CN109692794A - 共形含氟聚合物涂层 - Google Patents
共形含氟聚合物涂层 Download PDFInfo
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- CN109692794A CN109692794A CN201811171348.1A CN201811171348A CN109692794A CN 109692794 A CN109692794 A CN 109692794A CN 201811171348 A CN201811171348 A CN 201811171348A CN 109692794 A CN109692794 A CN 109692794A
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- fluoropolymer
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Abstract
本申请涉及共形含氟聚合物涂层。本公开内容提供了用于形成含氟聚合物涂布部件比如金属部件的方法,其包括将粘合促进剂施加部件的表面上;将有机材料施加到粘合促进剂上;和将包括含氟聚合物和选自呋喃或氟化溶剂的溶剂的混合物施加到有机材料上。本公开内容的方面进一步提供了含氟聚合物涂层,其在部件上具有从约5mil至约80mil的厚度,基于层的总体积从约20%至约70%的平均孔隙率,和从每cm3约1011至约1013个空隙的空隙密度。
Description
技术领域
本公开内容的方面提供了用于将共形含氟聚合物涂层沉积到非平坦表面上的方法。本公开内容的方面进一步提供含氟聚合物涂层。
背景技术
航空器上霜、冰或雪的积聚会改变航空器机翼上的气流,降低升力并增加阻力。积聚还增加了总重量,增加了起飞所需的升力。因此,通常在起飞之前除去霜、冰或雪。当处于飞行中时,热的发动机引气、电热毯、机械除冰带或其组合可用于使冰离开航空器的外表面。然而,这些措施消耗能量,增加航空器的重量,并降低燃料经济性。
在地面上,使用热的乙二醇喷涂形式的防冰液和除冰液。尽管有效,但是这种流体产生增加的费用并且可能引起门延迟另外的应用时间。结果,从航空器除去冰的新选择是期望的。
含氟聚合物可以涂布在表面上以减少或防止冰积聚。然而,在航空器部件不平坦(例如,具有曲率)的地方,例如在翼面的前缘上,含氟聚合物涂层具有波纹纹理,与光滑的涂层表面相比,当暴露于雨水或沙子时,含氟聚合物涂层磨损快得多。此外,由于沉积涂层的蠕变/流动,含氟聚合物涂层在航空器部件的弯曲表面上具有约10mil的最大厚度。
存在对于在非平坦表面上用于形成光滑防冰涂层的方法的需要。
发明内容
本公开内容提供了用于形成含氟聚合物涂布的金属的方法,其包括将粘合促进剂施加在表面上;将有机材料施加到粘合促进剂上;和将包括含氟聚合物和选自呋喃或氟化溶剂的溶剂的混合物施加到有机材料上。
本公开内容的方面进一步提供了含氟聚合物涂层,其在部件上具有从约5mil至约80mil的厚度,基于层的总体积从约20%至约70%的平均孔隙率,和从每cm3约1011至约1013个空隙的空隙密度。
附图说明
因而,可以详细地理解本公开内容的上述特征的方式,通过参考方面可获得以上简要总结的本公开内容的更具体描述,其中一些方面在附图中图解。然而,应该注意,附图仅图解了本公开内容的典型方面,并且因此不应被认为限制其范围,因为本公开内容可以允许其它同样有效的方面。
图1是根据一个方面的用于制造在其上布置有光滑防冰涂层的表面的方法的流程图。
图2是根据一个方面的机器人喷布器。
图3是根据一个方面的真空袋装置的透视图。
为了利于理解,在可能的情况下,已经使用了相同的附图标记来指定附图共有的相同元件。考虑一个方面的元件和特征可以被有利地并入其它方面中,而无需进一步叙述。
具体实施方式
本公开内容提供了用于形成含氟聚合物涂布的金属的方法,其包括将粘合促进剂施加在表面上;将有机材料施加到粘合促进剂上;和将包括含氟聚合物和选自呋喃或氟化溶剂的溶剂的混合物施加到有机材料上。本公开内容的方法提供了在非平坦表面比如非平坦金属表面上的光滑防冰涂层,其具有改善的防雨和防沙侵蚀性。
翼面的表面制备
图1是用于制造在其上布置有光滑防冰涂层的表面的方法100。在至少一个方面中,如图1中所显示,可以研磨和/或用溶剂冲洗表面,比如部件的表面(方框102)。部件可以是风力涡轮机、卫星或交通工具比如汽车、火车、轮船等的一部分。交通工具部件是交通工具的部件,比如结构部件,比如航空器的起落架(一个或多个)、面板或接头。交通工具部件的实例包括翼面(比如转子叶片)、辅助动力单元、航空器的机头、燃料箱、尾椎、面板、两个或更多个面板之间的涂布搭接接头、机翼-与-机身组件、结构航空器复合材料、机身主体-接头、翼肋-与-蒙皮接头、和/或其它内部部件。在至少一个方面中,用研磨垫研磨表面以提供暴露的表面。例如,铝表面被研磨以除去氧化铝并暴露元素铝表面。在至少一个方面中,研磨垫具有约100砂粒至约1,000砂粒,比如约400砂粒至约500砂粒的表面。合适的研磨垫包括可获得自3M Corporation的Scotch-BriteTM研磨垫。研磨表面可以用肥皂和水冲洗并擦洗以除去任何松散的表面材料或碎屑。在冲洗之后,可以将表面(比如交通工具部件的表面)引入包含洗涤剂的碱性溶液中。另外或可选地,可以将包含洗涤剂的碱性溶液喷涂到表面上。碱性溶液可以是水性氢氧化钠、碳酸氢钠、碳酸钾或碳酸钠。洗涤剂可以是可获得自International Products Corporation of Burlington,New Jersey的Micro-洗涤剂(其包括表面活性剂和螯合剂)。包含洗涤剂的碱性溶液的pH可以从约7至约12,比如约9。存在于具有洗涤剂的碱性溶液中的表面(比如交通工具部件的表面)可以被超声处理约1分钟至约1小时,比如约20分钟。具有洗涤剂的碱性溶液提供在表面上氧化的另外去除。然后可以从溶液移除表面(比如交通工具部件的表面),用水冲洗,并引入丙酮浴中。存在于丙酮浴中的表面可以被超声处理约1分钟至约1小时,比如约20分钟。从丙酮浴移除表面并且干燥。表面可以储存在惰性气氛比如氮或氩中,直到进一步使用。
