CN107810047B - 具有宏观纹理化表面的非对称聚四氟乙烯复合物及其制造方法 - Google Patents

具有宏观纹理化表面的非对称聚四氟乙烯复合物及其制造方法 Download PDF

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CN107810047B
CN107810047B CN201680035970.2A CN201680035970A CN107810047B CN 107810047 B CN107810047 B CN 107810047B CN 201680035970 A CN201680035970 A CN 201680035970A CN 107810047 B CN107810047 B CN 107810047B
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ptfe
composite article
ptfe membrane
membrane
strands
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CN107810047A (zh
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D·L·霍伦博格
B·海勒
G·V·巴拉吉
R·巴克斯鲍姆
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WL Gore and Associates GmbH
WL Gore and Associates Inc
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WL Gore and Associates GmbH
WL Gore and Associates Inc
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Abstract

具有宏观纹理化表面的聚四氟乙烯(PTFE)复合制品。复合制品包括层状或堆叠构造的至少两种不同PTFE膜。复合制品具有由从PTFE膜表面隆起的多根股线的宏观纹理化表面。所述股线要么可以由相互连接的PTFE节点形成、要么可以由至少一个PTFE节点团形成，并且具有等于或大于约1.5mm的长度。宏观纹理化表面为第一PTFE膜提供了形貌。复合制品的泡点为约3.0psi至约200psi，厚度为约0.01至约3.0mm，并且体积密度为约0.01g/cm3至约1.0g/cm3。

Description

具有宏观纹理化表面的非对称聚四氟乙烯复合物及其制造 方法
技术领域
本发明大体涉及聚四氟乙烯(PTFE)膜，更具体地涉及具有宏观纹理化表面的聚四氟乙烯复合制品。还公开了用于制造该复合制品的方法。
背景技术
制造膨胀型PTFE(ePTFE)层的常规方法描述于Gore的美国专利号3,953,566。在该文所述方法中，PTFE浆料通过混合PTFE树脂和润滑剂形成。可以将PTFE浆料挤出。在从挤出的浆料中去除润滑剂之后，对PTFE制品进行拉伸以产生多孔、高强度PTFE制品。膨胀型PTFE层的特征在于具有通过原纤维相互连接的节点的多孔开放微结构。
具有各种节点和原纤维微结构的ePTFE制品是本领域已知的。部分该制品描述于美国专利号4,902,423、US 5,814,405、US 5,476,589、US 6,342,294。
美国专利号6,780,497描述了将激光用于对ePTFE结构进行表面修改以产生能够彻底保持微孔的宏观粗糙化表面。该工艺产生了包括粗糙节点的结构。
需要改进ePTFE表面而不使用该额外工艺且仍能够产生图案化ePTFE表面。
发明内容
本发明的一个实施方式涉及复合制品，其包括：(1)具有第一表面和第二表面的第一聚四氟乙烯(PTFE)膜；以及(2)位于第一膜的第二表面上的第二PTFE膜，其中，第一PTFE膜的第一表面包括从所述第一表面隆起的多根股线。至少一根股线的长度大于约1.5mm。所述股线包括相互连接的PTFE节点。复合制品的体积密度为约0.01g/cm3至约1.0g/cm3，泡点为约3.0psi至约200psi，并且厚度为约0.01mm至约3.0mm。在至少一个实施方式中，所述股线是非线性的，并且在第一PTFE膜的第一表面上形成可视图案。在至少一个示例性实施方式中，第二PTFE膜的基质拉伸强度在x方向和y方向上比第一PTFE膜的基质拉伸强度大至少1.5倍。复合制品具有可以被光学观察到的宏观纹理化表面，并且所述宏观纹理化表面为第一PTFE膜提供了形貌。
本发明的第二实施方式涉及复合制品，其包括：(1)具有第一表面和第二表面的第一聚四氟乙烯(PTFE)膜；以及(2)位于第一膜的第二表面上的第二PTFE膜，其中，第一PTFE膜的第一表面包括从所述第一表面隆起的多根股线。至少一根股线的长度大于约1.5mm。所述股线包括至少一个PTFE节点团(nodal mass)。复合制品的体积密度为约0.01g/cm3至约1.0g/cm3，泡点为约3.0psi至约200psi，并且厚度为约0.01mm至约3.0mm。在至少一个实施方式中，所述股线是非线性的，并且在第一PTFE膜的第一表面上形成可视图案。在至少一个示例性实施方式中，第二PTFE膜的基质拉伸强度在x方向和y方向上比第一PTFE膜的基质拉伸强度大至少1.5倍。复合制品具有可以被光学观察到的宏观纹理化表面，并且所述宏观纹理化表面为第一PTFE膜提供了形貌。
