CN112500593A - 一种对基于ptfe膜进行纳米深度表面活化的方法 - Google Patents

一种对基于ptfe膜进行纳米深度表面活化的方法 Download PDF

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Publication number
CN112500593A
CN112500593A CN202011221828.1A CN202011221828A CN112500593A CN 112500593 A CN112500593 A CN 112500593A CN 202011221828 A CN202011221828 A CN 202011221828A CN 112500593 A CN112500593 A CN 112500593A
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China
Prior art keywords
ptfe
membrane
nano
temperature
film
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CN202011221828.1A
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CN112500593B (zh
Inventor
刘建平
向欣
吴建华
朱亚伟
赵景鑫
李文伟
帅争锋
吴弘
吴建平
赵方亮
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China Three Gorges Corp
China Three Gorges Renewables Group Co Ltd
Nanjing Haohui Hi Tech Co Ltd
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China Three Gorges Corp
China Three Gorges Renewables Group Co Ltd
Nanjing Haohui Hi Tech Co Ltd
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Priority to CN202011221828.1A priority Critical patent/CN112500593B/zh
Application filed by China Three Gorges Corp, China Three Gorges Renewables Group Co Ltd, Nanjing Haohui Hi Tech Co Ltd filed Critical China Three Gorges Corp
Priority to ES202290056A priority patent/ES2957007A1/es
Priority to DE112020005283.4T priority patent/DE112020005283T5/de
Priority to CA3161523A priority patent/CA3161523C/en
Priority to GB2208496.6A priority patent/GB2606082B/en
Priority to US17/785,074 priority patent/US20230257635A1/en
Priority to JP2022532598A priority patent/JP7426037B2/ja
Priority to PCT/CN2020/136604 priority patent/WO2022011959A1/zh
