CN111850492B - 一种基于摩擦诱导抗菌特性增强涂层的制备方法 - Google Patents
一种基于摩擦诱导抗菌特性增强涂层的制备方法 Download PDFInfo
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Abstract
本发明公开了一种基于摩擦诱导抗菌特性增强涂层的制备方法,包括以下步骤:基底材料的准备,涂层材料的制备,最后进行摩擦诱导增强处理。本发明提出的方法是通过利用摩擦诱导处理,诱导涂层表面生成氧化钼(MoOx),在人工模拟海水环境下形成钼酸,钼酸进一步生成水合氢离子(H3O+),从而破坏细菌内部的pH平衡、酶及传输系统,对革兰氏阴性菌(大肠杆菌)和阳性菌(金黄色葡萄球菌)有明显的抑制效果,实用性较强,可以广泛应用于海洋环境和海洋大气氛围下的金属传动部件表面。
Description
技术领域
本发明涉及一种基于摩擦诱导抗菌特性增强涂层的制备方法,属于抗菌技术领域。
背景技术
近年来,随着世界各国加快对海洋资源的勘探步伐,对于海洋资源探测开采设备的要求也越来越高。这些设备的关键部件要长期工作于具有腐蚀性的海水环境或者海洋大气氛围下,这就要求其在服役过程中,自身要具有良好的耐腐蚀性能。而在海水中微生物附着在金属部件表面形成生物膜,这些生物膜主要有细菌、真菌和微型藻类等微生物及其代谢物与水中的有机物粘结而成,由此生物膜引起的腐蚀都会直接或间接地影响金属部件的服役寿命。例如目前与海洋微生物附着有关的材料破坏占到涉海材料总量的70%~80%,这就要求金属部件要具有一定的抑菌杀菌特性。而提高金属部件抗菌特性的方法主要有以下几种:第一、金属部件自身具有抗菌特性,比如添加重金属元素、放射元素或者Ag等。但重金属/放射性元素会导致海水环境污染,且掺杂的元素(如Au、Ag)等在金属内部不能达到良好的抗菌效果,极大的限制了该方法的实用性。第二、在金属部件表面覆盖“抗菌层”,该抗菌层一般由无机涂层和有机涂层组成;有机涂层包括醇类、植物酚类等,可以达到有效的防止细菌黏附和杀菌抑菌的效果,但不适用于摩擦润滑工况下的金属部件表面;而无机涂层可以适用于水润滑工况,并且其抗菌特性通常通过添加Ag可以达到,且Ag是一种理化性质极为稳定的惰性过渡元素,多数以单质形式存在于涂层中,降低其机械性能;且Ag的扩散会导致涂层表面的致密性降低,附着力及耐海水腐蚀性下降,从而在润滑传动工况下会降低无机涂层的使用寿命。
目前,考虑到上述传统的抗菌方法和抗菌材料的适用条件,都不能满足金属部件在水润滑工况前提下,表现出良好的抗菌特性的要求。因此,考虑到提高在海洋环境中进行润滑传动的金属部件的服役寿命,需要设计一种能够在水润滑工况下具有抗菌性能的涂层及方法。
发明内容
本发明所要解决的技术问题是:提供一种基于摩擦诱导抗菌特性增强涂层的制备方法,在水润滑条件下利用摩擦诱导涂层表面产生抗菌效果,解决在海洋环境中金属传动部件的摩擦传动界面面临的微生物/细菌引起的腐蚀问题。
本发明为解决上述技术问题采用以下技术方案:
一种基于摩擦诱导抗菌特性增强涂层的制备方法,包括如下步骤:
步骤1,对金属基底表面进行抛光,随后依次用去离子水和无水乙醇各清洗30分钟去除油污,随后用氮气吹干并保存于真空干燥皿中;
步骤2,将经过步骤1处理后的金属基底置于磁控溅射设备的腔体内,并对腔体进行抽真空,利用离子束轰击去除金属基底表面的氧化层,随后采用氮气和三甲基硅烷作为工作气体,铬靶、钼靶和碳靶作为溅射靶材,对金属基底表面进行涂层的沉积;