含氟聚合物可以被直接施加至研磨表面(例如,以下面描述的方式)或研磨表面可以经历进一步表面制备,例如,如以下所描述。
用于喷涂应用的表面制备
在至少一个方面中,如图1中所显示,将金属粘合促进剂施加至表面(方框104)以增强有机材料与表面的结合。在至少一个方面中,该方法包括施加粘合促进剂,其为醋酸、四正丙氧化锆和(3-缩水甘油氧基丙基)三甲氧基硅烷的反应产物。粘合促进剂可以是比如3M Surface Pre-Treatment AC-131 CB。3%AC-131试剂盒可获得自3MCorporation。粘合促进剂可以是表面上的层。3%AC-131是非铬酸盐转化涂层并且通常布置在铝、镍、不锈钢、镁和钛合金上。AC-131具有部分A,其为冰醋酸(GAA)和四正丙氧化锆(TPOZ)的水性混合物,和部分B,其为(3-缩水甘油氧基丙基)三甲氧基硅烷(GTMS)。将这两部分混合在一起(部分A+部分B),并且混合物中硅与锆的摩尔比为2.77:1。部分A中醋酸与TPOZ的摩尔比为0.45:1。测量体积的GAA和TPOZ可以被剧烈地混合约10分钟,并且然后从AC-131试剂盒添加至部分A。然后可以将预先混合的部分A溶液从AC-131试剂盒添加至测量体积的部分B溶液并搅拌,随后是30分钟诱导期。然后通过喷涂、浸渍、刷涂和/或擦拭将该溶液布置在表面(比如交通工具部件的表面)上。例如,合适的喷涂形式包括用喷枪、高体积低压喷枪和/或手泵喷布器喷涂。然后将溶液(在室温下或升高的温度下)固化以形成溶胶-凝胶。在至少一个方面中,固化温度为从约10℃至约150℃,比如从约20℃至约100℃,比如从约30℃至约70℃,比如从约40℃至约50℃。固化可以进行从约15分钟至约72小时的时间段。粘合促进剂层可以具有从约0.5mil至约5mil,比如从约1mil至约2mil的厚度。
在至少一个方面中,如图1中所显示,将有机材料沉积在粘合促进剂上(方框106)。有机材料可以是粘合促进剂上的层。有机材料可以包括底漆比如环氧树脂、聚氨酯,底漆材料比如环氧树脂或氨基甲酸乙酯底漆,或纤维增强塑料。沉积可以包括喷漆、喷涂、浸渍、接触、粘附和/或粘合溶胶-凝胶与有机材料以形成有机材料层。有机材料层可以具有从约0.5mil至约5mil,比如从约1mil至约2mil的厚度。
含氟聚合物的喷涂应用
在至少一个方面中,如图1中所显示,将含氟聚合物沉积在粘合促进剂层或有机材料层或表面(例如,金属表面)上(方框108)。含氟聚合物包括氟代丙烯酸酯、氟代硅氧烷丙烯酸酯、氟代氨基甲酸乙酯、全氟聚醚、全氟聚氧杂环丁烷、聚偏二氟乙烯(PVDF)和全氟烷氧基烷烃(PFA)。氟乙烷包括聚四氟乙烯(PTFE)、氟化的乙烯丙烯聚合物(FEP)(其为六氟丙烯和四氟乙烯的共聚物)和乙烯四氟乙烯(ETFE)。
表面(比如交通工具部件的表面)可以被悬挂(比如通过夹具或环)以允许在喷涂时容易接近部件的两个或更多个面。
将含氟聚合物溶解在呋喃溶剂或氟化溶剂中的一种或两种中。典型地,由于含氟聚合物的氟原子的量,常规的喷涂和粘合沉积技术由于与含氟聚合物的溶剂不相容性不能被使用。已经发现,呋喃溶剂或氟化溶剂提供对于含氟聚合物的溶解(和流动性)足够的极性,和用于喷涂应用的足够低的挥发性(即,沸点足够高)。另外,呋喃溶剂或氟化溶剂的沸点足够低以容易从含氟聚合物层被去除,形成最小空隙,这可以提供含氟聚合物层的光滑的共形表面。在至少一个方面中,溶剂具有从约40℃至约200℃,比如从约50℃至约100℃,比如从约60℃至约90℃的沸点。
在至少一个方面中,氟化溶剂由式(I)表示:
R1—(CF2)n—R2 (I)
其中n是从约1至约25的整数;R1和R2独立地为-CF3、氢、羟基、羟烷基、氨基烷基、氨基芳基、芳氧基、烷基、芳基、具有从约1至约25个碳的羧酸基团、羰基、酮、醛和-CF3(CF2)q(CH2)p,其中q是从约0至约25的整数,和p是从约1至约25的整数,其中氟化溶剂具有从约40℃至约200℃的沸点。与本公开内容的含氟聚合物不同,大部分化合物不溶于氟化溶剂中。例如,许多有机分子和许多非氟化的或部分氟化的化合物不溶于氟化溶剂中。
在至少一个方面中,呋喃溶剂由式(IIa)或(IIb)表示:
其中R1、R2、R3和R4独立地为氢、羟基、羟烷基、氨基烷基、氨基芳基、芳氧基、烷基、芳基、具有从约1至约25个碳的羧酸基团、羰基和烷基酮羰基,其中呋喃溶剂具有从约40℃至约200℃的沸点。
相比之下,甲乙酮不溶解含氟聚合物。此外,含氟聚合物在氯化溶剂,比如氯仿和二氯甲烷中具有有限的溶解度,因为这些溶剂不够极性并且不能分散含氟聚合物。另外,大部分氯化溶剂比如二氯甲烷的挥发性对于喷涂应用来说过高。
混合物可以进一步包括一种或多种另外的聚合物,比如环氧树脂、聚丙烯酸酯、聚酯、聚醚、氨基甲酸酯(比如聚氨酯)和聚硅氧烷。例如,聚氨酯可以包括可获得自PPGAerospace of Sylmar,California的HS CA8800/B900,和可获得自Akzo Nobel Aerospace Coatings in Waukegan,Illinois的(ECL-G-7),两者均为溶剂光泽透明涂层。
本公开内容的含氟聚合物和溶剂的混合物可以具有如ASTM D445-17a所测定的在25℃下从约0.00046Pa*s至约1Pa*s,比如如ASTM D445-17a所测定的在25℃下从约0.001Pa*s至约0.8Pa*s的粘度。本公开内容的含氟聚合物和溶剂的混合物可以提供足够高的粘度,比如0.00046Pa*s或更高,以共形地涂布非平坦表面,比如非平坦金属表面(例如,共形地沉积在交通工具部件的弯曲表面上)。共形涂层在整个表面上具有基本上均匀的厚度。