本发明的第三实施方式涉及通过包括如下步骤的工艺生产的复合制品：(1)获得具有第一表面和第二表面的第一PTFE膜；(2)获得基质拉伸强度大于第一PTFE膜基质拉伸强度的第二PTFE膜；(3)将所述第二PTFE膜放置在所述第一膜的所述第二表面上，以形成层状产品；(4)以约0.5％/秒至约300％/秒的工程应变速率以及约10％至约350％的拉伸比使得所述层状产品沿y方向膨胀，以形成经膨胀的产品；以及(4)以约3％至约600％的工程应变速率以及约0％至约2000％的拉伸比使得所述经膨胀的产品沿x方向膨胀，以形成复合制品。所述复合制品的第一表面包括从第一表面隆起的多根股线。至少一根股线的长度等于大于约1.5mm。复合制品的第一表面对应于第一PTFE膜的第一表面。在另一步骤中，复合制品可以进行烧结。粘合剂可以施加到第一PTFE膜和所述第二PTFE膜中的一个上以将第一PTFE膜粘合到第二PTFE膜。
附图简要说明
采用附图以帮助进一步理解本公开内容，其纳入说明书中并构成说明书的一部分，附图显示了本公开内容的实施方式，与说明书一起用来解释本公开内容的原理。
图1是根据本发明一实施方式的实施例1的复合制品中第一PTFE膜表面的以7倍放大拍摄的光学显微镜图像；
图2是根据本发明一实施方式的实施例1的复合制品中第一PTFE膜表面以32倍放大拍摄的光学显微镜图像；
图2A是根据本发明至少一个实施方式的实施例1的复合制品中第一PTFE膜表面的100倍扫描电子显微照片；
图3是根据本发明一实施方式的实施例2的复合制品中第一PTFE膜表面以7倍放大拍摄的光学显微镜图像；
图4是根据本发明一实施方式的实施例2的复合制品中第一PTFE膜表面以32倍放大拍摄的光学显微镜图像；
图4A是根据本发明至少一个实施方式的实施例2的复合制品中第一PTFE膜表面以100倍放大拍摄的扫描电子显微照片；
图5是根据本发明一实施方式的实施例3的复合制品中第一PTFE膜表面以7倍放大拍摄的光学显微镜图像；
图6是根据本发明一实施方式的实施例3的复合制品中第一PTFE膜表面以32倍放大拍摄的光学显微镜图像；
图6A是根据本发明至少一个实施方式的实施例3的复合制品中第一PTFE膜表面以100倍放大拍摄的扫描电子显微照片；
图7是根据本发明一实施方式的实施例4的复合制品中第一PTFE膜表面以7倍放大拍摄的光学显微镜图像；
图8是根据本发明一实施方式的实施例4的复合制品中的第一PTFE膜的表面的32倍光学显微镜图像；
图8A是根据本发明至少一个实施方式的实施例4的复合制品中第一PTFE膜表面以100倍放大拍摄的扫描电子显微照片；
图9是根据本发明一实施方式的实施例5的复合制品中第一PTFE膜表面以7倍放大拍摄的光学显微镜图像；
图10是根据本发明一实施方式的实施例5的复合制品中第一PTFE膜表面以32倍放大拍摄的光学显微镜图像；
图10A是根据本发明至少一个实施方式的实施例5的复合制品中第一PTFE膜表面以100倍放大拍摄的扫描电子显微照片；
图11是根据本发明一实施方式的实施例6的复合制品中第一PTFE膜表面以7倍放大拍摄的光学显微镜图像；
图12是根据本发明一实施方式的实施例6的复合制品中第一PTFE膜表面以32倍放大拍摄的光学显微镜图像；
图12A是根据本发明至少一个实施方式的实施例6的复合制品中第一PTFE膜表面以100倍放大拍摄的扫描电子显微照片；
图13是根据本发明一实施方式的实施例7的复合制品中第一PTFE膜表面以7倍放大拍摄的光学显微镜图像；
图14是根据本发明一实施方式的实施例7的复合制品中第一PTFE膜表面以32倍放大拍摄的光学显微镜图像；
图14A是根据本发明至少一个实施方式的实施例7的复合制品中第一PTFE膜表面以100倍放大拍摄的扫描电子显微照片；
图15是根据本发明一实施方式的实施例8的复合制品中第一PTFE膜表面以7倍放大拍摄的光学显微镜图像；
图16是根据本发明一实施方式的实施例8的复合制品中第一PTFE膜表面以32倍放大拍摄的光学显微镜图像；
图16A是根据本发明至少一个实施方式的实施例8的复合制品中第一PTFE膜表面以100倍放大拍摄的扫描电子显微照片；以及
图16B是根据本发明至少一个实施方式的实施例8的复合制品中第一PTFE膜表面以2500倍放大拍摄的扫描电子显微照片。
术语表
如本文中所用，术语“可被光学观察到”意在表示物体可以使用光学显微镜和/或用肉眼进行观察。
如本文所用，术语“在……上”意在表示一个元件(例如聚四氟乙烯(PTFE)膜)直接在另一元件上，或者还可存在居间的元件。
如本文所用，术语“双轴”意在描述在至少两个方向上，要么同时膨胀要么依续膨胀的聚合物、膜、预制件、或制品。
如本文所用，术语“润滑剂”意在描述包括不可压缩流体的加工助剂、在一些实施方式中，描述由不可压缩流体组成的加工助剂，所述不可压缩流体不是加工条件下聚合物的溶剂。流体-聚合物表面相互作用使得能够产生均匀混合物。
如本文所用，术语“湿润状态”意在描述并未进行干燥以去除润滑剂的PTFE膜。
如本文所用，术语“干燥状态”意在描述并已进行干燥以去除润滑剂的PTFE膜。
本文中所用的“细粉末PTFE”意在表示PTFE树脂通过水性分散聚合技术进行制备。
如本文所用，术语“x方向”和“y方向”意在分别表示横向方向和纵向方向。
具体实施方式
本领域的技术人员应理解，可通过构造以实施所需作用的任何数量的方法和设备来实现本公开内容的各个方面。还应注意，本文参考的附图不一定是按比例绘制，而是有可能放大以说明本公开的各个方面，就此而言，附图不应视为限制性的。
本发明大体涉及具有可以被光学观察到的宏观纹理化表面的聚四氟乙烯复合制品。复合制品包括层状或堆叠构造的至少两种不同PTFE膜，各PTFE膜具有通过原纤维相互连接的节点微结构。复合制品中的第一PTFE膜具有比复合制品中第二PTFE膜更“开放”的微结构。复合制品的泡点为约3.0psi至约200psi，厚度为约0.01至约3.0mm，并且体积密度为小于约1.0g/cm3。
