CN110564229A - 一种快速制备铜/聚四氟乙烯超双疏性涂层的方法 - Google Patents
一种快速制备铜/聚四氟乙烯超双疏性涂层的方法 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
本发明涉及一种快速制备铜/聚四氟乙烯复合超双疏性涂层的方法,依次包括如下步骤:(1)基体材料表面的预处理(砂纸打磨,碱洗或酸洗,丙酮、无水乙醇、去离子水超声清洗,烘干);(2)配制包含组份A与组份B的化学置换制膜乳液;(3)化学置换反应沉积铜/聚四氟乙烯复合涂层;(4)真空热固化处理沉积的铜/聚四氟乙烯复合涂层,即可得到具有树枝状微纳米结构的铜/聚四氟乙烯复合超双疏性涂层。本发明所制备的铜/聚四氟乙烯复合超双疏性涂层具有超疏水性、超疏油性、热稳定性和耐腐蚀性等特性。本发明制备方法简单快速,成本低,环境友好,所制得的超双疏性表面性能稳定,适合工业化生产。
Description
技术领域
本发明涉及涂层制备、特殊润湿性表面、材料表面防护技术领域。具体涉及一种快速制备树枝状微纳米结构铜/聚四氟乙烯复合超双疏性(超疏水、超疏油)涂层的方法,依靠超双疏性表面的疏水、疏油、防垢、自清洁和防腐蚀特性,提高铝材、镁材、锌材、铁等金属材料的使用寿命和功能化应用。
背景技术
铝材、镁材、锌材、铁等金属材料都是常见的工程材料,在工业、社会发展中起到了重要作用;但这些金属材料在服役期间,容易在服役环境中发生腐蚀、污损,甚至损坏,这缩短了材料的使用年限,增加了维护成本。近些年,不断更新的防污防腐技术,延长了这些金属材料的使用寿命,特别是实现材料表面特殊润湿性的表面改性技术,越来越受到人们的关注;由于特殊润湿性表面具有超疏水或超疏油、防垢、自清洁和防腐蚀特性,为基体的防污防腐提供了一种新的思路。
依据制备特殊润湿性表面的理论,其两个必要条件:一是增加材料表面的粗糙度,二是降低材料表面的表面能。目前,含氟聚合物(如聚四氟乙烯PTFE)本身氟-碳链分子间作用力极低,具有极低的表面能及低摩擦和耐高温腐蚀性能,使其在疏水不粘领域得到广泛应用,但其本征疏水接触角为90°~110°,仍未达到超疏水(静态接触角大于150°)表面的要求,因此,还要结合其它技术手段实现表面的特殊润湿性。
中国专利(公开号为CN109233482A,公开日为2019年1月18日)公开了一种水性体系超双疏耐久涂层的制备方法;该方法先将种子乳液放入容器中,加入氟硅烷和表面活性剂,室温搅拌0.5-1h,然后在水中分散得到的乳液,然后将其喷涂到基材表面,喷涂厚度为200-800nm,然后在125-135℃下加热0.5-2h,得到超双疏涂层;此发明强调使用工业品乳液直接制备超双疏涂层,与使用纳米粒子相比操作简单,分散较好,所制备的超双疏涂层性能稳定。中国专利(申请公布号CN102776548A、申请公布日2012年11月14日)公开了一种在钢材表面制备超疏水膜层的复合电镀方法;其首先对钢材进行打磨、抛光、活化处理,再在复合镀液(包括镍磷镀液和纳米聚四氟乙烯颗粒)中,对钢材复合电镀处理后,在钢材表面形成一层微纳结构,最后再将此钢材转入真空炉中进行热处理;此发明强调其适用于各种类型钢铁材料的表面处理,应用范围广。中国专利(授权公告号为CN104072792B,授权公告日为2017年7月4号)公开了一种超疏水聚四氟乙烯薄膜的制备方法;该方法先将PTFE乳液15-40份、超纯水40-54份、醋酸锌8-25份、氯化钠或氯化钾1-20份,搅拌均匀;在基底上采用浸涂法制膜,干燥后,360-380℃煅烧20-40min,1mol/L醋酸溶液浸泡30min,得到的超疏水聚四氟乙烯薄膜,接触角为150.5°-155.6°,滚动角小于30°;此发明在PTFE乳液中添加醋酸锌、氯盐,利用相分离原理和浸涂制膜的方式,获得具有微米和纳米结构的聚四氟乙烯,煅烧处理后再用醋酸腐蚀处理后,从基底上取下交联固化的聚四氟乙烯薄膜,得到微米-纳米结构的多孔聚四氟乙烯薄膜;此发明中提及此技术方法简单,易于规模化生产,表面耐磨性好,且能再修复和反复使用,其反应原理主要是利用醋酸锌在分解温度下生成氧化锌,制成超疏水薄膜所需的粗糙度。