CN105713476B - 一种具有热能除冰性能的超光滑防覆冰涂层 - Google Patents
一种具有热能除冰性能的超光滑防覆冰涂层 Download PDFInfo
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Abstract
本发明公开了一种具有热能除冰性能的超光滑防覆冰涂层,该涂层的质量百分含量是:20‑69重量份的聚乙二醇丙烯酸环氧树脂,1‑5重量份的交联剂;30‑75重量份的无机颗粒,且该无机粒子为磁性粒子或磁性粒子与非磁性粒子的混合;润滑液。其中,超光滑防覆冰涂层通过聚乙二醇环氧丙烯酸树脂、无机粒子、交联剂三部分的交联反应构成的两亲性涂层,然后通过润滑液浸润两亲性表面而形成的。本发明的涂料与基材具有良好的附着力,抗结冰效果持久稳定,冰与表面的附着力极低易从表面上去除,并在外加磁场或光照条件下能够被加热从而达到热能除冰的效果。制备工艺简单,操作方便,环境友好,价格低廉,适宜工业化应用。
Description
技术领域
本发明涉及一种涂层,尤其涉及一种具有热能除冰性能的超光滑防覆冰涂层。
背景技术
覆冰是自然界十分普遍的现象,结构物大气覆冰,如飞机的机翼和外壳结冰、导线覆冰、道路覆冰、风机叶片覆冰、铁路轨道覆冰等,均是常见的自然现象。但这种现象严重时会给人们生产生活带来诸多不便,甚至威胁人们的生命财产安全。因此,防覆冰技术研究意义重大。防冰技术研究主要有四种类型即溶液防冰、机械除冰、热能防冰和涂层防冰。其中涂层防冰因为能耗小、适用范围广、且属于被动型防护,因此相比其他三种方法,涂层防冰是一种很理想的防冰方法。
仿猪笼草的超光滑涂层,由于液滴易从表面上滑落,而且可有效地降低冰与表面的附着力,成为了防覆冰领域的研究热点。目前的超光滑涂层,多是通过在表面上构建多孔结构,然后采用润滑油浸润表面,所得的表面具有明显的疏冰效果。然而,在使用过程中,液体润滑层会从表面脱落,冰与表面的粗糙结构铆合,从而大大增加冰与表面附着力,从而涂层失去防覆冰性能。常用的润滑液为全氟聚醚或长碳链全氟烷烃类,价格昂贵。
聚乙二醇类、甘油等常被用作抗冻剂,但是将抗冻剂直接使用,在结冰严重的情况下,会失去防覆冰性能,使用量大,污染环境。因此,在本专利有以下优点:①采用抗冻剂作为润滑层,会大大降低冰点,使得液滴不易在表面上结冰;②润滑层在表面形成连续相会极大的降低冰与表面的附着力;③采用具有磁热效应和光热效应的粒子填充,可使表面温度保持在0℃以上,从而不结冰,并当表面上结冰后可增强融冰过程。
发明内容
本发明针对覆冰的危害,提供了一种具有热能除冰性能的超光滑防覆冰涂层。本发明的目的是通过以下技术方案实现的:一种具有热能除冰性能的超光滑防覆冰涂层,制备方法如下:
(1)交联两亲性涂层的制备:将20-69重量份的两亲性聚合物、1-5重量份的交联剂、30-75重量份的无机粒子,搅拌均匀后,在室温(20~30℃)下预交联,得到防覆冰涂料;
(2)将步骤(1)所得到的涂料涂于基材表面,然后在125-170℃下高温固化,得到两亲涂层;然后采用润滑液浸润两亲涂层表面,即在基材表面得到具有热能除冰性能的超光滑防覆冰涂层。
进一步地,所述的无机粒子由15~100重量份的磁性粒子和0~85重量份的非磁性粒子的混合组成,所述的磁性粒子由四氧化三铁、三氧化二钴中的一种或两种按照任意配比混合组成;所述非磁性粒子由炭黑、二氧化硅、ZnO中的一种或多种按照任意配比组成;无机粒子的粒径为20nm~50μm。
进一步地,所述的两亲性聚合物为环氧改性后的聚乙二醇丙烯酸酯类树脂。其中,环氧改性剂与聚乙二醇丙烯酸酯类树脂的质量比为1:5~5:1。
进一步地,所述聚乙二醇丙烯酸酯类树脂由一种或多种聚乙二醇类单体按照任意配比聚合而成,所述聚乙二醇类单体为甲基丙烯酸酯类单体、聚乙二醇丙烯酸酯类单体。
进一步地,所述环氧改性采用的改性剂由甲基丙烯酸缩水甘油酯、丙烯酸缩水甘油酯中的一种或两种按照任意配比组成。
进一步地,所述交联剂选自乙二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、己二胺、间苯二甲胺、异佛尔酮二胺、4,4’-二氨基二苯甲烷、邻苯二甲酸酐或马来酸酐中的一种或多种。