在将含氟聚合物溶解在呋喃溶剂或氟化溶剂中的一种或两种之后,使用任何合适的喷涂装置,比如气枪,将含氟聚合物溶液喷涂到粘合促进剂层或有机材料层上。在至少一个方面中,在喷涂期间,将喷涂装置的喷嘴与粘合促进剂层或有机材料层的表面分离从约0.5英寸至约30英寸,比如从约2英寸至约10英寸,比如从约4英寸至约8英寸的距离,其为足够接近表面的距离以提供在表面的受控位置处的喷涂。在至少一个方面中,在从约7psi至约24psi,比如从约12psi至约18psi的压力下,将含氟聚合物溶液喷涂到粘合促进剂层或有机材料层上。其它喷布器/压力选择可以包括:从约10psi至约60psi的HVLP/LVLP;从约20psi至约50psi的气枪;从约500psi至约2000psi的液压喷布器;从约100至约1000psi的机器人喷布器。
喷涂装置的喷嘴平行于粘合促进剂层或有机材料层的表面移动。喷嘴平行于粘合促进剂层或有机材料层的表面的两次完整移动(“往返”)被称为一次“行程”。一次行程可以以从约0.5mil至约2mil,比如从约0.8mil至约1.2mil,比如约1mil的厚度将含氟聚合物溶液沉积在表面上。从一次行程到下一次行程的时间段可以从约0.1分钟至约30分钟,比如从约0.5分钟至约5分钟,比如从约1分钟至约2分钟。在行程之间提供时间促进从由单次行程沉积的层除去溶剂。这种逐层喷涂方法允许从每层蒸发溶剂,而不是从一个厚层蒸发溶剂,这将产生空隙。在几次行程之后,形成具有从约2mil至约20mil,比如从约5mil至约15mil,比如从约8mil至约12mil的厚度的含氟聚合物层。含氟聚合物层可以在室温下固化至少约10小时,比如至少约15小时,比如至少约16小时的时间段。可选地,通过在从约20℃至约100℃,比如从约30℃至约90℃,比如从约40℃至约80℃的温度下加热含氟聚合物层可以加速固化。固化可以进行从约15分钟至5小时,比如约4小时的时间段。在至少一个方面中,基于层的总体积,本公开内容的含氟聚合物层具有如通过压汞测定的从约20%至约70%,比如从约40%至约60%,比如从约45%至约55%的平均孔隙率,其可以提供含氟聚合物层的光滑共形表面。在至少一个方面中,本公开内容的含氟聚合物层具有如通过压汞试验(ASTMD4284-12)测定的从每cm3约1011至约1013个空隙,比如从每cm3约2x1011至约8x1012个空隙的平均空隙密度,其可以提供含氟聚合物层的光滑共形表面。在至少一个方面中,本公开内容的含氟聚合物层具有如通过ASTM D7127-05(使用便携式触针仪测量喷砂清洁金属表面的表面粗糙度的标准测试方法)测定的小于约100微英寸,比如小于约90微英寸,比如小于约80微英寸,比如小于约70微英寸,比如从约5微英寸至约100微英寸,比如从约20微英寸至约80微英寸的表面粗糙度。本公开内容的光滑含氟聚合物层可以提供含氟聚合物层上稳定的水层流。
在至少一个方面中,以与第一含氟聚合物层相似或相同的方式将第二含氟聚合物层沉积在第一含氟聚合物层上。使用任何合适的喷涂装置,比如气枪,将含氟聚合物溶液喷涂到第一含氟聚合物层上。在喷涂期间,喷涂装置的喷嘴与第一含氟聚合物层的表面分离从约0.5英寸至约30英寸,比如从约2英寸至约10英寸,比如从约4英寸至约8英寸的距离。在从约7psi至约24psi,比如从约12psi至约18psi的压力下将含氟聚合物溶液喷涂到第一含氟聚合物层上。其它喷布器/压力选择可以包括:从约10psi至约60psi的HVLP/LVLP;从约20psi至约50psi的气枪;从约500psi至约2000psi的液压喷布器;从约100至约1000psi的机器人喷布器。喷涂装置的喷嘴平行于第一含氟聚合物层的表面移动。一次行程可以将含氟聚合物以从约0.5mil至约2mil,比如从约0.8mil至约1.2mil,比如约1mil的厚度沉积到表面上。从一次行程到下一次行程的时间段可以为从约0.1分钟至约30分钟,比如从约0.5分钟至约5分钟,比如从约1分钟至约2分钟。在行程之间提供时间促进从由单次行程沉积的层除去溶剂。这种逐层喷涂方法允许从每层蒸发溶剂而不是从一个厚层蒸发溶剂,这将产生空隙。在几次行程之后,形成具有从约2mil至约20mil,比如从约5mil至约15mil,比如从约8mil至约12mil的厚度的第二含氟聚合物层。第二含氟聚合物层可以在室温下固化至少约10小时,比如至少约15小时,比如至少约16小时的时间段。可选地,通过在从约20℃至约100℃,比如从约30℃至约90℃,比如从约40℃至约80℃的温度下加热含氟聚合物层可以加速固化。固化可以进行从约15分钟至5小时,比如约4小时的时间段。
在至少一个方面中,用于沉积第一含氟聚合物层、第二含氟聚合物、粘合促进剂和/或有机材料的喷涂装置是机器人喷布器。图2是机器人喷布器。如图2中所显示,将材料(比如含氟聚合物和溶剂的混合物)装入具有一次性聚乙烯衬垫的压力罐201中。盖202被安装并且压紧密封锁住(clamped pressure tight)。将流体输送软管203连接到压力罐内的抽出管(pickup tube)204。通过管线205注入压力调节的氮或干燥空气以使罐加压并且迫使材料进入抽出管和管线。压力罐具有减压阀以防止过压和从罐释放压力,用于去除或添加材料。调节器位于枪206附近以控制正在输送的流体压力。控制在枪处的流体压力控制通过枪的喷涂喷嘴的体积流速。在枪附近安装调节器消除软管长度、软管直径或机器人臂高度的任何压降影响。喷嘴控制还需要控制流速。喷嘴孔口的微小制造差异可能产生不同的液体流速。喷嘴控制和枪的流体压力调节协同工作以给出通过喷嘴的一致的和可重复的体积流速。通过管线207的空气辅助雾化压力也被调节和控制以给出来自喷嘴的一致喷涂分散。
机器人208携带枪并且被编程为横穿部件的表面,其具有与非平坦表面209的恒定偏移和受控的速度。来自喷嘴的喷涂通常具有平坦的扇形图案。将大部分喷涂材料沉积在扇形中心处,在扇形边缘处输送逐渐减少的量。为了补偿喷涂扇形中的这种不均匀分布,机器人被编程为与相邻的行程重叠以使分布均匀。典型的行程指数是1/4扇形宽度。
