CN116554743B - 一种超疏水海洋防污涂层及其制备方法 - Google Patents
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Abstract
本发明公开了一种超疏水海洋防污涂层及其制备方法,属于海洋防污技术领域,所述制备方法包括制备涂层底膜和制备涂层表膜。本发明先将氟化改性微米TiO2喷涂在载体表面,再引入碳纳米管原位生长纳米SiO2,双层气膜的构建能够捕获空气,形成稳定气膜的微纳结构,不仅可提高涂层机械稳定性,还可改善超疏水表面与水持续接触时的疏水稳定性,提高涂层的使用寿命。与此同时,引入CTAB杀菌物质,使涂层表面在防止微生物粘附的同时,还可抑制细菌的生长,抗粘附与杀菌协同作用可增强涂层在海洋中的抗污效果。因此,本发明公开的涂层可以在海洋抑菌抗污领域得到广泛的应用。
Description
技术领域
本发明属于海洋防污技术领域,具体涉及一种超疏水海洋防污涂层及其制备方法。
背景技术
海洋中蕴含着丰富的资源,千百年来,人类对海洋探索的脚步未曾停下。为了满足人们日益增长的资源需求,发展海洋资源是解决能源危机的必要手段。海洋资源开发利用对国家安全、经济发展有着重要意义。如今,海洋资源开发利用已经是国家发展的重要战略。然而,海洋生物污染对海洋经济、海洋生态、海洋资源的开发利用等造成了严重的阻碍,这是全球面临的一个重大问题,是当前必须要攻克的难题。
海洋生物污染是指海洋中的附着生物在水下设施表面大量附着聚集以及生长繁殖形成的生物污垢。海洋中附着性生物种类繁多,包含细菌、藻类(硅藻和藻类孢子)、藤壶、贻贝等。海洋生物污染对海洋工业、海洋运输、元素吸附造成严重的危害。例如,藤壶分泌物会加速离岸钻机、海底管道等工业设备的腐蚀,导致设备出现机械故障、降低服役寿命,对处于海水中的设备造成了巨大的经济损失与安全隐患。藻类、贻贝附着在船体表面,造成航行阻力增加和增加油耗,增加了远洋运输的成本及有害气体的排放。甚至,船体表面粘附的生物随着船只到达新的海域给当地带来生物入侵风险,这可能会对生态环境带来严重的灾难。细菌、藻类附着在吸附剂的表面,造成孔道阻塞,降低了吸附剂吸附效率,对海水中元素的富集造成巨大的影响。基于海洋生物污垢研究现状,随着海洋防污这一领域研究不断深入,构建海洋防污涂层是解决海洋生物污染的有效途径。目前,超疏水涂层是最具有发展潜力的防污方法。
超疏水涂层材料具有特殊的润湿性,良好的自清洁、防腐蚀、防结冰等性能,能够有效地减少航行体在行驶过程中受到的海水阻力与能源消耗、抑制海洋生物附着、减缓海水腐蚀、降低冰附着力,在海洋领域具有良好的应用潜力。根据Wenzel模型及Cassie-Baxter模型基本理论,涂层表面的化学组分和表面微观形貌是构建超疏水涂层的两个必要条件。当前研究报道的超疏水抗污涂层存在以下两个挑战:第一,涂层机械强度低;第二,疏水持久性差。因此,急需研发具有高机械强度和持久疏水的海洋防污涂层。
发明内容
本发明的目的在于克服现有技术的缺点,提供一种超疏水海洋防污涂层及其制备方法。
本发明的目的通过以下技术方案来实现:一种超疏水海洋防污涂层的制备方法,它包括以下步骤:
S1.制备涂层底膜:
S11.室温下,将CTAB分散于Tris-HCI缓冲液中,再加入盐酸多巴胺,混合均匀后旋涂于载体表面;
S12.将十三氟辛基三乙氧基硅烷加入乙醇溶液中并搅拌20~40min,然后将平均粒径为1~10μm的TiO2微米颗粒缓慢加入溶液中,继续搅拌20~40min,得到乳白色的混合溶液,喷涂于旋涂后的载体表面;
S2.制备涂层表膜:
S21.将碳纳米管加入Tris-HCl缓冲液中,再加入盐酸多巴胺,以400~600r/min转速搅拌2~24h后真空干燥,得到CNTs@PDA;
S22.取S21制备的CNTs@PDA,加入到乙醇溶液中,常温下搅拌50~70min,加入氨水调节pH至8,加入TEOS搅拌6~24h后水洗至中性,离心收集沉淀并真空干燥,得到CNTs@PDA@SiO2;