Publication of CN112500593A publication Critical patent/CN112500593A/zh
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Publication of CN112500593B publication Critical patent/CN112500593B/zh
Priority to DKPA202270312A priority patent/DK181326B1/en
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Abstract

本发明公开了一种对基于PTFE膜进行纳米深度表面活化的方法，涉及高分子复材技术领域，将基于PTFE纳米功能复合膜功能面进行覆盖处理后，使施加粘接胶的膜单面进行表面活化处理，通过机械施胶装置将高韧性冷粘接胶胶带迁移复合在基于PTFE纳米功能复合膜具有了活化结构层的膜面上，形成了胶膜复合体。在膜与胶之间产生极强的亲和性和高强粘接性能，形成了膜胶复合体，实现了膜/胶粘接复合、膜/膜粘接复合、膜/粘贴基层粘接后的一体化，同时提高了胶的粘接强度与粘接剥离力及其粘接力的持久性，解决了PTFE材料无任何材料粘接的技术难题。

Description

一种对基于PTFE膜进行纳米深度表面活化的方法
技术领域
本发明涉及高分子复合材料技术领域，特别是涉及一种对基于PTFE膜进行纳米深度表面活化的方法。
背景技术
我国安装在高海拔、山区和低温、冰冻地区的风电机组受气候影响，每到冬季叶片都发生不同程度结冰，导致叶片工作异常，风机输出功率无法达到保证功率而停机，损失大量电费收益，甚至发生叶片断裂事故。叶片表面结冰和防除冰技术方法与效能的不足，对风电的直接影响是导致风电效益损失，构成分担机组运行的安全风险，解决风机叶片结冰问题是风电行业在世界范围内的重要课题。国内外科研机构及风电行业一直在对风机叶片防除冰技术材料进行着相关的研究。
通过对国外数据库、相关网站公开文献资料进行检索发现，专利JP2003113254发明了一种风电叶片涂层，采用聚氟乙烯、聚偏氟乙烯、干冰、碳粉、桐油、聚乙烯醇缩甲醛、聚醚酰亚胺、秸秆粉、防腐剂、分散剂和流平剂等为原料，形成多孔超疏水聚偏氟乙烯氟膜涂层，以期能达到良好的防抗覆冰效能。专利WO2006058233公开了一种同质双层SiO2与聚四氟乙烯复合的自清洁减反膜及制备方法用于叶片防冰，该减反膜是由致密二氧化硅层、多孔二氧化硅纳米棒层和聚四氟乙烯纳米棒复合而成，其制备方法是采用电子束蒸镀方法，在透明或半透明基底上依次沉积三层折射率逐步递减的致密二氧化硅、多孔二氧化硅和聚四氟乙烯纳米棒复合薄膜。专利US20170028361公开了一种PFSA/PTFE复合膜用于叶片防结冰，包括：低沸点有机醇溶剂的水溶液溶解全氟磺酸物质；然后向溶液中加入高沸点有机溶剂和二氧化硅溶胶，制成制膜用树脂溶液；成膜机械拖动基膜-膨体聚四氟乙烯微孔薄膜在成膜机的承载辊上运行，基膜先浸入到低浓度的树脂溶液中，后在40-100℃下干燥，干燥后的基膜继续浸入到高浓度的溶液中，然后再在40-100℃下干燥，此后在高浓度的溶液中反复的侵润、干燥，直至复合膜达到预定厚度后，将复合膜放入烘箱中在120-200℃干燥定型，得到完整性的复合膜。专利EP2767330公开了一种包括多孔PTFE膜的复合材料用于叶片防结冰，该多孔PTFE膜包括的中间PTFE膜具有从大约2纳米到大约20纳米的孔径，多孔PTFE膜被插设在和被粘合于具有较大孔径的多孔含氟聚合物膜之间。专利CN101821500A发明了一种风轮机的叶片除冰的方法、风轮机及其使用方法，该方法用于在风轮机已停机一段时间之后给风轮机叶片除冰，通过在叶片中形成加速状态并随后形成减速状态的方法将结冰从叶片上抖掉，但对于大型风力发电机而言，叶片根部振幅较小，此方案很难实现。
