CN102460756A - 可电转换的聚合物膜构造及其用途 - Google Patents
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Abstract
本发明涉及一种可电转换的聚合物膜构造,其具有第一和第二表面侧,该构造包含至少一个电极对(3,4)和聚合物基质(2),其中赋予结构的颗粒(5)能够嵌入到该聚合物基质中,并且该聚合物基质或该赋予结构的颗粒是由电活性聚合物组成的,其中进一步的,该第一和/或第二表面侧能够通过电转换该电活性聚合物来从平滑态转变成为结构化态。
Description
本发明涉及一种可电转换的聚合物膜构造,在其中该聚合物膜构造的第一和/或第二表面侧能够通过电转换电活性聚合物而从平滑态(电压施加前的状态)有源(aktiv)转化成为结构化态(电压施加后的状态)。本发明此外涉及这样的可电转换的聚合物膜构造的用途。
有源(aktiv)影响表面结构的能力在许多不同的应用中引起了非常大的技术关注,例如可变的触觉,视觉性能或者影响流体的流动行为。由于有利的和可有针对性调节的性能,例如低重量和可调整的机械性能,聚合物和聚合物复合材料已经用于许多商业应用中。功能聚合物已经在作为传感器或者促动器(Aktoranwendung)应用中的有源元件而变得越来越重要。在上下文中,电活性聚合物(EAP)类近年来已经日益成为研究的焦点。
专利文献US2008/0128027A1和WO2008/105861A2描述了用于变形表面的系统和方法,目的是有针对性地影响沿着它们的流体的流动。这样,例如可以避免了紊流,或者产生或者消除共振振动。作为促动器,尤其可以提到微机电系统,压电换能器,电活性聚合物,磁性或者液压促动器等等。该促动器垂直作用于表面上,并且依靠控制系统来控制。
EP1090835A1提到了一种扁平促动器,具有多个促动器元件,其是由形状记忆金属丝和/或压电元件制成的。这些扁平促动器可以用于有针对性影响沿着表面的流动。尽管促动器长度和可实现的提升(Hub)之间小的比率,和金属丝平行于所述表面的布置,但是仍然实现了小的变形,其可以通过回弹和各向异性硬化的扁平结构而放大。另外提出了在促动器元件的作用方向上通过凹槽和狭缝的表面结构化,目的是进一步提高通过促动器的变形。
DE10026264 A1公开了一种车辆外壳的可移动实施方案,将许多狭窄相邻的、可电操作的小圆柱形式的促动器以如下方式嵌入到该外壳中:使得在起始态时的促动器表面与外壳齐平地延伸,并且通过转换产生凹凸结构。这个凹凸结构目的是降低在超过某个速度时的空气阻力和减少风噪,或者还用于从外壳上除冰雪。为此目的,提出了聚合物和/或离子交换材料作为用于促动器元件的材料,其通过电过程或者通过pH、湿度或者温度的改变而经历了形状变化。
产生表面结构化的另外一种可能方式描述在WO2005/079187A2中。这种方式在于在平板型电极之间使用静电引力。在该电极之间,存在着介电弹性体,在其上当施加电压时,通过相互吸引的电极而施加了力。弹性体然后在电极之间被压出,这样该表面在这个区域中具有凹陷。在电极之外,被排挤的聚合物堆高和被挤出表面平面。这种方法产生了凹陷和凸起,其能通过预定的电极布置和互连而产生特定的表面结构化。三维的和特别是盲文排列,可移动的镜子,影响翼上的流动,步进发动机和泵被提及作为应用。
专利文献US7397166B1描述了一种蠕动泵,在其中使用了在电压施加下由聚合物-金属复合材料制成的促动器的变形,并且通过沿着柔性软管的长度方向布置相互隔开的电极,一定量的液体可以通过该电极的连续转换而在该软管内部传输。提到了人体中液体药物的传输作为一个应用的例子。
EP1843406A1公开了一种包含电活性聚合物的促动器(Aktor, Aktuator)。在这种聚合物基质中,混入了(陶瓷)颗粒。这些颗粒用于提高该聚合物基质的介电常数ε。EP1843406A1中公开的促动器能够调整表面粗糙度。该(陶瓷)颗粒不具有任何通过它们的单个体积、它们的尺寸、强度、形状和/或粗糙度而影响表面粗糙度意义上的物理/机械效应。
