CN112972780B - 一种胆道支架表面纳米涂层及其制备方法 - Google Patents

一种胆道支架表面纳米涂层及其制备方法 Download PDF

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CN112972780B
CN112972780B CN202110451950.6A CN202110451950A CN112972780B CN 112972780 B CN112972780 B CN 112972780B CN 202110451950 A CN202110451950 A CN 202110451950A CN 112972780 B CN112972780 B CN 112972780B
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substrate
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CN112972780A (zh
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肖瑶
姚磊
翟登高
孙慧
黄敏
欧阳锡武
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Xiangya Hospital of Central South University
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Abstract

一种胆道支架表面纳米涂层及其制备方法，为了克服胆道支架表面纳米银涂层的毒副作用，以部分金属元素钴替代金属元素银，以牺牲部分涂层的抗菌性能为代价，大大提高了胆道支架涂层材料的安全性。研究表明，当涂层中钴含量为29%时，支架涂层的抗菌性能及毒副作用达到最优异的平衡效果。

Description

一种胆道支架表面纳米涂层及其制备方法
技术领域
本发明涉及纳米涂层领域，具体涉及一种胆道支架表面纳米涂层及其制备方法。
背景技术
胆道系统具有分泌、储存、浓缩和输送胆汁的功能，对胆汁排入十二指肠有重要的调节作用，但是，胆道癌、肝癌、胰腺癌及转移癌等恶性肿瘤可能导致胆道梗阻。解除胆道梗阻最好的办法就是置入胆道支架，使得胆汁可以通过支架流至肠腔。为了增强引流效果，各种类型和材料的支架不断改进，各种材料的塑料支架、金属支架、药物获自带放射粒子支架以及生物可降解支架等应运而生。
临床实践中发现细菌生物膜可导致胆道支架再狭窄，而细菌感染则是细菌生物形成的关键因素。为了避免因细菌感染而引起的胆道支架狭窄，现有技术中常采用覆有纳米银涂层的胆道支架，其通过缓慢释放银离子抑制细菌生物膜的形成，继而延长胆道支架植入术后的非梗阻期。然而，银并非人体必需的微量元素，以纯银制备的胆道支架涂层对人体的健康存在潜在的毒副作用。有鉴于此，如何保证胆道支架表面涂层优异抗菌性能并消除其毒副作用是当下急需解决的问题。
发明内容
针对现有技术存在的问题，本发明旨在提供一种胆道支架表面纳米涂层，该涂层在兼顾纳米银涂层的抗菌性能的情况下，消除了金属银带来的毒副作用。
一种胆道支架表面纳米涂层的制备方法，包括以下步骤：
以支架材料为衬底，对衬底进行预处理。
将烘干后的衬底放入磁控溅射镀膜机中，以Ag-Co复合靶材作为溅射源，以氩气为工作气体，在衬底表面溅射沉积Ag-Co涂层。溅射镀膜时，本底真空度为5×10-5Pa，氩气流量80-120sccm，衬底温度100-120℃，溅射压力1.0-2.0Pa，溅射功率80-120W。
将覆有Ag-Co涂层的支架衬底放入超音速微粒轰击装置内进行表面纳米化处理，处理过程中以粒径为0.1-0.3mm的BN为硬质微粒，气体压力为1.0-2.0MPa，微粒流量为12-15g/s，电压15-20V,处理时间20-30min。
进一步地，所述支架材料为塑料支架或金属支架。
进一步地，所述塑料支架为聚乙烯、聚氨酯或聚四氟乙烯。
进一步地，所述支架为S形支架、双层支架或Cotton-Leung支架。
进一步地，所述预处理包括酸洗、除油、打磨、清洗和烘干，其中酸洗液为10%-25%的HCl溶液，打磨分别选用400#、600#、800#和1200#的砂纸进行，除油选用10%-15%的碳酸钠溶液，清洗选用去离子水配合超声辅助清洗，烘干在保护性气氛下进行。