S23.将制得的CNTs@PDA@SiO2分散于溶有POTS的乙醇溶液中反应0.5~5h,离心收集沉淀并真空干燥,得到CNTs@PDA@SiO2@POTS;
S24.取CNTs@PDA@SiO2@POTS溶解在溶有乙酸乙酯的乙醇溶液中,加入PVDF,FEVE和固化剂,搅拌均匀后喷涂于覆载有涂层底膜的载体上。
进一步地,所述载体为金属板、木板或合金板。
进一步地,步骤S11中所述CTAB与盐酸多巴胺的重量比为3~7:4。
进一步地,步骤S12中所述十三氟辛基三乙氧基硅烷与TiO2微米颗粒的重量比为0.1~1:1,十三氟辛基三乙氧基硅烷与乙醇溶液的质量体积比为1~10g:100mL。
进一步地,步骤S21中所述碳纳米管与盐酸多巴胺的质量比为1~3:1,碳纳米管与Tris-HCI缓冲液的质量体积比为0.05~1g:100mL。
进一步地,步骤S22中所述CNTs@PDA与乙醇溶液的质量体积比为0.3~0.8g:100mL,乙醇溶液与TEOS的体积比为50:1~10。
进一步地,步骤S23中所述CNTs@PDA@SiO2与溶有POTS的乙醇溶液的质量体积比为1g:40~60mL,所述溶有POTS的乙醇溶液中乙醇与POTS的体积比为50~10:1。
进一步地,步骤S24中所述溶有乙酸乙酯的乙醇溶液中乙酸乙酯与乙醇的体积比为1:3~5,CNTs@PDA@SiO2@POTS与溶有乙酸乙酯的乙醇溶液的质量体积比为0.5~1g:10mL。
进一步地,所述真空干燥的干燥温度为70~85℃。
上述方法制备的超疏水海洋防污涂层。
本发明具有以下优点:
1、本发明将氟化改性微米TiO2喷涂在载体表面,再引入碳纳米管(CNTs)原位生长纳米SiO2,双层气膜的构建能够捕获空气,形成稳定气膜的微纳结构,不仅提高涂层机械稳定性,还有利于提高超疏水表面与水持续接触时的疏水稳定性,提高涂层的使用寿命。
2、本发明引入杀菌物质CTAB,在超疏水抗粘附的同时,可杀灭已粘附的少量细菌,起到杀菌和超疏水抗粘附的双重作用,1)超疏水配体抗粘附,可防止海洋微生物粘附在海洋设备材料表面;2)当微生物附着在表面,涂层释放杀菌物质可杀死细菌,有效抗菌。
附图说明
图1为CNTs微观结构图。
图2为CNTs@PDA@SiO2@POTS微观结构图。
图3为超疏水抗污表面疏水性能测试图。
图4为超疏水抗污表面抗污性能对比图。
具体实施方式
下面结合附图及实施例对本发明做进一步的描述,本发明的保护范围不局限于以下所述:实施例1:一种超疏水海洋防污涂层及其制备方法,它包括以下步骤:
S1.制备涂层底膜:
S11.室温下,将CTAB分散于Tris-HCI缓冲液中,再加入盐酸多巴胺,所述CTAB与盐酸多巴胺的重量比为3:4,混合均匀后旋涂于铝板上;
S12.将十三氟辛基三乙氧基硅烷加入乙醇溶液中并搅拌20min,然后将平均粒径为1~10μm的TiO2微米颗粒缓慢加入溶液中,继续搅拌20min,得到乳白色的混合溶液,喷涂于旋涂后的载体表面;其中,所述十三氟辛基三乙氧基硅烷与TiO2微米颗粒的重量比为0.1:1,十三氟辛基三乙氧基硅烷与乙醇溶液的质量体积比为1g:100mL;
S2.制备涂层表膜:
S21.将碳纳米管加入Tris-HCl缓冲液中,再加入盐酸多巴胺,以400r/min转速搅拌2h后在70℃的温度下真空干燥,得到CNTs@PDA;所碳纳米管与盐酸多巴胺的质量1:1,碳纳米管与Tris-HCI缓冲液的质量体积比为0.05g:100mL;
S22.取S21制备的CNTs@PDA,加入到乙醇溶液中,常温下搅拌50min,加入氨水调节pH至8,加入TEOS搅拌6h后水洗至中性,离心收集沉淀并在70℃的温度下真空干燥,得到CNTs@PDA@SiO2;其中,所述CNTs@PDA与乙醇溶液的质量体积比为0.3g:100mL,乙醇溶液与TEOS的体积比为50:1;