我国的学术、科研机构及风电行业也从未间断过对风机叶片防除覆冰的相关研究，公开文献报道的方法包括机械、溶液、涂层、热气、微波、振动、电热、超声波等多种除冰形式。武汉大学电气工程学院姚刚等为了制备超疏水性纳米复合材料并研究它对结冰的影响，利用高速搅拌和超声波分散相结合的方法，将经过偶联剂处理的纳米SiO2-x均匀分散在具有疏水性能的氟化有机硅树脂中，制备出的超疏水性纳米复合涂料用于叶片防结冰。专利201610675902.4公开了一种用于风电叶片防抗覆冰的基于PTFE与聚酯复合膜制备方法及应用，包括采用粘接复合剂进行层压复合、界面胶施加、采用压敏胶进行光引发压敏胶施加，其中粘接复合剂由3-异氰酸甲基-3,5,5-三甲基环己基异氰酸酯、醋酸乙烯酯、氨基甲酸乙酯、α-亚麻酸、过氧化苯甲酰、(4)乙氧化双酚A二甲基丙烯酸酯等组成。光引发压敏胶由聚[丙烯酸丁酯-甲基丙烯酸缩水甘油酯-正丁氧基甲基丙烯酰胺]共聚物、丙烯酸丁酯、(4)乙氧化双酚A二甲基丙烯酸酯、4,4'-双（二乙基氨基）二苯甲酮、二甲基甲酰胺等组成，解决基于PTFE聚酯复合膜无法通过胶粘剂直接粘贴在风电叶片表面的不粘附性技术问题，提高了粘接剥离强度，用于各种型号的风电叶片的防抗结冰。专利201610670830.4公开了一种用于防抗风电叶片覆冰的纳米改性PTFE与聚酯基复合膜制备方法及应用，包括采用通过对PTFE改性的膜、层压复合和光交联粘结胶施加，由锑掺杂氧化锡纳米晶、纳米二氧化钛、纳米碳化硅、有机氟防水剂、季戊四醇三 (3 氮丙啶基) 丙酸酯组成改性剂；层压复合由3 异氰酸甲基 3,5,5 三甲基环己基异氰酸酯、醋酸乙烯酯、氨基甲酸乙酯、α 亚麻酸、(2)乙氧化双酚A二甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、过氧化苯甲酰组成；光交联粘结胶由聚[丙烯酸丁酯-甲基丙烯酸缩水甘油酯-正丁氧基甲基丙烯酰胺]共聚物、醋酸乙烯酯、丙烯酸丁酯、丙烯酸酯衍生物、光引发剂、二甲基甲酰胺组成，解决改性PTFE与聚酯基复合膜无法直接通过胶粘剂粘贴在风机叶片表面的问题。《风能》2016年09期发表的“风机叶片防覆冰技术研究分析”论文，通过在热压复合工艺作用下，制得的纳米改性PTFE膜与聚酯基织物进行高温粘接复合，制得纳米改性PTFE膜与聚酯织物复合膜，有望成为能解决风机叶片结冰这一世界难题的新一代防抗覆冰新材料和新技术。专利201610675902.4公开了一种用于风电叶片防抗覆冰的基于PTFE与聚酯复合膜制备方法及应用，包括采用粘接复合剂进行层压复合、界面胶施加、采用压敏胶进行光引发压敏胶施加。专利201610452541.7公开了一种自粘的碳纤维、钢纤维改性聚四氟乙烯材料及其制备方法用于叶片防结冰，使用钢纤维、碳纤维来提高聚四氟乙烯的抗拉伸强度、磨擦性能，同时利用改进过的熔融法将细的填料如SiO2、Al粉等在高温下烧结到聚四氟乙烯表面，改善了聚四氟乙烯的表面烧结状态，使胶接强度得到明显提高。专利201310018649.1公开了一种用于叶片防结冰的PTFE自粘结软性膜带的制备方法，其采用聚四氟乙烯分散树脂，加入一定量的有机硅和溶剂油，均匀混合，在50℃的烘箱中熟化12h以上；将熟化后的粉料预压成柱状毛坯；放入挤出机中挤出直径大小在20-25mm的圆形条状物料，并放在温水中进行保温，然后通过大滚筒压延机压制成薄膜，通过去油、横向拉伸、纵向拉伸和横向拉伸、定型及分切等工序，最终获得性能优异的密封行业用聚四氟乙烯膜带产品，密度范围为400-1100g/m3，拉伸强度为15-25MPa。专利201720057571.8公开了一种光控隔热膜用于叶片防结冰，其由内向外依次为PET膜、二氧化钛层、聚四氟乙烯膜、热熔胶层、PET基膜、抗划伤层和阻红外线层。专利201610990370.3公开了一种用于叶片防冰的双层纺丝膜及其制备方法，防冰双层纺丝膜的上层为喷有二氧化硅涂层的超疏水纺丝膜，下层为注有防冰液的亲水纺丝膜。