电活性聚合物(EAP)原则上可以再分为两个主要的组。第一组包含所谓的场活化的聚合物。场活化的EAP典型地意指聚合物,聚合物混合物和聚合物复合材料,其能够通过施加电场而直接转换。它们需要至多200V·µm-1的电场。场活化EAP组的一个优点是它们通常能够以毫秒的速度来转换。场活化的聚合物包括介电弹性体,铁电聚合物,压电聚合物和电致伸缩聚合物。
EAP的第二主要的组是所谓的离子电活性聚合物(ionisch elektroaktive Polymer)。该组特征在于它是基于这样的作用机理,其涉及离子和/或溶剂化离子和/或溶剂分子的扩散。属于离子EAP的聚合物材料的例子是这样的聚合物或者聚合物复合材料(其包含可移动的离子),导电聚合物,离子凝胶和聚合物复合材料(具有碳纳米管和/或石墨烯)。
不同的电活性聚合物(EAP)的基本类型和作用机理描述在论文MRS Bulletin,2008年3月,第33卷第3期等和各个其中引用的文献中。
离子EAP大多结合到液体介质例如电解质上,并因此经常依赖于环境条件例如温度和相对湿度。没有另外的措施时,它们会在空气中随着时间流逝而干透,并因此失去它们作为EAP的功能。因此降低了对于环境条件的依赖性的EAP系统是令人感兴趣的。一种可能性在于使用离子液体(IL)作为聚合物基质中的电解质溶液,这样由聚合物基质和离子液体组成的整个系统是固体。IL是有机盐,其在室温作为熔融态而存在,具有可忽略的低的蒸气压,并因此能够防止干透和离子EAP的功能损失。
功能聚合物和聚合物膜构造在商业应用中的吸引力越来越大,例如用于传感器和促动器系统,以及用于主动影响表面和表面性能。
本发明因此提供一种可电转换的聚合物膜构件,其具有彼此相对布置的第一表面侧和第二表面侧。该聚合物膜构件包含由阳极和阴极组成的至少一个电极对和聚合物基质,其中赋予结构的颗粒可以布置在该聚合物基质中。
根据本发明,该赋予结构的颗粒的存在可以是优选的。但是,不包含任何这样的赋予结构的颗粒的实施方案根据本发明也可以是优选的。
该聚合物基质和/或该任选存在的赋予结构的颗粒是由电活性聚合物组成的。通过电转换该电活性聚合物,该第一和/或第二表面侧可以从平滑态转变成结构化态。
换句话说,通过将电压施加到本发明的聚合物膜结构上,在至少一个表面侧上能够有利地主动产生具有凸起和凹陷的结构化表面。该聚合物膜结构的至少一个表面侧上的这种结构化是可逆的,并且可以通过另外的电转换来有利地重复引起。根据本发明,该聚合物基质是作为聚合物膜配置的。
本发明的聚合物膜构造的该可主动影响的表面可以例如用于在诸多应用中通过电转换,来产生触觉可察觉的信号和使用可主动产生的粗糙化。另一优点是还可以通过电转换本发明的聚合物膜构造来实现光学效应。例如,该聚合物膜构造在未转换的平滑态时可以是透明的和在施加电压之后是不透明的。
根据本发明,在备选的实施方案中,该聚合物膜构造同样优选地可以包含场活化的或者离子电活性聚合物作为电活性聚合物(EAP)。
例如,场活化的聚合物可以选自介电弹性体,铁电聚合物,电致伸缩聚合物和压电聚合物。
作为铁电和压电聚合物,根据本发明例如可以使用聚(偏1,1-二氟乙烯)(PVDF)和VDF的共聚物,例如VDF与三氟乙烯的共聚物。该介电弹性体根据本发明例如可以是硅氧烷,聚氨酯,聚丙烯酸酯,橡胶,苯乙烯-乙烯-丁烯-苯乙烯(SEBS)或者苯乙烯-丁二烯橡胶。
该离子电活性聚合物根据本发明可以选自例如包含可移动离子的聚合物,导电聚合物,离子凝胶和聚合物复合材料(具有碳纳米管和/或石墨烯)。
离子凝胶的一个例子是聚(乙烯醇)凝胶,具有二甲亚砜。可以根据本发明使用的导电聚合物例如聚吡咯,聚苯胺和聚噻吩。
合适的EAP材料和它们的作用机理原则上是已知的,并且描述在例如Y.
