CN114225124A - 一种具有超亲水性的Ti-Cu/聚多巴胺复合涂层及其制备方法 - Google Patents

一种具有超亲水性的Ti-Cu/聚多巴胺复合涂层及其制备方法 Download PDF

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CN114225124A
CN114225124A CN202111578233.6A CN202111578233A CN114225124A CN 114225124 A CN114225124 A CN 114225124A CN 202111578233 A CN202111578233 A CN 202111578233A CN 114225124 A CN114225124 A CN 114225124A
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dopamine
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景凤娟
王永
杨明远
岳方宇
江业浩
谢东
姜欣
冷永祥
黄楠
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Southwest Jiaotong University
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Abstract

本发明公开了一种具有超亲水性的Ti‑Cu/聚多巴胺复合涂层及其制备方法。其制备过程为：对基底材料进行预处理后，在其上形成Ti‑Cu复合涂层，再依次置于多巴胺溶液和PBS溶液中浸泡即可。本发明制备得到的涂层稳定性好，具有优良的超亲水性能，具有抗菌性能和良好的生物相容性能，制备方法比较简单，应用范围较广，可用于血管支架、人工心瓣、人工关节等植入性医用生物材料的制备。

Description

一种具有超亲水性的Ti-Cu/聚多巴胺复合涂层及其制备方法
技术领域
本发明属于医用材料技术领域，具体涉及一种具有超亲水性的Ti-Cu/聚多巴胺复合涂层及其制备方法。
背景技术
316L不锈钢、医用钴合金、超高分子量聚乙烯、涤纶等材料具有较好的力学性能和生物相容性，常用于制备血管支架、人工心瓣、人工关节等植入性的医疗器械和人工器官；然而，这些植入物在病患体内容易引起细菌感染，并且其生物相容性能不能满足临床要求；细菌感染、生物相容性不足容易导致植入失败，增加了医疗器械和人工器官植入的风险。
Ti-Cu硬质薄膜具有良好的生物相容性，能够释放Cu离子催化体内的供体产生一氧化氮发生其抗凝血功能，并具有抗菌性能。聚多巴胺薄膜是一种致密的连续膜，可以附着在几乎所有材料如金属及其氧化物、半导体以及合成高聚物的表面，在水基环境中具有较好的粘附性和良好的生物相容性。
目前，在国际、国内还未见利用Ti-Cu薄膜和聚多巴胺涂层制备超亲水涂层的报道。虽然在PVC管表面制备的聚多巴胺/银的复合纳米颗粒，具有超亲水性能，并且具有良好的抗凝和抗菌性能。但其是在PVC表面采用Ag离子和多巴胺聚合以及高碘酸钠氧化后产生的超亲水效果，Ag离子有可能随着植入时间增加流失，可能失去抗菌等效果。Lei Wang等人先在Ti表面制备了浓度为2mg/ml的多巴胺溶液，然后在浸入CuCl2中制备出在Cu离子的多巴胺涂层，研究发现，Cu离子浓度为0.1mmol/L和0.5mmol/L的Ti-PDA-Cu0.1和Ti-PDA-Cu0.5样品对金黄色葡萄球菌和大肠杆菌均表现出良好的抑菌活性。但此涂层未产生超亲水表面。上面研究均将是溶液中的Cu离子或Ag离子和多巴胺聚合后形成涂层，存在着Cu离子或Ag离子随着植入时间增加流失的可能性。
发明内容
针对现有技术中的上述不足，本发明提供一种具有超亲水性的Ti-Cu/聚多巴胺复合涂层及其制备方法，此涂层稳定性好，具有优良的超亲水性能，具有抗菌性能和良好的生物相容性能，制备方法比较简单，应用范围较广，可用于血管支架、人工心瓣、人工关节等植入性医用生物材料的制备。
为实现上述目的，本发明解决其技术问题所采用的技术方案是：
一种具有超亲水性的Ti-Cu/聚多巴胺复合涂层的制备方法，对基底材料进行预处理，在其上形成Ti-Cu复合涂层，再依次置于多巴胺溶液和PBS溶液中浸泡即可。
进一步地，在基底材料上附着Ti-Cu复合涂层的过程为：
将基底材料清洗后，通过磁控溅射、弧源离子镀等方式，在基底材料上形成铜含量为40～90at.％的Ti-Cu复合涂层。
进一步地，磁控溅射的具体过程为：
(1)将基底材料置于样品台上，调节Cu靶、Ti靶与样品台的距离，将真空室抽真空至1～2.0×10-3Pa以下，再通入氩气调节气压至0.1～0.6Pa；