长沙理工大学刘胜先等通过对不同结冰状态下的风机叶片动力特性的模拟实验分析，定义叶片结冰状态参数，仿真计算并得到叶片结冰状态下的特征值指标，研究了一种基于振动检测的风力机叶片覆冰状态诊断技术。金风科技开发了一种电热除冰技术方案，在叶片涂层内预埋碳纤维电热膜或电阻丝等加热元件，如：碳纤维、发热电阻、金属加热网、导电加热膜或其他加热元件等，与过热保护转换器、电源等组成电热防除冰系统，通过电加热温度融化叶片表面结冰，达到防除冰效果。运达风电开发一种往叶片空腔内输入电加热产生的热气除冰技术，通过在叶片空腔内布置热气通气管道，在风机轮毂内加设加热装置，让热气或由其他辐射源加热的热气在通气管道内形成循环，通过叶片壳体将热量传递到叶片外表面，使叶片具有一定温度，在热气作用下使叶片间接加热，阻止过冷水滴的冻结，达到防除冰目的。
综上所述，国内外对于风机叶片防除冰的技术方法归纳起来有许多种，这些技术方法中，有些仅处在基理研究上，有些虽然进行过试验性应用，但都达不到防除结冰的理想效果。尤其是采用电阻丝、电热风的防除冰方法，除了防除冰效果不明显，还给每支叶片增加重量达200kg，整机叶片增重达600kg，增加了风机叶片的重量荷载，提高厂用电消率达8-10%以上。如果一支叶片电加热故障或失败，整个电加热除冰系统就必须停止运行，否则就会叶片因结冰质量不同而导致配重失衡、重心严重偏移而引起故障或事故，同时还存在容易遭到雷击的安全隐患。
基于PTFE材料虽然具有低表面张力的性能优势，但制成基于PTFE膜后，仅仅依靠其低表面张力的不粘附性能，依然无法抵抗冰晶在风机叶片上的粘附，进而达不到真正防抗风机叶片表面结冰的效果和目的。而如果不采取对PTFE进行改性的措施方法，制成的基于PTFE膜也无法在风机叶片表面直接牢固粘接，而通过改性后的基于PTFE膜，其具有的低表面张力性能优势也将会大大降低。
发明内容
为了解决以上技术问题，本发明提供一种对基于PTFE膜进行纳米深度表面活化的方法，将具有纳米级和微米级尺寸凹凸几何状超微结构形貌的基于PTFE纳米功能复合膜功能面进行覆盖处理后，使施加粘接胶的膜单面在真空环境下且低于40℃的氮氢混合介质氛围中，以1.5～3m/min的速度进行表面活化处理，使膜的施胶面产生具有纳米深度的活化结构层；通过机械施胶装置将高韧性冷粘接胶胶带迁移复合在基于PTFE纳米功能复合膜具有了活化结构层的膜面上，使胶的特性基团与膜的活化结构层发生化学键合作用，形成了胶膜复合体；
其中，高韧性冷粘接胶制备如下：将PVA-1788 0.2kg、丙烯酸丁酯18kg、丙烯酸0.5kg、乙酸乙烯酯1.0kg、甲基丙烯酸甲酯1.0kg、有机硅单体1.5kg、TO-7 0.01kg、十二烷基苯磺酸钠0.01kg、过氧化苯甲酰0.05kg、水80kg加入制备罐中，制备温度85℃，制备时间5h，抽真空和除水后，制得固含量为18.7%的胶带状压敏胶带，复合上离型纸后卷取在PVC管芯上。
技术效果：本发明通过对基于PTFE纳米功能复合膜进行纳米深度表面活化，使基于PTFE纳米功能复合膜表面能够产生具有纳米深度的活性结构层，活性结构层能与胶的特性基团发生化学键合作用，在膜与胶之间产生极强的亲和性和高强粘接性能，形成了膜胶复合体，实现了膜/胶粘接复合、膜/膜粘接复合、膜/粘贴基层粘接后的一体化，同时提高了胶的粘接强度与粘接剥离力及其粘接力的持久性，解决了PTFE材料无任何材料粘接的技术难题。
本发明进一步限定的技术方案是：
进一步的，基于PTFE纳米功能复合膜功能面用PE膜进行覆盖处理。
前所述的一种对基于PTFE膜进行纳米深度表面活化的方法，其特征在于：具有纳米级和微米级尺寸凹凸几何状超微结构形貌的基于PTFE纳米功能复合膜按如下步骤制备：
(1)单体融合聚合与微量聚合制得基于PTFE纳米功能复合膜
1)共混、预压、推压制棒
