CN115198268A - 金属基表面耐蚀抗菌复合涂层制备方法及复合涂层和用途 - Google Patents
金属基表面耐蚀抗菌复合涂层制备方法及复合涂层和用途 Download PDFInfo
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- CN115198268A CN115198268A CN202210737643.9A CN202210737643A CN115198268A CN 115198268 A CN115198268 A CN 115198268A CN 202210737643 A CN202210737643 A CN 202210737643A CN 115198268 A CN115198268 A CN 115198268A
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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Abstract
金属基表面耐蚀抗菌复合涂层制备方法及复合涂层和用途,步骤(1)取不同的二水合醋酸锌和无水乙醇于容器中;步骤(2)搅拌并保温70℃,后加乙醇胺稳定剂;步骤(3)温度降至室温后,加入无水乙醇定容为不同浓度的溶液;步骤(4)搅拌形成溶胶;步骤(5)将TC4/PDA浸入溶胶中,真空干燥从室温升至60℃保温1h后升至80℃,后以20℃的升温间隔升至140℃保温2 h至200℃,真空干燥16h停止加热,待降至室温后破真空,转至马弗炉中,升温至500℃‑600℃保温1h;步骤(6)保温后待其降至室温,形成的耐蚀结合涂层为聚多巴胺涂层‑PDA涂层;抗菌层是纳米氧化锌涂层‑ZnO涂层。用途是用于植入性医疗器械。
Description
技术领域
本发明属于金属材料表面改性技术领域,涉及纳米复合涂层的制备技术。
背景技术
随着疾病或意外伤害等导致的硬组织损伤日益增多,钛合金作为人工骨替代物,由于具有优异的生物相容性、良好的机械性能,在植入医学领域引起了极大的关注。增材制造技术的发展使得多孔钛合金加工成为可能,该技术也有效解决了钛合金植入体存在的“应力屏蔽”问题。然而,钛合金作为永久硬组织植入物,在考虑其力学性能的同时还必须兼顾抗菌、耐腐蚀和促进骨细胞生长等综合性能。表面改性涂层设计在优化钛合金的使用性能方面发挥着重要的作用。
钛合金由于具有较好的力学性能和生物相容性,在外科植入领域被广泛使用。增材制造技术(3D打印)的出现打破了传统钛合金植入体的制造方法,使得钛合金在骨科领域向精密化、个性化方向发展。3D打印虽然为钛植入体解决了适配性、应力屏蔽等诸多问题,但无法对材料本身做出改变,其抗菌耐蚀性有待改善。专家学者关于3D 打印在骨科植入体方面做了大量的研究,但仍处于探索阶段。Ti6A14V作为一款传统医用钛合金,由于其优异的性能在3D打印制造领域有着相对成熟的加工制造工艺,被广泛应用于植入假体。但因其本身具有生物惰性且含有Al、V等毒元素限制了它在人体内长期稳定的使用。因此对TC4表面进行功能性改性以提高它的耐蚀性、抗菌性及生物相容性有着重要意义。
发明内容
本发明的目的是提供一种金属基表面耐蚀抗菌复合涂层制备方法及复合涂层和用途。
本发明是金属基表面耐蚀抗菌复合涂层制备方法及复合涂层和用途,金属基表面耐蚀抗菌复合涂层制备方法,首先在植入体TC4基底的表面制备PDA涂层; 然后在所得植入体表面制备纳米ZnO涂层,得到兼具抗菌和耐蚀性能的聚多巴胺-纳米氧化锌纳米复合涂层,即ZP纳米复合涂层;
具体步骤为:
步骤(1)用电子天平准确称取不同质量的二水合醋酸锌三份于容器中,分别放入无水乙醇;
步骤(2)搅拌并保持温度70℃,保温预设时间后加入预设量的乙醇胺稳定剂,继续搅拌10min后取出;
步骤(3)温度降至室温后,用50 ml容量瓶加入无水乙醇进行定容配置不同浓度的溶液;
步骤(4)定容完毕后在的恒温磁力搅拌器中搅拌,形成均一透明的溶胶,静置预设时间后待用;
步骤(5)TC4/PDA在超纯水中超声清洗后吹干待用;将制备好的TC4/PDA 浸入制备好的溶胶中,取出后放置在培养皿中,放入真空干燥箱真空干燥处理,采用梯度温度,从室温升至60℃保温1h后升至80℃,同样保温1h,随后采用20℃的温度间隔升温各自保温1h,当温度升至140℃以后保温时间延长至2 h,当温度达到200℃以后,继续真空干燥,16h后停止加热,待降至室温以后破真空将试样取出转移至马弗炉中,设置程序,温度升至500℃-600℃后保温1h;
步骤(6)保温结束后待其降至室温将其取出,重复清洗两次后将其吹干收存贴签。
以上所述的金属基表面耐蚀抗菌复合涂层制备方法制备的复合涂层,所述复合涂层包括耐蚀结合层和抗菌层;所述的耐蚀结合层为聚多巴胺涂层-PDA涂层;所述的抗菌层是单独的纳米氧化锌涂层-ZnO涂层。
以上所述的金属基表面耐蚀抗菌复合涂层的用途;用于植入性医疗器械,包括骨钉﹑骨板、心脏支架、人工关节或心脏起搏器中的任意一种或至少两种的组合。
与现有技术相比,本发明具有如下有益效果:提供兼具抗菌和耐蚀性能的纳米复合涂层,可有效延长植入体的使用寿命,通过表面抗菌元素纳米化,不仅增强了涂层的活性,而且提高了抗菌效果。通过组合配比抗菌涂层和耐蚀结合涂层的厚度和组成成分,使得抗菌元素释放速度适中,结合层在所述条件下不影响抗菌元素的释放与抗菌性能的发挥,同时促进细胞增殖,是植入性医疗器械的理想涂层。
本发明提供的在长有PDA薄膜涂层的TC4上制备纳米ZnO薄膜涂层的方法,不仅制备成本低,而且工艺简单,有较大的应用及推广价值。
附图说明
图1 为本发明中金属基表面耐蚀抗菌复合涂层的制备方法的流程图,图2为植入体表面所制备纳米ZnO涂层的实际效果图,图3为PDA/T试样在大肠杆菌培养基上测试抗菌效果图,图4为PDA/T试样在金黄色葡萄球菌培养基上测试抗菌效果图,图5为ZnO-PDA/T试样在金黄色葡萄球菌培养基上测试抗菌效果图,图6为ZnO-PDA/T试样在大肠杆菌培养基上测试抗菌效果图,图7为TC4、TC4/PDA、TC4/PDA/ZnO的极化曲线,图8为TC4/PDA/ZnO的腐蚀形貌图,图9为TC4/ ZnO的腐蚀形貌图。
具体实施方式
本发明是金属基表面耐蚀抗菌复合涂层制备方法及复合涂层和用途,金属基表面耐蚀抗菌复合涂层制备方法,首先在植入体TC4基底的表面制备PDA涂层; 然后在所得植入体表面制备纳米ZnO涂层,得到兼具抗菌和耐蚀性能的聚多巴胺-纳米氧化锌纳米复合涂层,即ZP纳米复合涂层;
具体步骤为:
步骤(1)用电子天平准确称取不同质量的二水合醋酸锌( Zn(CH3COO)2 2H2O) 三份于烧杯中,分别放入无水乙醇(CH3CH2OH);
步骤(2)用磁力搅拌器搅拌并保持温度70℃,保温预设时间后加入预设量的乙醇胺稳定剂,继续搅拌10min后取出;
步骤(3) 温度降至室温后,用50 ml容量瓶加入无水乙醇进行定容配置不同浓度的溶液;
步骤(4)定容完毕后在的恒温磁力搅拌器中搅拌,形成均一透明的溶胶,静置一段时间后待用;