Bar-Cohen,Q. Zhang的论文第173-181页,MRS Bulletin,2008年3月第33卷第3期以及各个其中引述的文献中。
关于EAP的诸多备选的选择可能性能够有利地使得调整本发明的可转换的聚合物构造的基础性能成为可能和能够有利地专门适配于具体的应用。根据本发明,本发明的聚合物膜构造的第一和/或第二表面侧能够实现良好的可转换性和表面结构化。
本发明的聚合物膜构造(包含至少一个电极对、聚合物基质和任选的嵌入其中的赋予结构的颗粒)可以处于未转换的平滑态(即,不施加电压),厚度为≥10µm和≤1mm,优选厚度是≥50到≤500µm,特别优选≥100到≤300µm。该聚合物膜构造特别合适的厚度可以有利地分别取决于具体用于该聚合物基质和用于该颗粒的材料来选择,特别是相对于所选择的一种或多种EAP,和相对于各自打算的应用来选择。该赋予结构的颗粒(如果存在的话)的直径是该聚合物膜构造厚度的50-90%,优选是该聚合物膜构造厚度的70-80%。
根据本发明,有利地可以通过各种各样的参数来影响该结构化的表现。这样的参数可以提及的例子是所施加的电场的强度,电极的尺寸、形状和结构化,颗粒的尺寸和体积份额和聚合物基质的厚度。
在本发明的可电转换的聚合物膜构造的另一种实施方案中,电极(即,阳极和阴极)可以布置在该聚合物基质的相对置表面上,该聚合物膜构造的一个表面侧是作为柔性盖电极而配置的,而每一情况下的另一个表面是作为硬底电极而配置的。换句话说,在这种实施方案中,本发明的聚合物构造是作为层构造来提供的,其由下列组成:在底部平滑配置的底电极、施加到其上的其中布置有赋予结构的颗粒的聚合物基质膜、和施加到这种聚合物基质上的平滑柔性盖电极。该底电极和盖电极的厚度在这种情况中彼此独立地是10nm-100µm,优选100nm-10µm。
在本发明的意义上,盖电极(Deckelektrode)指的是这样一种电极,其布置在聚合物膜构造表面侧上,其可以通过转换该电活性聚合物而转变成结构化态。与此不同,根据本发明,底电极意指这样的电极,其布置在聚合物膜构造表面侧上,其不是通过电转换来结构化的。具有正极性和负极性的两种电极可以同时是本发明的聚合物膜构造中的底电极。
在本发明说明书中,术语上部、底部、下方和上方仅仅指的是所述部件相对于彼此的位置,并且有时候是可交替使用的。
根据本发明,柔性盖电极意指这种电极是这样配置的,即,它可以承担和塑造形状变化和赋予结构(其是通过电活性聚合物的转换特别是在聚合物基质表面上产生的形状变化和赋予结构)。以此方式,当施加合适的电压时,该盖电极因此形成了聚合物膜构造的朝外的结构化表面侧。
该电极(盖电极和底电极二者)可以是本领域技术人员已知的导电材料。根据本发明,可考虑用于此的是例如金属,金属合金,导电低聚物或者聚合物,例如聚噻吩,聚苯胺,聚吡咯,导电氧化物,例如混合氧化物例如ITO,或者用导电填料填充的聚合物。作为用于使用导电填料填充的聚合物的填料,可以考虑的是例如金属,导电性碳基材料例如炭黑,碳纳米管(CNT),或者还有导电性低聚物或者聚合物。该聚合物的填料含量高于突增界限(Perkolationsschwelle),这样该导电填料形成了连贯的导电路径。
该电极可以依靠本身已知的方法实现,例如通过表面的金属化,通过溅射,蒸镀,化学气相沉积(CVD),物理气相沉积(PVD),印刷,刮刀涂覆,旋涂,粘结或者以预制的形式在导电层上压印,或者通过导电塑料制成的喷雾电极。
在本发明的聚合物膜构造的另外一种实施方案中,该电极可以布置到聚合物基质的相对置表面上,该电极是以结构化方式布置在该聚合物膜构造的一个或者两个表面侧上的。在聚合物膜构造的这种实施方案中,该聚合物基质也作为聚合物膜布置在电极之间,在本发明意义上,结构化电极意指该电极之一或者之二在该聚合物膜构造各自的表面侧上形成了规则的或者不规则的图案。该电极可以例如是作为条形或者栅格形来配置的。在这种情况中,该电极可以交替地施加到该聚合物基质的表面上或者至少部分地嵌进该聚合物基质中。该电极还可以完全嵌进该聚合物基质中。该电极然后可以用分别布置到它们之间的聚合物基质表面平齐地密封,并且用它在至少未转换态时形成该聚合物膜构造的平滑表面。