如上述所讨论的，复合制品可以由至少两种PTFE膜形成，所述至少两种PTFE膜可以由相同或不同PTFE原材料形成。此外，第一和第二PTFE膜微结构彼此不同。第一PTFE膜的微结构与第二PTFE膜的微结构之间的差异以及因此造成的复合制品的不对称性可能由以下原因造成，例如，孔径差异、节点和/或原纤维几何形状或尺寸的差异、以及/或者密度差异。尽管所采用的复合制品内实现不同微结构的机制，第一PTFE膜具有比第二PTFE层的微结构更“开放”的微结构。本文所用的与“紧闭”相反的术语“开放”表示第一“开放”的微结构的孔径比第二“紧闭”的微结构的孔径大，如泡点或表征孔径的任意合适的方式所示。
用于形成第一和第二PTFE膜的PTFE原材料可以是导致其本身在膨胀时形成原纤维和节点的任意类型的PTFE树脂。在一示例性实施方式中，PTFE原材料可以是PTFE均聚物或PTFE均聚物的掺混物。在另一实施方式中，PTFE原材料可以是PTFE均聚物和PTFE共聚物的掺混物，其中共聚单体单元不会导致共聚物失去纯均聚物PTFE的非可熔融加工特性。PTFE共聚物中的合适共聚单体的示例包括但不限于：烯烃，例如乙烯和丙烯；卤代烯烃，如六氟丙烯(HFP)、偏二氟乙烯(VDF)和氯氟乙烯(CFE)；全氟烷基乙烯基醚(PPVE)和全氟磺酰基乙烯基醚(PSVE)。在另一实施方式中，第一和/或第二PTFE膜可以由高分子量PTFE均聚物和较低分子量的改性PTFE聚合物的掺混物形成。
对第一和第二PTFE原材料进行选择，以使得当与所选加工条件结合时，所获得的第一PTFE膜具有低于第二PTFE膜的基质拉伸强度。在至少一个示例性实施方式中，第二PTFE膜的基质拉伸强度在x方向和y方向上比第一PTFE膜的基质拉伸强度大至少1.5倍。
第一PTFE膜可以通过将合适的第一PTFE原材料与润滑剂混合来形成。本文所用润滑剂的非限制性示例包括轻质矿物油、脂族烃、芳族烃、和卤代烃。所获得的PTFE树脂和润滑剂混合物可以形成为圆柱形颗粒，并以约10:1至约150:1、或约25:1至约90:1的缩小比通过模头挤出以形成带状物。然后可以将带状物在辊之间以约1.1:1至约50:1、或约1.1:1至约20:1的压延比压延为所需厚度，以形成第一PTFE膜。
在至少一个实施方式中，使得第一PTFE膜形成而无需干燥步骤，并且在湿润状态下与第二PTFE膜层叠。然而，与第二PTFE膜层叠之前对带状物(预压延)或第一PTFE膜(后压延)进行干燥的做法也在本发明的范围内。
请注意，尽管在本文中为了便于讨论参考第一和第二PTFE膜，但是在复合制品中可以包括更多数量的PTFE膜。此外，在复合制品中的PTFE膜可以源自相同的PTFE原材料、不同的PTFE原材料、或者PTFE原材料的组合。同样，复合制品中的部分或全部PTFE膜彼此可以在组成、泡点、厚度、空气渗透率、质量/面积等发生变化。
第二PTFE膜可以通过将合适的第二PTFE原材料与润滑剂混合来形成。本文所用润滑剂的非限制性示例包括轻质矿物油、脂族烃、芳族烃、和卤代烃。所获得的混合物可以形成为圆柱形颗粒，并以约10:1至约150:1、或约50:1至约120:1的缩小比通过模头柱塞挤出以形成带状物。然后可以将带状物在辊之间以约1.1至约20:1、或约1.1:至约10:1的压延比压延为所需厚度。然后，经压延的带状物可在一个或多个方向上膨胀，并进行干燥以去除润滑剂。例如，经压延的带状物可以1.1:1至约20:1、或约1.1:1至约6:1的膨胀比沿纵向方向和/或横向方向膨胀。所获得的第二PTFE膜具有节点及原纤维微结构。优选使得第二PTFE膜形成而无需对带状物和/或膜进行干燥，并且可以在湿润状态下与第一PTFE膜层叠。
在形成复合制品时，第一PTFE膜和第二PTFE膜层叠或以堆叠构造一层层放置以形成层状产品。第一和第二PTFE膜可以堆叠构造进行放置，例如，通过将膜简单放置在彼此顶部。采用两种共挤出的PTFE原材料以生产层状产品的实施方式也可以被认为在本发明的范围内。然后，将层状产品缩小至所需厚度，例如，通过压延或将层状产品放置在压制机中进行。所述层状产品的厚度范围可以为约0.01mm至约3.0mm、约0.01mm至约2mm、约0.03mm至约1.0mm、约0.05mm至约0.7mm、或约0.1mm至约0.5mm。任选地，层状产品可以进行加热以去除所存在的任意润滑剂。层状产品进行双轴拉伸，并且任选地在高于PTFE结晶熔融温度的温度处进行烧结以形成复合制品。
层状产品可以沿x方向和y方向拉伸，要么同时拉伸要么依续拉伸。例如，层状产品可以约0.5％/秒至约300％/秒、或约0.5％/秒至约150％/秒的平均工程应变速率和约10％至约350％、或约10％至约300％的拉伸量沿y方向进行拉伸，随后，以约3％至约600％、或约10％至约400％平均工程应变率和约0％至约2000％、或约1.0％至约1600％的拉伸量沿x方向进行拉伸；或者反过来(例如，首先沿x方向拉伸，然后沿y方向拉伸)。在至少一个实施方式中，层状产品以约10％/秒至约500％/秒、或约20％/秒至约250％/秒的平均工程应变速率以及约10％至约2000％的拉伸量同时沿x方向和y方向拉伸。
所获得的复合制品具有独特的宏观纹理化表面，其特征为由相互连接的PTFE节点形成的股线、或者由至少一个PTFE节点团形成的股线。股线的长度等于或大于约1.5mm，并且从膜表面隆起。此外，股线可以在视觉上观察到，并且在光学显微镜图像中容易识别。参见作为示例性实施方式的图7和图8，股线易于在第一PTFE膜表面的7倍和32倍放大下看到。相互连接的节点可以使用扫描电子显微镜进行单独观察。图7中所示的第一PTFE膜的表面以100倍下拍摄的扫描电子显微照片清楚地显示了形成股线的单独节点。各节点是固体或基本呈固体的PTFE团，并且在第一PTFE膜的形成和随后的膨胀期间排列或组合在一起，以在膜的表面上形成一根或多根股线。应理解，在单独节点之间可能存在节点的残余物。
