CN108893070A - 一种光热型低温防覆冰贴膜 - Google Patents

一种光热型低温防覆冰贴膜 Download PDF

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CN108893070A
CN108893070A CN201810774914.1A CN201810774914A CN108893070A CN 108893070 A CN108893070 A CN 108893070A CN 201810774914 A CN201810774914 A CN 201810774914A CN 108893070 A CN108893070 A CN 108893070A
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潘荣德
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Yinjinda (Shanghai) new material Co.,Ltd.
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Abstract

本发明涉及一种光热型低温防覆冰贴膜，该贴膜由功能膜层和黏胶层组成，功能膜层由基底膜，光热层，自修复超疏水层，银纳米线层组成，基底膜上设置有光热层，光热层上设置有自修复超疏水层，自修复超疏水层上设置有银纳米线层，可对户外运行设备与仪表进行防冰冻保护以及在冰雪冻雨侵袭后表面快速除冰。

Description

一种光热型低温防覆冰贴膜
技术领域
本发明涉及保护膜领域，尤其涉及一种光热型低温防覆冰贴膜。
背景技术
覆冰是常见的自然现象，尤其在低温高湿地区，空气中的水蒸气接触到温度低于冰点温度的材料表面时，就会发生相变形成冰霜，冻雨、霜雪等冰雪灾害也容易造成覆冰，覆冰给人们的生产和生活造成诸多的不便和损失，如冷冻设备覆冰会导致设备传热效率降低甚至失效，覆冰还会导致一些户外特殊设备、精密仪表等的失灵，严重的覆冰还会大量破坏生态环境、交通、电力设施等。
目前的防冰技术主要有两大类，第一类是主动方法，包括机械除冰和电热、光热除冰，但机械除冰的成本高、效率低，加热除冰能耗大，工艺及设备仍需完善；第二类是被动方法，使用疏水性防冰材料等，但疏水材料表面的低表面能物质容易在环境刺激下发生降解，另一方面，疏水材料表面结构容易在机械摩擦或刮擦下受到损伤，这些损伤都会使疏水材料失去其疏水性能。
发明内容
本申请针对上述提出的现有技术问题，将两类防冰方法结合起来，提供一种可对户外运行设备与仪表进行防冰冻保护以及在冰雪冻雨侵袭后表面快速除冰的光热型低温防覆冰贴膜。
本发明的实施例中提供了一种光热型低温防覆冰贴膜，包括功能膜层和黏胶层，
优选地，所述功能膜层包括基底膜，光热层，自修复超疏水层，银纳米线层，基底膜上设置有光热层，光热层上设置有自修复超疏水层，自修复超疏水层上设置有银纳米线层；
优选地，所述黏胶层为透明丙烯酸酯胶黏剂；
优选地，所述基底膜为聚偏二氟乙烯，聚四氟乙烯，聚六氟丙烯及其共聚物经静电纺丝制成；
优选地，所述光热层由Ti3C2TX纳米片与纳米氧化铁颗粒经抽滤堆积在基底膜上，再经酸处理除去纳米氧化铁颗粒致孔得到；
优选地，所述自修复超疏水层为聚丙烯酸酯-聚硅氧烷-硬脂胺-二氧化硅超疏水涂层。