在本发明聚合物膜构造的另外一种实施方案中,该电极可以以结构化方式,作为底电极布置到第一或者第二表面侧上。在本发明这种变化中,阳极和阴极位于该聚合物膜构造的相同表面侧上。远离该电极的另一表面侧在这种实施方案中是通过聚合物基质形成的。同样在这种实施方案中,该电极可以交替地施加到聚合物基质表面或者至少部分地嵌进该聚合物基质中。该电极还可以完全嵌进该聚合物基质中。该电极然后可以用分别布置到它们之间的聚合物基质表面平齐地密封,并且用它在至少未转换态时形成该聚合物膜构造的平滑表面侧。这个平滑表面侧(其因此是由电极表面和聚合物基质表面一起形成的)可以例如施加到基材上。
在本发明意义上,也针对这种实施方案,底电极的结构化布置意指阳极和阴极在该聚合物膜构造的两个表面侧之一上形成了规则的或者不规则的图案。例如,在通常施加到一个表面侧上时,该阳极和阴极可以交替布置。简单实现此的一种可能的方式是使用所谓的梳状电极,其可以叉指式(interdigitierend)和互相啮合(ineinandergreifend)来布置。有利地,由此以相同方式极化的各个电极可以连接在一起。
如果该电极是以结构化方式作为底电极布置到该聚合物膜构造的一个表面侧上,根据另外一种实施方案,该聚合物基质可以由离子电活性聚合物组成,并且没有任何赋予结构的颗粒布置在该聚合物基质中。在这种实施方案中,该聚合物基质优选是由包含可移动离子的弹性体组成。换句话说,在本发明这种实施方案中的可电转换的聚合物膜构造的聚合物膜是由包含离子的聚合物复合材料形成的,在其中至少一种类型的离子,阴离子或者阳离子,是自由移动的。该离子可以例如是以离子液体的形式引入到该弹性体基质中的。如果施加电压,则该可自由移动的离子迁移到相应的电极中。取决于聚合物基质中是仅仅一种还是两种类型的离子(阴离子,阳离子)是可移动的,作为在施加的电场作用下离子扩散的结果,两种电极类型(阳极,阴极)之一的周围区域因此将膨胀,并因此可以在该表面侧上塑造该电极结构。电极之间的区域变成贫离子的,这会导致体积收缩,其进一步提高了与相应的电极周围的抬起之间的差异。该聚合物膜构造的结构化表面侧因此可以通过简单的方式来形成。底电极厚度在这种情况中是10nm-900µm,优选100nm-500µm,特别优选1
µm-200µm。
根据本发明的另外一种实施方案,该聚合物基质由电活性聚合物组成,并且该赋予结构的颗粒是非导电性硬质材料颗粒,该非导电性硬质材料颗粒不包括陶瓷硬质材料颗粒。特别优选地,该非导电性硬质材料颗粒可以由玻璃或者非导电性聚合物材料制成。在本发明意义上,硬质材料颗粒意指这样的颗粒,其在电转换过程中保持它们的形状和尺寸。玻璃和非导电性聚合物材料例如诸如聚乙烯(PE),聚丙烯(PP),聚氯乙烯(PVC),聚甲基丙烯酸甲酯(PMMA),聚碳酸酯(PC)或者聚氨酯(PU)是特别优选的,因为它们是非常廉价的。在该聚合物膜构造的电转换过程中,颗粒的尺寸,形状和分布因此可以转移到具有柔性盖电极的表面上。例如,在一种组合的实施方案(具有扁平配置的硬底电极和扁平配置的柔性盖电极,和布置在它们之间的由介电弹性体制成的电活性聚合物基质)中,当施加电压时,该聚合物基质被挤压,而该颗粒保持了它们的形状。该颗粒的形状和分布因此可以通过升高具有盖电极的表面侧来塑造。底电极和盖电极的厚度在这种情况中彼此独立的是10nm-100µm,优选100nm-10µm。
根据本发明的一种备选的实施方案,该赋予结构的颗粒是由电活性聚合物组成的,并且该聚合物基质是由弹性体形成的。该可转换的赋予结构的颗粒是这样的颗粒,其能够在电转换过程中经历可逆的形状和/或体积变化。由于这种性能,该颗粒可以将它们的形状和分布转移到例如弹性聚合物基质上和任选地转移到柔性盖电极上,这样能够形成结构化表面侧。这具有优点,即,实际的聚合物膜仅仅只需匹配它的刚度,以使得在该聚合物膜构造的电转换过程中它能够承担该赋予结构的颗粒的形状变化。因此对于聚合物基质来说,已知的漆料系统可以有利的想到,其已经在它们的其他性能方面适于可能的具体技术应用,例如光泽度,耐磨强度,长期稳定性或者可加工性等等。
