CN116396679A - 耐磨超疏水涂料的制备方法及耐磨超疏水表面处理方法 - Google Patents
耐磨超疏水涂料的制备方法及耐磨超疏水表面处理方法 Download PDFInfo
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Abstract
本发明公开了耐磨超疏水涂料的制备方法,分别制备涂层液和打底液;涂层液的制备具体为:将PDMS、疏水SiO2纳米粒子共混于乙酸乙酯中得到PDMS/SiO2悬浮液,将α‑氰基丙烯酸酯胶黏剂加入到PDMS/SiO2悬浮液中冰浴超声,得到涂层液;打底液的制备具体为:将α‑氰基丙烯酸酯胶黏剂加入到乙酸乙酯中共混得到打底液,本发明提高了耐磨疏水涂料的物理稳定性和化学稳定性。本发明还公开了耐磨超疏水表面处理方法,应用耐磨超疏水涂料处理基材表面,将打底液喷涂在基底上,再喷涂涂层液覆盖打底液,将喷涂好打底液和涂层液的基底放入烘箱干燥,在基底表面形成PDMS基耐磨超疏水复合材料,完成表面处理,本发明使基材表面具有耐磨性和超疏水性。
Description
技术领域
本发明属于耐磨超疏水复合材料技术领域,涉及耐磨超疏水涂料的制备方法,还涉及耐磨超疏水表面处理方法。
背景技术
超疏水表面是指与水的接触角大于150°,而滚动角小于5°的表面。超疏水表面的制备灵感来源于自然现象,比如玫瑰花瓣、水稻的叶片、蜻蜓的翅膀,其中最典型的是“出淤泥而不染”的荷叶。研究表明,荷叶表面之所以具有超疏水性,是因为其独特的微纳粗糙结构以及低表面能的蜡质。这种独特的微纳粗糙结构可以捕获大量空气,从而在水滴与表面形成空气层使水滴与荷叶表面的实际接触面积非常小,所以液体在其表面可以轻松滚落。目前,超疏水表面因其在自清洁、防冰、防腐蚀、油水分离等方面的应用前景而引起学术界和工业界的广泛关注。常用于制备超疏水表面的方法有溶胶-凝胶法、层层组装法、水热法、化学气相沉积法、纳米颗粒负载法等。然而,现阶段制备的超疏水材料存在的最大问题是超疏水性能不稳定,当超疏水表面暴露在外界环境中,如在太阳光、沙尘、摩擦等作用的影响下,超疏水性会下降,进而影响超疏水表面的使用寿命,因此,限制了其在工业中的广泛应用。近年来,制备耐磨持久超疏水表面已成为超疏水领域的研究热点。
发明内容
本发明的目的是提供耐磨超疏水涂料的制备方法,提高了耐磨疏水涂层的物理稳定性和化学稳定性。
本发明的另一目的是提供耐磨超疏水表面处理方法,应用耐磨超疏水涂料处理基材表面,使基材表面具有耐磨性和超疏水性。
本发明采用的第一种技术方案是,耐磨超疏水涂料的制备方法,分别制备涂层液和打底液;
涂层液的制备具体为:
将PDMS、疏水SiO2纳米粒子共混于乙酸乙酯中得到PDMS/SiO2悬浮液,将α-氰基丙烯酸酯胶黏剂加入到PDMS/SiO2悬浮液中冰浴超声,得到涂层液;
打底液的制备具体为:
将α-氰基丙烯酸酯胶黏剂加入到乙酸乙酯中共混得到打底液。
本发明的特点还在于,
PDMS/SiO2悬浮液的制备具体为,将PDMS溶解于乙酸乙酯中,PDMS完全溶解后加入疏水SiO2纳米粒子,搅拌均匀,得到PDMS/SiO2悬浮液。
PDMS/SiO2悬浮液中PDMS、疏水SiO2纳米粒子、乙酸乙酯的质量百分数分别是3.3%~6.6%,2%~5%,78%~90%,上述各组分的质量百分数之和为100%。
PDMS包括质量比为10:1的PDMS主剂和PDMS固化剂。