步骤3,将步骤2沉积的涂层依次放在蒸馏水、无水乙醇和丙酮中各清洗10分钟去除表面污染物,随后在喷水或喷雾或水润滑的条件下进行摩擦试验,对涂层表面进行诱导增强处理,得到最终的摩擦诱导抗菌特性增强涂层。
作为本发明的一种优选方案,步骤1所述抛光的要求是金属基底表面粗糙度小于等于30nm。
作为本发明的一种优选方案,步骤1所述金属基底的材料为钛合金或耐海水腐蚀用钢,耐海水腐蚀用钢的型号包括304、304L、316和316L。
作为本发明的一种优选方案,所述步骤2所述涂层的沉积过程中,离子束轰击时间为30分钟,腔体真空度为4×104Pa,腔体工作压强为0.22Pa,铬靶的功率控制在1400~1500W,钼靶的功率控制在500~600W,碳靶的功率控制在2000~2200W,三甲基硅烷的流量为5~30sccm,氮气流量由光发射监测器控制在50%,沉积时间为50~100分钟,沉积温度为150℃。
作为本发明的一种优选方案,步骤3所述摩擦试验为球-盘摩擦试验,对磨小球选取碳化硅小球,直径为8mm,摩擦时间设置为7200s,速度0.1m/s,载荷3N,润滑方式为喷雾润滑,喷雾间隔10分钟,喷雾时间15s。
作为本发明的一种优选方案,步骤3所述摩擦试验的温度为室温环境。
作为本发明的一种优选方案,步骤3所述摩擦试验产生的抗菌剂的成分为氧化钼和钼酸。
本发明采用以上技术方案与现有技术相比,具有以下技术效果:
1、本发明利用金属传动部件之间的摩擦传动过程,自动诱导表面产生抗菌性能,不需要额外添加杀菌剂或者涂覆抗菌涂层,运用范围广泛且实用性更强。
2、涂层经过本发明摩擦诱导处理后,涂层中提供产生摩擦诱导抗菌效应的Mo所占原子百分比含量至少为10.1%,对大肠杆菌和金黄色葡萄球菌的抑制和杀灭作用明显,抗菌性能显著提升。
附图说明
图1是本发明一种基于摩擦诱导抗菌特性增强涂层的制备方法的流程图。
图2是实施例1中的效果对比图,其中,(a)是基底表面涂层,(b)是摩擦诱导后的效果图。
图3是实施例1中的摩擦系数曲线图。
图4是实施例2中大肠杆菌活菌平板计数照片,其中,(a)是对照组,(b)是实验组。
图5是实施例2中台盼蓝染色法计数大肠杆菌死菌数目的显微镜照片,其中,(a)是对照组,(b)是实验组。
图6是实施例3中金黄色葡萄球菌活菌平板计数照片,其中,(a)是对照组,(b)是实验组。
图7是实施例3中台盼蓝染色法计数金黄色葡萄球菌死菌数目的显微镜照片,其中,(a)是对照组,(b)是实验组。
具体实施方式
下面详细描述本发明的实施方式,所述实施方式的示例在附图中示出。下面通过参考附图描述的实施方式是示例性的,仅用于解释本发明,而不能解释为对本发明的限制。
本发明针对于在海洋环境下金属传动部件的微生物腐蚀问题,提供一种有效的、简便的涂层摩擦诱导增强抗菌特性的方法,如图1所示,包括如下步骤:
(1)基底的预处理:将金属基底表面打磨光滑,随后用去离子水和无水乙醇分别清洗30分钟去除油污,随后用氮气吹干保存于真空干燥皿中备用。
(2)涂层的制备:将步骤(1)中进行预处理的金属基底置于非闭合式磁控溅射系统,采用铬(Cr)靶、钼(Mo)靶和碳(C)靶作为溅射靶材,氮气(N2)和三甲基硅烷(C3H10Si,TMS)作为工作气体,进行涂层的制备。
(3)摩擦诱导抗菌增强处理:将步骤(2)中制备的涂层,在喷(水)雾/水润滑的条件下进行摩擦试验,对涂层表面进行诱导增强处理,得到最终的摩擦诱导抗菌增强涂层。
第一步中基底抛光要求表面粗糙度(Ra)≤30nm。
第一步中基底的材料优选为海洋环境下金属传动部件常用材料表面,包括钛合金(TC4)或耐海水腐蚀用钢如304、304L、316、316L等中的至少一种。