在另一示例性实施方式中，例如如图13中所示，股线同样在第一PTFE膜表面上视觉上可观察到，并且用光学显微镜图像可识别。股线同样从第一PTFE膜表面隆起。然而，通常不存在单独节点，并且一个或多个PTFE节点团形成了股线。
当进行光学观察(例如用光学显微镜(例如放大7倍或32倍))时，在沿着股线在任意两点处进行测定的情况下，相互连接的节点的股线和/或包含一个或多个PTFE节点团的股线中的至少一种股线的长度等于或大于约1.5mm、2.0mm、3.0mm或4.0mm。在示例性实施方式中，当进行光学观察(例如用光学显微镜(例如放大7倍或32倍))时，在沿着股线在任意两点处进行测定的情况下，部分或全部股线的长度等于或大于约1.5mm、2.0mm、3.0mm或4.0mm。股线形成第一PTFE膜上可视图案，并且可以用肉眼和/或光学显微镜进行观察。线股可以彼此大致平行的构造沿y方向在第一PTFE膜中延伸。此外，股线通常是非线性的，并且可以大体曲线的方式延伸。此外，单独股线可以在一股线或多股线上的一个或多个点处相互交叉或横穿。
复合制品的泡点为约3.0psi至约200psi、约5psi至约100psi、约10psi至约85psi、或约15psi至约80psi；厚度为约0.01mm至约3.0mm、约0.3mm至约1.5mm、或约0.05mm至约0.7mm；并且体积密度为约0.01g/cm3至约1.0g/cm3、约0.01g/cm3至约0.5g/cm3、或约0.05g/cm3至约0.25g/cm3。此外，复合制品的质量/面积高达约3000g/m2。在示例性实施方式中，复合制品的质量/面积为约0.5g/m2至约750g/m2、约0.5g/m2至约450g/m2、约5.0g/m2至约150g/m2、或约10g/m2至约100g/m2；并且格利值为约0.01秒至约1000秒、或约1秒至约100秒。在一个或多个实施方式中，复合制品是片材、带状物或管。宏观纹理化表面为第一PTFE膜提供了形貌。
任选的支撑层可以位于第一和第二PTFE膜之间或与第一和/或第二PTFE膜相邻。合适的支撑层的非限制性示例包括聚合物编织材料、无纺材料、针织物、网状物和/或多孔膜。此外，第一和第二PTFE膜可以用热塑性树脂或其它粘合剂、连续地或者不连续地彼此粘附、或者粘附到另一膜或支撑结构上，例如，所用粘合剂包括氟化乙烯丙烯(FEP)、全氟烷氧基聚合物树脂(PFA)、以及四氟乙烯六氟丙烯和偏二氟乙烯(THV)、和/或聚偏二氟乙烯(PVDF)。
上文已经中概括性地并且结合具体实施方式描述本申请的发明。对本领域的技术人员来说显而易见的是，可以在不偏离本发明的精神和范围的情况下，对本文所述的实施方式进行各种修改和变动。因此，实施方式旨在覆盖对本发明的这些修改和变动，只要这些修改和变动在所附权利要求及其等同方案的范围之内。
测试方法
应理解，虽然下文描述了某些方法和设备，但也可选择性地采用本领域普通技术人员确定适用的其它方法或设备。
厚度
通过将膜放置在Mitutoyo Tektronix卡规(部件编号：547-400S)的两个板之间来测定膜厚度。
单位面积质量(质量/面积)
膜的质量/面积是通过使用标尺测量样品明确限定面积的质量来计算的。使用模具或任何精确切割仪器将样品切割至限定面积。
密度
密度通过单位面积质量除以厚度进行计算。
格利(Gurley)空气流量
格利(Gurley)空气流量测试测量在12.4厘米水压下100厘米3空气流通过6.45cm2样品的时间(以秒计)。样品在格利密度计型号4340自动密度计(Gurley Densometer Model4340Automatic Densometer)中测量。
泡点
使用毛细管流动气孔计(型号3Gzh，购自Quantachrome Instrument公司)，根据ASTM F316 6-03的一般教导来测定泡点。样品架包括直径25.4mm的多孔金属片(部件编号：04150-10030-25，Quantachrome Instrument公司)、以及直径20mm内径(I.D.)x 24.5mm外径(O.D.)的塑料罩(plastic mask)(部件编号：ABF-300，Professional Plastics公司)。将样品置于金属片和塑料罩之间。然后，夹紧样品(clamped down)并使用O环密封(部件编号：51000-25002000，Quantachrome Instrument公司)。样品用测试流体(表面张力为20.1达因/cm的硅酮流体)润湿。使用3GWin软件2.1版本，将按照表I和表II所示设定以下参数。
表1
Figure BDA0001514447370000101
表2
Figure BDA0001514447370000102
Figure BDA0001514447370000111
光学显微图片
使用奥林巴斯(Olympus)SZX12显微镜以7倍和32倍的放大倍数产生光学显微图像。
SEM样品制备方法
使用高分辨率场致发射低温显微镜(日立(Hitachi)S4700FE-SEM)产生SEM图像。
实施例
实施例1
第一聚四氟乙烯(PTFE)膜按照如下进行制备。高分子量聚四氟乙烯细粉末和较低分子量改性聚四氟乙烯聚合物的掺混物根据授予Branca等人的美国专利第5,814,405号的启示进行制备，然后与0.244lb/lb的润滑剂(IsoparTMK，德克萨斯州休斯顿的埃克森公司(Exxon))结合。所获得的混合物随后进行混合，并压制为圆柱形颗粒，并且在25℃温度下热调节18小时。随后圆柱形颗粒以47:1的缩小比通过矩形孔模头挤出，以形成带状物。随后，带状物以14.39:1的压延比在辊之间进行压延，以形成第一PTFE膜。