涂层液中α-氰基丙烯酸酯胶黏剂与PDMS/SiO2悬浮液的质量比是3~6:94~97。
涂层液制备过程中冰浴超声的温度是5~10℃,时间是5~10min。
打底液中α-氰基丙烯酸酯胶黏剂和乙酸乙酯的质量分数分别是6%~12%,90%~96%,上述两组分的质量百分数之和为100%。
本发明采用的第二种技术方案是,耐磨超疏水表面处理方法,应用本发明的耐磨超疏水涂料的制备方法制备的耐磨超疏水涂料进行表面处理,将打底液喷涂在基底上,再喷涂涂层液覆盖打底液,将喷涂好打底液和涂层液的基底放入烘箱干燥,在基底表面形成PDMS基耐磨超疏水复合材料,完成表面处理。
本发明的特点还在于,
烘箱的干燥时间为1~3h,烘箱温度为80℃以上。
打底液的喷涂量为0.6g/cm2~2.4g/cm2,涂层液的喷涂量为1.48g/cm2~5.92g/cm2。
本发明的有益效果是:
本发明耐磨超疏水涂料的制备方法,所制备的耐磨超疏水材料中,PDMS提供低表面能,疏水纳米SiO2提供表面粗糙度,与水滴的静态接触角大于150°,使得涂层具有超疏水性;同时制备得到的材料具有还有较好的物理稳定性与化学稳定性,这是由于PDMS作为耐磨弹性体受到机械外力会有一定的回弹,并且其化学性质稳定;同时α-氰基丙烯酸酯胶黏剂的加入,由于氢键的存在使的涂层间各物质、以及涂层与基底的粘附力大大增强,增加了其物理稳定性。
本发明耐磨超疏水表面处理方法,应用本发明的耐磨超疏水涂料的制备方法制备的耐磨超疏水涂料进行表面处理,通过共混喷涂法在基底表面形成耐磨超疏水复合材料,具有普适性,适用不同的基底,如金属、织物、玻璃等,应用前景广泛。
附图说明
图1是实施例1在基底表面形成的PDMS基耐磨超疏水复合材料的表面形貌及接触角图;
图2是实施例1在基底表面形成的PDMS基耐磨超疏水复合材料的润湿性能图;
图3是实施例5在基底表面形成的PDMS基耐磨超疏水复合材料的耐摩擦性能数据图;
图4是实施例5在基底表面形成的PDMS基耐磨超疏水复合材料的化学稳定性数据图,其中,图4(a)是0.1mol/L HCl溶液浸泡后的CA和SA数据,图4(b)是0.1mol/L NaOH溶液浸泡后的CA和SA数据,图4(c)是5wt%NaCl溶液浸泡后的CA和SA数据。
具体实施方式
下面结合附图和具体实施方式对本发明进行详细说明。
本发明耐磨超疏水涂料的制备方法,分别制备涂层液和打底液;
涂层液的制备具体为:
将PDMS溶解于乙酸乙酯中,PDMS包括质量比为10:1的PDMS主剂和PDMS固化剂,PDMS完全溶解后加入疏水SiO2纳米粒子,搅拌均匀,得到PDMS/SiO2悬浮液,将α-氰基丙烯酸酯胶黏剂加入到PDMS/SiO2悬浮液中冰浴超声,冰浴超声的温度是5~10℃,时间是5~10min,得到涂层液;
PDMS/SiO2悬浮液中PDMS、疏水SiO2纳米粒子、乙酸乙酯的质量百分数分别是3.3%~6.6%,2%~5%,78%~90%,上述各组分的质量百分数之和为100%。
涂层液中α-氰基丙烯酸酯胶黏剂与PDMS/SiO2悬浮液的质量比是3~6:94~97。
打底液的制备具体为:
将α-氰基丙烯酸酯胶黏剂加入到乙酸乙酯中共混得到打底液。
打底液中α-氰基丙烯酸酯胶黏剂和乙酸乙酯的质量分数分别是6%~12%,90%~96%,上述两组分的质量百分数之和为100%。