进一步地，所述复合靶材中Co的原子含量为25%-40%。
优选地，所述复合靶材中Co的原子含量为29%。
本发明还提供了一种胆道支架表面纳米涂层，所述纳米涂层由上述方法制备而得。
钴是人体必备的微量元素之一，对人体没有毒副作用，并且钴本身具有一定的抗菌性能。为了克服胆道支架表面纳米银涂层的毒副作用，选用部分金属元素钴替代金属元素银，以牺牲部分涂层的抗菌性能为代价，大大提高了胆道支架涂层材料的安全性。研究发现，当涂层中钴的含量为29%时，支架涂层的抗菌性能及毒副作用达到最优异的平衡效果。
具体实施方式
下面通过具体实施例来验证本发明的技术效果，但是本发明的实施方式不局限于此。
实施例1
一种胆道支架表面纳米涂层的制备方法，包括以下步骤：
以金属材料作为支架衬底，对衬底进行预处理，预处理包括酸洗、除油、打磨、清洗和烘干，其中酸洗液为15%的HCl溶液，打磨分别选用400#、600#、800#和1200#的砂纸进行，除油选用15%的碳酸钠溶液，清洗选用去离子水配合超声辅助清洗，烘干在保护性气氛下进行。
将烘干后的衬底放入磁控溅射镀膜机中，以Ag-25at%Co复合靶材作为溅射源，以氩气为工作气体，在衬底表面溅射沉积Ag-Co涂层。溅射镀膜时，本底真空度为5×10-5Pa，氩气流量80sccm，衬底温度120℃，溅射压力1.0Pa，溅射功率120W。
将覆有Ag-Co涂层的支架衬底放入超音速微粒轰击装置内进行表面纳米化处理，处理过程中以粒径为0.3mm的BN为硬质微粒，气体压力为2.0MPa，微粒流量为12g/s，电压15V,处理时间30min。
实施例2
一种胆道支架表面纳米涂层的制备方法，包括以下步骤：
以金属材料作为支架衬底，对衬底进行预处理，预处理包括酸洗、除油、打磨、清洗和烘干，其中酸洗液为15%的HCl溶液，打磨分别选用400#、600#、800#和1200#的砂纸进行，除油选用15%的碳酸钠溶液，清洗选用去离子水配合超声辅助清洗，烘干在保护性气氛下进行。
将烘干后的衬底放入磁控溅射镀膜机中，以Ag-29at%Co复合靶材作为溅射源，以氩气为工作气体，在衬底表面溅射沉积Ag-Co涂层。溅射镀膜时，本底真空度为5×10-5Pa，氩气流量80sccm，衬底温度120℃，溅射压力1.0Pa，溅射功率120W。
将覆有Ag-Co涂层的支架衬底放入超音速微粒轰击装置内进行表面纳米化处理，处理过程中以粒径为0.3mm的BN为硬质微粒，气体压力为2.0MPa，微粒流量为12g/s，电压15V,处理时间30min。
实施例3
一种胆道支架表面纳米涂层的制备方法，包括以下步骤：
以金属材料作为支架衬底，对衬底进行预处理，预处理包括酸洗、除油、打磨、清洗和烘干，其中酸洗液为15%的HCl溶液，打磨分别选用400#、600#、800#和1200#的砂纸进行，除油选用15%的碳酸钠溶液，清洗选用去离子水配合超声辅助清洗，烘干在保护性气氛下进行。
将烘干后的衬底放入磁控溅射镀膜机中，以Ag-35at%Co复合靶材作为溅射源，以氩气为工作气体，在衬底表面溅射沉积Ag-Co涂层。溅射镀膜时，本底真空度为5×10-5Pa，氩气流量80sccm，衬底温度120℃，溅射压力1.0Pa，溅射功率120W。
将覆有Ag-Co涂层的支架衬底放入超音速微粒轰击装置内进行表面纳米化处理，处理过程中以粒径为0.3mm的BN为硬质微粒，气体压力为2.0MPa，微粒流量为12g/s，电压15V,处理时间30min。
实施例4
一种胆道支架表面纳米涂层的制备方法，包括以下步骤：
以金属材料作为支架衬底，对衬底进行预处理，预处理包括酸洗、除油、打磨、清洗和烘干，其中酸洗液为15%的HCl溶液，打磨分别选用400#、600#、800#和1200#的砂纸进行，除油选用15%的碳酸钠溶液，清洗选用去离子水配合超声辅助清洗，烘干在保护性气氛下进行。
将烘干后的衬底放入磁控溅射镀膜机中，以Ag-40at%Co复合靶材作为溅射源，以氩气为工作气体，在衬底表面溅射沉积Ag-Co涂层。溅射镀膜时，本底真空度为5×10-5Pa，氩气流量80sccm，衬底温度120℃，溅射压力1.0Pa，溅射功率120W。