用具有软化PTFE作用的硅油浸润PTFE树脂，对浸润后的PTFE树脂进行共混，通过温度为60～90℃，速度为20～30m/min，压力为5～8MPa的热预压、热推压，制得单体聚合PTFE棒料，同时具有表面润滑性；
2)热压延融合聚合制膜
将制备的PTFE棒料在热压延作用下进行融合聚合，热压延温度60～90℃，速度20～30/min，在温度作用下，掺在PTFE树脂中具有单体聚合作用的硅油被热压延机挤出，制得具有微米级孔隙的基于PTFE纳米功能复合膜，卷取成卷；
在温度和热压延的拉伸作用下，膜裂后发生层状剥离后的纤维状结构，生成具有微孔隙的纳米级和微米级尺寸的凹凸几何状超微结构形貌的基于PTFE膜，基于PTFE膜的厚度为100～120um，膜颜色呈乳白色；
3)微量聚合制成同均质膜
将具有微米级微形凹凸表面结构的基于PTFE纳米功能复合膜在除油烘箱内通过温度作用完成微量聚合，除油烘箱内温度180～200℃，未被热压延机挤干净的浸润在PTFE树脂中进行单体聚合的硅油通过温度作用发生聚合反应而聚合固结在PTFE树脂内，制得基于PTFE同均质膜，成卷状的基于PTFE膜在除油烘箱内以6～8m/min的速度进行卷取；
(2)高温高线压力微共晶制备基于PTFE纳米功能复合膜
高温高线压力微共晶腔体内温度设定为70～420℃，基于PTFE纳米功能复合膜以6～8m/min速度向前推送，利用腔体内高温使膜分子链收缩并产生共晶，微孔隙变成纳米级和超微米级尺寸，控制PTFE膜表面线压力50～80N/m，使膜由乳白色成为透明色且透明度均匀一致，保持了基于PTFE纳米功能复合膜原有的纳米级和微米级尺寸的凹凸几何状超微结构形貌。
本发明的有益效果是：
（1）本发明在充分利用基于PTFE材料低表面张力性能的基础上，采用单体融合聚合与微量聚合技术，将膜制备成具有多重纳米级和微米级尺寸的凹凸几何状超微结构形貌，使基于PTFE膜具超低表面张力、疏水性、不粘附性、高抗污性、抗吸湿性和自清洁性等功能特性；采用超高温超高压强微共晶技术，增强膜结构强度，解决了PTFE在高温中膜裂时发生层状剥离后呈纤维状结构，耐磨性能被降低的技术瓶颈，通过温度作用使孔隙变成小，提高膜透明度及其透明度的一致性，在保持了基于PTFE纳米功能复合膜具有超微结构表面形貌的同时，使膜具有较高耐磨擦性、耐磨韧性和耐冲击性；采用纳米深度表面活化技术，使膜与粘接胶发生化学键合作用，增强粘接强度和粘接剥离力与粘接力的持久性；
（2）本发明针对基于PTFE膜性能特性、应用要求和使用环境，特制了具有冷粘贴功能的高韧性冷粘贴粘接胶，可直接进行冷粘贴粘接，高韧性冷粘接胶剥离强度高，拉伸断裂伸长率与抗冲击强度较大，硬度和拉伸弹性模量相对较小，耐紫外线老化和耐老化时间较长，无明显塑性变形性质，热胀冷缩应力小于胶的弹性限度，使胶始终处于韧性状态，具有较高的粘接强度和持久的粘接剥离力；
（3）本发明制得的基于PTFE纳米功能复合膜具有更高的透明度，不会改变粘贴叶片原有表面颜色，厚度100～200um，重量200～300g/m2，表面粗糙度0.18um，不增加风机叶片载荷，能够改善叶片翼型气动性能，提高叶片运行效率；
（4）本发明制得的基于PTFE纳米功能复合膜不对PTFE材料进行改性就能与粘接胶的特性基团发生化学键合作用，使胶与膜之间产生极强的亲和性和粘接强度，拓展了粘贴胶的选用范围；
（5）本发明制得的基于PTFE纳米功能复合膜具有PTFE材料优良的抗紫外线和耐候性，相当于叶片的保护外衣，能增强叶片表面强度，起到整体固定作用，提高叶片整体承载能力和抵抗侵蚀能力，消除叶片老化、开裂等安全隐患，进而提高风机叶片的使用寿命。
附图说明
图1为扫描电镜SEM下的膜表面纳米深度活性结构层处理前膜表面；
图2为扫描电镜SEM下的膜表面纳米深度活性结构层处理后膜表面。
具体实施方式