(2)调节Cu靶电压为600～800V、脉冲10～50μs、频率200～400Hz；Ti靶电流为0.5～1A，电压为300～380V；样品台电压为-50V，处理20～40min，即可制备得到Cu含量为40～90at.％的Ti-Cu复合涂层。
进一步地，基底材料为金属基材料。
进一步地，基底材料为金属不锈钢。
进一步地，Ti-Cu涂层中Cu含量为85at.％。
进一步地，在多巴胺溶液中的浸泡时间为22～30h。
进一步地，浸泡时间为24h。
进一步地，多巴胺溶液的浓度为1～2mg/mL，pH值为8.5。
进一步地，多巴胺溶液的浓度为2mg/mL。
进一步地，在PBS溶液中浸泡时间为3～30天。
进一步地，在PBS溶液中浸泡时间为7天。
采用上述方法制备得到的具有超亲水性的Ti-Cu/聚多巴胺复合涂层。
本发明的有益效果：
本申请首先在传统的医用材料表面采用磁控溅射等方法制备出Ti-Cu薄膜，在其表面制备聚多巴胺涂层，然后将Ti-Cu/聚多巴胺复合涂层在PBS溶液中浸泡一段时间后，使Ti-Cu薄膜释放出Cu离子与聚多巴胺和PBS相互作用，使其粗糙度达到微米级别，形成超亲水复合涂层，利用其超亲水性能和Cu离子的抗凝、抗菌的生理功能，提高传统材料的抗菌性能和生物相容性能。
本申请制备得到的超亲水复合涂层植入体内后还能够通过Ti-Cu薄膜长期释放Cu离子并螯合在聚多巴胺表面，Cu离子流失较少，稳定性好，具有优良的超亲水性能，具有抗菌性能和良好的生物相容性能，制备方法比较简单，应用范围较广，可应用于金属、高分子等医用材料表面。
附图说明
图1为本发明实施例1中的超亲水复合涂层(TiCu-PDA-PBS)的傅立叶红外光谱(FTIR)；
图2为本发明实施例1中的TiCu/多巴胺涂层(TiCu-PDA)及超亲水复合涂层(TiCu-PDA-PBS)的粗糙度(Ra)；
图3为本发明实施例1中的超亲水复合涂层(TiCu-PDA-PBS)的水接触角(WCA)结果；
图4为本发明实施例1中超亲水复合涂层(TiCu-PDA-PBS)表面Cu元素含量的检测；
图5为本发明实施例1中超亲水复合涂层的血小板粘附检测结果；
图6为本发明实施例1中的超亲水复合涂层的抗菌(绿脓杆菌(阴))性能；
图7为本发明实施例1中的超亲水复合涂层的抗菌(金黄色葡萄球菌(阳))性能。
具体实施方式
下面对本发明的具体实施方式进行描述，以便于本技术领域的技术人员理解本发明，但应该清楚，本发明不限于具体实施方式的范围，对本技术领域的普通技术人员来讲，只要各种变化在所附的权利要求限定和确定的本发明的精神和范围内，这些变化是显而易见的，一切利用本发明构思的发明创造均在保护之列。
实施例1
一种具有超亲水性的Ti-Cu/聚多巴胺复合涂层，在316L不锈钢表面，采用磁控溅射方法制备出Cu含量为85％的Ti-Cu涂层，将钛铜薄膜浸入多巴胺溶液中24h后，取出清洗干燥。最后将TiCu薄膜在PBS中浸泡7天，使其形成超亲水复合涂层，具体过程如下：
(1)将金属不锈钢样品打磨、抛光、清洗后放入磁控溅射设备的真空室中的样品台上，控制Cu靶与样品台的距离为140mm，Ti靶与样品台的距离为140mm，将真空室抽真空至2.0×10-3Pa；镀膜前通入60sccm的氩气对靶材和基片清洗以提高表面活性。通入氩气调节工作气压至0.6Pa。调节Cu靶参数为电压800V、脉冲50μs、频率400Hz，接高功率电源。调节Ti靶参数为电流1A，接直流电源。镀膜时基体采用-50V偏压。开启双电源，沉积时间20分钟，制备出Ti-Cu薄膜；
(2)多巴胺涂层的制备：将以上的Ti-Cu涂层放置在浓度为2.0mg/ml的多巴胺溶液中(溶剂为浓度是2mg/ml、pH＝8.5的Tris溶液)浸泡24h，制备出TiCu/多巴胺的复合涂层，取出用去离子水分别清洗后，在60℃的通风干燥箱中干燥后备用；
(3)将以上干燥好的复合涂层放入PBS中浸泡7天后，取出清洗，在60℃的通风干燥箱中干燥后即可获得聚多巴胺/Cu的超亲水复合涂层。
实施例2
一种具有超亲水性的Ti-Cu/聚多巴胺复合涂层，在金属不锈钢等表面，采用磁控溅射方法制备出Cu含量为58％的Ti-Cu涂层，再将钛铜薄膜浸入多巴胺溶液中24h后，取出清洗干燥。最后将TiCu薄膜在PBS中浸泡7天，使其形成超亲水复合涂层，具体过程如下：
(1)将金属不锈钢样品打磨、抛光、清洗后放入磁控溅射设备的真空室中的样品台上，控制Cu靶与样品台的距离为140mm，Ti靶与样品台的距离为140mm，将真空室抽真空至2.0×10-3Pa；镀膜前通入60sccm的氩气对靶材和基片清洗以提高表面活性。调节Cu靶参数为电压600V、脉冲50μs、频率400Hz，接高功率电源。调节Ti靶参数为电流2A，接直流电源。基体采用-50V偏压。开启双电源，沉积时间20分钟，制备出Cu含量为58％的Ti-Cu薄膜。