进一步地,所述润滑液选自水、多元醇、甘油、硅油、脂肪酸类。
进一步地,所述多元醇为乙二醇、一缩二乙二醇、二缩三乙二醇、PEG400、PEG600。
本发明的有益效果在于:本发明主要利用聚乙二醇丙烯酸酯类,富含羟基与水,多元醇类,甘油,硅油,油酸等都具有良好的亲和性;所添加的含环氧基丙烯酸酯类,与油类具有较好的亲和力,并且可增强涂层的机械强度。另外涂层中添加无机粒子,可为涂层构建出复合微纳结构,可增大润滑液与表面的接触面积。更重要的是,利用该无机颗粒具有磁热性能和光热性能,使得涂层在可见光或者外加交变磁场下产热,从而能够缓解结冰或者除去在涂层表面上形成的冰,并且保护涂层的微纳结构不会被破坏。
具体实施方式
为了更好的理解本发明,下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1
四氧化三铁的质量75g;聚乙二醇甲基丙烯酸与甲基丙烯酸缩水甘油酯的共聚物以质量比为5:1制备共聚物,聚合物为20g;二亚乙基三胺的质量比为5g;搅拌均匀之后,涂膜与基材表面,室温下溶剂挥发,然后140℃,真空烘箱内固化9h,退火。最后采用乙二醇浸润表面形成光滑的液体浸润表面形成光滑的液体浸润层。
对所制的样品,接触角进行了测定,液滴在涂层表面瞬间铺展。通过DSC测试发现,降低冰点至-36℃。在温度为-18℃条件下,延长结霜时间至3000s。冰与表面附着力为0.01N。当涂层表面形成冰层后,降低融冰时间至500s。
实施例2
四氧化三铁与SiO2粒子的总质量为30g(其中SiO2粒子的质量为3.9g);聚乙二醇甲基丙烯酸与丙烯酸缩水甘油酯以质量比为4:2制备共聚物,聚合物为19g;马来酸酐为1g;搅拌均匀之后,涂膜与基材表面,室温下溶剂挥发,然后170℃,真空烘箱内固化5h,退火。最后采用二缩三乙二醇浸润表面形成光滑的液体浸润表面形成光滑的液体浸润层。
对所制的样品,接触角进行了测定,液滴在涂层表面瞬间铺展。通过DSC测试发现,降低冰点至-40℃。在温度为-18℃条件下,延长结霜时间至3080s。冰与表面附着力为0.12N。当涂层表面形成冰层后,降低融冰时间至520s。
实施例3
四氧化三铁与炭黑粒子的总质量含量100g(其中炭黑的质量为23g);聚乙二醇甲基丙烯酸与丙烯酸缩水甘油酯以质量比为3:3制备共聚物,聚合物为94g;己二胺为6g;搅拌均匀之后,涂膜与基材表面,室温下溶剂挥发,然后125℃,真空烘箱内固化14h,退火。最后采用PEG400浸润表面形成光滑的液体浸润表面形成光滑的液体浸润层。
对所制的样品,接触角进行了测定,液滴在涂层表面瞬间铺展。通过DSC测试发现,降低冰点至-34℃。在温度为-18℃条件下,延长结霜时间至2080s。冰与表面附着力为0.15N。当涂层表面形成冰层后,降低融冰时间至530s。
实施例4
四氧化三铁与炭黑粒子的总质量为8g(其中炭黑占四氧化三铁粒子的3.6g);聚乙二醇甲基丙烯酸与丙烯酸缩水甘油酯的共聚物以质量比为2:4制备共聚物,聚合物为11.2g;邻苯二甲酸酐为4%;搅拌均匀之后,涂膜与基材表面,室温下溶剂挥发,然后130℃,真空烘箱内固化12h,退火。最后采用PEG600浸润表面形成光滑的液体浸润表面形成光滑的液体浸润层。
对所制的样品,接触角进行了测定,液滴在涂层表面瞬间铺展。通过DSC测试发现,降低冰点至-25℃。在温度为-18℃条件下,延长结霜时间至1080s。冰与表面附着力为0.12N。当涂层表面形成冰层后,降低融冰时间至610s。
实施例5
四氧化三铁与ZnO粒子的总质量为40.5g(其中ZnO粒子的质量为13.5g);聚乙二醇甲基丙烯酸与丙烯酸缩水甘油酯以质量比为1:5制备共聚物,聚合物为93.15g;4,4’-二氨基二苯甲烷为1.35g;搅拌均匀之后,涂膜与基材表面,室温下溶剂挥发,然后160℃,真空烘箱内固化8h,退火。最后采用甘油浸润表面形成光滑的液体浸润表面形成光滑的液体浸润层。
对所制的样品,接触角进行了测定,液滴在涂层表面瞬间铺展。通过DSC测试发现,降低冰点至-28℃。在温度为-18℃条件下,延长结霜时间至1030s。冰与表面附着力为0.12N。当涂层表面形成冰层后,降低融冰时间至650s。