本实施例提供的一种对基于PTFE膜进行纳米深度表面活化的方法，将具有纳米级和微米级尺寸凹凸几何状超微结构形貌的基于PTFE纳米功能复合膜功能面用PE膜进行覆盖处理后，使施加粘接胶的膜单面在真空环境下且低于40℃的氮氢混合介质氛围中，以3m/min的速度进行表面活化处理，使膜的施胶面产生具有纳米深度的活化结构层；通过机械施胶装置将高韧性冷粘接胶胶带迁移复合在基于PTFE纳米功能复合膜具有了活化结构层的膜面上，使胶的特性基团与膜的活化结构层发生化学键合作用，形成了胶膜复合体。
其中，高韧性冷粘接胶制备如下：将PVA-1788 0.2kg、丙烯酸丁酯18kg、丙烯酸0.5kg、乙酸乙烯酯1.0kg、甲基丙烯酸甲酯1.0kg、有机硅单体1.5kg、TO-7 0.01kg、十二烷基苯磺酸钠0.01kg、过氧化苯甲酰0.05kg、水80kg加入制备罐中，制备温度85℃，制备时间5h，抽真空和除水后，制得固含量为18.7%的胶带状压敏胶带，复合上离型纸后卷取在PVC管芯上。
其中，具有纳米级和微米级尺寸凹凸几何状超微结构形貌的基于PTFE纳米功能复合膜按如下步骤制备：
(1)单体融合聚合与微量聚合制得基于PTFE纳米功能复合膜
1)共混、预压、推压制棒
用具有软化PTFE作用的硅油浸润PTFE树脂，乙烯基硅油与PTFE树脂按质量比2.5：100掺入，对浸润后的PTFE树脂进行共混，通过温度为60℃，速度为25m/min，压力为8MPa的热预压、热推压，制得单体聚合的Ф17mm的PTFE棒料，同时具有表面润滑性；
2)热压延融合聚合制膜
将制备的PTFE棒料在热压延作用下进行融合聚合，热压延温度60℃，速度25/min，在温度作用下，掺在PTFE树脂中具有单体聚合作用的硅油被热压延机挤出，制得具有微米级孔隙的基于PTFE纳米功能复合膜，卷取成卷；
在温度和热压延的拉伸作用下，膜裂后发生层状剥离后的纤维状结构，生成具有微孔隙的纳米级和微米级尺寸的凹凸几何状超微结构形貌的基于PTFE膜，基于PTFE膜的厚度为100um，膜颜色呈乳白色；
3)微量聚合制成同均质膜
将具有微米级微形凹凸表面结构的基于PTFE纳米功能复合膜在除油烘箱内通过温度作用完成微量聚合，除油烘箱内温度200℃，未被热压延机挤干净的浸润在PTFE树脂中进行单体聚合的硅油通过温度作用发生聚合反应而聚合固结在PTFE树脂内，制得基于PTFE同均质膜，成卷状的基于PTFE膜在除油烘箱内以6m/min的速度进行卷取；
(2)高温高线压力微共晶制备基于PTFE纳米功能复合膜
高温高线压力微共晶腔体内温度设定为380℃，基于PTFE纳米功能复合膜以6m/min速度向前推送，利用腔体内高温使膜分子链收缩并产生共晶，微孔隙变成纳米级和超微米级尺寸，控制PTFE膜表面线压力60N/m，使膜由乳白色成为透明色且透明度均匀一致，密度2.1kg/m³，保持了基于PTFE纳米功能复合膜原有的纳米级和微米级尺寸的凹凸几何状超微结构形貌。
PTFE材料本身就具有无任何粘接材料能够直接粘接的特性，而对于应用在风机叶片上起着防除叶片冬季结冰的基于PTFE纳米功能复合膜，为了提高其超低表面张力和不粘附性能，采用单体融合聚合与微量聚合方法制得的具有了纳米级和微米级尺寸的凹凸几何状超微结构形貌特征，又通过超高温超高压强微共晶具有了较高耐磨性、耐磨韧性和膜结构强度及高透明度，就更难取得适合的粘接胶进行粘接和获得良好的粘接性能。所以，必须对基于PTFE纳米功能复合膜的施胶面进行纳米深度表面活化。
如图1-2所示，上述方案制得的基于PTFE纳米功能复合膜不仅利用PTFE具有润滑的低表面张力一项性能来达到不粘附性目的，同时不对PTFE改性，将膜制备成具有纳米级和微米级尺寸的凹凸几何状超微结构表面形貌，使膜更加具有超低表面固体张力，疏水性能更好，不粘附性和高抗污性更高，膜表面同时具有自清洁功能，这是其他措施方法不能比拟的。通过超高温高压强制得的基于PTFE纳米功能复合膜，具有的较高耐磨擦性、耐磨韧性和耐冲击性，更加具有抵抗沙尘、冰雹、冻雨、雨蚀的磨擦、撞击能力和雷电电弧的冲击能力功能特性，使其能够在风机叶片叶尖300km/h线速度下长期使用而不被磨损，同时具有不燃烧性特性，不会因为雷电电弧而引起燃烧。