本发明耐磨超疏水表面处理方法,应用本发明的耐磨超疏水涂料的制备方法制备的耐磨超疏水涂料进行表面处理,将打底液喷涂在基底上,打底液的喷涂量为0.6g/cm2~2.4g/cm2,再喷涂涂层液覆盖打底液,涂层液的喷涂量为1.48g/cm2~5.92g/cm2,将喷涂好打底液和涂层液的基底放入烘箱干燥,干燥时间为1~3h,烘箱温度为80℃以上,在基底表面形成PDMS基耐磨超疏水复合材料,完成表面处理。
实施例1
本实施例提供耐磨超疏水涂料的制备方法,分别制备涂层液和打底液;
涂层液的制备具体为:
将2.5gPDMS主剂及0.25gPDMS固化剂溶解于42.75g乙酸乙酯中,PDMS完全溶解后加入1.5g疏水SiO2纳米粒子,搅拌均匀,得到PDMS/SiO2悬浮液,将3gα-氰基丙烯酸酯胶黏剂加入到PDMS/SiO2悬浮液中冰浴超声,冰浴超声的温度是5℃,时间是10min,得到涂层液;
打底液的制备具体为:
将2gα-氰基丙烯酸酯胶黏剂加入到23g乙酸乙酯中共混得到打底液。
本实施例提供还提供耐磨超疏水表面处理方法,应用本实施例的耐磨超疏水涂料的制备方法制备的耐磨超疏水涂料进行表面处理,将打底液喷涂在基底上,打底液的喷涂量为0.6g/cm2,再喷涂涂层液覆盖打底液,涂层液的喷涂量为1.48g/cm2,将喷涂好打底液和涂层液的基底放入烘箱干燥,干燥时间为1h,烘箱温度为100℃以上,在基底表面形成PDMS基耐磨超疏水复合材料,完成表面处理。
如图1所示,本实施例最终在基底表面形成的PDMS基耐磨超疏水复合材料的接触角达到162.3°,滚动角达到3.5°。如图2所示,不同液滴在该复合材料表面都呈球状,表明其拥有优异的超疏水性。
实施例2
本实施例提供耐磨超疏水涂料的制备方法,分别制备涂层液和打底液;
涂层液的制备具体为:
将2gPDMS溶解于46.3g乙酸乙酯中,PDMS完全溶解后加入0.5g疏水SiO2纳米粒子,搅拌均匀,得到PDMS/SiO2悬浮液,将1gα-氰基丙烯酸酯胶黏剂加入到PDMS/SiO2悬浮液中冰浴超声,冰浴超声的温度是7℃,时间是8min,得到涂层液;
打底液的制备具体为:
将3gα-氰基丙烯酸酯胶黏剂加入到22g乙酸乙酯中共混得到打底液。
本实施例提供还提供耐磨超疏水表面处理方法,应用本实施例的耐磨超疏水涂料的制备方法制备的耐磨超疏水涂料进行表面处理,将打底液喷涂在基底上,打底液的喷涂量为2.4g/cm2,再喷涂涂层液覆盖打底液,涂层液的喷涂量为5.92g/cm2,将喷涂好打底液和涂层液的基底放入烘箱干燥,干燥时间为1h,烘箱温度为100℃以上,在基底表面形成PDMS基耐磨超疏水复合材料,完成表面处理。
本实施例最终在基底表面形成的PDMS基耐磨超疏水复合材料的接触角达到158.3°,滚动角达到7.2°。
实施例3
本实施例提供耐磨超疏水涂料的制备方法,分别制备涂层液和打底液;
涂层液的制备具体为:
将2.5g PDMS溶解于42.75g乙酸乙酯中,PDMS完全溶解后加入2.5g疏水SiO2纳米粒子,搅拌均匀,得到PDMS/SiO2悬浮液,将2gα-氰基丙烯酸酯胶黏剂加入到PDMS/SiO2悬浮液中冰浴超声,冰浴超声的温度是10℃,时间是5min,得到涂层液;
打底液的制备具体为:
将2gα-氰基丙烯酸酯胶黏剂加入到23g乙酸乙酯中共混得到打底液。