第二PTFE膜按照如下方式进行制备：根据授予Malhotra等人的美国专利第4,576,869号的启示所制备的聚四氟乙烯聚合物细粉末与0.21lb/lb的润滑剂(IsoparTMK，德克萨斯州休斯顿的埃克森公司(Exxon))结合。所获得的混合物随后进行混合，并压制为圆柱形颗粒，并且在49℃温度下热调节8小时。随后圆柱形颗粒以81:1的缩小比通过矩形孔模头挤出，以形成带状物。随后，带状物以3:1的压延比在辊之间进行压延。经压延的带状物随后以3.6:1的比例横向拉伸，并随后在220℃温度下进行干燥。所获得的第二PTFE膜的宽度进行修整以与第一PTFE膜的宽度匹配，从而促进下文所述的层叠(layering)工艺。
第一PTFE膜层叠在第二PTFE膜上，并且将层状产品在辊之间进行压延，并且使得厚度减小36.4％。所获得的层状层叠体在250℃的温度下进行干燥以去除润滑剂。然后，经干燥的层叠体在300℃下以2.26％/秒的平均工程应变速率和等于60％的拉伸量沿y方向膨胀。随后，所获得的材料在约330℃温度下以19％/秒的平均工程应变速率和等于761％的拉伸量沿x方向膨胀。然后，材料在360℃下烧结不超过60秒。
如上所述，所获得的复合制品具有分别是第一PTFE膜和第二PTFE膜代表的第一表面和第二表面。图1中显示了以7倍放大拍摄的复合制品第一表面的光学显微镜图像。图2中显示了以32倍放大拍摄的复合制品第一表面的光学显微镜图像。图1和图2显示出在复合制品第一表面(即，第一PTFE膜)上形成可视图案的相互连接的节点的股线。图2A是复合制品中第一PTFE膜表面以100倍放大拍摄的扫描电子显微照片(SEM)，显示出形成股线的相互连接的节点。
复合制品的体积密度为0.24g/cc。泡点使用运行设定BP_9-50psi进行测定。运行两个测试条件。在第一测试中，复合制品的PTFE膜面对金属板。在第二测试中，复合制品的第二PTFE膜面对金属板。泡点分别测定为19.89psi和18.91。
实施例2
第一聚四氟乙烯(PTFE)膜按照如下进行制备。高分子量聚四氟乙烯细粉末和较低分子量改性聚四氟乙烯聚合物的掺混物根据授予Branca等人的美国专利第5,814,405号的启示进行制备，然后与0.244lb/lb的润滑剂(IsoparTMK，德克萨斯州休斯顿的埃克森公司(Exxon))结合。所获得的混合物随后进行混合，并压制为圆柱形颗粒，并且在25℃温度下热调节18小时。随后圆柱形颗粒以47:1的缩小比通过矩形孔模头挤出，以形成带状物。随后，带状物以2.97:1的压延比在辊之间进行压延，以形成第一PTFE膜。
第二PTFE膜按照如下进行制备。根据授予Malhotra等人的美国专利第4,576,869号的启示所制备的聚四氟乙烯聚合物细粉末与0.21lb/lb的润滑剂(IsoparTMK，德克萨斯州休斯顿的埃克森公司(Exxon))结合。所获得的混合物随后进行混合，并压制为圆柱形颗粒，并且在49℃温度下热调节8小时。随后圆柱形颗粒以84:1的缩小比通过模头挤出，以形成带状物。随后，带状物以3:1的压延比在辊之间进行压延。经压延的带状物随后以3.6:1的比例横向拉伸，并随后在220℃温度下进行干燥。所获得的第二PTFE膜的宽度进行修整以与第一PTFE膜的宽度匹配，从而促进下文所述的层叠(layering)工艺。
第一PTFE膜层叠在第二PTFE膜上，并且将层状产品在辊之间进行压延，并且使得厚度减小3.5％。所获得的层状层叠体在250℃的温度下进行干燥以去除润滑剂。然后，经干燥的层叠体在300℃下以2.26％/秒的平均工程应变速率和等于60％的拉伸量沿y方向膨胀。随后，所获得的材料在约300℃的温度下以19.33％/秒的平均工程应变速率和等于761％的拉伸量沿x方向膨胀。然后，材料在390℃下烧结不超过60秒。
如上所述，所获得的复合制品具有分别是第一PTFE膜和第二PTFE膜代表的第一表面和第二表面。图3中显示了以7倍放大拍摄的复合制品第一表面的光学显微镜图像。图4中显示了以32倍放大拍摄的复合制品第一表面的光学显微镜图像。图3和图4显示出在复合制品第一表面(即，第一PTFE膜)上形成可视图案的相互连接的节点的股线。图4A是复合制品中第一PTFE膜表面以100倍放大拍摄的扫描电子显微照片(SEM)，显示出形成股线的相互连接的节点。
复合制品的体积密度为0.14g/cc。泡点使用运行设定BP_9-50psi进行测定。运行两个测试条件。在第一测试中，复合制品的第一PTFE膜面对金属板。在第二测试中，复合制品的第二PTFE膜面对金属板。泡点分别测定为21.03psi和23.97psi。
实施例3
第一聚四氟乙烯(PTFE)膜按照如下进行制备。高分子量聚四氟乙烯细粉末和较低分子量改性聚四氟乙烯聚合物的掺混物根据授予Branca等人的美国专利第5,814,405号的启示进行制备，然后与0.244lb/lb的润滑剂(IsoparTMK，德克萨斯州休斯顿的埃克森公司(Exxon))结合。所获得的混合物随后进行混合，并压制为圆柱形颗粒，并且在25℃温度下热调节18小时。随后圆柱形颗粒通过矩形孔挤出，以形成带状物。随后，带状物以3.74:1的压延比在辊之间进行压延，以形成第一PTFE膜。
第二PTFE膜按照如下进行制备。根据授予Malhotra等人的美国专利第4,576,869号的启示所制备的聚四氟乙烯聚合物细粉末与0.21lb/lb的润滑剂(IsoparTMK，德克萨斯州休斯顿的埃克森公司(Exxon))结合。所获得的混合物随后进行混合，并压制为圆柱形颗粒，并且在49℃温度下热调节8小时。随后圆柱形颗粒以84:1的缩小比通过模头挤出，以形成带状物。随后，带状物以3:1的压延比在辊之间进行压延。经压延的带状物随后以3.6:1的比例横向拉伸，并随后在220℃温度下进行干燥。所获得的第二PTFE膜的宽度进行修整以与第一PTFE膜的宽度匹配，从而促进下文所述的层叠(layering)工艺。