本发明对磁控溅射过程中的参数设置并无限制,本领域技术人员依据经验及设备对相关制备参数进行调控即可;沉积步骤为:将步骤(1)打磨好的金属基底放入磁控溅射设备腔体,进行抽真空,离子束轰击去除表面氧化层,随后在氮气(N2)和三甲基硅烷(C3H10Si,TMS)作为工作气体,铬(Cr)靶、钼(Mo)靶和碳(C)靶作为溅射靶材进行溅射制备涂层。
本发明中涂层制备过程参数优选为:离子束轰击时间:30分钟;真空度:4×104Pa;工作压强:0.22Pa;Cr靶、Mo靶、C靶的功率分别控制在以下范围:1400~1500W、500~600W和2000~2200W;TMS流量:5~30sccm;N2:50%(OEM);沉积时间:50~100分钟;沉积温度:150℃。
本发明对所述的摩擦试验诱导的方法并无特殊要求,本领域技术人员公知的摩擦试验方法即可满足要求。摩擦诱导试验参数优选为:球-盘摩擦试验,载荷3N,速度0.1m/s,持续时间7200s,润滑方式:喷雾润滑。
摩擦诱导过程中的环境为室温环境。
摩擦诱导过程的润滑剂由以下环境提供:包括喷(水)雾环境或水润滑环境如蒸馏水、海水、或质量分数3.5%NaCl溶液等其中至少一种。
摩擦试验中对磨材料的选取包括陶瓷材料,如:如氮化硅(Si3N4)、碳化硅(SiC)、氧化铝(Al2O3)等或金属材料,如黄铜、合金钢(YG6)和不锈钢(SUS440C)等其中一种。
涂层的抗菌增强机制是由摩擦试验过程中诱导强化的,摩擦诱导产生的抗菌剂的主要成分为氧化钼(MoOx)和钼酸(H2MoO4)。
摩擦诱导涂层中提供产生摩擦诱导抗菌效应的Mo所占原子百分比含量至少为10.1%。
实施例1
摩擦诱导试验:基底选取钛合金(TC4)材料,利用磁控溅射设备在钛合金(TC4)基底上制备好的涂层(如图2的(a))分别放在蒸馏水、无水乙醇和丙酮中各清洗10分钟以去除表面污染物,采用杠杆式“球-盘”摩擦磨损试验机来对样品进行摩擦诱导试验。其中,对磨小球选取碳化硅(SiC)小球,直径为8mm,摩擦诱导时间设置为7200s,速度0.1m/s,载荷3N,润滑方式为喷(水)雾润滑,喷雾间隔10分钟,喷雾时间15s。图2的(b)为摩擦诱导后的样品效果图。图3为摩擦诱导过程中摩擦系数的记录曲线图。
实施例2
(1)通过摩擦诱导抗菌增强涂层的抗菌效果试验,具体操作如下:在无菌操作条件下,用磷酸盐缓冲液(PBS)将提前制备好的大肠杆菌菌悬液稀释至浓度为1.6×104cfu/mL,在对照组和实验组样品表面同时均匀涂布0.1mL的大肠杆菌菌悬液,并置于无菌平皿中,放入霉菌培养箱中37℃接触培养24小时。
(2)取出培养24小时后的样品,用1mL磷酸盐缓冲液(PBS)反复冲洗对照组和实验组样品表面6-8次,保证样品表面大肠杆菌完全冲洗下来,随后冲洗下的溶液在离心机中以转速2000转/分钟离心3分钟收集大肠杆菌,随后溶解在1mL的细菌重悬液中。
(3)取步骤(2)中得到的大肠杆菌菌悬液用本领域技术人员所熟知的平板菌落计数法来对对照组和实验组大肠杆菌活菌进行计数,如图4的(a)和(b)。可以看出,经过摩擦诱导处理的涂层的大肠杆菌活菌数量要远远低于对照组,抗菌效果显著。
(4)取步骤(2)中得到的大肠杆菌菌悬液用台盼蓝染色剂进行染色,如图5的(a)和(b),本领域技术人员所熟知的台盼蓝染色剂能够将死亡的细菌染成淡蓝色,经过摩擦诱导处理的涂层的大肠杆菌的被染色的死亡细菌数量要远高于对照组,同样证明杀菌效果显著。
实施例3