中国专利(授权公告号CN103992701B,授权公告日为2016年9月7日)公开了一种含有纳米粒子的超疏水高分子复合涂层的制备方法;该方法先将偶联剂与水解促进剂和去离子水混合进行常温水解,加入纳米粒子,磁力搅拌下、50~100℃反应0.25~5h经后处理得到改性纳米粒子粉末(氧化铝、二氧化硅);再将所述的改性纳米粒子粉末过筛后,与含氟聚合物乳液(聚四氟乙烯、聚全氟乙丙烯)混合,经稀释剂稀释后搅拌均匀,涂布在金属基底上,经高温固化、退火处理后冷却至室温;此发明强调提出了一种简单的制备含有纳米粒子的超疏水性高分子复合涂层的方法,通过对纳米粒子进行偶联剂修饰,同时省去纳米粒子疏水化处理过程中pH的调节过程,将改性后的纳米粒子加入高分子复合膜涂料中,通过纳米粒子-偶联剂的成键与含氟聚合物分子长链的相互作用达到稳定的目的。尽管上述专利技术都能制备出含PTFE的特殊润湿性表面,但这些技术方法都或多或少存在成本高、环境污染物多、工艺步骤多、各流程控制条件复杂、需特定仪器设备支持、涂层均匀性与基体结合性差等缺点,不适合大规模工业应用。
本发明制备特殊湿润性表面的工艺与上面的技术方法有所不同,通过乳液化学置换、热固化成膜的“两步法”,简单、快速、高效地在铝材等基体上制备出具有良好的超疏水性、超疏油性、热稳定性和耐腐蚀性的超双疏表面。本发明中的制备方法、工艺过程简单,成本低廉,制备的树枝状微纳米结构铜(Cu)/聚四氟乙烯(PTFE)复合涂层结构稳定;此外,该方法不但可应用于铝材表面上,也可应用于镁、锌、铁等金属材料表面上,适合工业化生产。
发明内容
本发明的目的在于研发一种能简单、快速制备具有良好的超疏水、超疏油、热稳定和耐腐蚀等特性的超双疏性涂层的方法,采用该方法在基体表面制备具有超双疏性的铜/聚四氟乙烯复合结构涂层,从而增加铝、镁、锌、铁等金属材料表面的防水、防油、耐腐蚀性,延长材料的使用寿命。
为实现上述目的,本发明所述的一种快速制备树枝状微纳米结构铜/聚四氟乙烯复合超双疏性涂层的方法,依次包括如下步骤:
(1)基体材料表面的预处理
以铝、镁、锌、铁及其合金等金属材料中的任意一种作为基体材料,按使用或设计要求切割成所需大小,用砂纸将基体材料表面粉尘、铁锈杂质打磨掉,并将打磨好的试样依次放入到丙酮、无水乙醇、去离子水中进行超声波清洗5-15min,进一步去除基体材料表面的粉尘、铁锈、油污等杂质和污染物,然后放入恒温鼓风干燥箱中,在30-100℃下烘干,备用;若杂质和污染物不容易打磨处理时,可使用3%-10%氢氧化钠的碱性水洗液中碱洗30s-2min,或使用20%-30%硝酸的酸洗液中酸洗30s-2min;再依次放入到丙酮、无水乙醇中超声清洗5-15min;
(2)采用混合溶液法配制化学置换制膜乳液
取质量份为:五水硫酸铜或硝酸铜或氯化铜等含铜离子的可溶性无机盐5-40份、氯化钠或氯化钾1-3份、去离子水或纯水40-200份,搅拌均匀,制成制膜乳液组份A;
取质量份为:水溶性PTFE乳液10-50份,为制膜乳液组份B;
将制膜乳液组份A与组份B混合,搅拌均匀,形成稳定的乳液;
(3)化学置换反应沉积Cu/PTFE复合涂层
将步骤(1)中预处理后的基体,浸渍于步骤(2)中配制的化学置换制膜乳液中,浸渍时间为30s-8min,在基体材料表面上生成偏红色的Cu/PTFE复合涂层,取出后备用;反应过程中会有气泡产生,当化学置换制膜乳液的各组份质量份较小时,浸渍时间靠近时间窗口上限8min,当化学置换制膜乳液的各组份质量份较大时,浸渍时间靠近时间窗口下限30s;
(4)真空热固化成膜处理
将步骤(3)中表面覆盖有Cu/PTFE复合涂层的基体试样放到真空管式炉或真空加热炉中进行热固化处理,保证炉内真空度<-0.1MPa的真空条件,适当控制升温速率,热处理温度为150~380℃,保温时间为1~5h,热固化处理结束后,随炉冷却至室温,即可制得具有超疏水性、超疏油性、热稳定性和耐腐蚀性的偏红色的树枝状微纳米结构Cu/PTFE复合超双疏性涂层。