步骤(5)TC4/PDA在超纯水中超声清洗后吹干待用;将制备好的TC4/PDA 浸入制备好的溶胶中,取出后放置在培养皿中,放入真空干燥箱真空干燥处理,采用梯度温度,从室温升至60℃保温1h后升至80℃,同样保温1h,随后采用20℃的温度间隔升温各自保温1h,当温度升至140℃以后保温时间延长至2 h,当温度达到200℃以后,继续真空干燥,l6h后停止加热,待降至室温以后破真空将试样取出转移至马弗炉中,设置程序,温度升至500℃-600℃后保温1h;
步骤(6)保温结束后待其降至室温将其取出,重复清洗两次后将其吹干收存贴签。
以上所述的制备方法,步骤(1)所述的制备PDA涂层的方法为溶液氧化法,首先利用三羟基氨基甲烷盐酸盐制成缓冲液,之后加入盐酸多巴胺盐,在合适的温度和碱性环境下以氧气为氧化剂的条件下,多巴胺单体能在碱性溶液中进行自聚合反应形成PDA涂层。
以上所述的制备方法,在步骤(2)中制备ZP纳米复合涂层的方法为溶胶凝胶法;将二水合醋酸锌放入无水乙醇中搅拌均匀后加入乙醇胺稳定剂,用磁力搅拌器搅拌均匀,形成均一透明的溶胶后静置待用;在合适的温度下,将步骤(1)所得植入体放入混合溶液中,快速升温至预设温度,反应预设时间后,溶液为无色透明状,使用去离子水冲洗,在预设干燥温度下干燥预设时间后得到ZP纳米复合涂层。
以上所述的制备方法,其特征在于,步骤(1)所述植入体为医用金属,优选为钛合金。
以上所述的金属基表面耐蚀抗菌复合涂层制备方法制备的复合涂层,所述复合涂层包括耐蚀结合层和抗菌层;所述的耐蚀结合层为聚多巴胺涂层-PDA涂层;所述的抗菌层是单独的纳米氧化锌涂层-ZnO涂层。
以上所述的金属基表面耐蚀抗菌复合涂层的用途;用于植入性医疗器械,包括骨钉﹑骨板、心脏支架、人工关节或心脏起搏器中的任意一种或至少两种的组合。
下面进一步展开本发明的内容:本发明中,通过利用PDA对金属离子的螯合作用和本身具有丰富官能团的特性,在TC4表面形成一层耐蚀的PDA涂层,之后在PDA涂层上采用溶胶凝胶法制备抗菌涂层即纳米ZnO薄膜层,制得兼具抗菌和耐蚀性能的聚多巴胺-纳米氧化锌纳米复合涂层(简称ZP涂层),通过控制实验条件,使纳米ZnO调整到最佳的形态达到较好的抗菌效果。
所述的PDA涂层的厚度为1~50nm,可以是1nm、2nm、3nm、4nm、5nm、6nm、7nm、8nm、9nm、10nm、11nm、12nm、13nm、14nm、15nm、16nm、17nm、18nm、19nm、20nm、21nm、22nm、23nm、24nm、25nm、26nm、27nm、28nm、29nm、30nm、31nm、32nm、33nm、34nm、35nm、36nm、37nm、38nm、39nm、40nm、41nm、42nm、43nm、44nm、45nm、46nm、47nm、48nm、49nm、50nm,优选为40~50nm。
所述的纳米ZnO涂层的厚度为10~160nm,可以是10nm、20nm、30nm、40nm、50nm、60nm、70nm、80nm、90nm、100nm、110nm、120nm、130nm、140nm、150nm、160nm,优选为40~120nm。
所述的纳米复合涂层的层数为2层,分别为PDA薄膜涂层和纳米ZnO薄膜涂层。
本发明中,所述的PDA涂层作为结合层与其他基底和抗菌涂层之间实现牢固结合的方法相比,使用PDA共价接枝对于具有复杂结构的材料表层形成功能化且具有粘附性的活性涂层更为有利。这是因为PDA 与金属离子螯合的主要原因是PDA 中含有的许多官能团(诸如酚基、氨基、邻醌等)与金属离子键相结合,表现出了在水环境中的强粘附性质,并且这种性质没有材料选择性,在几乎任何种类、形态、尺寸的材料表面都能够吸附,进行材料表面修饰的方法也很方便,易于在无机和有机的材料表面沉积,简单的浸泡或浸润方式就可以得到很好的修饰效果,且PDA可以长期稳定的存在于植入体表面。PDA 涂层同时可提高可光交联的明胶基水凝胶在钛植入物上的涂层稳定性,将阳离子抗菌肽和硅酸纳米粒子加载到水凝胶中后,该种植体具有良好的抗菌活性和增强成骨作用。