如果备选地,使用本发明的以结构化方式配置的底电极的构思,则由电活性聚合物制成的可转换的颗粒在一种电极类型附近会膨胀或者改变它们的形状,而相反极化的电极保持不变或者收缩。该颗粒的尺寸和直径适宜地以如此方式适应聚合物基质的厚度,这样由于电转换而引起的颗粒形状和/或体积的变化被转移到位于与底电极相对置的表面侧上,这样所形成的抬起反映了该电极结构化和颗粒的分布。底电极厚度在这种情况中是10nm-900µm,优选100nm-500µm,特别优选1
µm-200µm。
在本发明的实施方案中,在其中使用由电活性聚合物制成的赋予结构的颗粒(即,可转换的颗粒),它们会接触到电极之一。在这种情况中,换句话说,这里因此会存在着单个颗粒与电极的电接触,其任选地会允许电子交换。电极在这种情况中可以与多个颗粒接触。
本发明的可电转换的聚合物膜构造可以用所述的描述变体,作为自持性(freitragend)聚合物膜构造来实现。
根据本发明,在另外一种优选的实施方案中,该可电转换的聚合物膜构造的第一或者第二表面侧可以施加到基材上,其中在每一情形下另一表面侧可以通过电活性聚合物的电转换来进行结构化。该基材可以有利地充当载体和支持体,用于该聚合物膜构造。此外,该基材还可以是一种物体,本发明的聚合物膜构造作为表面涂层施加到其上。
本发明提供一种可电转换的聚合物膜构造,其具有彼此相对布置的第一表面侧和第二表面侧,包含由阳极和阴极组成的至少一个电极对和聚合物基质,特征在于任选地将赋予结构的颗粒布置在聚合物基质中的,并且该聚合物基质和/或该任选存在的赋予结构的颗粒是由电活性聚合物组成的,其中该第一和/或第二表面侧是通过电转换该电活性聚合物来从平滑态转变成为结构化态的。
本发明此外提供一种可电转换的聚合物膜构造,其具有彼此相对布置的第一表面侧和第二表面侧,包含由阳极和阴极组成的至少一个电极对和赋予结构的颗粒布置在其中的聚合物基质,特征在于该赋予结构的颗粒是非导电性硬质材料颗粒和该聚合物基质是由电活性聚合物组成的,或者该赋予结构的颗粒是由电活性聚合物组成的,其中该第一和/或第二表面侧是通过电转换该电活性聚合物来从平滑态转变成为结构化态的。
本发明此外提供一种可电转换的聚合物膜构造,其具有彼此相对布置的第一表面侧和第二表面侧,包含由阳极和阴极组成的至少一个电极对和由电活性聚合物组成的聚合物基质,其中该第一和/或第二表面侧是通过电转换该电活性聚合物来从平滑态转变成为结构化态的,特征在于该阳极和阴极是作为底电极配置的,并且以结构化方式配置在第一或者第二表面侧上。
本发明此外包含本发明的聚合物膜构造的用途。特别地,本发明涉及一种可电转换的表面涂层,其包含本发明的上述变体和实施方案中所述的可电转换的聚合物膜构造。这种表面涂层可以施涂到例如物体上,例如车身或者船体上。该本发明的表面涂层可以有利地通过该聚合物膜构造的电转换来主动影响。这种主动影响可以静态或者以不同的频率来进行。
本发明还包含将这样的可电转换的表面涂层用于产生触觉,听觉和/或视觉信号。这可以例如包括可变的触觉,例如平滑表面和粗糙表面之间的转变。这种效应可以例如用于表面自洁,表面除冰和船体表面抗污。光学性能也可以通过本发明聚合物膜构造的转换来进行影响,这样例如可以在透明表面和不透明表面之间转换。
此外,这些触觉和视觉效应还可以用于人机界面,例如情景驱动的菜单管理。
根据本发明,此外还可以影响流体的流动行为。例如,本发明因此可以用于避免紊流或者减少流动阻力。
有利地,本发明因此可以用于各式各样的应用中。
本发明将在下面结合附图进行示例性说明,但并非限于这些优选的实施方案。
图1a和图1b示出了本发明的可电转换的聚合物膜构造的示意性截面图,该聚合物膜构造具有可转换的电活性聚合物基质和布置在其中的硬质材料颗粒,