本发明的实施例提供的技术方案可以包括以下有益效果：
本发明提供的一种光热型低温防覆冰贴膜，将主动和被动防冰方法结合起来，具有自修复的超疏水表面和光热效应，由于水滴在超疏水表面不能完全铺展，接触面积小，接触角大，有利于增大水凝固的势垒，延缓了水滴的凝固，而且，超疏水表面粗糙的微纳结构所具有的的气垫，使得液滴在超疏水表面形成固-液-气三相共存界面，具有良好的绝热作用，结冰速度大大减低，具有良好的防覆冰效果；冰雪侵袭后，贴膜的光热效应可以实现表面快速除冰，可对户外运行设备与仪表进行防冰冻保护。
本发明附加的方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本发明的实践了解到。应当理解的是，以上的一般描述和后文的细节描述仅是示例性和解释性的，并不能限制本发明。
附图说明
利用附图对本发明作进一步说明，但附图中的实施例不构成对本发明的任何限制，对于本领域的普通技术人员，在不付出创造性劳动的前提下，还可以根据以下附图获得其它的附图。
图1是本发明的基本结构示意图。
附图标记：1-黏胶层；2-基底膜层；3-光热层；4-自修复超疏水层；5-银纳米线层。
具体实施方式
这里将详细地对示例性实施例进行说明，其示例表示在附图中。下面的描述涉及附图时，除非另有表示，不同附图中的相同数字表示相同或相似的要素。以下示例性实施例中所描述的实施方式并不代表与本发明相一致的所有实施方式。相反，它们仅是与如所附权利要求书中所详述的、本发明的一些方面相一致的装置和方法的例子。
本发明的实施例涉及一种光热型低温防覆冰贴膜，包括功能膜层和黏胶层，
优选地，所述功能膜层包括基底膜，光热层，自修复超疏水层，银纳米线层，基底膜上设置有光热层，光热层上设置有自修复超疏水层，自修复超疏水层上设置有银纳米线层；
光热层将光能转化为热能，贴膜表面温度升高，使靠近膜表面的冰雪融化，疏水作用加速冰雪的滑落；自修复超疏水层可在光热层提供的热作用下进行自修复，为贴膜提供稳定持久的超疏水性；银纳米线层的设置进一步增强了膜层的光热效应，协同光热层与自修复超疏水层形成夹层结构，保护超疏水层并促进其自修复，形成超疏水性所需的微纳结构；
优选地，所述黏胶层为透明丙烯酸酯胶黏剂；
优选地，所述基底膜为聚偏二氟乙烯，聚四氟乙烯，聚六氟丙烯及其共聚物经静电纺丝制成；
以疏水性有机高分子材料为基底膜，提高成膜的疏水性能，增强成膜的使用稳定性，优选为含氟高分子材料，其具有强的抗腐蚀性能和低的表面能，采用静电纺丝可制得多孔纳米纤维膜；
优选地，所述光热层由Ti3C2TX纳米片与纳米氧化铁颗粒经抽滤堆积在基底膜上，再经酸处理除去纳米氧化铁颗粒致孔得到；
相关技术是在表面增加加热器，如喷涂碳纳米管，或在制膜时混入银纳米粒子来进行膜表面加热，本发明通过在基底膜上堆积Ti3C2TX纳米片层并造孔得到具有多孔结构的光热层；Ti3C2TX纳米片是一种二维层状过渡金属碳化物，有优良的微波吸收和电磁屏蔽性能，兼具金属和陶瓷特点，具有在高吸光率条件下高效地进行光热转换的特点，在膜上堆积该纳米片层可以利用其光热效应，将光热转化所得的能量限制在界面附近的区域，大大提高能量利用率，致孔增加了膜表面的粗糙度，进一步增强膜的疏水性；
进一步优选地，Ti3C2TX纳米片的沉积密度为5-10g/m2；
进一步优选地，致孔剂为粒径在10-30nm的纳米氧化铁颗粒；
进一步优选地，真空热压处理时间为1-3h，温度为80-300℃，热压压力为0.2-5MPa；