本发明中,所使用的纳米ZnO涂层作为抗菌材料相较于其他抗菌材料,能够在人体内降解且锌作为人体的微量元素,在提高生物相容性的同时,还可以降低细胞毒性。ZnO 作为无机抗菌试剂比有机试剂更稳定纳米 ZnO 被证明是一种有用的抗菌和抗真菌剂。锌作为一种必需元素且纳米ZnO 被认为是无毒的,毒性研究表明锌离子不会对人类细胞的 DNA造成任何损伤。关于 ZnO 的抗菌机理人们做了大量研究,目前存在三种抗菌机理:
(a)光催化机理,纳米 ZnO 粒子在可见光或者紫外线条件下产生大量自由基(如超氧根离子自由基、羟基自由基、H2O2),自由基与细菌、病毒、部分污染物发生作用,将其分解成 H2O、CO2 和无机物等无害物质以达到抗菌目的。
(b)锌离子作为抗菌元素,在水溶液中纳米 ZnO 与细菌接触时, ZnO 释放锌离子与细菌表面游离的羧基结合,使细菌细胞壁破损并阻碍细胞壁形成,最终使细菌细胞膜丧失生物功能使得细菌死亡达到抗菌目的。
(c)ZnO 产生的活性氧抗菌物质,在溶液中 ZnO 可激发出活性羟基,活性羟基最终生成 H2O2 等活性氧基团,活性氧基团可以损伤细胞膜、蛋白质,从而杀死细菌。
本发明在长有PDA薄膜涂层的TC4上利用溶胶凝胶法制备纳米ZnO薄膜涂层,其步骤为:
步骤(1)在植入体TC4基底的表面制备PDA涂层;
步骤(2)在步骤(1)所得植入体表面制备纳米ZnO涂层,得到兼具抗菌和耐蚀性能的聚多巴胺-纳米氧化锌纳米复合涂层,即ZP纳米复合涂层。
步骤(1)所述制备 PDA涂层的方法为溶液氧化法,首先利用三羟基氨基甲烷盐酸盐制成缓冲液,之后加入盐酸多巴胺盐,在合适的温度和碱性环境下,多巴胺单体能在碱性溶液中进行自聚合反应形成PDA涂层,氧气为氧化剂。
所述三羟基氨基甲烷盐酸盐的用量为0.07~0.08g,可以是0.0711g,0.0722g,0.0733g,0.0744g,0.0755g,0.0766g,0.0777g,0.0788g,0.0799g,0.0800g,优选为0.0788g。
所述盐酸多巴胺盐的用量为0.05~0.15g,可以是0.05g,0.06g,0.07g,0.08g,0.09g,0.10g,0.11g,0.12g,0.13g,0.14g,0.15g,优选为0.10g。
所述碱性环境的pH值为7~9,可以是7,7.5,8,8.5,9,优选为8.5。
所述合适的温度15~30℃,例如可以是,15℃,20℃,25℃,30℃,优选为25℃。
在缓冲液的pH调到8.5后加入多巴胺盐酸盐,pH将降低0.05左右。在25℃下将缓冲液中加入多巴胺盐酸盐调节pH至8.5测其pH,发现在前30min反应较快,溶液pH在8.27-8.29时变为棕色,40min后溶液(pH为8.23)变为棕黑色,继续反应90min后pH在8.21-8.23区间变动,其后反应pH变化较为缓慢,13h后pH为8.12,16h后为8.09,24h反应结束pH值为8.04。由此推测整个反应为消耗OH-释放H+的反应,反应处于平衡时则消耗H+。因此,在室温(25℃)下,氧气较为充足的溶液(pH为8.5)为制备PDA涂层的最佳条件。
以上所述的制备方法,在步骤(2)中制备ZnO纳米涂层的方法为溶胶凝胶法。具体步骤为:
分步骤(1′)用电子天平准确称取不同质量的二水合醋酸锌(Zn(CH3COO)2 2H2O)三份于烧杯中,分别放入无水乙醇(CH3CH2OH);
分步骤(2′)用磁力搅拌器搅拌并保持温度70℃,保温一段时间后加入一定量的乙醇胺稳定剂,继续搅拌10min后取出;