图2a和图2b示出了本发明的可电转换的聚合物膜构造的示意性截面图,该聚合物膜构造具有在弹性体基质中的可转换的赋予结构的颗粒,
图3a和3b示出了本发明的可电转换的聚合物膜构造的示意性截面图,该聚合物膜构造具有在弹性体基质中的可转换的赋予结构的颗粒和以结构化方式设置的电极,
图4a和图4b示出了本发明的可电转换的聚合物膜构造的示意性截面图,该聚合物膜构造具有以结构化方式设置的电极和在弹性体基质中自由移动的阴离子和阳离子。
所示的实施方案(其用“a”表示)分别示出了在施加电压之前的聚合物膜构造,和用“b”表示的图分别示出了施加电压之后相应的聚合物膜构造。图1a和1b示出了本发明的可电转换的聚合物膜构造1,其具有可转换的聚合物基质2,其嵌入到扁平电极3和4之间。该聚合物基质2可以例如是由介电弹性体组成的,例如硅氧烷弹性体,聚氨酯弹性体,聚丙烯酸酯弹性体或者橡胶。非导电性硬质材料颗粒5可以此外作为赋予结构的颗粒布置于聚合物基质2中。仅仅为了清楚起见,在每种情况中仅仅示出了三个颗粒5。这些颗粒5可以由例如玻璃,碳化硅,陶瓷或者非导电性硬质聚合物组成。在所示的实施方案中,电极3是作为柔性盖电极3配置的。电极4是作为底电极配置的,并且布置在基材6上。如图1a所示,颗粒5是如此定制的:使得聚合物基质2和盖电极4在不施加电场时具有平滑表面。换句话说,聚合物膜构造1具有第一平滑表面侧。然后,当施加电压时,如图1b所示,在电极3、4之间的介电弹性体被压到一起,而硬颗粒5保持了它们的形状。根据本发明,颗粒5是此外如此定制的,并且匹配于聚合物基质2的厚度,以使得当电压施加到该聚合物膜构造1上时,能够在第一表面侧上借助凸起7和凹陷8形成触觉和/或视觉可察觉的结构化。在本发明的意义上,可察觉的结构化意指它至少是可检测的。检测可以例如通过光学方法例如衍射或者折射来实施。该表面结构的尺寸和形状可以有利地如下来影响和可变地调整:通过硬颗粒5的尺寸、形状和分布,通过用于聚合物基质2的聚合物材料选择和所施加的电场。
图2a和图2b示出了本发明的可电转换的聚合物膜构造1的示意性横截面图,其具有在弹性聚合物基质2中的可转换的颗粒5。在所示的实施方案中,电极3是作为柔性盖电极3配置的。电极4是作为底电极配置的,并且布置在基材6上。颗粒5可以例如由离子EAP或者场活化的EAP组成,当电压施加到电极3、4上时,其经历了形状和/或体积变化。颗粒5可以与聚合物构造1中的电极3、4之一接触。颗粒5在这种情况中在它们的尺寸上是这样来配置的,这样当施加电压时,它们的形状和在聚合物基质2上分布是通过柔性盖电极3来塑造(abbilden)的,并且由此可以产生具有凸起7和凹陷8的表面结构。这种优选的实施方案的一个优点是聚合物基质2仅仅只需调整它的刚度,以便它能够适应于可转换的颗粒5的形状变化和将它赋予柔性盖电极3。因此对于这种聚合物层2来说,可以考虑已知的漆系统,其已经在它们的其他性能方面适配于具体技术应用,例如光泽度,耐磨强度,长期稳定性和可加工性。在另外一种实施方案中,弹性体基质2除了颗粒5之外,还可以包含可移动离子,阴离子和/或阳离子。这些可移动离子可以在转换过程中从聚合物基质2扩散到颗粒5中,或者从后者中扩散出来,这样可以实现颗粒5的形状和/或体积变化。
图3a和3b示出了本发明的一种可电转换的聚合物膜构造1的示意性横截面图,其具有在弹性基质2中的可转换的赋予结构的颗粒5,和以结构化方式布置的底电极3、4。电极3、4是交替布置的。它们可以配置成叉指式的梳状电极,其有利的可以分别一起极化。在这个图中,将电极3、4嵌入聚合物基质2中,并且在一个表面侧上与之平齐。这个表面侧布置在基材6上。可转换的颗粒5可以优选由离子EAP组成。颗粒5可以与聚合物构造1中的电极3、4之一接触。为了清楚起见,每个电极3、4仅仅示出了一个颗粒5。颗粒5可以在转换过程中在一个电极3上膨胀,而在相反极化的电极4上的颗粒5保持几乎不变或者收缩。颗粒5的尺寸适宜地以如下方式适配于聚合物基质2的厚度:这样由于电转换引起的颗粒5的形状和/或体积变化被转移到与电极3、4相对置的表面上。所形成的凸起7和凹陷8可以有利地反映电极结构化和颗粒5的分布。在另外一种实施方案中,弹性体基质2除了颗粒5之外还可以包含可移动离子、阴离子和/或阳离子。这些可移动离子可以在转换过程中从聚合物基质2扩散到它们的颗粒5中,或者从后者扩散出来,这样可以实现颗粒5的形状和/或体积变化。