(2)多巴胺涂层的制备：将多巴胺溶解在2mg/ml、pH＝8.5的Tris溶液中，浓度为2.0mg/ml，然后将制备好的钛铜薄膜浸入到多巴胺溶液中沉积24h，取出清洗后干燥。
(3)将制备好复合涂层在PBS中浸泡7天后，取出清洗，在60℃的通风干燥箱中干燥后即可制得聚多巴胺/Cu的超亲水复合涂层。
实施例3
一种具有超亲水性的Ti-Cu/聚多巴胺复合涂层，在超高分子量聚乙烯表面，采用金属弧源离子镀方法制备出Cu含量为85％的Ti-Cu涂层，再将钛铜薄膜浸入多巴胺溶液中24h后，取出清洗干燥。最后将TiCu薄膜在PBS中浸泡7天，使其形成超亲水复合涂层，具体过程如下：
(1)将超高分子量聚乙烯样品放入阴极弧源设备的真空室中，真空室抽真空至2×10-3Pa；在工件上施加-50V的偏压，通入氩气调节工作气压为0.6Pa；采用阴极弧源沉积方法制备Ti-Cu涂层，阴极靶采用Ti-Cu镶嵌靶，靶中Cu/(Cu+Ti)的面积比例为10％；Ti-Cu镶嵌靶接直流电源，其功率密度约为0.5w/cm2；所得涂层中Cu的掺杂量为约50at％。
(2)多巴胺涂层的制备：将多巴胺溶解在2mg/ml、pH＝8.5的Tris溶液中，浓度为2.0mg/ml，然后将制备好的Ti-Cu薄膜浸入到多巴胺溶液中沉积24h，取出清洗后干燥。
(3)将制备好复合涂层在PBS中浸泡7天后，取出清洗，在60℃的通风干燥箱中干燥后即可制得聚多巴胺/Cu的超亲水复合涂层。
实施例4
一种具有超亲水性的Ti-Cu/聚多巴胺复合涂层，在金属不锈钢样品表面，采用磁控溅射方法制备出Cu含量为85％的Ti-Cu涂层，再将钛铜薄膜浸入多巴胺溶液中24h后，取出清洗干燥。最后将TiCu薄膜在PBS溶液中浸泡30天，使其形成超亲水复合涂层，具体过程如下：
(1)将金属不锈钢样品打磨、抛光、清洗后放入磁控溅射设备的真空室中的样品台上，控制Cu靶与样品台的距离为140mm，Ti靶与样品台的距离为140mm，将真空室抽真空至2.0×10-3Pa；镀膜前通入60sccm的氩气对靶材和基片清洗以提高表面活性。通入氩气调节工作气压至0.6Pa。调节Cu靶参数为电压800V、脉冲50μs、频率400Hz，接高功率电源。调节Ti靶参数为电流1A，接直流电源。镀膜时基体采用-50V偏压。开启双电源，沉积时间20分钟，制备出Ti-Cu薄膜。
(2)多巴胺涂层的制备：将多巴胺溶解在2mg/ml、pH＝8.5的Tris溶液中，浓度为2.0mg/ml，然后将制备好的钛铜薄膜浸入到多巴胺溶液中沉积24h，取出清洗后干燥。
(3)将制备好复合涂层在PBS中浸泡30天后，取出清洗，在60℃的通风干燥箱中干燥后即可制得聚多巴胺/Cu的超亲水复合涂层。
试验例
1、图1为本申请实施例1制备得到的超亲水复合涂层(TiCu-PDA-PBS)的傅立叶红外光谱(FTIR)检测结果，结果显示，TiCu/多巴胺涂层(TiCu-PDA)在PBS中浸泡7天后，在950-1200cm-1出现了Cu离子与多巴胺的螯合峰(TiCu-PDA-PBS)。(图1中曲线由上至下依次为TiCu、TiCu-PDA、TiCu-PDA-PBS)
2、按常规方式检测本申请实施例1制备得到的TiCu/多巴胺涂层(TiCu-PDA)及超亲水复合涂层(TiCu-PDA-PBS)的粗糙度(Ra)和水接触角，其结果见图2和图3。
如图2所示，超亲水复合涂层(TiCu-PDA-PBS)的粗糙度约为5.298μm，其值明显大于TiCu/多巴胺涂层(TiCu-PDA)的0.564μm。
如图3所示，TiCu/多巴胺涂层(TiCu-PDA)在PBS中浸泡3-30天后，其水接触角小于5°，显示出优良的超亲水性能，也进一步的说明了，超亲水性能的实现与其表面微米级粗糙度(图2)密切相关。
3、检测TiCu及超亲水复合涂层(TiCu-PDA-PBS)表面的Cu元素含量，其结果见图4。
如图4中a图为利用X射线光电子能谱(XPS)测出的TiCu及超亲水复合涂层(TiCu-PDA-PBS)表面的Cu元素含量，结果显示，超亲水复合涂层(TiCu-PDA-PBS)比TiCu涂层的铜含量较高。b图为采用原子吸收光谱(AAS)的方法获得的Cu离子释放量。结果说明与Ti-Cu薄膜相比较，其Cu离子流失较少。由此可见，本申请制备得到的超亲水复合涂层(TiCu-PDA-PBS)表面Cu含量较高，且Cu离子的流失较少。
4、抗粘附性和抗菌性检测
(1)血小板黏附检测
如图5所示，本申请制备得到的超亲水复合涂层比不锈钢(316L SS)更能够抑制血小板的粘附。
(2)抗菌性能检测
如图6和图7所示，超亲水复合涂层的抗菌(绿脓杆菌(阴))和抗菌(金黄色葡萄球菌(阳))行为，显示聚乙烯(PE)无抗菌效果，超亲水复合涂层(TiCu-PDA-PBS)对绿脓杆菌和金黄色葡萄球菌的抗菌效果均大于99.9％。表明本申请制备得到的超亲水复合涂层具有优异的抗菌性能。