分步骤(3′) 温度降至室温后,用50 ml容量瓶加入无水乙醇进行定容配置不同浓度的溶液;
分步骤(4′)定容完毕后在的恒温磁力搅拌器中搅拌,形成均一透明的溶胶,静置一段时间后待用;
分步骤(5′)TC4/PDA在超纯水中超声清洗后吹干待用;将制备好的TC4/PDA 浸入制备好的溶胶中,取出后放置在培养皿中,放入真空干燥箱真空干燥处理,采用梯度温度,从室温升至60℃保温1h后升至80℃,同样保温1h,随后采用20℃的温度间隔升温各自保温1h,当温度升至140℃以后保温时间延长至2 h,当温度达到200℃以后,继续真空干燥,l6h后停止加热,待降至室温以后破真空将试样取出转移至马弗炉中,设置程序,温度升至500℃-600℃后保温1h;
分步骤(6)保温结束后待其降至室温将其取出,重复清洗两次后将其吹干收存贴签。
所述分步骤(1)中无水乙醇(CH3CH2OH)的用量为20~40ml,可以是20ml、25ml、30ml、35ml、40ml,优选为30ml。
所述分步骤(2)中保温时间为5~15min,可以是5min、6min、7min、8min、9min、10min、11min、12min、13min、14min、15min,优选为10min。
所述分步骤(2)中乙醇胺稳定剂的用量为4~5ml,可以是4.0ml、4.1ml、4.2ml、4.3ml、4.4ml、4.5ml、4.6ml、4.7ml、4.8ml、4.9ml、5.0ml,优选为4.6ml。
所述分步骤(3)中配置溶液的浓度分别为0.75mol/L、0.45mol/L、0.25mol/L。
所述分步骤(4)中恒温磁力搅拌器的温度设定为50~80℃,可以是50℃、55℃、60℃、65℃、70℃、75℃、80℃,优选为70℃。
所述分步骤(4)中搅拌时间为1h。
所述分步骤(4)中静置时间为45~55h,可以是45h、46h、47h、48h、49h、50h、51h、52h、53h、54h、55h,优选为48h。
所述分步骤(4)中TC4/PDA为25℃,pH=8.5,Tris-HCl 浓度为10mM,DA-HCl浓度为2mmol/L的溶液中聚合24h所得。
所述分步骤(5)中升温速度为5~8℃/min ,可以是5℃/min、6℃/min、7℃/min、8℃/min,优选为5℃/min。
所述分步骤(5)中清洗方法为放入超纯水中进行超声清洗。
PDA的螯合作用可以增强反应初期纳米ZnO晶核的稳定性,在PDA涂层上形成大量细小的簇状纳米ZnO。簇状纳米ZnO呈规则的六棱柱型,具有较高的表面能和反应活性,不仅可以通过释放Zn+和光诱导产生H2O2等化学相互作用来达到杀菌的目的,而且有利于成骨细胞在其表面加速附着和增殖。
本发明的纳米复合涂层可以用于修饰植入性医疗器械中。所述的植入性医疗器械包括骨钉、骨板、硬组织替代物、心脏支架、人工关节或心脏起搏器中的任意一种或至少两种的组合。
为更进一步阐述本发明所采取的技术手段及其效果,以下通过对实验制备样品进行结合力测试以及腐蚀性能分析来进一步说明本发明的技术方案,但本发明并非局限在实施例范围内。
实施例1:抗菌性能测试
以革兰氏阴性菌大肠杆菌菌株和革兰氏阳性菌金黄色葡萄球菌菌株为试验株,鉴于报道已经证实PDA层对大肠杆菌和金黄色葡萄球菌均不具有抗菌性,因此以PDA涂层做对照组(PDA/Ti6Al4V),采用贴膜法(GB/T21510-2008)检验Ti6Al4V合金表面涂层的抗菌性能。
LB(肉汤)培养基:氯化钠5.0g、蛋白胨10.0g、牛肉膏5.0g、蒸馏水1000mL。调节pH=7.2~7.4,灭菌处理。