图4a和4b示出了本发明的可电转换的聚合物膜构造1的示意性横截面图,其具有以结构化方式布置的底电极3、4和在弹性体基质2中可自由移动的阴离子9和阳离子10。其中,聚合物基质2施加到基材6的表面侧上。可电转换的聚合物膜构造1的聚合物膜(其包含聚合物基质2和离子9,10)在本发明的这种实施方案中可以由包含离子的聚合物复合材料来形成,在其中至少一种类型的离子是可自由移动的。如果施加电压,则该可自由移动的离子迁移到相应的电极中。取决于聚合物基质2中仅仅一种类型的离子还是(如图4a和4b所示)阴离子9和阳离子10都是可移动的,作为在施加的电场作用下离子扩散的结果,两个电极类型3,4之一或者两者的周围区域因此将膨胀,并因此可以在该表面侧塑造该电极结构。电极3、4之间的区域变成贫离子的,这会导致体积收缩和因此表面侧上的凹陷8,其进一步提高了与相应的电极3、4周围的凸起7之间的差异。结构化表面因此可以通过简单的方式来形成。本发明这样的实施方案可以例如通过将离子液体混入作为聚合物膜的聚氨酯(PUR)基质材料中来生产。本发明将进一步通过下面给出的实施例来解释,但不限于此。
实施例
实施例 1:具有结构化底电极的可电转换的聚合物膜构造的生产。
使用组成如下的聚氨酯(PUR)配制剂:82-99重量%的作为异氰酸酯的Desmodur®
E15(Bayer MaterialScience AG)和1重量%的作为交联剂的三乙醇胺(TEA)。为了提高与离子液体的可混合性,加入了0-17重量%的聚乙二醇(PEG 600),所述成分合计为100重量%。将这个反应配制剂与1-丁基-3-甲基咪唑双(三氟甲基磺酰基)亚氨盐作为离子液体(IL)手工搅拌,混合比例为1:1,并且用刮墨刀涂覆到已经布置到基材上的梳状电极上。该电极由叉指式的铜电路组成,具有0.25mm-4mm的规则的电极间隔,将其施加到环氧化物基材(FR4)上。该导电Cu电极高于所用环氧化物基材的高度是70µm。将该聚合物反应性混合物在至多60°C的温度固化。这产生了透明的、均匀的膜,具有平滑表面,并且厚度是150µm。在2V的电压研究了尺寸为大约10cmx10cm的样品的电流-电压特性。当施加2V的电压时,记录了明显的电流峰;该电流随后降低直到恒定的剩余电流。当切断该电压时,大的电流开始在相反方向上流动,然后逐渐返回到0A。这样不发生电解,和因此不发生化学反应过程,所施加的电压保持在低于离子液体和聚氨酯基质的离子的电化学势。离子向该PUR基质中的电压诱导的迁移是在秒的时间规模上发生的,并且是可逆转换的。借助于从本发明的聚合物膜构造表面侧反射的激光束的位移,能够观察到通过离子迁移到PUR膜中而产生的本发明聚合物膜构造表面结构的转换。
实施例
2
:
在另外的试验中,将2K 聚氨酯(其是在名称“ISO-PUR A 776”下从ISO-Elektra
GmbH作为“自修复性凝胶”获得的)用作聚合物基质。将其类似于实施例1,以与作为离子液体的甲基乙基咪唑-辛基硫酸盐以1:1的重量比进行混合。将该混合物如实施例1所述,作为膜施加到其上布置有叉指式底电极的基材上,并且通过电场转换。当将2V电压施加到这种非常软的PUR-IL复合材料上时,从本发明的聚合物膜构造表面侧上反射的激光束的位移比实施例1所述的PUR配制剂变化得更大。由此可以得出结论,即,本发明的可电转换的聚合物膜构造的表面结构相比较而言变化得更大。
总之,本发明提供了可电转换的聚合物膜构造,使用其时,能够主动转换和影响表面和表面涂层的结构。