本实施例提供还提供耐磨超疏水表面处理方法,应用本实施例的耐磨超疏水涂料的制备方法制备的耐磨超疏水涂料进行表面处理,将打底液喷涂在基底上,打底液的喷涂量为1.2g/cm2,再喷涂涂层液覆盖打底液,涂层液的喷涂量为3.26g/cm2,将喷涂好打底液和涂层液的基底放入烘箱干燥,干燥时间为2h,烘箱温度为90℃以上,在基底表面形成PDMS基耐磨超疏水复合材料,完成表面处理。
本实施例最终在基底表面形成的PDMS基耐磨超疏水复合材料的接触角达到159.3°,滚动角达到5.3°。
实施例4
本实施例提供耐磨超疏水涂料的制备方法,分别制备涂层液和打底液;
涂层液的制备具体为:
将2.5gPDMS溶解于43.75g乙酸乙酯中,PDMS完全溶解后加入0.5g疏水SiO2纳米粒子,搅拌均匀,得到PDMS/SiO2悬浮液,将1gα-氰基丙烯酸酯胶黏剂加入到PDMS/SiO2悬浮液中冰浴超声,冰浴超声的温度是8℃,时间是7min,得到涂层液;
打底液的制备具体为:
将3gα-氰基丙烯酸酯胶黏剂加入到22g乙酸乙酯中共混得到打底液。
本实施例提供还提供耐磨超疏水表面处理方法,应用本实施例的耐磨超疏水涂料的制备方法制备的耐磨超疏水涂料进行表面处理,将打底液喷涂在基底上,打底液的喷涂量为2.2g/cm2,再喷涂涂层液覆盖打底液,涂层液的喷涂量为4.52g/cm2,将喷涂好打底液和涂层液的基底放入烘箱干燥,干燥时间为1h,烘箱温度为100℃以上,在基底表面形成PDMS基耐磨超疏水复合材料,完成表面处理。
本实施例最终在基底表面形成的PDMS基耐磨超疏水复合材料的接触角达到152.3°,滚动角达到8.3°。
实施例5
本实施例提供耐磨超疏水涂料的制备方法,分别制备涂层液和打底液;
涂层液的制备具体为:
将2g PDMS溶解于44.3g乙酸乙酯中,PDMS完全溶解后加入1.5g疏水SiO2纳米粒子,搅拌均匀,得到PDMS/SiO2悬浮液,将2gα-氰基丙烯酸酯胶黏剂加入到PDMS/SiO2悬浮液中冰浴超声,冰浴超声的温度是9℃,时间是6min,得到涂层液;
打底液的制备具体为:
将3gα-氰基丙烯酸酯胶黏剂加入到22g乙酸乙酯中共混得到打底液。
本实施例还提供耐磨超疏水表面处理方法,应用本实施例的耐磨超疏水涂料的制备方法制备的耐磨超疏水涂料进行表面处理,将打底液喷涂在基底上,打底液的喷涂量为1.8g/cm2,再喷涂涂层液覆盖打底液,涂层液的喷涂量为2.75g/cm2,将喷涂好打底液和涂层液的基底放入烘箱干燥,干燥时间为2h,烘箱温度为96℃以上,在基底表面形成PDMS基耐磨超疏水复合材料,完成表面处理。
本实施例最终在基底表面形成的PDMS基耐磨超疏水复合材料的接触角达到155.6°,滚动角达到6.5°。
机械稳定性试验:
如图3,为了测试复合涂层的耐摩擦性能,使用不同目数的砂纸,不同重量的载荷对实施例5在基底表面形成的PDMS基耐磨超疏水复合材料进行摩擦实验,复合材料在分别经过120目、320目、600目砂纸,200g、500g载重磨擦经过10m的距离。因即使经过50次磨损,涂层的CA(接触角)仍大于154°,SA(滚动角)小于10°,这表明在基底表面形成的PDMS基耐磨超疏水复合材料表面粗糙结构稳定,这是因为PECA(聚α-氰基丙烯酸乙酯,Poly ethylcyanoacrylate)增强了涂层间各物质的作用力,及时经受磨损,PDMS新暴露的SiO2颗粒与结合,使新形成的表面仍具有微纳米粗糙度,与低表面能的PDMS结合,在每次磨损循环后都会赋予磨损后的新涂层超疏水性。