将覆有Ag-Co涂层的支架衬底放入超音速微粒轰击装置内进行表面纳米化处理，处理过程中以粒径为0.3mm的BN为硬质微粒，气体压力为2.0MPa，微粒流量为12g/s，电压15V,处理时间30min。
对比例1
一种胆道支架表面纳米涂层的制备方法，包括以下步骤：
以金属材料作为支架衬底，对衬底进行预处理，预处理包括酸洗、除油、打磨、清洗和烘干，其中酸洗液为15%的HCl溶液，打磨分别选用400#、600#、800#和1200#的砂纸进行，除油选用15%的碳酸钠溶液，清洗选用去离子水配合超声辅助清洗，烘干在保护性气氛下进行。
将烘干后的衬底放入磁控溅射镀膜机中，以Ag-18at%Co复合靶材作为溅射源，以氩气为工作气体，在衬底表面溅射沉积Ag-Co涂层。溅射镀膜时，本底真空度为5×10-5Pa，氩气流量80sccm，衬底温度120℃，溅射压力1.0Pa，溅射功率120W。
将覆有Ag-Co涂层的支架衬底放入超音速微粒轰击装置内进行表面纳米化处理，处理过程中以粒径为0.3mm的BN为硬质微粒，气体压力为2.0MPa，微粒流量为12g/s，电压15V,处理时间30min。
对比例2
一种胆道支架表面纳米涂层的制备方法，包括以下步骤：
以金属材料作为支架衬底，对衬底进行预处理，预处理包括酸洗、除油、打磨、清洗和烘干，其中酸洗液为15%的HCl溶液，打磨分别选用400#、600#、800#和1200#的砂纸进行，除油选用15%的碳酸钠溶液，清洗选用去离子水配合超声辅助清洗，烘干在保护性气氛下进行。
将烘干后的衬底放入磁控溅射镀膜机中，以Ag-50at%Co复合靶材作为溅射源，以氩气为工作气体，在衬底表面溅射沉积Ag-Co涂层。溅射镀膜时，本底真空度为5×10-5Pa，氩气流量80sccm，衬底温度120℃，溅射压力1.0Pa，溅射功率120W。
将覆有Ag-Co涂层的支架衬底放入超音速微粒轰击装置内进行表面纳米化处理，处理过程中以粒径为0.3mm的BN为硬质微粒，气体压力为2.0MPa，微粒流量为12g/s，电压15V,处理时间30min。
对比例3
一种胆道支架表面纳米涂层的制备方法，包括以下步骤：
以金属材料作为支架衬底，对衬底进行预处理，预处理包括酸洗、除油、打磨、清洗和烘干，其中酸洗液为15%的HCl溶液，打磨分别选用400#、600#、800#和1200#的砂纸进行，除油选用15%的碳酸钠溶液，清洗选用去离子水配合超声辅助清洗，烘干在保护性气氛下进行。
将烘干后的衬底放入磁控溅射镀膜机中，以Ag靶材作为溅射源，以氩气为工作气体，在衬底表面溅射沉积Ag涂层。溅射镀膜时，本底真空度为5×10-5Pa，氩气流量80sccm，衬底温度120℃，溅射压力1.0Pa，溅射功率120W。
将覆有Ag涂层的支架衬底放入超音速微粒轰击装置内进行表面纳米化处理，处理过程中以粒径为0.3mm的BN为硬质微粒，气体压力为2.0MPa，微粒流量为12g/s，电压15V,处理时间30min。
对实施例1-4及对比例1-3的抗菌性能进行测试，测试方法为：选择菌液浓度为5×107cfu/ml的金黄色葡萄球菌作为试验用菌液，分别取0.2ml试验用菌液滴加在样品表面，在37℃、相对湿度RH>90%的条件下，培养48h，然后取出样品进行活菌计数，并通过计数得到抗菌率。每个样品做5个平行试验，另外选择没有涂层的金属衬底支架作为对照组。其中，抗菌率计算公式为：
R（%）=（A-B）/A×100
式中：R表示抗菌率；
A表示对照组平均回收菌数；
B表示实施例/对比例样品平均回收菌数。
为了客观公正地评价各实验样品的抗菌性能，选用超高浓度的菌液进行试验，目的在于确保每一样品都无法达到100%的抗菌率。需要说明的是，抗菌性能由抗菌率和细菌浓度共同衡量，在医疗实践中不可能达到本实验采用的细菌浓度，也就是说，支架涂层实际使用过程中的抗菌率会高于下述实验数据。
实施例1-4及对比例1-3的抗菌率如表1所示。
表1
实施例1 实施例2 实施例3 实施例4 对比例1 对比例2 对比例3
抗菌率/% 79.17 86.27 71.23 67.49 85.56 53.11 92.31
进一步地，发明人对实施例1-4及对比例1-3的毒副作用进行了研究，具体方法为：将上述7组胆道涂层支架植入小鼠体内，其中对比例3在31天后发现小鼠肠腺上皮细胞损坏（细胞损坏处有Ag聚集），对比例1在49天后发现小鼠肠腺上皮细胞损坏，而实施例1-4以及对比例2的小鼠在80天时均未发现肠腺上皮细胞损坏的情况。