S23.将制得的CNTs@PDA@SiO2分散于溶有POTS的乙醇溶液中反应0.5h,离心收集沉淀并在70℃的温度下真空干燥,得到CNTs@PDA@SiO2@POTS;所述CNTs@PDA@SiO2与溶有POTS的乙醇溶液的质量体积比为1g:40mL,所述溶有POTS的乙醇溶液中乙醇与POTS的体积比为50:1;
S24.取CNTs@PDA@SiO2@POTS溶解在溶有乙酸乙酯的乙醇溶液中,加入PVDF,FEVE和固化剂Bayer N3390,搅拌均匀后喷涂于覆载有涂层底膜的载体上,其中,所述溶有乙酸乙酯的乙醇溶液中乙酸乙酯与乙醇的体积比为1:3,CNTs@PDA@SiO2@POTS与溶有乙酸乙酯的乙醇溶液的质量体积比为0.5g:10mL。
实施例2:一种超疏水海洋防污涂层及其制备方法,它包括以下步骤:
S1.制备涂层底膜:
S11.室温下,将CTAB分散于Tris-HCI缓冲液中,再加入盐酸多巴胺,所述CTAB与盐酸多巴胺的重量比为7:4,混合均匀后旋涂于木板上;
S12.将十三氟辛基三乙氧基硅烷加入乙醇溶液中并搅拌40min,然后将平均粒径为1~10μm的TiO2微米颗粒缓慢加入溶液中,继续搅拌40min,得到乳白色的混合溶液,喷涂于旋涂后的载体表面;其中,所述十三氟辛基三乙氧基硅烷与TiO2微米颗粒的重量比为1:1,十三氟辛基三乙氧基硅烷与乙醇溶液的质量体积比为10g:100mL;
S2.制备涂层表膜:
S21.将碳纳米管加入Tris-HCl缓冲液中,再加入盐酸多巴胺,以600r/min转速搅拌24h后在85℃的温度下真空干燥,得到CNTs@PDA;所述碳纳米管与盐酸多巴胺的质量比为3:1,碳纳米管与Tris-HCI缓冲液的质量体积比为1g:100mL;
S22.取S21制备的CNTs@PDA,加入到乙醇溶液中,常温下搅拌70min,加入氨水调节pH至8,加入TEOS搅拌24h后水洗至中性,离心收集沉淀并在85℃的温度下真空干燥,得到CNTs@PDA@SiO2;其中,所述CNTs@PDA与乙醇溶液的质量体积比为0.8g:100mL,乙醇溶液与TEOS的体积比为50:10;
S23.将制得的CNTs@PDA@SiO2分散于溶有POTS的乙醇溶液中反应5h,离心收集沉淀并在85℃的温度下真空干燥,得到CNTs@PDA@SiO2@POTS;所述CNTs@PDA@SiO2与溶有POTS的乙醇溶液的质量体积比为1g:60mL,所述溶有POTS的乙醇溶液中乙醇与POTS的体积比为10:1;
S24.取CNTs@PDA@SiO2@POTS溶解在溶有乙酸乙酯的乙醇溶液中,加入PVDF,FEVE和固化剂Bayer N3390,搅拌均匀后喷涂于覆载有涂层底膜的载体上,其中,所述溶有乙酸乙酯的乙醇溶液中乙酸乙酯与乙醇的体积比为1:5,CNTs@PDA@SiO2@POTS与溶有乙酸乙酯的乙醇溶液的质量体积比为1g:10mL。
实施例3:一种超疏水海洋防污涂层及其制备方法,它包括以下步骤:
S1.制备涂层底膜:
S11.室温下,将CTAB分散于Tris-HCI缓冲液中,再加入盐酸多巴胺,所述CTAB与盐酸多巴胺的重量比为5:4,混合均匀后旋涂于合金板上;
S12.将十三氟辛基三乙氧基硅烷加入乙醇溶液中并搅拌30min,然后将平均粒径为1~10μm的TiO2微米颗粒缓慢加入溶液中,继续搅拌35min,得到乳白色的混合溶液,喷涂于旋涂后的载体表面;其中,所述十三氟辛基三乙氧基硅烷与TiO2微米颗粒的重量比为0.5:1,十三氟辛基三乙氧基硅烷与乙醇溶液的质量体积比为5g:100mL;
S2.制备涂层表膜:
S21.将碳纳米管加入Tris-HCl缓冲液中,再加入盐酸多巴胺,以500r/min转速搅拌12h后在80℃的温度下真空干燥,得到CNTs@PDA;所述碳纳米管与盐酸多巴胺的质量比为2:1,碳纳米管与Tris-HCI缓冲液的质量体积比为0.5g:100mL;