第一PTFE膜分层堆积在第二PTFE膜上，并且层状产品厚度减小20.1％。然后，所获得的层状层叠体在250℃的温度下进行干燥以去除润滑剂。然后，经干燥的层叠体在300℃下以3.33％/秒的平均工程应变速率和等于85％的拉伸量沿y方向膨胀。随后，所获得的材料在约300℃的温度下以19.33％/秒的平均工程应变速率和等于761％的拉伸量沿x方向膨胀。然后，材料在390℃下烧结不超过60秒。
如上所述，所获得的复合制品具有分别是第一PTFE膜和第二PTFE膜代表的第一表面和第二表面。图5中显示了以7倍放大拍摄的复合制品第一表面的光学显微镜图像。图6中显示了以32倍放大拍摄的复合制品第一表面的光学显微镜图像。图5和图6显示出在复合制品第一表面(即，第一PTFE膜)上形成可视图案的相互连接的节点的股线。图6A是复合制品中第一PTFE膜表面以100倍放大拍摄的扫描电子显微照片(SEM)，显示出形成股线的相互连接的节点。
复合制品的体积密度为0.15g/cc。泡点使用运行设定BP_9-50psi进行测定。运行两个测试条件。在第一测试中，复合制品的第一PTFE膜面对金属板。在第二测试中，复合制品的第二PTFE膜面对金属板。泡点分别测定为35.05psi和45.16。
实施例4
第一聚四氟乙烯(PTFE)膜按照如下进行制备。高分子量聚四氟乙烯细粉末和较低分子量改性聚四氟乙烯聚合物的掺混物根据授予Branca等人的美国专利第5,814,405号的启示进行制备，然后与0.259lb/lb的润滑剂(IsoparTMK，德克萨斯州休斯顿的埃克森公司(Exxon))结合。所获得的混合物随后进行混合，并压制为圆柱形颗粒，并且在25℃温度下热调节18小时。随后圆柱形颗粒以47:1的缩小比通过矩形孔模头挤出，以形成带状物。随后，带状物以15.9:1的压延比在辊之间进行压延，以形成第一PTFE膜。
第二PTFE膜按照如下进行制备。根据授予Ballie的美国专利第6,541,589号的启示所制备的聚四氟乙烯聚合物细粉末与0.185lb/lb的润滑剂(IsoparTMK，德克萨斯州休斯顿的埃克森公司(Exxon))结合。所获得的混合物随后进行混合，并压制为圆柱形颗粒，并且在49℃温度下热调节8小时。随后圆柱形颗粒以87:1的缩小比通过矩形孔模头挤出，以形成带状物。随后，带状物以3.9:1的压延比在辊之间进行压延。经压延的带状物随后以2.8:1的比例横向拉伸，并随后在210℃温度下进行干燥。所获得的第二PTFE膜的宽度进行修整以与第一PTFE膜的宽度匹配，从而促进下文所述的层叠(layering)工艺。
第一PTFE膜层叠在第二PTFE膜上，并且层状产品厚度减小33.3％。然后，所获得的层状层叠体在210℃的温度下进行干燥以去除润滑剂。然后，经干燥的层叠体在300℃下以3.7％/秒的平均工程应变速率和等于300％的拉伸量在加热的滚筒之间沿y方向膨胀。随后，所获得的材料在约300℃的温度下以3.66％/秒的平均工程应变速率和等于162％的拉伸量沿x方向膨胀。然后，材料在390℃下烧结不超过60秒。
如上所述，所获得的复合制品具有分别是第一PTFE膜和第二PTFE膜代表的第一表面和第二表面。图7中显示了以7倍放大拍摄的复合制品第一表面的光学显微镜图像。图8中显示了以32倍放大拍摄的复合制品第一表面的光学显微镜图像。图7和图8显示出在复合制品第一表面(即，第一PTFE膜)上形成可视图案的相互连接的节点的股线。图8A是复合制品中第一PTFE膜表面以100倍放大拍摄的扫描电子显微照片(SEM)，显示出形成股线的相互连接的节点。
复合制品的体积密度为0.43g/cc。泡点使用运行设定BP_50-150psi进行测定。运行两个测试条件。在第一测试中，复合制品的第一PTFE膜面对金属板。在第二测试中，复合制品的第二PTFE膜面对金属板。泡点分别测定为78.10psi和81.58。
实施例5
第一聚四氟乙烯(PTFE)膜按照如下进行制备。根据授予Branca等人的美国专利第5,814,405号的启示所制备的高分子量聚四氟乙烯细粉末和较低分子量改性聚四氟乙烯聚合物的掺混物与0.259lb/lb的润滑剂(IsoparTMK，德克萨斯州休斯顿的埃克森公司(Exxon))结合。所获得的混合物随后进行混合，并压制为圆柱形颗粒，并且在25℃温度下热调节18小时。随后圆柱形颗粒以47:1的缩小比通过矩形孔模头挤出，以形成带状物。随后，带状物以4.97:1的压延比在辊之间进行压延，以形成第一PTFE膜。
第二PTFE膜按照如下进行制备。根据授予Baillie的美国专利第6,541,589号的启示所制备的聚四氟乙烯聚合物细粉末与0.185lb/lb的润滑剂(IsoparTMK，德克萨斯州休斯顿的埃克森公司(Exxon))结合。所获得的混合物随后进行混合，并压制为圆柱形颗粒，并且在49℃温度下热调节8小时。随后圆柱形颗粒以87:1的缩小比通过矩形孔模头挤出，以形成带状物。随后，带状物以3.9:1的压延比在辊之间进行压延。然后，经压延的带状物以3.38:1的比率横向拉伸，并且在180℃和210℃的温度下分别在第一和第二烘箱中进行干燥，以形成第二PTFE膜。
第一PTFE膜层叠在第二PTFE膜上，并且层状产品厚度减小41.6％。然后，所获得的层状层叠体在210℃的温度下进行干燥以去除润滑剂。然后，经干燥的层叠体在300℃下以0.9％/秒的平均工程应变速率和等于50％的拉伸量在加热的滚筒之间沿y方向膨胀。随后，所获得的材料在约300°的温度下以61％/秒的平均工程应变速率和等于1,565％的拉伸量沿x方向膨胀。然后，材料在380℃下烧结不超过60秒。