实施例6
四氧化三铁与炭黑的总质量为320g,其中炭黑的质量为120g;聚乙二醇丙烯酸与甲基丙烯酸缩水甘油酯以质量比为3:3,聚合物为400g;异佛尔酮二胺为8g;搅拌均匀之后,涂膜与基材表面,室温下溶剂挥发,然后150℃,真空烘箱内固化5h,退火。最后采用水浸润表面形成光滑的液体浸润表面形成光滑的液体浸润层。
对所制的样品,接触角进行了测定,液滴在涂层表面瞬间铺展。通过DSC测试发现,降低冰点至-26℃。在温度为-18℃条件下,延长结霜时间至2080s。冰与表面附着力为0.65N。当涂层表面形成冰层后,降低融冰时间至680s。
实施例7
四氧化三铁与炭黑粒子的总质量为225g(其中炭黑的质量为51.9g);聚乙二醇甲基丙烯酸与丙烯酸缩水甘油酯的共聚物以质量比为2:4制备共聚物,聚合物为255g;邻苯二甲酸酐为20g;搅拌均匀之后,涂膜与基材表面,室温下溶剂挥发,然后130℃,真空烘箱内固化16h,退火。最后采用硅油浸润表面形成光滑的液体浸润表面形成光滑的液体浸润层。
对所制的样品,接触角进行了测定,液滴在涂层表面的接触角为68°。通过DSC测试发现,降低冰点至-15℃。在温度为-18℃条件下,延长结霜时间至600s。冰与表面附着力为5.4N。当涂层表面形成冰层后,降低融冰时间至610s。
从以上具体实施例中的产品数据可以看出,本发明制备的涂料具有较长的抗结霜性能使得液滴在结冰之前就能被去除冰与表面附着力低使得液滴在涂层表面结冰之后也容易除去,同时,还具有很好的光热性能和磁热性能能够有效的提高表面温度,可增强表面的除冰性能。
以上内容描述了本发明的基本原理、主要特征、工艺流程和本发明的优势。本行业的技术员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述得只是说明发明的原理,在不脱离本发明精神和范围的前提下本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。
Claims (5)
1.一种具有热能除冰性能的超光滑防覆冰涂层,其特征在于,制备方法如下:
(1)交联两亲性涂层的制备:将20-69重量份的两亲性聚合物、1-5重量份的交联剂、30-75重量份的无机粒子,搅拌均匀后,在室温20~30℃下预交联,得到防覆冰涂料;
(2)将步骤1所得到的涂料涂于基材表面,然后在125-170℃下高温固化,得到两亲涂层;然后采用润滑液浸润两亲涂层表面,即在基材表面得到具有热能除冰性能的超光滑防覆冰涂层;
所述的无机粒子由15~100重量份的磁性粒子和0~85重量份的非磁性粒子的混合组成,所述的磁性粒子由四氧化三铁、三氧化二钴中的一种或两种按照任意配比混合组成;所述非磁性粒子由炭黑、二氧化硅、ZnO中的一种或多种按照任意配比组成;无机粒子的粒径为20 nm~50μm;
所述的两亲性聚合物为环氧改性后的聚乙二醇丙烯酸酯类树脂,其中,环氧改性采用的环氧改性剂与聚乙二醇丙烯酸酯类树脂的质量比为1:5~5:1;
所述润滑液选自水、多元醇、硅油、脂肪酸类。
2.根据权利要求1所述的具有热能除冰性能的超光滑防覆冰涂层,其特征在于:所述聚乙二醇丙烯酸酯类树脂由一种或多种聚乙二醇类单体按照任意配比聚合而成,所述聚乙二醇类单体为甲基丙烯酸酯类单体、聚乙二醇丙烯酸酯类单体。
3.根据权利要求1所述的具有热能除冰性能的超光滑防覆冰涂层,其特征在于:所述环氧改性剂由甲基丙烯酸缩水甘油酯、丙烯酸缩水甘油酯中的一种或两种按照任意配比组成。
4.根据权利要求1所述的具有热能除冰性能的超光滑防覆冰涂层,其特征在于:所述交联剂选自乙二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、己二胺、间苯二甲胺、异佛尔酮二胺、4,4’-二氨基二苯甲烷、邻苯二甲酸酐或马来酸酐中的一种或多种。
5.根据权利要求1所述的具有热能除冰性能的超光滑防覆冰涂层,其特征在于:所述多元醇为乙二醇、一缩二乙二醇、二缩三乙二醇、PEG400、PEG600。
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