S22.取S21制备的CNTs@PDA,加入到乙醇溶液中,常温下搅拌60min,加入氨水调节pH至8,加入TEOS搅拌12h后水洗至中性,离心收集沉淀并在80℃的温度下真空干燥,得到CNTs@PDA@SiO2;其中,所述CNTs@PDA与乙醇溶液的质量体积比为0.5g:100mL,乙醇溶液与TEOS的体积比为50:6;
S23.将制得的CNTs@PDA@SiO2分散于溶有POTS的乙醇溶液中反应3h,离心收集沉淀并在75℃的温度下真空干燥,得到CNTs@PDA@SiO2@POTS;所述CNTs@PDA@SiO2与溶有POTS的乙醇溶液的质量体积比为1g:50mL,所述溶有POTS的乙醇溶液中乙醇与POTS的体积比为30:1;
S24.取CNTs@PDA@SiO2@POTS溶解在溶有乙酸乙酯的乙醇溶液中,加入PVDF,FEVE和固化剂Bayer N3390,搅拌均匀后喷涂于覆载有涂层底膜的载体上,其中,所述溶有乙酸乙酯的乙醇溶液中乙酸乙酯与乙醇的体积比为1:4,CNTs@PDA@SiO2@POTS与溶有乙酸乙酯的乙醇溶液的质量体积比为0.8g:10mL。
以下通过实验说明本发明的有益效果:
一种超疏水海洋防污涂层及其制备方法,它包括以下步骤:
S1.制备涂层底膜:
S11.室温下,将10-3M CTAB(十六烷基三甲基溴化铵)分散于Tris-HCI(10mM,pH=8.5)缓冲液中,再加入2mg/mL盐酸多巴胺,以100rpm的速度旋涂在铝片表面,旋涂时间30s,旋涂三次;铝板在旋涂之前用砂纸打磨后,将其放在无水乙醇中,超声清洗30min,去除表面氧化膜及污渍;
S12.将1.2g十三氟辛基三乙氧基硅烷(POTS)加入50mL乙醇溶液中并搅拌30min,然后将4.8g平均粒径为1~10μm的TiO2微米颗粒缓慢加入溶液中,继续搅拌30min,得到乳白色的混合溶液,喷涂于旋涂后的载体表面,置于空气中使溶剂自然挥发;
S2.制备涂层表膜:
S21.将0.4g碳纳米管(CNTs)加入200mL Tris-HCl缓冲液(10mM,pH=8.5)中,再加入0.2g盐酸多巴胺,以500r/min转速磁性搅拌24h后在80℃的温度下真空干燥,得到CNTs@PDA;
S22.称取S21制备的CNTs@PDA 0.2g,加入到50mL的乙醇溶液(乙醇与去离子水的体积比为10:1)中,常温下搅拌60min,充分分散在溶液中,加入氨水调节pH至8,逐滴加入6mL TEOS搅拌12h后水洗至中性,离心收集沉淀并在80℃的温度下真空干燥,得到CNTs@PDA@SiO2;
S23.取1g制得的CNTs@PDA@SiO2分散于50mL溶有POTS的乙醇溶液(乙醇与POTS的体积比为24:1)中反应2h,离心收集沉淀并在70℃的温度下真空干燥,得到CNTs@PDA@SiO2@POTS;
S24.取0.6gCNTs@PDA@SiO2@POTS溶解在溶有乙酸乙酯的乙醇溶液(乙醇8mL,乙酸乙酯2mL)中,加入0.75g PVDF,0.25g FEVE和0.025g固化剂Bayer N3390,搅拌30min,利用喷枪喷涂于覆载有涂层底膜的载体上,100℃固化2h。
1.SEM测试
电镜下观察碳纳米管(CNTs)和制备的CNTs@PDA@SiO2@POTS的微观结构,结果如图1和图2所示,图1为碳纳米管微观结构图,CNTs具有表面光滑的一维管状结构,分布均匀。图2为CNTs@PDA@SiO2@POTS微观结构图,管状CNTs上原位生长了纳米SiO2球;与图1的一维管状结构相比,CNTs@PDA@SiO2@POTS颗粒产生粗糙的结构,在构建超疏水表面具有更大的优势。
2.疏水性能测试
用水接触角测试仪考察了制备的超疏水抗污涂层的疏水性能,如图3所示,水接触角(WCA)为154.37°,其具有良好的超疏水效果。水滴的不浸润,可将表面污渍、微生物、细菌等物质冲走,其在复杂的海洋环境中有较大的应用前景。