如上所述，所获得的复合制品具有分别是第一PTFE膜和第二PTFE膜代表的第一表面和第二表面。图9中显示了以7倍放大拍摄的复合制品第一表面的光学显微镜图像。图10中显示了以32倍放大拍摄的复合制品第一表面的光学显微镜图像。图9和图10显示出在复合制品第一表面(即，第一PTFE膜)上形成可视图案的相互连接的节点的股线。图10A是复合制品中第一PTFE膜表面以100倍放大拍摄的扫描电子显微照片(SEM)，显示出形成股线的相互连接的节点。
复合制品的体积密度为0.09g/cc。泡点使用运行设定BP_50-120psi进行测定。运行两个测试条件。在第一测试中，复合制品的第一PTFE膜面对金属板。在第二测试中，复合制品的第二PTFE膜面对金属板。泡点分别测定为75.8psi和81.93psi。
实施例6
第一聚四氟乙烯(PTFE)膜按照如下进行制备。聚四氟乙烯聚合物细粉末((部件编号：T62，西弗吉尼亚州的帕克斯堡的杜邦公司)与0.235lb/lb的润滑剂(IsoparTMK，德克萨斯州休斯顿的埃克森公司(Exxon))结合。所获得的混合物随后进行混合，并压制为圆柱形颗粒，并且在16℃温度下热调节8小时。随后圆柱形颗粒以74:1的缩小比通过矩形孔模头挤出，以形成带状物。随后，带状物以1.65:1的压延比在辊之间进行压延，以形成第一PTFE膜。
第二PTFE膜按照如下进行制备。根据授予Malhotra等人的美国专利第4,576,869号的启示所制备的聚四氟乙烯聚合物细粉末与0.226lb/lb的润滑剂(IsoparTMK，德克萨斯州休斯顿的埃克森公司(Exxon))结合。所获得的混合物随后进行混合，并压制为圆柱形颗粒，并且在49℃温度下热调节8小时。随后圆柱形颗粒以74:1的缩小比通过模头挤出，以形成带状物。随后，带状物以3.7:1的压延比在辊之间进行压延，以形成第二PTFE膜。
第一PTFE膜层叠在第二PTFE膜上，并且层状产品厚度减小19％。层状层叠体以3.6:1的比例横向拉伸，并随后在250℃温度下进行干燥以去除润滑剂。然后，经干燥的层叠体在300℃下以109％/秒的平均工程应变速率和等于25％的拉伸量在加热的滚筒之间沿y方向膨胀。随后，所获得的材料在约260℃的温度下以399％/秒的平均工程应变速率和等于467％的拉伸量沿x方向膨胀。然后，材料在373℃下烧结不超过60秒。
如上所述，所获得的复合制品具有分别是第一PTFE膜和第二PTFE膜代表的第一表面和第二表面。图11中显示了以7倍放大拍摄的复合制品第一表面的光学显微镜图像。图12中显示了以32倍放大拍摄的复合制品第一表面的光学显微镜图像。图11和图12显示出在复合制品第一表面(即，第一PTFE膜)上形成可视图案的相互连接的节点的股线。图12A是复合制品中第一PTFE膜表面以100倍放大拍摄的扫描电子显微照片(SEM)，显示出形成股线的相互连接的节点。
复合制品的厚度为0.139mm，并且体积密度为0.25g/cc。泡点使用运行设定BP_9-50psi进行测定。运行两个测试条件。在第一测试中，复合制品的第一PTFE膜面对金属板。在第二测试中，复合制品的第二PTFE膜面对金属板。泡点分别测定为23.64psi和24.29psi。
实施例7
第一聚四氟乙烯(PTFE)膜按照如下进行制备。聚四氟乙烯聚合物细粉末((部件编号：T62，西弗吉尼亚州的帕克斯堡的杜邦公司)与0.253lb/lb的润滑剂(IsoparTMK，德克萨斯州休斯顿的埃克森公司(Exxon))结合。所获得的混合物随后进行混合，并压制为圆柱形颗粒，并且在16℃温度下热调节8小时。随后圆柱形颗粒以74:1的缩小比通过矩形孔模头挤出，以形成带状物。随后，带状物以1.65:1的压延比在辊之间进行压延，以形成第一PTFE膜。
第二PTFE膜按照如下进行制备。根据授予Malhotra等人的美国专利第4,576,869号的启示所制备的聚四氟乙烯聚合物细粉末与0.226lb/lb的润滑剂(IsoparTMK，德克萨斯州休斯顿的埃克森公司(Exxon))结合。所获得的混合物随后进行混合，并压制为圆柱形颗粒，并且在49℃温度下热调节8小时。随后圆柱形颗粒以74:1的缩小比通过矩形孔模头挤出，以形成带状物。随后，带状物以3.7:1的压延比在辊之间进行压延，以形成第二PTFE膜。
第一PTFE膜层叠在第二PTFE膜上，并且层状产品厚度减小50.8％。层状层叠体以3.6:1的比例横向拉伸，并随后在250℃温度下进行干燥以去除润滑剂。然后，经干燥的层叠体在300℃下以14％/秒的平均工程应变速率和等于103％的拉伸量在加热的滚筒之间沿y方向膨胀。随后，所获得的材料在约260℃的温度下以273％/秒的工程应变速率和等于467％的拉伸量沿x方向膨胀。然后，材料在373℃下烧结不超过60秒。
如上所述，所获得的复合制品具有分别是第一PTFE膜和第二PTFE膜代表的第一表面和第二表面。图13中显示了以7倍放大拍摄的复合制品第一表面的光学显微镜图像。图14中显示了以32倍放大拍摄的复合制品第一表面的光学显微镜图像。图13和图14显示出在复合制品第一表面(即，第一PTFE膜)上形成可视图案的相互连接的节点的股线。图14A是复合制品中第一PTFE膜表面以100倍放大拍摄的扫描电子显微照片(SEM)，显示出形成股线的相互连接的节点。
复合制品的厚度为0.134mm，并且体积密度为0.17g/cc。泡点使用运行设定BP_9-50psi进行测定。运行两个测试条件。在第一测试中，复合制品的第一PTFE膜面对金属板。在第二测试中，复合制品的第二PTFE膜面对金属板。泡点分别测定为21.03psi和20.87psi。
实施例8
第一聚四氟乙烯(PTFE)膜按照如下进行制备。聚四氟乙烯聚合物细粉末树脂((部件编号：F104，阿拉巴马州的大金公司(Daikin.,AL))与0.252lb/lb的润滑剂(IsoparTMK，德克萨斯州休斯顿的埃克森公司(Exxon))结合。所获得的混合物随后进行混合，并压制为圆柱形颗粒，并且在23℃温度下热调节8小时。随后圆柱形颗粒以40:1的缩小比通过矩形孔模头挤出，以形成带状物。随后，带状物以2.75:1的压延比在辊之间进行压延，以形成第一PTFE膜。
