gmbh | Biodegradeable implant comprising coated metal alloy product |
CN114340689A (zh) * | 2019-08-21 | 2022-04-12 | 百优瑞泰克有限公司 | 复合材料、包括其的植入物、复合材料的用途以及制备复合材料和医疗装置的方法 |
CN114369808A (zh) * | 2021-12-20 | 2022-04-19 | 中国兵器科学研究院宁波分院 | 一种镁及镁合金表面制备抗菌涂层的方法 |
CN114288471A (zh) * | 2021-12-31 | 2022-04-08 | 清华大学 | 镁合金医用植入物及其制备方法 |
CN115522175A (zh) * | 2022-05-07 | 2022-12-27 | 东莞宜安科技股份有限公司 | 一种可降解纯镁或镁合金表面改性方法及纯镁或镁合金材料 |
Non-Patent Citations (2)
Title |
---|
SAIFEI XU 等: "EffectsofCuonthecorrosionbehaviorandmicrostructure of Mg–Zn–Ca bulk metallic glass", 《MATERIALS AND CORROSION》, vol. 72, pages 1547 * |
TIANXIAO WANG 等: "Enhancing the Antibacterial Properties of Magnesium Alloys with Copper-Doped Anhydrous Calcium Phosphate Nanoparticles Embedded into the Polycaprolactone Coating for Medical Implants", 《 ACS APPLIED NANO MATERIALS》, vol. 5, pages 18965 * |
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