优选地，所述自修复超疏水层为聚丙烯酸酯-聚硅氧烷-硬脂胺-二氧化硅超疏水涂层；
超疏水层破坏后，在膜的光热效应热作用下，内部未反应的含氢聚二甲基硅氧烷和硬脂胺链段往外层迁移，遇到空气中水分固化，降低表面自由能，涂层具有优良的热响应自修复超疏水特性；
优选地，自修复超疏水层上设置有银纳米线层；
银纳米线由于具有特殊的纳米结构，易发生等离子体共振光热效应，进一步提高了边界层的温度，协同光热层为超疏水膜的自修复提供热作用，为超疏水涂层表面提供微纳米粗糙结构；
进一步优选地，银纳米线直径60-70nm，长度15-35μm。
下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。
实施例1
本实施例中，一种光热型低温防覆冰贴膜包括功能膜层和黏胶层，所述功能膜层包括基底膜，光热层，自修复超疏水层，银纳米线层，基底膜上设置有光热层，光热层上设置有自修复超疏水层，自修复超疏水层上设置有银纳米线层；所述黏胶层为透明丙烯酸酯胶黏剂；所述自修复超疏水层为聚丙烯酸酯-聚硅氧烷-硬脂胺-二氧化硅超疏水涂层，
功能膜层的制备包括以下步骤：
S1、高压静电纺丝制基底膜
将聚偏二氟乙烯溶于四氢呋喃中，质量百分比为12％，经搅拌得到高聚物纺丝液，设定高压静电纺丝参数为：电压20kv，针头内径0.5mm，纺丝液推注速度为0.1mm/min，接收滚筒转速为200r/min，喷丝口到接收滚筒的距离为20cm，纺丝环境温度25℃，相对湿度50％，进行静电纺丝制膜，得到纳米纤维膜；
S2、光热层
钛碳化铝粉体过400目筛，缓慢加入到两倍质量的质量百分比为50％的HF溶液中，室温下500rpm搅拌2h后，5000rpm离心10min，沉淀用去离子水洗涤，重复离心和洗涤，至上清液pH呈中性，将沉淀按1:180比例分散于去离子水中，按与沉淀1:2的比例加入粒径30nm的纳米氧化铁颗粒，超声处理2h，抽滤于基底膜上，沉积密度为5g/m2，烘箱中70℃干燥24h，真空热压，热压时间1-3h，温度为80-300℃，热压压力为0.2-5MPa，热压完成后用1mol/L盐酸溶液浸泡处理1h，去离子水洗涤至中性，烘箱中70℃干燥24h；
S3、自修复超疏水膜
将甲基丙烯酸己酯、甲基丙烯酸十二酯、含氢聚二甲基硅氧烷、硬脂胺、硅烷偶联剂KH570按比例为2.5:4：4:1.5:4.5搅拌溶解在无水乙醇中，加入溶液5％质量分数的纳米SiO2，超声分散，加入溶液0.1％质量分数的辛酸亚锡，加入溶液0.5％质量分数的DMPA，搅拌1h，涂布于膜上，进行紫外处理，光强150mW/cm2，固化时间2min，烘箱中70℃保温缩合12h；
S4、银纳米线层
取190mL甘油在100℃下回流30min，边缓慢搅拌边加入5.8g的PVP，继续加热1h至完全溶解，待温度下降至室温后，加入1.58g硝酸银粉末，丙三醇10ml，氯化钠0.06g，去离子水0.5ml，加热，保持搅拌速率在50rpm，温度升至210℃后停止加热，自然冷却至室温后进行8000rpm×10min离心，用无水乙醇洗涤，体积比1:1，重复三次离心和洗涤，最后向产物中加入无水乙醇得到银纳米线的乙醇分散液，将银纳米线的乙醇分散液滴涂到膜上，乙醇挥发后，在膜上形成一层银纳米线膜。
测试实验
接触角测定实验：使用DSA30型光学接触角分析仪观测膜表面水滴的接触角变化情况。将4μL去离子水滴于膜表面，通过分析仪实时记录水滴在薄膜表面的形状变化。