本发明中的超双疏性涂层形成原理是:首先,对基体材料表面进行简单的物理或化学清洗过程,在基体材料表面获得具有一定粗糙度、高清洁度、多活性中心的基体表面,目的是提高后续步骤中沉积涂层与基体的结合性,并减少杂质与污染物对涂层的影响;在配制的化学置换制膜乳液中,发生的反应主要是基体材料置换溶液中的铜离子为铜单质,并吸附于基体材料表面,形成沉积的偏红色的Cu/PTFE复合涂层;在直接热固化过程中,沉积于基体表面的Cu/PTFE复合涂层中的聚四氟乙烯在一定温度条件下被固化成膜,最终在基体表面生成了偏红色的Cu/PTFE复合超双疏性涂层。
与现有技术相比,本发明的有益效果是:
(1)本发明采用常见的化学试剂与材料,以简单、低成本的“两步法”制备方式快速制备出稳定、可靠的超双疏性表面,省略了以往制备特殊润湿性表面中低表面能修饰的单独操作,整个工艺过程更直接,可控性更高;
(2)本发明的制备原理简单直接,基体材料在化学置换制膜乳液中发生置换反应,且无污染与有毒性物质产生,避免对人体和环境产生危害;
(3)本发明中的微观结构主要是通过化学置换沉积生成的Cu/PTFE复合涂层热固化后的树枝状微纳米结构,其结构稳定,保证了涂层的超疏水性、超疏油性和热稳定性;
(4)本发明采用的处理过程对试样的形状和尺寸没有特殊要求,增加了本发明的推广应用性,且可推广到镁、锌、铁等其它金属材料表面。
附图说明
图1是Cu/PTFE复合超双疏性涂层的SEM图;
图2是Cu/PTFE复合超双疏性涂层的自清洁测试图;
图3是Cu/PTFE复合超双疏性涂层对去离子水的接触角;
图4是Cu/PTFE复合超双疏性涂层对乙二醇的接触角;
图5是Cu/PTFE复合超双疏性涂层在260℃保温过程中保温时间与水、乙二醇接触角的关系图;
图6是Cu/PTFE复合超双疏性涂层在质量分数为3.5%的氯化钠溶液中浸泡时间与水、乙二醇接触角的关系图。
具体实施方式
下面结合附图对本发明作详细说明:
本发明的目的在于研发一种简单、快速制备具有树枝状微纳米结构的铜/聚四氟乙烯复合超双疏性涂层的方法,依靠其表面良好的超疏水、超疏油、热稳定和耐腐蚀性,提高基体材料的使用寿命和功能性应用。
为达到上述目的,本发明以纯铝和6061铝合金为研究对象,在基体表面制备了铜/聚四氟乙烯复合超双疏性涂层。
具体实施方式一:
(1)选取大小为20×40×2mm的6061铝合金为基底试样,用砂纸将基底试样打磨光滑,并将打磨好的试样依次放入到丙酮,无水乙醇中超声波清洗5min,以去除试样表面的油脂和污染物;
(2)将上述清洗好的6061铝合金试样采用浸渍制膜法在(质量份:五水硫酸铜10份、氯化钠1份、去离子水(纯水)50份,水溶性PTFE乳液20份)化学置换制膜乳液中,浸渍时间为4min,在基体材料表面上生成偏红色的Cu/PTFE复合涂层,取出后备用;
(3)将上一步中表面覆盖有Cu/PTFE复合涂层的基体试样放到真空管式炉中直接进行热处理,炉内真空度<-0.1MPa,控制升温速率为5℃/min,热处理温度为300℃,保温时间为1.5h,热处理结束后,随炉冷却至室温,即可制得具有本发明所述热稳定性、耐磨性的树枝状微纳米结构Cu/PTFE复合超双疏性涂层(如图1所示),对其进行自清洁测试(如图2所示);3μL去离子水液滴在该Cu/PTFE复合超双疏性涂层的接触角约为152.52°(如图3所示),3μL乙二醇液滴在该Cu/PTFE复合超双疏性涂层的接触角约为151.14°(如图4所示)。
(4)在260℃保温一段时间,测试去离子水、乙二醇液滴的接触角变化情况,证明该Cu/PTFE复合超双疏性涂层具有良好的热稳定性(如图5所示);在3.5%(质量分数)的氯化钠溶液中浸泡一段时间,测试去离子水、乙二醇液滴的接触角变化情况,证明该Cu/PTFE复合超双疏性涂层具有良好的耐腐蚀性(如图6所示)。
具体实施方式二:
(1)选取大小为20×40×2mm的6061铝合金为基底试样,用砂纸将基底试样打磨光滑,使用3%氢氧化钠的碱性水洗液中碱洗2min,并将打磨好的试样依次放入到丙酮,无水乙醇中超声波清洗10min,以去除试样表面的油脂和污染物;
(2)将上述清洗好的6061铝合金试样采用浸渍制膜法在(质量份:五水硫酸铜20份、氯化钠1.5份、去离子水(纯水)100份,水溶性PTFE乳液30份)化学置换制膜乳液中,浸渍时间为3min,在基体材料表面上生成偏红色的Cu/PTFE复合涂层,取出后备用;