在至少一个方面中,如图1中所显示,方法100包括在将含氟聚合物沉积到表面上之前、期间和/或之后加热表面(比如交通工具部件的表面)(方框110)。例如,当将含氟聚合物沉积到表面上时加热表面可以提供原位溶剂去除和包含含氟聚合物和溶剂的混合物的增加的粘度,提供在交通工具部件的弯曲(非平坦)表面上的共形沉积。当将含氟聚合物沉积到表面上时加热表面可以提供含氟聚合物的另外的均匀层以实现整体更厚的涂层(例如,10mil至20mil),因为溶剂已经被去除,该涂层具有由捕获的溶剂引起的减少的或消除的空隙。当将含氟聚合物沉积到表面上时加热表面进一步提供与室温固化层相比更光滑的层。共形涂层在整个表面上具有基本上均匀的厚度。在加热期间,表面(比如交通工具部件的表面)可以具有如通过接触表面的任何合适的热电偶比如K型或J型热电偶所测定的从约30℃至约70℃,比如从约45℃至约55℃的温度。可以使用表面的曝光(例如,紫外光)进行加热表面。光可以是红外线(IR)或紫外线(UV)。将表面暴露于光(并且加热)可以使用装配有最大发射强度为365nm的H+灯泡的FUSION UV固化单元进行。在至少一个方面中,UV/IR固化单元的灯泡相对于从喷涂装置的喷嘴流出的材料的流动方向约45°取向。在至少一个方面中,UV/IR固化单元的灯泡与表面分开从约8英寸至约3英尺,比如约11英寸至约1.5英尺的距离。例如,IR固化单元提供涂层的光滑表面纹理,其否则具有更多的波纹效应,提供表面抵抗雨水和沙子侵蚀的改善的耐久性。
形成自支撑膜
在至少一个方面中,如图1中所显示,方法100包括形成自支撑含氟聚合物膜(方框112)。使用任何合适的喷涂装置,比如气枪将如上所述的含氟聚合物与呋喃溶剂或氟化溶剂中的一种或两种的混合物喷涂到聚脂薄膜片材比如硅烷化的聚酯薄膜上。在至少一个方面中,在喷涂期间,将喷涂装置的喷嘴与聚脂薄膜片材的表面分离从约0.5英寸至约30英寸,比如从约2英寸至约10英寸,比如从约4英寸至约8英寸的距离。在至少一个方面中,在从约7psi至约24psi,比如从约12psi至约18psi的压力下将含氟聚合物溶液喷涂到聚脂薄膜片材上。其它喷布器/压力选择可以包括:从约10psi至约60psi的HVLP/LVLP;从约20psi至约50psi的气枪;从约500psi至约2000psi的液压喷布器;从约100至约1000psi的机器人喷布器。喷涂装置的喷嘴平行于聚脂薄膜片材的表面移动。平行于聚脂薄膜片材的表面的喷嘴的两次完整移动(“往返”)被称为一次“行程”。一次行程可以将含氟聚合物溶液以从约0.5mil至约2mil,比如从约0.8mil至约1.2mil,比如约1mil的厚度沉积到表面上。从一次行程到下一次行程的时间段可以为从约0.1分钟至约30分钟,比如从约0.5分钟至约5分钟,比如从约1分钟至约2分钟。在行程之间提供时间促进从由单次行程沉积的层除去溶剂。这种逐层喷涂方法允许从每层蒸发溶剂而不是从一个厚层蒸发溶剂,这将产生空隙。在几次行程之后,形成具有从约2mil至约20mil,比如从约5mil至约15mil,比如从约8mil至约12mil的厚度的含氟聚合物层。含氟聚合物层可以在室温下固化至少约10小时,比如至少约15小时,比如至少约16小时的时间段。可选地,通过在从约20℃至约100℃,比如从约30℃至约90℃,比如从约40℃至约80℃的温度下加热含氟聚合物层可以加速固化。固化可以进行从约15分钟至5小时,比如约4小时的时间段。
在至少一个方面中,将第二含氟聚合物层沉积到第一含氟聚合物层上以与第一含氟聚合物层相似或相同的方式形成自支撑膜。使用任何合适的喷涂装置,比如气枪,将含氟聚合物溶液喷涂到第一含氟聚合物层上。在至少一个方面中,在喷涂期间,喷涂装置的喷嘴与第一含氟聚合物层的表面分离从约0.5英寸至约30英寸,比如从约2英寸至约10英寸,比如从约4英寸至约8英寸的距离。在至少一个方面中,在从约7psi至约24psi,比如从约12psi至约18psi的压力下将含氟聚合物溶液喷涂到第一含氟聚合物层上。其它喷布器/压力选择可以包括:从约10psi至约60psi的HVLP/LVLP;从约20psi至约50psi的气枪;从约500psi至约2000psi的液压喷布器;从约100至约1000psi的机器人喷布器。喷涂装置的喷嘴平行于第一含氟聚合物层的表面移动。一次行程可以将含氟聚合物以从约0.5mil至约2mil,比如从约0.8mil至约1.2mil,比如约1mil的厚度沉积到表面上。从一次行程到下一次行程的时间段可以为从约0.1分钟至约30分钟,比如从约0.5分钟至约5分钟,比如从约1分钟至约2分钟。在几次行程之后,形成具有从约2mil至约20mil,比如从约5mil至约15mil,比如从约8mil至约12mil的厚度的第二含氟聚合物层。第二含氟聚合物层可以在室温下固化至少约10小时,比如至少约15小时,比如至少约16小时的时间段。可选地,通过在从约20℃至约100℃,比如从约30℃至约90℃,比如从约40℃至约80℃的温度下加热含氟聚合物层可以加速固化。固化可以进行从约15分钟至5小时,比如约4小时的时间段。
自支撑膜可以在从约90℃至约150℃,比如约100℃的温度下被热压制。在至少一个方面中,将两个压板加热至期望的温度(例如,100℃)。自支撑膜被置于两个剥离层(例如,硅烷化的聚酯薄膜)之间并且置于热压板之间。热压板然后关闭,在膜上提供压力和热。热塑性塑料将流动,并且可以使用垫片控制膜的厚度。然后在压力被移除之前使压板冷却下来。选择用于热压制的温度取决于热塑性塑料或聚合物膜。在至少一个方面中,压板的温度高于聚合物的Tg(玻璃化转变温度),但是低于分解温度。
自支撑膜与含氟聚合物涂布表面的粘合
在至少一个方面中,如图1中所显示,方法100包括粘合自支撑膜至含氟聚合物涂布表面(方框114)。粘合剂可以被施加至自支撑膜的暴露的(例如,外部)含氟聚合物表面或含氟聚合物涂布部件的暴露的(例如,外部)含氟聚合物表面的一个或两个上。利用压力可以将粘合剂压制到自支撑膜的含氟聚合物表面或含氟聚合物涂布部件的含氟聚合物表面中的一个或两个上,以减少或消除粘合剂和施加的表面之间的空气含量。粘合剂包括任何合适的粘合剂比如环氧树脂,比如获得自3M Corporation的AF163-2K。如果粘合剂被施加至自支撑膜的含氟聚合物表面,则粘合剂的相对表面上的保护衬垫被去除并定位在含氟聚合物涂布部件的含氟聚合物表面上,并且然后利用压力压制在含氟聚合物涂布部件的含氟聚合物表面上。如果粘合剂被施加至含氟聚合物涂布部件的含氟聚合物表面,则粘合剂的相对表面上的保护衬垫被去除并定位在自支撑膜的含氟聚合物表面上,并且然后利用压力压制在自支撑膜的含氟聚合物表面上。