化学稳定性试验:
如图4,为了对本发明制备的PDMS基耐磨超疏水复合材料形成的复合涂层的耐化学稳定性进行检测,如图4(a)~(c)分别为将实施例5在基底表面形成的PDMS基耐磨超疏水复合材料分别浸泡在0.1mol/L HCl、0.1mol/L NaOH和5wt%NaCl的强腐蚀性水溶液中,在一定浸泡时间后,测定了涂层的CA和SA。结果发现,浸渍7d后,涂层表面CA和SA变化不明显,所有样品均保持超疏水状态,CA>155°,SA<10°,值得注意的是,即使铝合金基底被碱性溶液的腐蚀出很多肉眼可见的孔洞但涂层的仍保持超疏水状态,这是由于其表面的空气层有效地阻止了溶液和涂层的接触,从而避免了腐蚀破坏表面结构。表明涂层具有持久的化学稳定性。
通过上述内容可知,本发明的耐磨超疏水表面处理方法处理后表面形成的PDMS基耐磨超疏水复合材料具有还有较好的物理稳定性与化学稳定性,同时,超疏水性能优越。
Claims (10)
1.耐磨超疏水涂料的制备方法,其特征在于,分别制备涂层液和打底液;
所述涂层液的制备具体为:
将PDMS、疏水SiO2纳米粒子共混于乙酸乙酯中得到PDMS/SiO2悬浮液,将α-氰基丙烯酸酯胶黏剂加入到PDMS/SiO2悬浮液中冰浴超声,得到涂层液;
所述打底液的制备具体为:
将α-氰基丙烯酸酯胶黏剂加入到乙酸乙酯中共混得到打底液。
2.根据权利要求1所述的耐磨超疏水涂料的制备方法,其特征在于,所述PDMS/SiO2悬浮液的制备具体为,将PDMS溶解于乙酸乙酯中,PDMS完全溶解后加入疏水SiO2纳米粒子,搅拌均匀,得到PDMS/SiO2悬浮液。
3.根据权利要求1所述的耐磨超疏水涂料的制备方法,其特征在于,所述PDMS/SiO2悬浮液中PDMS、疏水SiO2纳米粒子、乙酸乙酯的质量百分数分别是3.3%~6.6%,2%~5%,78%~90%,上述各组分的质量百分数之和为100%。
4.根据权利要求1所述的耐磨超疏水涂料的制备方法,其特征在于,所述PDMS包括质量比为10:1的PDMS主剂和PDMS固化剂。
5.根据权利要求1所述的耐磨超疏水涂料的制备方法,其特征在于,所述涂层液中α-氰基丙烯酸酯胶黏剂与PDMS/SiO2悬浮液的质量比是3~6:94~97。
6.根据权利要求1所述的耐磨超疏水涂料的制备方法,其特征在于,所述涂层液制备过程中冰浴超声的温度是5~10℃,时间是5~10min。
7.根据权利要求1所述的耐磨超疏水涂料的制备方法,其特征在于,所述打底液中α-氰基丙烯酸酯胶黏剂和乙酸乙酯的质量分数分别是6%~12%,90%~96%,上述两组分的质量百分数之和为100%。
8.耐磨超疏水表面处理方法,应用如权利要求1所述的耐磨超疏水涂料的制备方法制备的耐磨超疏水涂料进行表面处理,其特征在于,将打底液喷涂在基底上,再喷涂涂层液覆盖打底液,将喷涂好打底液和涂层液的基底放入烘箱干燥,在基底表面形成PDMS基耐磨超疏水复合材料,完成表面处理。
9.根据权利要求8所述的耐磨超疏水表面处理方法,其特征在于,所述烘箱的干燥时间为1~3h,烘箱温度为80℃以上。
10.根据权利要求8所述的耐磨超疏水表面处理方法,其特征在于,所述打底液的喷涂量为0.6g/cm2~2.4g/cm2,涂层液的喷涂量为1.48g/cm2~5.92g/cm2。
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