3.抗污性能测试
取未覆载有本发明涂层的铝板为对照,对喷涂有本发明涂层的铝板和对照组测试抗污性,实验结果如图4所示,结果发现,未喷涂涂层铝板,浸入到泥浆溶液中,表面会被泥浆污染;喷涂有本发明涂层的铝板,其浸入泥浆20个周期后,表面依旧干净,没有泥浆滞留在表面,具有良好的自清洁、抗污染效果,其在海洋环境抗污领域有较大的应用前景。
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,根据本发明的技术方案及其发明构思加以等同替换或改变,都涵盖在本发明的保护范围之内。
Claims (10)
1.一种超疏水海洋防污涂层的制备方法,其特征在于,它包括以下步骤:
S1. 制备涂层底膜:
S11. 室温下,将CTAB分散于Tris-HCI缓冲液中,再加入盐酸多巴胺,混合均匀后旋涂于载体表面;
S12. 将十三氟辛基三乙氧基硅烷加入乙醇溶液中并搅拌20~40 min,然后将平均粒径为1~10 μm的TiO2 微米颗粒缓慢加入溶液中,继续搅拌20~40 min,得到乳白色的混合溶液,喷涂于旋涂后的载体表面;
S2. 制备涂层表膜:
S21. 将碳纳米管加入Tris-HCl缓冲液中,再加入盐酸多巴胺,以400~600 r/min转速搅拌2~24 h后真空干燥,得到CNTs@PDA;
S22. 取S21制备的CNTs@PDA,加入到乙醇溶液中,常温下搅拌50~70 min,加入氨水调节pH至8,加入TEOS搅拌6~24 h后水洗至中性,离心收集沉淀并真空干燥,得到CNTs@PDA@SiO2;
S23. 将制得的CNTs@PDA@SiO2分散于溶有POTS的乙醇溶液中反应0.5~5 h,离心收集沉淀并真空干燥,得到CNTs@PDA@SiO2@POTS;
S24. 取CNTs@PDA@SiO2@POTS溶解在溶有乙酸乙酯的乙醇溶液中,加入PVDF,FEVE和固化剂,搅拌均匀后喷涂于覆载有涂层底膜的载体上。
2.根据权利要求1所述的一种超疏水海洋防污涂层的制备方法,其特征在于,所述载体为金属板或木板。
3.根据权利要求1所述的一种超疏水海洋防污涂层的制备方法,其特征在于,步骤S11中所述CTAB与盐酸多巴胺的重量比为3~7:4。
4.根据权利要求1所述的一种超疏水海洋防污涂层的制备方法,其特征在于,步骤S12中所述十三氟辛基三乙氧基硅烷与TiO2 微米颗粒的重量比为0.1~1:1,十三氟辛基三乙氧基硅烷与乙醇溶液的质量体积比为1~10 g:100 mL。
5.根据权利要求1所述的一种超疏水海洋防污涂层的制备方法,其特征在于,步骤S21中所述碳纳米管与盐酸多巴胺的质量比为1~3:1,碳纳米管与Tris-HCI缓冲液的质量体积比为0.05~1 g:100 mL。
6.根据权利要求1所述的一种超疏水海洋防污涂层的制备方法,其特征在于,步骤S22中所述CNTs@PDA与乙醇溶液的质量体积比为0.3~0.8 g:100 mL,乙醇溶液与TEOS的体积比为50:1~10。
7.根据权利要求1所述的一种超疏水海洋防污涂层的制备方法,其特征在于,步骤S23中所述CNTs@PDA@SiO2与溶有POTS的乙醇溶液的质量体积比为1 g:40~60 mL,所述溶有POTS的乙醇溶液中乙醇与POTS的体积比为50~10:1。
8.根据权利要求1所述的一种超疏水海洋防污涂层的制备方法,其特征在于,步骤S24中所述溶有乙酸乙酯的乙醇溶液中乙酸乙酯与乙醇的体积比为1:3~5,CNTs@PDA@SiO2@POTS与溶有乙酸乙酯的乙醇溶液的质量体积比为0.5~1 g:10 mL。
9.根据权利要求1所述的一种超疏水海洋防污涂层的制备方法,其特征在于,所述真空干燥的干燥温度为70~85℃。
10.根据权利要求1-9中任意一项所述的方法制备的超疏水海洋防污涂层。
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