然后将整个(压制的)组件密封在真空袋中。图3是真空袋装置300的透视图。如图3中所显示,包括连接至真空密封件304的真空软管302。真空密封件304被连接至真空袋306。真空袋306布置在金属板308和位置310a和310b处显示的两个组件上。金属板308提供改善的真空效率。金属板可以是平坦金属板并且可以包括铝或不锈钢。已经发现,没有连接至真空袋的金属板,真空袋在组件周围自由缠绕,在袋中产生可能影响组件上的涂层纹理的空隙和/或折痕,这取决于折痕和/或褶的位置。
施加真空至袋306,确保自支撑膜与组件的含氟聚合物涂布的金属接触。在真空装袋过程期间,袋306内的压力可以为从约1psi至约20psi,比如从约7psi至约10psi。一旦从自支撑膜和组件的含氟聚合物涂布的金属之间的结合线基本上或完全去除空气,将袋装的组件转移到烘箱以固化(压制组件)的粘合剂。烘箱的温度可以为从约100°F至约300°F,比如从150°F至约250°F,例如约210°F。升温速率可以为从约1°F/分钟至约20°F/分钟,比如约2°F/分钟。固化可以进行从约15分钟至5小时,比如约3小时的时间段。在固化之后,可以从部件的边缘修剪多余的膜(如果存在)。真空袋可包含布置在真空袋内的一种或多种通气孔材料,比如多孔棉花材料。通气孔材料提供真空与组件表面的连接。
在真空装袋程序之后,组件可以具有如下的含氟聚合物层,该含氟聚合物层具有从约5mil至约80mil的厚度,基于层的总体积从约20%至约70%的平均孔隙率,和从每cm3约1011至约1013个空隙的空隙密度,如通过压汞试验(ASTM D4284-12)所测定。在至少一个方面中,本公开内容的含氟聚合物层具有如通过ASTM D7127-05(使用便携式触针仪测量喷砂清洁金属表面的表面粗糙度的标准测试方法)所测定的小于约100微英寸,比如小于约90微英寸,比如小于约80微英寸,比如小于约70微英寸,比如从约5微英寸至约100微英寸,比如从约20微英寸至约80微英寸的表面粗糙度。本公开内容的光滑含氟聚合物层可以在含氟聚合物层上提供稳定的水层流。
用于改善涂层行为的添加剂
尽管将添加剂添加至涂料和涂层是本行业的公知常识,但重要的是保留涂层的防冰性能。许多添加剂可用于产生更光滑的成品,被涂布表面的更好润湿,和环境影响和条件比如水分、热和UV暴露的更好抗性。这些添加剂中的一些通过修改涂层组合物的表面能起作用,这可以改变该技术的任何不相容的化学组合物的微观结构。不相容的化学物质的微观结构和相分离对于具有高防冰性能是重要的并且不应该被显著改变。这些添加剂还可以迁移至涂层表面,这可以改变冰与涂层表面的相互作用,这也可能影响冷冻延迟和冰粘附。
涂布技术中部件的化学性质容易从环境吸收水分,这可引起涂层的过早固化和二氧化碳的产生。为了缓解该问题,可以将水分清除剂(例如唑烷,例如Incozol-2)添加到本公开内容的含氟聚合物和溶剂的混合物。为了改善涂层在部件上的表面润湿和扩展,润湿剂(例如,嵌段共聚物比如Disperbyk-166,其为具有颜料亲和基团的高分子量嵌段共聚物)和/或消泡剂(例如BYK-051N,其为不含硅氧烷的消泡剂)可以包括在本公开内容的含氟聚合物和溶剂的混合物中。这些添加剂不是颗粒,而是小分子添加剂。它们是水分清除剂或减少空隙形成。较低量的空隙促进膜的完整性/强度。可以使用显微镜宏观地观察空隙。
本公开内容的添加剂包括任何合适的水分清除剂、润湿剂和/或消泡剂。水分清除剂可以包括异佛尔酮二异氰酸酯(IPDI)和唑烷(比如4-乙基-2-甲基-2-(3-甲基丁基)-1,3-唑烷)。润湿剂可以包括聚酰胺、具有长链脂肪酸部分的聚酰胺和对十二烷基苯磺酸(DDBSA)。消泡剂可以包括聚(二甲基硅氧烷)流体、聚(丙烯酸辛酯)、SiO2、具有聚醚末端基团的硅氧烷和三聚磷酸钾。
由于在加工本公开内容的含氟聚合物涂层中的增强,已经发现,与使用常规的沉积、固化和真空装袋方法制备的含氟聚合物涂层相比,可以从本公开内容的涂层减少或消除这些添加剂的量。在至少一个方面中,本公开内容的含氟聚合物层具有小于约1wt%,比如小于约0.5wt%的添加剂含量,与常规的防冰层的更高的添加剂含量相比,这节省了制造时间和成本;并且是足够低的量以减少或防止添加剂在含氟聚合物表面的积聚。
实施例
在下述实施例中,使用铝转子叶片(并且被称为“翼面”)。
实施例1:
翼面的表面制备:使用3M Scotch-BriteTM 400-500磨石,翼面的表面被均匀地磨损以暴露下面的铝。用肥皂和水冲洗翼面,擦洗以除去留下的松散的铝和碎屑。在冲洗之后,将样品置于装有含Micro90洗涤剂的温碱水的烧杯中,并置于浴超声波仪中,20分钟。彻底地冲洗样品以除去肥皂,并置于丙酮烧杯中,并且浴超声处理,20分钟。在置于填充氮(N2)的箱中之前干燥翼面,直到进一步使用。
用于喷涂应用的表面制备:翼面的表面制备中的下一步是添加金属粘合促进剂(3M Surface Pre-treatment AC-131 CB)以增强有机材料与铝表面的粘合。按照制造商的说明制备促进剂,并且在翼面表面喷涂一次行程之前允许静置30分钟的最短诱导时间。一旦AC-131被干燥(在施加之后最少15min但不长于72h),将底漆施加至翼面。按照制造商的说明制备CA7502底漆,并且允许1小时的诱导时间。不久之后,将底漆作为轻涂层(1至2mil厚)喷涂在翼面表面上。