对上述制备获得的PTFE膜的5个试样进行各项性能测试，结果如下：（1）膜平均厚度100um；（2）膜平均重量210g/m2；（3）胶粘接剥离力50N，180°粘接剥离强度1000N/m；（4）通过14400h的氙灯老化测验、冻融循环性能测验（温度：-60℃～150℃，湿度：5～98%）、臭氧老化测验、紫外线老化测验、人造气氛腐蚀与海盐溶液浸泡测验，老化前后的抗拉强度平均值25Mpa，伸长率平均值＞90%,均未发生老化现象；（5）采用GB/T 9266-2009“建筑外墙涂料涂层耐洗刷性的测定”方法，经37次／min循环往复磨擦40000次后，膜表面未见毛糙现象，未观察到破损至露出底材现象，具有较强耐磨损性；（6）采用动风压测验平台模拟36.9m/s风速（12级台风）进行动风压测验耐雨水冲刷性能，经1000h强风速吹水测验，膜表面未见毛糙现象，具有优良的耐雨蚀性能；（7）采用扫描电镜SEM对膜表面形貌进行测验，膜表面形貌表现为经纬方向均匀分布着平均大小20～40um、高度10～20um、间距30～50um微米级微形凹凸表面结构；（8）采用水接触角测试仪测得的膜表面水珠接触角为115.89°～125.46°之间；（9）采用表面粗糙度仪测得的膜表面粗糙度平均为值0.18um。
综上，本发明对基于PTFE膜进行纳米深度表面活化，制备的基于PTFE纳米功能复合膜具有超微表面结构形貌的超低表面张力、抗粘附、耐沾污、疏水性、抗吸湿、自清洁性功能；超高的耐磨强度和耐磨韧性，具有耐磨擦、耐冲击、耐雨蚀功能；极具耐化学腐蚀性，能够抗腐蚀、抗高低温、耐老化、耐化学性、耐紫外线、耐疲劳性，增强风机叶片表面强度，起到整体固定作用，提高叶片整体承载能力和抵抗侵蚀能力，消除叶片老化、开裂等安全隐患，增强了叶片抵挡外物的长期侵蚀，使叶片获得双重保护，延长叶片使用寿命；具有的电绝缘性和不燃性，能够抵抗15000伏高压电，具有耐高温特性，雷电电弧击中膜表面无痕迹，更不会引起膜燃烧；超薄的厚度，超轻的重量，超低的表面粗糙度能够改善翼型气动性能，提高了风能使用效率；自粘性冷粘接功能方便了在风机叶片上的应用。
除上述实施例外，本发明还可以有其他实施方式。凡采用等同替换或等效变换形成的技术方案，均落在本发明要求的保护范围。

Claims (5)

1.一种对基于PTFE膜进行纳米深度表面活化的方法，其特征在于：将具有纳米级和微米级尺寸凹凸几何状超微结构形貌的基于PTFE纳米功能复合膜功能面进行覆盖处理后，使施加粘接胶的膜单面在真空环境下且低于40℃的氮氢混合介质氛围中，以1.5～3m/min的速度进行表面活化处理，使膜的施胶面产生具有纳米深度的活化结构层；通过机械施胶装置将高韧性冷粘接胶胶带迁移复合在基于PTFE纳米功能复合膜具有了活化结构层的膜面上，使胶的特性基团与膜的活化结构层发生化学键合作用，形成了胶膜复合体；
其中，高韧性冷粘接胶制备如下：将PVA-1788 0.2kg、丙烯酸丁酯18kg、丙烯酸0.5kg、乙酸乙烯酯1.0kg、甲基丙烯酸甲酯1.0kg、有机硅单体1.5kg、TO-7 0.01kg、十二烷基苯磺酸钠0.01kg、过氧化苯甲酰0.05kg、水80kg加入制备罐中，制备温度85℃，制备时间5h，抽真空和除水后，制得固含量为18.7%的胶带状压敏胶带，复合上离型纸后卷取在PVC管芯上。
2.根据权利要求1所述的一种对基于PTFE膜进行纳米深度表面活化的方法，其特征在于：基于PTFE纳米功能复合膜功能面用PE膜进行覆盖处理。
3.根据权利要求1所述的一种对基于PTFE膜进行纳米深度表面活化的方法，其特征在于：具有纳米级和微米级尺寸凹凸几何状超微结构形貌的基于PTFE纳米功能复合膜按如下步骤制备：
(1)单体融合聚合与微量聚合制得基于PTFE纳米功能复合膜
1)共混、预压、推压制棒