归因于本发明的可电转换的聚合物膜构造性能可变的可调整性,它们可以有利地适配于特定应用的各式各样的需求。
Claims (14)
1.可电转换的聚合物膜构造,其具有彼此相对布置的第一表面侧和第二表面侧,该聚合物膜构造包含聚合物基质和由阳极和阴极组成的至少一个电极对,特征在于任选地将赋予结构的颗粒布置在该聚合物基质中,并且该聚合物基质和/或该任选存在的赋予结构的颗粒是由电活性聚合物组成的,其中该第一表面侧和/或第二表面侧通过电转换该电活性聚合物来从平滑态转变成为结构化态。
2.根据权利要求1的可电转换的聚合物膜构造,特征在于该电活性聚合物是场活化的或者离子电活性聚合物。
3.根据权利要求1的可电转换的聚合物膜构造,特征在于它在平滑态时的厚度≥10µm和≤1mm。
4.根据权利要求1的可电转换的聚合物膜构造,特征在于该赋予结构的颗粒的直径是该聚合物膜构造厚度的50-90%。
5.根据权利要求1的可电转换的聚合物膜构造,特征在于该阳极和阴极布置在所述聚合物基质的相对置的表面上,该聚合物膜构造的一个表面侧经配置作为柔性盖电极,而在每一情形下另一表面侧经配置作为硬底电极。
6.根据权利要求1的可电转换的聚合物膜构造,特征在于阳极和阴极布置在所述聚合物基质的相对置表面上,并且该电极是以结构化方式布置在该聚合物膜构造的一个或者两个表面侧上。
7.根据权利要求1的可电转换的聚合物膜构造,特征在于该聚合物基质由电活性聚合物组成,并且该赋予结构的颗粒是非导电性硬质材料颗粒,该非导电性硬质材料颗粒不包括陶瓷硬质材料颗粒。
8.根据权利要求1的可电转换的聚合物膜构造,特征在于该硬质材料颗粒由玻璃或者选自下面的至少一种非导电性聚合物材料制成:聚乙烯、聚丙烯、聚氯乙烯、聚甲基丙烯酸甲酯、聚碳酸酯或者聚氨酯。
9.根据权利要求6的可电转换的聚合物膜构造,特征在于该聚合物基质由离子电活性聚合物组成,并且在该聚合物基质中没有布置赋予结构的颗粒。
10.根据权利要求1的可电转换的聚合物膜构造,特征在于该赋予结构的颗粒由电活性聚合物组成,并且该聚合物基质由弹性体形成。
11.根据权利要求1的可电转换的聚合物膜构造,特征在于将该第一或者第二表面侧施加到基材上,其中通过电转换该电活性聚合物来将在每一情况下另一个表面侧转换成结构化态。
12.可电转换的表面涂层,其包含权利要求1的可电转换的聚合物膜构造。
13.权利要求11的可电转换的表面涂层的用途,用作自洁性表面涂层,抗菌表面涂层、自除冰表面涂层和/或用于影响流体的流动行为。
14.权利要求11的可电转换的表面涂层的用途,其用于产生触觉、听觉和/或视觉信号。
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Also Published As
Publication number | Publication date |
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EP2417644B1 (de) | 2015-02-25 |
KR20120030044A (ko) | 2012-03-27 |
US9231186B2 (en) | 2016-01-05 |
WO2010115549A1 (de) | 2010-10-14 |
JP5668050B2 (ja) | 2015-02-12 |
TWI557958B (zh) | 2016-11-11 |
EP2417644A1 (de) | 2012-02-15 |
EP2239793A1 (de) | 2010-10-13 |
JP2012523809A (ja) | 2012-10-04 |
US20120128960A1 (en) | 2012-05-24 |
CN102460756B (zh) | 2015-01-07 |
TW201108481A (en) | 2011-03-01 |
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