Claims (10)

1.一种具有超亲水性的Ti-Cu/聚多巴胺复合涂层的制备方法，其特征在于，对基底材料进行预处理后，在其上形成Ti-Cu复合涂层，再依次置于多巴胺溶液和PBS溶液中浸泡即可。
2.根据权利要求1所述的制备方法，其特征在于，在基底材料上附着Ti-Cu复合涂层的过程为：
将基底材料清洗后，通过磁控溅射的方式，在基底材料上形成铜含量为40～90at.％的Ti-Cu复合涂层。
3.根据权利要求2所述的制备方法，其特征在于，所述磁控溅射的具体过程为：
(1)将基底材料置于样品台上，调节Cu靶、Ti靶与样品台的距离，将真空室抽真空至1～2.0×10-3Pa以下，再通入氩气调节气压至0.1～0.6Pa；
(2)调节Cu靶电压为600～800V、脉冲10～50μs、频率200～400Hz；Ti靶电流为0.5～1A，电压为300～380V；样品台电压为-50V，处理20～40min，即可制备得到Cu含量为40～90at.％的Ti-Cu复合涂层。
4.根据权利要求2或3所述的制备方法，其特征在于，所述Ti-Cu涂层中Cu含量为85at.％。
5.根据权利要求1所述的制备方法，其特征在于，在多巴胺溶液中的浸泡时间为22～30h。
6.根据权利要求1或5所述的制备方法，其特征在于，所述多巴胺溶液的浓度为1～2mg/mL。
7.根据权利要求6所述的制备方法，其特征在于，所述多巴胺溶液的浓度为2mg/mL。
8.根据权利要求1所述的制备方法，其特征在于，在PBS溶液中浸泡时间为3～30天。
9.根据权利要求8所述的制备方法，其特征在于，在PBS溶液中浸泡时间为7天。
10.采用权利要求1～9任一项所述方法制备得到的具有超亲水性的Ti-Cu/聚多巴胺复合涂层。
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