(3)将上一步中表面覆盖有Cu/PTFE复合涂层的基体试样放到马弗炉中直接进行热处理,炉内真空度<-0.1MPa,控制升温速率为6℃/min,热处理温度为380℃,保温时间为2h,热处理结束后,随炉冷却至室温,即可制得具有本发明所述热稳定性、耐磨性的树枝状微纳米结构Cu/PTFE复合超双疏性涂层。
具体实施方式三:
(1)选取大小为20×40×2mm的6061纯铝为基底试样,用砂纸将基底试样打磨光滑,使用30%硝酸的酸洗液中酸洗2min,并将打磨好的试样依次放入到丙酮,无水乙醇中超声波清洗15min,以去除试样表面的油脂和污染物;
(2)将上述清洗好的纯铝试样采用浸渍提拉法在(质量份:五水硫酸铜25份、氯化钾2份、去离子水(纯水)150份,水溶性PTFE乳液30份)化学置换制膜乳液中,浸渍时间为5min,在基体材料表面上生成偏红色的Cu/PTFE复合涂层,取出后备用;
(3)将上一步中表面覆盖有Cu/PTFE复合涂层的基体试样放到马弗炉中直接进行热处理,炉内真空度<-0.1MPa,控制升温速率为5℃/min,热处理温度为350℃,保温时间为2h,热处理结束后,随炉冷却至室温,即可制得具有本发明所述热稳定性、耐磨性的树枝状微纳米结构Cu/PTFE复合超双疏性涂层。
Claims (1)
1.一种快速制备铜/聚四氟乙烯复合超双疏性涂层的方法,依次包括如下步骤:
(1)基体材料表面的预处理
以铝、镁、锌、铁及其合金等金属材料中的任意一种作为基体材料,按照使用或设计要求切割成所需大小,用砂纸将基体材料表面粉尘、铁锈等杂质打磨掉,并将打磨好的试样依次放入丙酮、无水乙醇、去离子水中进行超声波清洗5-15min,进一步去除基体材料表面的粉尘、铁锈、油污等杂质和污染物,然后放入恒温鼓风干燥箱中,在30-100℃下烘干,备用;若杂质和污染物不容易打磨处理时,可使用3%-10%氢氧化钠的碱性水洗液碱洗30s-2min,或使用20%-30%硝酸的酸洗液酸洗30s-2min;再依次放入丙酮、无水乙醇中超声清洗5-15min;
(2)采用混合溶液法配制化学置换制膜乳液
取质量份为:五水硫酸铜或硝酸铜或氯化铜等含铜离子的可溶性无机盐5-40份、氯化钠或氯化钾1-3份、去离子水或纯水40-200份,搅拌均匀,制成制膜乳液组份A;
取质量份为:水溶性PTFE乳液10-50份,为制膜乳液组份B;
将制膜乳液组份A与组份B混合,搅拌均匀,形成稳定的乳液;
(3)化学置换反应沉积Cu/PTFE复合涂层
将步骤(1)中预处理后的基体,浸渍于步骤(2)中配制的化学置换制膜乳液中,浸渍时间为30s-8min,在基体材料表面上生成偏红色的Cu/PTFE复合涂层,取出后备用;反应过程中会有气泡产生,当化学置换制膜乳液的各组份质量份较小时,浸渍时间靠近时间窗口上限8min,当化学置换制膜乳液的各组份质量份较大时,浸渍时间靠近时间窗口下限30s;
(4)真空热固化成膜处理
将步骤(3)中表面覆盖有Cu/PTFE复合涂层的基体试样放到马弗炉或管式炉等加热炉中进行热氧化处理,保证炉内真空度<-0.1MPa的真空条件,适当控制升温速率,热处理温度为150~380℃,保温时间为1~5h,热固化处理结束后,随炉冷却至室温,即可制得具有超疏水性、超疏油性、热稳定性和耐腐蚀性的偏红色的树枝状微纳米结构Cu/PTFE复合超双疏性涂层。
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Publication number | Priority date | Publication date | Assignee | Title |
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CN104072792A (zh) * | 2014-07-04 | 2014-10-01 | 无锡市顺业科技有限公司 | 一种超疏水聚四氟乙烯薄膜 |
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