Claims (7)

1.一种胆道支架表面纳米涂层的制备方法，包括以下步骤：
以胆道支架材料为衬底，对衬底进行预处理；
将烘干后的衬底放入磁控溅射镀膜机中，以Ag-Co复合靶材作为溅射源，以氩气为工作气体，在衬底表面溅射沉积Ag-Co涂层；溅射镀膜时，本底真空度为5×10-5Pa，氩气流量80-120sccm，衬底温度100-120℃，溅射压力1.0-2.0Pa，溅射功率80-120W，所述复合靶材中Co的原子含量为25%-40%；
将覆有Ag-Co涂层的胆道支架衬底放入超音速微粒轰击装置内进行表面纳米化处理，处理过程中以粒径为0.1-0.3mm的BN为硬质微粒，气体压力为1.0-2.0MPa，微粒流量为12-15g/s，电压15-20V,处理时间20-30min。
2.一种如权利要求1所述的制备方法，其特征在于：所述支架材料为塑料支架或金属支架。
3.一种如权利要求2所述的制备方法，其特征在于：所述塑料支架为聚乙烯、聚氨酯或聚四氟乙烯。
4.一种如权利要求1所述的制备方法，其特征在于：所述胆道支架为S形支架、双层支架或Cotton-Leung支架。
5.一种如权利要求1所述的制备方法，其特征在于，所述预处理包括酸洗、除油、打磨、清洗和烘干，其中酸洗液为10%-25%的HCl溶液，打磨分别选用400#、600#、800#和1200#的砂纸进行，除油选用10%-15%的碳酸钠溶液，清洗选用去离子水配合超声辅助清洗，烘干在保护性气氛下进行。
6.一种如权利要求1-5中任一项所述的制备方法，其特征在于，所述复合靶材中Co的原子含量为29%。
7.一种胆道支架表面纳米涂层，其特征在于，所述纳米涂层由权利要求1-6中任一所述方法制备而得。
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