(1)通过摩擦诱导抗菌增强涂层的抗菌效果试验,具体操作如下:在无菌操作条件下,用磷酸盐缓冲液(PBS)将提前制备好的大金黄色葡萄球菌菌悬液稀释至浓度为2.2×104cfu/mL,在对照组和实验组样品表面同时均匀涂布0.1mL的金黄色葡萄球菌菌悬液,并置于无菌平皿中,放入霉菌培养箱中37℃接触培养24小时。
(2)取出培养24小时后的样品,用1mL磷酸盐缓冲液(PBS)反复冲洗对照组和实验组样品表面6-8次,保证样品表面金黄色葡萄球菌完全冲洗下来,随后冲洗下的溶液在离心机中以转速2000转/分钟离心3分钟收集金黄色葡萄球菌,随后溶解在1mL的细菌重悬液中。
(3)取步骤(2)中得到的金黄色葡萄球菌菌悬液用本领域技术人员所熟知的平板菌落计数法来对对照组和实验组金黄色葡萄球菌活菌进行计数,如图6的(a)和(b)。可以看出,经过摩擦诱导处理的涂层的金黄色葡萄球菌活菌数量要远远低于对照组,抗菌效果显著。
(4)取步骤(2)中得到的金黄色葡萄球菌菌悬液用台盼蓝染色剂进行染色,如图7的(a)和(b),本领域技术人员所熟知的台盼蓝染色剂能够将死亡的细菌染成淡蓝色,经过摩擦诱导处理的涂层的金黄色葡萄球菌的被染色的死亡细菌数量要远高于对照组,同样证明杀菌效果显著。
以上实施例仅为说明本发明的技术思想,不能以此限定本发明的保护范围,凡是按照本发明提出的技术思想,在技术方案基础上所做的任何改动,均落入本发明保护范围之内。
Claims (7)
1.一种基于摩擦诱导抗菌特性增强涂层的制备方法,其特征在于,包括如下步骤:
步骤1,对金属基底表面进行抛光,随后依次用去离子水和无水乙醇各清洗30分钟去除油污,随后用氮气吹干并保存于真空干燥皿中;
步骤2,将经过步骤1处理后的金属基底置于磁控溅射设备的腔体内,并对腔体进行抽真空,利用离子束轰击去除金属基底表面的氧化层,随后采用氮气和三甲基硅烷作为工作气体,铬靶、钼靶和碳靶作为溅射靶材,对金属基底表面进行涂层的沉积;
步骤3,将步骤2沉积的涂层依次放在蒸馏水、无水乙醇和丙酮中各清洗10分钟去除表面污染物,随后在喷雾或水润滑的条件下进行摩擦试验,对涂层表面进行诱导增强处理,得到最终的摩擦诱导抗菌特性增强涂层。
2.根据权利要求1所述基于摩擦诱导抗菌特性增强涂层的制备方法,其特征在于,步骤1所述抛光的要求是金属基底表面粗糙度小于等于30nm。
3.根据权利要求1所述基于摩擦诱导抗菌特性增强涂层的制备方法,其特征在于,步骤1所述金属基底的材料为钛合金或耐海水腐蚀用钢,耐海水腐蚀用钢的型号包括304、304L、316和316L四种型号中的一种。
4.根据权利要求1所述基于摩擦诱导抗菌特性增强涂层的制备方法,其特征在于,所述步骤2所述涂层的沉积过程中,离子束轰击时间为30分钟,腔体真空度为4×10-4Pa,腔体工作压强为0.22Pa,铬靶的功率控制在1400~1500W,钼靶的功率控制在500~600W,碳靶的功率控制在2000~2200W,三甲基硅烷的流量为5~30sccm,氮气流量由光发射监测器控制在50%,沉积时间为50~100分钟,沉积温度为150℃。
5.根据权利要求1所述基于摩擦诱导抗菌特性增强涂层的制备方法,其特征在于,步骤3所述摩擦试验为球-盘摩擦试验,对磨小球选取碳化硅小球,直径为8mm,摩擦时间设置为7200s,速度0.1m/s,载荷3N,润滑方式为喷雾润滑,喷雾间隔10分钟,喷雾时间15s。
6.根据权利要求1所述基于摩擦诱导抗菌特性增强涂层的制备方法,其特征在于,步骤3所述摩擦试验的温度为室温环境。
7.根据权利要求1所述基于摩擦诱导抗菌特性增强涂层的制备方法,其特征在于,步骤3所述摩擦试验产生的抗菌剂的成分为氧化钼和钼酸。
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