固体LB(营养琼脂)培养基:氯化钠5.0g、蛋白胨10.0g、牛肉膏5.0g、琼脂20.0g、蒸馏水1000mL。调节pH=7.2~7.4,灭菌处理。
PBS(磷酸盐缓冲液):Na2HPO42.83g、KH2PO41.36g、吐温−80 1.0g、蒸馏水1000mL制备含质量分数0.1%的吐温−80 PBS溶液,高压蒸汽121℃、20min灭菌,用于菌液和样液稀释。采用20mm×20mm×2mm抛光处理(砂纸400#,800#,1200#,2000#)的钛合金板作基材。对照样品(PDA/Ti6Al4V)和实验组样品采用灭菌处理后无菌干燥。简要步骤按照GB/T21510-2008办法制备菌种斜面,首先将LB斜面18h~24h之间的培养菌液,通过适量0.03mol/LPBS从斜面试管冲洗菌液。洗下的菌液混合均匀后,经0.03mol/LPBS溶液稀释到105cfu/mL的浓度范围。之后将高压蒸汽灭菌处理的待测试样分别放入培养皿中,吸取10μL菌悬液滴加在改性基材表面,每个样品做3个平行样,使用聚乙烯(HDPE)薄膜覆盖在试样表面,在37℃、相对湿度90%的恒温培养箱(安装光源)中培养24h,之后使用洗脱液多次洗脱样品及聚乙烯薄膜并移入烧瓶中,震荡均匀后适当稀释,每组溶液倒入2个培养皿,做活细菌菌落计数培养,菌落数取平均值。根据公式(R%)=(A − B)/A× 100%计算改性涂层的抗菌率。其中A为对照组活细菌平均菌落数,B为实验组活细菌平均菌落数。
测试结果发现PDA/T试样表面大肠杆菌和金黄色葡萄球菌平均菌落数量为222和1602,原位生长ZnO涂层后,两种细菌菌落数大幅减小到约为5和46,ZnO/T试样对大肠杆菌和金黄色葡萄球菌的抑菌率η分别为97.75% 和97.13%,杀菌作用明显。这是由于纳米ZnO可以通过破坏细菌细胞的膜来有效遏制细菌的增殖。抗菌结果表明,纳米ZnO/PDA涂层对两种细菌表现出出色的抗菌效果,归因于高表面能的六棱柱型ZnO能与细菌细胞产生活性氧(ROS)、ZnO释放 Zn2+离子、光诱导产生H2O2等化学相互作用以及ZnO 通过物理作用损坏细菌细胞结构进而达到杀菌目的。
实施例2:耐蚀性能分析
利用CHI电化学工作站获得TC4/ZnO的Tafel极化曲线来测定其自腐蚀电位和自腐蚀电流密度。运行时间100s,采样间隔0.1 s,高电位限制1 V,低电位限制1 V,初始电位-1.5 V,终点电位1.5 V,扫描速度0.01 V/s。
测试结果中图7为TC4、TC4/PDA、TC4/PDA/ZnO的极化曲线,可以看出ZnO涂层的附着确实对基底的耐腐蚀性能有一定的提升作用,图8为TC4/PDA/ZnO腐蚀后的形貌图,其表面没有明显的腐蚀痕迹,但是表面出现一些颗粒状物质,图9为TC4/ZnO腐蚀后的形貌图,可以看到其表面具有明显的烧蚀痕迹,使得表面变得更加不平整,而且也出现了一些颗粒状物质,相比之下TC4/PDA/ZnO具有更好的耐腐蚀性,根据腐蚀形貌图可看出,PDA确实对ZnO涂层的耐蚀性有一定的作用。通过分析试样腐蚀前后的质量、致密度发现,试样在腐蚀后致密度都会变小,可能是由于腐蚀空位所造成的,通过分析极化曲线得到的自腐蚀电位和自腐蚀电流密度可知,ZnO涂覆以后确实跟极化曲线表现一致对基底的耐蚀性具有较大的提升,而且在PDA表面涂覆ZnO对基底耐腐蚀性能比直接在基底表面涂覆ZnO的耐腐蚀性能提升大,这可能是由于PDA使ZnO更均匀致密的分布在基底所致。用ICP对腐蚀液成分进行测试分析发现,ZnO涂层可以减少基底Al元素的释放,而涂覆有PDA的TC4/PDA/ZnO相比TC4/ZnO,Al元素释放进一步被控制,极化曲线以及腐蚀数据分析表现一致,腐蚀液中Ca、P元素的检测可发现,在涂覆ZnO后,腐蚀液中两种元素与SBF相比,变化不大,但是与TC4腐蚀液相比差值较大,从而推测Ca、P的存在可能对TC4的腐蚀具有一定的贡献。