第二PTFE膜按照如下进行制备。根据授予Malhotra等人的美国专利第4,576,869号的启示所制备的聚四氟乙烯聚合物细粉末与0.186lb/lb的润滑剂(IsoparTMK，德克萨斯州休斯顿的埃克森公司(Exxon))结合。所获得的混合物随后进行混合，并压制为圆柱形颗粒，并且在70℃温度下热调节8小时。随后圆柱形颗粒以78:1的缩小比通过矩形孔模头挤出，以形成带状物。随后，带状物以3.4:1的压延比在辊之间进行压延，以形成第二PTFE膜。
第一PTFE膜层叠在第二PTFE膜上，并且层状产品在辊之间进行压延。然后，所获得的层状层叠体在250℃的温度下进行干燥以去除润滑剂。然后，经干燥的层叠体在300℃下以99％/秒的平均工程应变速率和等于30％的拉伸量在加热的滚筒之间沿y方向膨胀。随后，所获得的材料在约300℃的温度下以228％/秒的平均工程应变速率和等于1600％的拉伸量沿x方向膨胀。然后，材料在380℃下烧结不超过60秒。
如上所述，所获得的复合制品具有分别是第一PTFE膜和第二PTFE膜代表的第一表面和第二表面。图15中显示了以7倍放大拍摄的复合制品第一表面的光学显微镜图像。图16中显示了以32倍放大拍摄的复合制品第一表面的光学显微镜图像。图15和图16显示出在复合制品第一表面(即，第一PTFE膜)上形成可视图案的相互连接的节点的股线。图16A是复合制品中第一PTFE膜表面以100倍放大拍摄的扫描电子显微照片(SEM)，显示出形成股线的相互连接的节点。
复合制品的厚度为0.171mm，并且体积密度为0.16g/cc。泡点使用运行设定BP_9-50psi进行测定。运行两个测试条件。在第一测试中，复合制品的第一PTFE膜面对金属板。在第二测试中，复合制品的第二PTFE膜面对金属板。泡点分别测定为23.64psi和26.25psi。
上文已经中概括性地并且结合具体实施方式描述本申请的发明。对本领域的技术人员来说显而易见的是，可以在不偏离本发明的精神和范围的情况下，对本文所述的实施方式进行各种修改和变动。因此，实施方式旨在覆盖对本发明的这些修改和变动，只要这些修改和变动在所附权利要求及其等同方案的范围之内。

Claims (14)

1.一种复合制品，其包括：
具有第一表面和第二表面的第一聚四氟乙烯(PTFE)膜；和
位于所述第一PTFE膜的所述第二表面上的第二PTFE膜，所述第二PTFE膜具有节点及原纤维微结构，
其中，所述第一PTFE膜包括由互相连接的PTFE节点形成的股线、或者由至少一个PTFE节点团形成的股线，各节点是固体的PTFE团，
当用肉眼进行观察时，沿股线的任意两个点测量时，相互连接的PTFE节点形成的股线和/或包含一个或多个PTFE节点团的股线中的至少一种股线的长度等于或大于1.5mm。
2.如权利要求1所述的复合制品，其特征在于，所述第二PTFE膜的基质拉伸强度大于第一PTFE膜的基质拉伸强度。
3.如权利要求2所述的复合制品，其特征在于，所述第二PTFE膜的基质拉伸强度在x方向和y方向比所述第一PTFE膜的基质拉伸强度大至少1.5倍。
4.如权利要求1所述的复合制品，其特征在于，所述股线是非线性的，并且在所述第一PTFE膜的所述第一表面上形成可视图案。
5.如权利要求1所述的复合制品，其特征在于，所述复合制品的体积密度为0.1g/cm3至1.0 g/cm3。
6.如权利要求1所述的复合制品，其特征在于，所述复合制品的泡点为3psi至200psi。
7.如权利要求1所述的复合制品，其特征在于，所述复合制品的厚度为0.01mm至3.0mm。
8.如权利要求1所述的复合制品，其特征在于，所述复合制品进一步包含粘合剂以粘合所述第一PTFE膜和所述第二PTFE膜。
9.如权利要求8所述的复合制品，其特征在于，所述粘合剂是热塑性树脂的不连续层或连续层。
10.如权利要求9所述的复合制品，其特征在于，所述热塑性树脂选自：氟化乙烯丙烯(FEP)、全氟烷氧基聚合物树脂(PFA)、四氟乙烯六氟丙烯和偏二氟乙烯(THV)、聚偏二氟乙烯(PVDF)、以及它们的组合。
11.如权利要求1所述的复合制品，其特征在于，至少一根所述股线的长度等于或大于2.0mm。
12.一种形成复合制品的方法，所述方法包括：
获得具有第一表面和第二表面的第一PTFE膜；
获得基质拉伸强度大于第一PTFE膜基质拉伸强度的第二PTFE膜，所述第二PTFE膜具有节点及原纤维微结构；
将所述第二PTFE膜放置在所述第一PTFE膜的所述第二表面上，以形成层状产品；
以0.5%/秒至300%/秒的工程应变速率以及10%至350%的拉伸比使得所述层状产品沿y方向膨胀，以形成经膨胀的产品；以及
以3%/秒至600%/秒的工程应变速率以及0%至2000%的拉伸比使得所述经膨胀的产品沿x方向膨胀，以形成复合制品，
其中，所述复合制品包括由互相连接的PTFE节点形成的股线、或者由至少一个PTFE节点团形成的股线，各节点是固体的PTFE团，
当用肉眼进行观察时，沿股线的任意两个点测量时，相互连接的PTFE节点形成的股线和/或包含一个或多个PTFE节点团的股线中的至少一种股线的长度等于或大于1.5mm，
其中，所述复合制品的所述第一表面等于所述第一PTFE膜的所述第一表面。
13.如权利要求12所述的方法，所述方法进一步包括对所述复合制品进行烧结。
14.如权利要求12所述的方法，所述方法进一步包括：将粘合剂施加到所述第一PTFE膜和所述第二PTFE膜中的一个上以将所述第一PTFE膜粘合到所述第二PTFE膜。
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