翼面的制备:将含氟聚合物溶解在塑料容器中的四氢呋喃中。使溶液涡旋并且置于2300rpm的FlackTek速度混合器中,15秒。将溶液转移至专用于底部进料的Iwata气枪的玻璃瓶。对于这种喷涂应用,使用具有0.5mm针/喷嘴的Iwata Eclipse HP-BCS气枪,这是由于其处理中等至大量涂料的能力。气枪被连接至压力为40psi的空气压缩机。翼面被悬挂在杆(杆直径最大为0.625-英寸)上,杆被牢固地连接至环架,以允许在喷涂时容易操作样品的两侧面。利用平行于表面的缓慢行程,以开始于前缘向下至后缘的4至8英寸的距离喷涂翼面的每一侧面。为了以最小喷涂重叠覆盖翼面的一侧面,3次行程(行程近似等于向右往返)是足够的。一旦喷涂了两面,利用1至2次行程覆盖前缘。在下一轮施加之前,允许溶剂闪蒸1至2分钟。每个行程的速度将确定获得10mil厚涂层所需要的轮数(平均8-12轮)。一旦达到目标厚度,允许翼面在环境条件下静置最少16h,以允许固化和溶剂蒸发。在16h时间段之后,按照相同的方案将第二10mil涂层施加至翼面。再次,使样品静置,然后在80℃下最终固化4h。对于这种含氟聚合物混合物,发现喷涂厚度大于10mil的涂层导致膜内的气泡和内聚破坏。
自支撑膜:将含氟聚合物溶解在塑料容器中的四氢呋喃中。使该溶液快速涡漩,并且置于2300rpm的FlackTek速度混合器中,15秒。将溶液倾倒至用于底部进料的Iwata气枪的玻璃瓶中。对于该喷涂应用,使用具有0.5mm针/喷嘴的Iwata Eclipse HP-BCS气枪,这是由于其处理中度至大量涂料的能力。将含氟聚合物溶液直接喷涂在已硅烷化的聚酯薄膜片材上。使气枪保持在聚酯薄膜上方4至8英寸的距离处,并且以平行于表面的行程喷涂。膜的总目标厚度为20mil,每个涂层具有10mil的厚度限制。将第一个10mil厚的膜施加至表面,并且允许干燥16h。第二天,将新鲜的含氟聚合物溶液喷涂到第一涂层上,得到20mil的总厚度。使涂层固化16h,然后在80℃下最终固化4h。然后在100℃下热压制自支撑膜以使厚度均匀。
膜与翼面的粘合:在制备翼面和自支撑膜之后,使用环氧树脂膜粘合剂(AF163-2K)将它们粘合在一起。从原料辊切下足以覆盖翼面区域的一部分AF163-2K。将粘合剂的暴露面抵靠自支撑膜放置,确保其间的所有空气被去除。粘合剂的相对侧上的保护衬垫被去除并定位在沿着0%弦(前缘)开始的翼面表面上。沿着表面朝向样品的后缘逐渐压制膜/粘合剂,去除所有的空隙。一旦粘合剂被固定在部件表面上,它将抵靠清洁的平坦表面滚动,然后将整个组件密封在真空袋内。然后使用图3中显示的装置(具有金属板)对组件真空装袋。施加真空(7至10psi)至袋,确保与翼面的膜表面的密切接触。一旦从粘合线除去所有的空气,将袋装的样品转移至设定为210°F,3h,以2°F/min升温的烘箱中以固化粘合剂。在粘合剂固化之后,从样品的边缘修整多余的膜。
真空装袋的新程序提供了同时制备多个翼面的途径。我们已经将平坦金属板并入该方案并且使用通气孔材料,我们获得了更好的真空效率。在没有金属板的情况下,真空袋更自由地围绕翼面缠绕,在袋中产生影响翼面的涂层纹理的可能的空隙和折痕,这取决于折痕和褶的位置。
实施例2:
用于增加涂层厚度的方法:第二翼面以与上述类似的方式制备,但是在喷涂过程中加热。这通过使用IR灯来实现,IR灯在被涂布的部件或表面上提供高达55℃。IR灯有助于产生涂布技术的光滑的表面纹理,其否则会显示更多的橘皮、波纹效果。具有光滑表面纹理的期望是改善抵抗雨水和沙子侵蚀的耐久性。通过提供沙子和雨水利用的锚,涂层表面上的粗糙表面纹理或突出加速侵蚀。该技术显示了平坦表面和航空航天相关几何形状二者的改善。IR灯有助于更快地闪蒸出有机溶剂,允许涂层干燥和固化。这允许添加更多的涂层,导致整体更厚的涂层,其具有降低的负面影响,比如由试图逃逸的捕获溶剂引起的空隙。加热还允许涂层流动并在整个表面上平整,产生光滑纹理。
此外,本公开内容包括根据下述条款的实例:
条款1.用于形成含氟聚合物涂布部件的方法,包括:将粘合促进剂施加到部件的表面上;将有机材料施加到粘合促进剂上;和将包括含氟聚合物和选自呋喃或氟化溶剂的溶剂的混合物施加到有机材料上。
条款2.条款1所述的方法,其中施加粘合促进剂包括将粘合促进剂施加到部件的非平坦金属表面上。
条款3.条款2所述的方法,其中施加粘合促进剂包括将粘合促进剂施加到包括铝、镍、钢、镁或钛合金中的一种或多种的金属表面上。
条款4.条款1-3中任一项所述的方法,其中施加粘合促进剂包括施加作为醋酸、四正丙氧化锆和(3-缩水甘油氧基丙基)三甲氧基硅烷的反应产物的粘合促进剂。
条款5.条款4所述的方法,进一步包括在从约30℃至约70℃的温度下固化粘合促进剂。
条款6.条款1-5中任一项所述的方法,其中将有机材料施加到粘合促进剂上包括施加为环氧树脂、聚氨酯或纤维增强塑料中的一种或多种的有机材料。
条款7.条款6所述的方法,其中将有机材料施加到粘合促进剂上包括施加为具有从约0.5mil至约5mil的厚度的层的有机材料,和施加为具有从约0.5mil至约5mil的厚度的层的粘合促进剂。
条款8.条款1-7中任一项所述的方法,其中含氟聚合物选自氟代丙烯酸酯、氟代硅氧烷丙烯酸酯、氟代氨基甲酸乙酯、全氟聚醚、全氟聚氧杂环丁烷、聚偏二氟乙烯和全氟烷氧基烷烃。
条款9.条款8所述的方法,其中溶剂是具有从约40℃至约200℃的沸点的氟化溶剂。
条款10.条款9所述的方法,其中氟化溶剂由式(I)表示:
R1—(CF2)n—R2 (I)
其中n是从约1至约25的整数;R1和R2独立地为-CF3、氢、羟基、羟烷基、氨基烷基、氨基芳基、芳氧基、烷基、芳基、具有从约1至约25个碳的羧酸基团、醛、酮和-CF3(CF2)q(CH2)p,其中q是从约0至约25的整数,和p是从约1至约25的整数。
条款11.条款1-10中任一项所述的方法,其中溶剂是具有从约40℃至约200℃的沸点的呋喃。
条款12.条款11所述的方法,其中呋喃溶剂由式(IIa)或(IIb)表示:
其中R1、R2、R3和R4独立地为氢、羟基、羟烷基、氨基烷基、氨基芳基、芳氧基、烷基、芳基、具有从约1至约25个碳的羧酸基团、醛和酮。
条款13.条款1-12中任一项所述的方法,其中混合物进一步包括选自环氧树脂、聚丙烯酸酯、聚酯、聚醚、氨基甲酸酯和聚硅氧烷的一种或多种的另外聚合物。
条款14.条款1-13中任一项所述的方法,其中混合物在25℃下具有从约0.00046Pa*s至约1Pa*s的粘度。