经模拟测得接触角为158°，滚动角为3°，经空气等离子体破坏后，测得接触角为86°，经热处理后，测得接触角为156°，相比较空白膜，处理膜的膜表温度高2-3℃。
融雪实验，将10g雪放置在倾斜角为10°的贴膜上，融化与滑落过程所需的时间为22s，相比较处理膜，空白膜的融化与滑落过程所需的时间为58s。
实施例2
本实施例中，一种光热型低温防覆冰贴膜包括功能膜层和黏胶层，所述功能膜层包括基底膜，光热层，自修复超疏水层，银纳米线层，基底膜上设置有光热层，光热层上设置有自修复超疏水层，自修复超疏水层上设置有银纳米线层；所述黏胶层为透明丙烯酸酯胶黏剂；所述自修复超疏水层为聚丙烯酸酯-聚硅氧烷-硬脂胺-二氧化硅超疏水涂层；
功能膜层的制备包括以下步骤：
S1、高压静电纺丝制基底膜
将聚四氟乙烯溶于四氢呋喃中，质量百分比为12％，经搅拌得到高聚物纺丝液，设定高压静电纺丝参数为：电压20kv，针头内径0.5mm，纺丝液推注速度为0.1mm/min，接收滚筒转速为200r/min，喷丝口到接收滚筒的距离为20cm，纺丝环境温度25℃，相对湿度50％，进行静电纺丝制膜，得到纳米纤维膜；
S2、光热层
钛碳化铝粉体过400目筛，缓慢加入到两倍质量的质量百分比为50％的HF溶液中，室温下500rpm搅拌2h后，5000rpm离心10min，沉淀用去离子水洗涤，重复离心和洗涤，至上清液pH呈中性，将沉淀按1:180比例分散于去离子水中，按与沉淀1:2的比例加入粒径10nm的纳米氧化铁颗粒，超声处理2h，抽滤于基底膜上，沉积密度为10g/m2，烘箱中70℃干燥24h，真空热压，热压时间1-3h，温度为80-300℃，热压压力为0.2-5MPa，热压完成后用1mol/L盐酸溶液浸泡处理1h，去离子水洗涤至中性，烘箱中70℃干燥24h；
S3、自修复超疏水膜
将甲基丙烯酸己酯、甲基丙烯酸十二酯、含氢聚二甲基硅氧烷、硬脂胺、硅烷偶联剂KH570按比例为2.5:4：4:1.5:4.5搅拌溶解在无水乙醇中，加入溶液5％质量分数的纳米SiO2，超声分散，加入溶液0.1％质量分数的辛酸亚锡，加入溶液0.5％质量分数的DMPA，搅拌1h，涂布于膜上，进行紫外处理，光强150mW/cm2，固化时间2min，烘箱中70℃保温缩合12h；
S4、银纳米线层
取190mL甘油在100℃下回流30min，边缓慢搅拌边加入5.8g的PVP，继续加热1h至完全溶解，待温度下降至室温后，加入1.58g硝酸银粉末，丙三醇10ml，氯化钠0.06g，去离子水0.5ml，加热，保持搅拌速率在50rpm，温度升至210℃后停止加热，自然冷却至室温后进行8000rpm×10min离心，用无水乙醇洗涤，体积比1:1，重复三次离心和洗涤，最后向产物中加入无水乙醇得到银纳米线的乙醇分散液，将银纳米线的乙醇分散液滴涂到膜上，乙醇挥发后，在膜上形成一层银纳米线膜。
测试实验
接触角测定实验：使用DSA30型光学接触角分析仪观测膜表面水滴的接触角变化情况。将4μL去离子水滴于膜表面，通过分析仪实时记录水滴在薄膜表面的形状变化。
经模拟测得接触角为159°，滚动角为4°，经空气等离子体破坏后，测得接触角为85°，经热处理后，测得接触角为158°，相比较空白膜，处理膜的膜表温度高2-3℃。
融雪实验，将10g雪放置在倾斜角为10°的贴膜上，融化与滑落过程所需的时间为21s，相比较处理膜，空白膜的融化与滑落过程所需的时间为55s。