综上,通过层层组装的结构设计,采用纳米氧化锌作为联合抗菌剂,利用聚多巴胺对金属离子的鳌合作用,在TC4表面制备出一种与植入体强结合并兼具抗菌和耐蚀性能的纳米复合涂层。所述纳米复合涂层由耐蚀结合涂层和抗菌涂层组成,其中耐蚀结合层为聚多巴胺涂层;抗菌涂层为纳米氧化锌涂层。该纳米复合涂层制备工艺简单,涂层兼具抗菌性及耐蚀性。
本发明通过上述实施例来说明本发明的详细方法,但本发明并不局限于上述详细方法,即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (6)
1.金属基表面耐蚀抗菌复合涂层制备方法,其特征在于,首先在植入体TC4基底的表面制备PDA涂层; 然后在所得植入体表面制备纳米ZnO涂层,得到兼具抗菌和耐蚀性能的聚多巴胺-纳米氧化锌纳米复合涂层,即ZP纳米复合涂层;
具体步骤为:
步骤(1)用电子天平准确称取不同质量的二水合醋酸锌三份于容器中,分别放入无水乙醇;
步骤(2)搅拌并保持温度70℃,保温预设时间后加入预设量的乙醇胺稳定剂,继续搅拌10min后取出;
步骤(3) 温度降至室温后,用50 ml容量瓶加入无水乙醇进行定容配置不同浓度的溶液;
步骤(4)定容完毕后在的恒温磁力搅拌器中搅拌,形成均一透明的溶胶,静置预设时间后待用;
步骤(5)TC4/PDA在超纯水中超声清洗后吹干待用;将制备好的TC4/PDA 浸入制备好的溶胶中,取出后放置在培养皿中,放入真空干燥箱真空干燥处理,采用梯度温度,从室温升至60℃保温1h后升至80℃,同样保温1h,随后采用20℃的温度间隔升温各自保温1h,当温度升至140℃以后保温时间延长至2 h,当温度达到200℃以后,继续真空干燥,16h后停止加热,待降至室温以后破真空将试样取出转移至加热炉中,设置程序,温度升至500℃-600℃后保温1h;
步骤(6)保温结束后待其降至室温将其取出,重复清洗两次后将其吹干收存贴签。
2.根据权利要求1所述的金属基表面耐蚀抗菌复合涂层制备方法,其特征在于,步骤(1)所述的制备PDA涂层的方法为溶液氧化法,首先利用三羟基氨基甲烷盐酸盐制成缓冲液,之后加入盐酸多巴胺盐,在合适的温度和碱性环境下以氧气为氧化剂的条件下,多巴胺单体能在碱性溶液中进行自聚合反应形成PDA涂层。
3.根据权利要求1 所述的金属基表面耐蚀抗菌复合涂层制备方法,其特征在于,在步骤(2)中制备ZP纳米复合涂层的方法为溶胶凝胶法;将二水合醋酸锌放入无水乙醇中搅拌均匀后加入乙醇胺稳定剂,用磁力搅拌器搅拌均匀,形成均一透明的溶胶后静置待用;在合适的温度下,将步骤(1)所得植入体放入混合溶液中,快速升温至预设温度,反应预设时间后,溶液为无色透明状,使用去离子水冲洗,在预设干燥温度下干燥预设时间后得到ZP纳米复合涂层。
4.根据权利要求1所述的金属基表面耐蚀抗菌复合涂层制备方法,其特征在于,步骤(1)所述植入体为医用金属,优选为钛合金。
5.权利要求1所述的金属基表面耐蚀抗菌复合涂层制备方法制备的复合涂层,其特征在于,所述复合涂层包括耐蚀结合层和抗菌层;所述的耐蚀结合层为聚多巴胺涂层-PDA涂层;所述的抗菌层是单独的纳米氧化锌涂层-ZnO涂层。
6.权利要求5所述的金属基表面耐蚀抗菌复合涂层的用途;用于植入性医疗器械,包括骨钉﹑骨板、心脏支架、人工关节或心脏起搏器中的任意一种或至少两种的组合。
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