条款15.条款1-14中任一项所述的方法,其中施加混合物包括在从约12psi至约18psi的压力下将混合物喷涂到有机材料层上。
条款16.条款15所述的方法,其中施加混合物包括喷涂多层混合物以在有机材料上形成具有从约2mil至约20mil的厚度的含氟聚合物层。
条款17.条款16所述的方法,其中含氟聚合物层具有基于层的总体积从约20%至约70%的平均孔隙率。
条款18.条款16或17所述的方法,其中含氟聚合物层具有从每cm3约1011至约1013个空隙的空隙密度。
条款19.条款16-18中任一项所述的方法,其中含氟聚合物层具有小于约1wt%的添加剂含量。
条款20.条款16-19中任一项所述的方法,进一步包括通过喷涂多层包括含氟聚合物和选自呋喃或氟化溶剂的溶剂的第二混合物将第二混合物施加到第一含氟聚合物层上,以形成具有从约2mil至约20mil的厚度的第二含氟聚合物层。
条款21.条款1-20中任一项所述的方法,进一步包括当将混合物施加到有机材料上时,加热金属表面至约45℃至约55℃。
条款22.条款1-21中任一项所述的方法,进一步包括通过将包括含氟聚合物和选自呋喃或氟化溶剂的溶剂的第二混合物施加到聚脂薄膜片材上来形成自支撑膜。
条款23.条款22所述的方法,进一步包括在从约90℃至约150℃的温度下热压制自支撑膜。
条款24.条款23所述的方法,进一步包括将环氧树脂粘合剂施加到自支撑膜或含氟聚合物涂布的金属,并将自支撑膜压制到含氟聚合物涂布的金属或将含氟聚合物涂布的金属压制到自支撑膜以形成压制组件。
条款25.条款24所述的方法,进一步包括将压制组件布置在金属板上,将袋布置在压制组件上,并且在从约1psi至约20psi的压力下施加真空至真空袋。
条款26.条款25所述的方法,进一步包括以从约1°F/分钟至约20°F/分钟的升温速率在从约100°F至约300°F的温度下固化压制组件。
条款27.一种组件,其包括:金属部件;和布置在金属部件上的含氟聚合物层,该含氟聚合物层具有从约5微英寸至约100微英寸的表面粗糙度。
条款28.条款27所述的组件,其中含氟聚合物选自氟代丙烯酸酯、氟代硅氧烷丙烯酸酯、氟代氨基甲酸乙酯、全氟聚醚、全氟聚氧杂环丁烷、聚偏二氟乙烯和全氟烷氧基烷烃。
条款29.条款28所述的组件,其中含氟聚合物层具有小于约1wt%的添加剂含量。
总体上,本公开内容的方法提供在非平坦表面上具有改善的防雨和防沙侵蚀性的光滑防冰涂层。尽管在航空用途的背景下进行了讨论,还考虑本公开内容的方法的其它可能的用途,比如在风力涡轮机叶片上,在非航空航天运输中,和在通信中,包括卫星天线。
定义
术语“非平坦表面”包括具有至少一些曲率的表面。例如,在至少一个方面中,非平坦表面可以具有从约1/16”至约5英尺的曲率半径(比如最小曲率半径)。
术语“烷基”包括包含1至约20个碳原子的取代的或未取代的、直链或支链无环烷基自由基。在至少一个方面中,烷基是C1-10烷基、C1-7烷基或C1-5烷基。烷基的实例包括但不限于甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基和其结构异构体。
术语“环烷基”包括包含1至约20个碳原子的取代的或未取代的、环状烷基自由基。
术语“芳基”指在每个环中具有高达6个原子的任何单环、双环或三环碳环,其中至少一个环是芳族的,或5至14个碳原子的芳环系统,其包括与5-或6-元环烷基基团稠合的碳环芳族基团。芳基的实例包括但不限于苯基、萘基、蒽基或芘基。
术语“烷氧基”是RO--,其中R是本文限定的烷基。术语烷氧基(alkyloxy)、烷氧基(alkoxyl)和烷氧基(alkoxy)可以互换使用。烷氧基的实例包括但不限于甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基、癸氧基和其结构异构体。
术语“杂环基”指在每个环中具有至多10个原子的单环、双环或三环,其中至少一个环是芳族,并且在环中包含选自N、O和S的1至4个杂原子。杂环基的非限制性实例包括但不限于吡啶基、噻吩基、呋喃基、嘧啶基、咪唑基、吡喃基、吡唑基、噻唑基、噻二唑基、异噻唑基、唑基、异唑基、吡咯基、哒嗪基、吡嗪基、喹啉基、异喹啉基、苯并呋喃基、二苯并呋喃基、二苯并苯硫基、苯并噻吩基、吲哚基、苯并噻唑基、苯并唑基、苯并咪唑基、异吲哚基、苯并三唑基、嘌呤基、硫茚基和吡嗪基。杂环基的连接可以经由芳环或通过非芳环或不含杂原子的环发生。
术语“羟基(hydroxy)”和“羟基(hydroxyl)”每个指–OH。
术语“氨基”指包含伯胺、仲胺或叔胺的自由基。氨基自由基的实例是-NH2。氨基自由基可以用R4或R5取代(例如,),其中R4可以是例如氰基、卤酰基、链烯基羰基、羟基链烯基羰基、氨基链烯基羰基、单烷基氨基链烯基羰基、二烷基氨基链烯基羰基、卤链烯基羰基、氰基链烯基羰基、烷氧基羰基链烯基羰基、炔基羰基、羟基炔基羰基、烷基羰基链烯基羰基、环烷基羰基链烯基羰基、芳基羰基链烯基羰基、氨基羰基链烯基羰基、单烷基氨基羰基链烯基羰基、二烷基氨基羰基链烯基羰基或链烯基磺酰基;和R5可以是例如H、烷基或环烷基。
本公开内容的化合物包括化合物的互变异构、几何或立体异构形式。本公开内容还包含化合物的酯、肟、水合物、溶剂化物和N-氧化物形式。本公开内容考虑所有这些化合物,包括顺式和反式几何异构体(Z-和E-几何异构体)、R-和S-对映体、非对映体、d-异构体、l-异构体、阻转异构体、差向异构体、构象异构体、旋转异构体、其异构体和外消旋体的混合物。
已经出于说明的目的呈现了本公开内容的各个方面的描述,但是并不旨在是穷举的或限于公开的方面。在不背离描述的方面的范围和精神的情况下,许多改进和变型对本领域技术人员将是显而易见的。选择本文使用的术语以最好的解释方面的原理、实际应用或相对于市场中发现的技术的技术改进,或使本领域其它普通技术人员理解本文公开的方面。尽管前述涉及本公开内容的方面,可以想到本公开内容的其它和进一方面而不背离其基本范围。
Claims (29)
1.一种用于形成含氟聚合物涂布部件的方法,其包括:
将粘合促进剂施加到部件的表面上;
将有机材料施加到所述粘合促进剂上;和
将包括含氟聚合物和选自呋喃或氟化溶剂的溶剂的混合物施加到所述有机材料上。
2.根据权利要求1所述的方法,其中施加所述粘合促进剂包括将所述粘合促进剂施加到所述部件的非平坦金属表面上。
3.根据权利要求2所述的方法,其中施加所述粘合促进剂包括将所述粘合促进剂施加到包括铝、镍、钢、镁或钛合金中的一种或多种的金属表面上。
4.根据权利要求1所述的方法,其中施加所述粘合促进剂包括施加作为醋酸、四正丙氧化锆和(3-缩水甘油氧基丙基)三甲氧基硅烷的反应产物的粘合促进剂。
5.根据权利要求4所述的方法,进一步包括在从约30℃至约70℃的温度下固化所述粘合促进剂。
6.根据权利要求1所述的方法,其中将有机材料施加到所述粘合促进剂上包括施加为环氧树脂、聚氨酯或纤维增强塑料中的一种或多种的有机材料。
7.根据权利要求6所述的方法,其中将有机材料施加到所述粘合促进剂上包括施加为具有从约0.5mil至约5mil的厚度的层的有机材料,和施加为具有从约0.5mil至约5mil的厚度的层的粘合促进剂。
8.根据权利要求1所述的方法,其中所述含氟聚合物选自氟代丙烯酸酯、氟代硅氧烷丙烯酸酯、氟代氨基甲酸乙酯、全氟聚醚、全氟聚氧杂环丁烷、聚偏二氟乙烯和全氟烷氧基烷烃。
9.根据权利要求8所述的方法,其中所述溶剂是具有从约40℃至约200℃的沸点的氟化溶剂。
10.根据权利要求9所述的方法,其中所述氟化溶剂由式(I)表示:
R1—(CF2)n—R2 (I)
其中n是从约1至约25的整数;R1和R2独立地为-CF3、氢、羟基、羟烷基、氨基烷基、氨基芳基、芳氧基、烷基、芳基、具有从约1至约25个碳的羧酸基团、醛、酮和-CF3(CF2)q(CH2)p,其中q是从约0至约25的整数,和p是从约1至约25的整数。
11.根据权利要求1所述的方法,其中所述溶剂是具有从约40℃至约200℃的沸点的呋喃。
12.根据权利要求11所述的方法,其中所述呋喃溶剂由式(IIa)或(IIb)表示:
其中R1、R2、R3和R4独立地为氢、羟基、羟烷基、氨基烷基、氨基芳基、芳氧基、烷基、芳基、具有从约1至约25个碳的羧酸基团、醛和酮。
13.根据权利要求1所述的方法,其中所述混合物进一步包括选自环氧树脂、聚丙烯酸酯、聚酯、聚醚、氨基甲酸酯和聚硅氧烷的一种或多种另外的聚合物。
14.根据权利要求1所述的方法,其中所述混合物在25℃下具有从约0.00046Pa*s至约1Pa*s的粘度。
15.根据权利要求1所述的方法,其中施加所述混合物包括在从约12psi至约18psi的压力下将所述混合物喷涂到所述有机材料层上。
16.根据权利要求15所述的方法,其中施加所述混合物包括喷涂多层混合物以在所述有机材料上形成具有从约2mil至约20mil的厚度的含氟聚合物层。
17.根据权利要求16所述的方法,其中所述含氟聚合物层具有基于层的总体积从约20%至约70%的平均孔隙率。
18.根据权利要求16所述的方法,其中所述含氟聚合物层具有从每cm3约1011至约1013个空隙的空隙密度。
19.根据权利要求16所述的方法,其中所述含氟聚合物层具有小于约1wt%的添加剂含量。
20.根据权利要求16所述的方法,进一步包括通过喷涂多层包括含氟聚合物和选自呋喃或氟化溶剂的溶剂的第二混合物,将第二混合物施加到第一含氟聚合物层上,以形成具有从约2mil至约20mil的厚度的第二含氟聚合物层。
21.根据权利要求1所述的方法,进一步包括当将所述混合物施加到所述有机材料上时,将金属表面加热到约45℃至约55℃。
22.根据权利要求1所述的方法,进一步包括通过将包括含氟聚合物和选自呋喃或氟化溶剂的溶剂的第二混合物施加到聚脂薄膜片材上来形成自支撑膜。
23.根据权利要求22所述的方法,进一步包括在从约90℃至约150℃的温度下热压制所述自支撑膜。
24.根据权利要求23所述的方法,进一步包括将环氧树脂粘合剂施加到所述自支撑膜或所述含氟聚合物涂布金属,并且将所述自支撑膜压制到所述含氟聚合物涂布金属或将所述含氟聚合物涂布金属压制到所述自支撑膜以形成压制组件。
25.根据权利要求24所述的方法,进一步包括将所述压制组件布置在金属板上,将袋布置在所述压制组件上,并且在从约1psi至约20psi的压力下施加真空至所述真空袋。
26.根据权利要求25所述的方法,进一步包括以从约1°F/分钟至约20°F/分钟的升温速率在从约100°F至约300°F的温度下固化所述压制组件。
27.一种组件,其包括:
金属部件;和
布置在所述金属部件上具有从约5微英寸至约100微英寸的表面粗糙度的含氟聚合物层。
28.根据权利要求27所述的组件,其中所述含氟聚合物选自氟代丙烯酸酯、氟代硅氧烷丙烯酸酯、氟代氨基甲酸乙酯、全氟聚醚、全氟聚氧杂环丁烷、聚偏二氟乙烯和全氟烷氧基烷烃。
29.根据权利要求28所述的组件,其中所述含氟聚合物层具有小于约1wt%的添加剂含量。
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US11712716B2 (en) | 2023-08-01 |
JP2019108522A (ja) | 2019-07-04 |
JP7320344B2 (ja) | 2023-08-03 |
AU2018253510A1 (en) | 2019-05-09 |
EP3485987A3 (en) | 2019-08-21 |
KR102599253B1 (ko) | 2023-11-06 |
EP3485987A2 (en) | 2019-05-22 |
US20210008593A1 (en) | 2021-01-14 |
KR20190045828A (ko) | 2019-05-03 |
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US20190118221A1 (en) | 2019-04-25 |
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