以上所述仅为本发明的较佳方式，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (6)

1.一种光热型低温防覆冰贴膜，其特征在于，包括功能膜层和黏胶层，所述功能膜层由基底膜，光热层，自修复超疏水层，银纳米线层组成，基底膜上设置有光热层，光热层上设置有自修复超疏水层，自修复超疏水层上设置有银纳米线层。
2.根据权利要求1所述的一种光热型低温防覆冰贴膜，其特征在于，所述基底膜为聚偏二氟乙烯，聚四氟乙烯，聚六氟丙烯及其共聚物经静电纺丝制成。
3.根据权利要求1所述的一种光热型低温防覆冰贴膜，其特征在于，所述光热层由Ti3C2TX纳米片与纳米氧化铁颗粒经抽滤堆积在基底膜上，再经酸处理除去纳米氧化铁颗粒致孔得到。
4.根据权利要求1所述的一种光热型低温防覆冰贴膜，其特征在于，所述自修复超疏水层为聚丙烯酸酯-聚硅氧烷-硬脂胺-二氧化硅超疏水涂层。
5.根据权利要求1所述的一种光热型低温防覆冰贴膜，其特征在于，所述光热型自修复超疏水膜的制备包括以下步骤：
S1、高压静电纺丝制基底膜
将基底膜原料溶于四氢呋喃中，质量百分比为12％，经搅拌得到高聚物纺丝液，设定高压静电纺丝参数为：电压20kv，针头内径0.5mm，纺丝液推注速度为0.1mm/min，接收滚筒转速为200r/min，喷丝口到接收滚筒的距离为20cm，纺丝环境温度25℃，相对湿度50％，进行静电纺丝制膜，得到纳米纤维膜；
S2、光热层
钛碳化铝粉体过400目筛，缓慢加入到两倍质量的质量百分比为50％的HF溶液中，室温下500rpm搅拌2h后，5000rpm离心10min，沉淀用去离子水洗涤，重复离心和洗涤至上清液pH呈中性，得到Ti3C2TX纳米片沉淀，将沉淀按1:180比例分散于去离子水中，按与沉淀1:2的比例加入粒径10-30nm的纳米氧化铁颗粒，超声处理2h，抽滤于基底膜上，沉积密度为5-10g/m2，烘箱中70℃干燥24h，真空热压，热压时间1-3h，温度为80-300℃，热压压力为0.2-5MPa，热压完成后用1mol/L盐酸溶液浸泡处理1h，去离子水洗涤至中性，烘箱中70℃干燥24h；
S3、自修复超疏水膜
将甲基丙烯酸己酯、甲基丙烯酸月十二酯、含氢聚二甲基硅氧烷、硬脂胺、硅烷偶联剂KH570按比例为2.5:4：4:1.5:4.5搅拌溶解在无水乙醇中，加入溶液5％质量分数的纳米SiO2，超声分散，加入溶液0.1％质量分数的辛酸亚锡，加入溶液0.5％质量分数的DMPA，搅拌1h，涂布于膜上，进行紫外处理，光强150mW/cm2，固化时间2min，烘箱中70℃保温缩合12h；
S4、银纳米线层
取190ml甘油在100℃下回流30min，边缓慢搅拌边加入5.8g的PVP，继续加热1h至完全溶解，待温度下降至室温后，加入1.58g AgNO3粉末，甘油10ml，氯化钠0.06g，去离子水0.5ml，加热，保持搅拌速率在50rpm，温度升至210℃后停止加热，自然冷却至室温后进行8000rpm×10min离心，用无水乙醇洗涤，体积比1:1，重复三次离心和洗涤，最后向产物中加入无水乙醇得到银纳米线的乙醇分散液，将银纳米线的乙醇分散液滴涂到膜上，乙醇挥发后，在膜上形成一层银纳米线膜。
6.根据权利要求3所述的一种光热型低温防覆冰贴膜，其特征在于，所述银纳米线直径60-70nm，长度15-35μm。
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