用具有软化PTFE作用的硅油浸润PTFE树脂，对浸润后的PTFE树脂进行共混，通过温度为60～90℃，速度为20～30m/min，压力为5～8MPa的热预压、热推压，制得单体聚合PTFE棒料，同时具有表面润滑性；
2)热压延融合聚合制膜
将制备的PTFE棒料在热压延作用下进行融合聚合，热压延温度60～90℃，速度20～30/min，在温度作用下，掺在PTFE树脂中具有单体聚合作用的硅油被热压延机挤出，制得具有微米级孔隙的基于PTFE纳米功能复合膜，卷取成卷；
在温度和热压延的拉伸作用下，膜裂后发生层状剥离后的纤维状结构，生成具有微孔隙的纳米级和微米级尺寸的凹凸几何状超微结构形貌的基于PTFE膜，基于PTFE膜的厚度为100～120um，膜颜色呈乳白色；
3)微量聚合制成同均质膜
将具有微米级微形凹凸表面结构的基于PTFE纳米功能复合膜在除油烘箱内通过温度作用完成微量聚合，除油烘箱内温度180～200℃，未被热压延机挤干净的浸润在PTFE树脂中进行单体聚合的硅油通过温度作用发生聚合反应而聚合固结在PTFE树脂内，制得基于PTFE同均质膜，成卷状的基于PTFE膜在除油烘箱内以6～8m/min的速度进行卷取；
(2)高温高线压力微共晶制备基于PTFE纳米功能复合膜
高温高线压力微共晶腔体内温度设定为70～420℃，基于PTFE纳米功能复合膜以6～8m/min速度向前推送，利用腔体内高温使膜分子链收缩并产生共晶，微孔隙变成纳米级和超微米级尺寸，控制PTFE膜表面线压力50～80N/m，使膜由乳白色成为透明色且透明度均匀一致，保持了基于PTFE纳米功能复合膜原有的纳米级和微米级尺寸的凹凸几何状超微结构形貌。
4.根据权利要求3所述的一种对基于PTFE膜进行纳米深度表面活化的方法，其特征在于：乙烯基硅油与PTFE树脂按质量比（2～3）：100掺入。
5.根据权利要求4所述的一种对基于PTFE膜进行纳米深度表面活化的方法，其特征在于：具有纳米级和微米级尺寸凹凸几何状超微结构形貌的基于PTFE纳米功能复合膜按如下步骤制备：
(1)单体融合聚合与微量聚合制得基于PTFE纳米功能复合膜
1)共混、预压、推压制棒
用具有软化PTFE作用的硅油浸润PTFE树脂，乙烯基硅油与PTFE树脂按质量比2.5：100掺入，对浸润后的PTFE树脂进行共混，通过温度为60℃，速度为25m/min，压力为8MPa的热预压、热推压，制得单体聚合的Ф17mm的PTFE棒料，同时具有表面润滑性；
2)热压延融合聚合制膜
将制备的PTFE棒料在热压延作用下进行融合聚合，热压延温度60℃，速度25/min，在温度作用下，掺在PTFE树脂中具有单体聚合作用的硅油被热压延机挤出，制得具有微米级孔隙的基于PTFE纳米功能复合膜，卷取成卷；
在温度和热压延的拉伸作用下，膜裂后发生层状剥离后的纤维状结构，生成具有微孔隙的纳米级和微米级尺寸的凹凸几何状超微结构形貌的基于PTFE膜，基于PTFE膜的厚度为100um，膜颜色呈乳白色；
3)微量聚合制成同均质膜
将具有微米级微形凹凸表面结构的基于PTFE纳米功能复合膜在除油烘箱内通过温度作用完成微量聚合，除油烘箱内温度200℃，未被热压延机挤干净的浸润在PTFE树脂中进行单体聚合的硅油通过温度作用发生聚合反应而聚合固结在PTFE树脂内，制得基于PTFE同均质膜，成卷状的基于PTFE膜在除油烘箱内以6m/min的速度进行卷取；
(2)高温高线压力微共晶制备基于PTFE纳米功能复合膜
高温高线压力微共晶腔体内温度设定为380℃，基于PTFE纳米功能复合膜以6m/min速度向前推送，利用腔体内高温使膜分子链收缩并产生共晶，微孔隙变成纳米级和超微米级尺寸，控制PTFE膜表面线压力50～80N/m，使膜由乳白色成为透明色且透明度均匀一致，密度2.1kg/m³，保持了基于PTFE纳米功能复合膜原有的纳米级和微米级尺寸的凹凸几何状超微结构形貌。
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