CN102822252A - 带有气体减排部件的高表面积聚合物致动器 - Google Patents
带有气体减排部件的高表面积聚合物致动器 Download PDFInfo
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- F03G—SPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
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- H—ELECTRICITY
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Abstract
本文描述了一种聚合物致动器部件,聚合物致动器组件,电源以及利用激活机制启动的方法。致动器组件包括阳极、阴极、电解质,以及与阳极或阴极接触的体积可变的聚合物致动器,其中,电极彼此由多孔膜隔开,以利于通过电荷或离子分离对pH值调节。
Description
技术领域
本发明部分地得到了政府支持,通过合同号08348528由国家科学基金提供资助。政府可享有本发明的一定权利。
背景技术
本发明涉及体积可变材料,特别涉及到随pH值改变而体积发生变化的聚合材料。这种材料有利地应用于激活剂,例如施用治疗液体的泵中所用到的致动器,尽管其他应用方式可以预期的,但本发明将通过此类应用进行描述。
致动器是为多种不同应用产生位移或力的装置,可以呈现为许多形式,仅举几例:发动机、气缸、液压缸、电磁螺线管等。这些致动器用于多种不同的应用,并已使用多年。
已开发的一种特定类型的基于聚合物的致动器是基于弹性环氧树脂水凝胶聚合物的聚合物致动器。这种激活剂通过生成电极附近离子不平衡状态来工作的,利用与聚合物接触或接近的电极附近的正电荷或负电荷和电解质的离子种类来生成这种不平衡。通过增加胺基的密度或数量,例如伯胺或仲胺,使水凝胶的膨胀压增大,这也会影响膨胀和退溶胀的次数。
实现这一目标的方法之一是纳入聚酰胺胺(PAMAM)聚醚树状大分子、聚丙烯亚胺(PPI)树状大分子,氨基官能化树状大分子,或它们的组合,作为聚合物结构的一部分。树状大分子高度分支化,并且能提供数量极为庞大的聚合物交联点。而且带有表面伯氨基和内核氨基的树状大分子都有市售。这使得对凝胶材料进行设计成为了可能,以便特定的性能参数,例如凝胶能产生的压强,可以由材料的配比或对聚合物结构本身的组织、大小和分支数量进行控制来决定。水凝胶的密度和孔隙率则由胺官能度的量和聚醚胺的分子量控制。凝胶的密度和孔隙率也由聚乙二醇二缩水甘油醚的量,和/或水或用于聚合材料的水或溶剂的比例来控制。
这种凝胶优选的一种醚是聚乙二醇-十二烷基醚(polyEGDE),但其他醚类也可以使用,例如环己烷二甲醇缩水甘油醚。这些醚类可以制出非常澄清和牢固的水凝胶,这种水凝胶对于高pH值的水溶液表现出疏水性,而且暴露于低pH值或酸性溶液时则会膨胀。水凝胶的密度和孔隙率也可以通过在聚合过程中向聚合物中加入的一定量的氧化剂来进行控制。无论是在溶液中或在干燥状态下,在聚合过程中这些氧化剂都可以进一步通过电学方法、化学方法或由光子激活,以实现所需的性能。
离子水凝胶的膨胀动力学性质由水凝胶内外的溶液中的pH值、离子、阳离子或质子的差异,或水凝胶的聚合物的组成来实现。这些性能特点可以通过多种方法来控制。例如,在聚合过程中向聚合物内加入酸制成的水凝胶,具有较高的pH值膨胀性能。
水凝胶的膨胀动力学性质也可以通过在聚合过程中向聚合物中添加盐和碱性溶液来控制,这可以通过对环氧聚合物或是其水化的溶液进行化学、电学、电化学、光学或光化学激发而获得。
通过在电解质中水合环氧树脂水凝胶,将一个电极插在凝胶上,另一个电极置于距离水凝胶不远处,然后通过电极流通少量的电流以获得电激活的聚合物(EAP)是可能的。例如,以盐水作为电解液,环氧树脂水凝胶的膨胀在铂电极的区域可增加。当极性反转时,水凝胶将退膨胀或收缩。疏水性和亲水性的控制也可以通过这些方法实现。
这些聚合物致动器面临的一个挑战是产生足以泵送液体的驱动力和应变率。
这种聚合物致动器的另一个挑战是在操作过程中产生气体。利用电极和含水电解质的聚合物致动器特别有利于高效率的驱动,但可能水解产生氧和氢。
聚合物致动器中生成的气体会带来不良后果,它们对电荷迁移和机械系统都可能产生影响。气泡形成的绝缘袋会妨碍通过系统的电荷迁移。这会有效地降低电极和/或聚合物的表面积,从而降低聚合物的膨胀率。更糟的是,气袋的大小和具体成分都是可变并无法预知的,因而降低了任何使用聚合物致动器的设备的精确度。
此外,气体的膨胀会导致致动器出现明显的膨胀,在稍后由于气体的压缩或吸收致动器又会松弛。气体的产生因此降低了致动器的可重复性、可预见性和精确度。
加剧这些一致性问题的是致动器聚合物到非活性基质不一致的粘结。水凝胶容易分层,在水环境通常并不稳定,例如,妨碍了薄膜特性和在水介质中的使用。粘结可能需要增加化学物质和过程步骤的数量的溶液,从而增加了复杂性,而且可能会用到对环境有害的化学物质。
因此,需要一种致动器,既具有高致动率,又没有水解作用或其他气体产生的缺点。
更进一步的需求则是一种方便地附着在疏水表面上的水凝胶致动器。
传统的致动器不能满足这种应用的所有需求。此外,现有技术水平的聚合物致动器不会在电极的阳极或阴极一侧隔离和产生出明显的电解质的离子或pH值边界。
用于聚合物致动器的典型的电极材料是金属、碳或一些导电聚合物。电极的类型在一定程度上取决于致动器类型和需要产生所需反应的电解质化学性质。多数金属在使用上的缺点之一是它们在每个电极处进行的氧化和氧化还原反应中都不稳定。贵金属,如金和铂因性能稳定可以采用,但它们价格太高,并不适于工业化的实际应用。其他材料,例如碳和石墨是可行的,但其工作时的机械加工性质不好,导致它们也不实用。导电聚合物和其他聚合物的化学相容性非常有限。另一个所有电极都有的缺点是在电极和电解质接触的界面上会产生电化学气体。气体的产生,无论是类型还是体积,都取决于电极的极性和加载在致动器或致动器组件中电极上与电解质的电流。气体在一个封闭或密封的致动器系统中会产生显著的可压缩压力的问题,实际上超过聚合物的驱动或者体积变化的速度,从而在驱动循环中产生不可靠的结果。
发明内容
本发明克服了现有技术的上述和其他问题。本发明一方面提供了一聚合物致动器组件,该聚合物致动器组件具有由电解质中的多孔膜隔开的阳极和阴极,与一个或多个电极的表面接触的金属氢化物材料,以及与阳极或阴极接触的聚合物致动器。多孔膜作为屏障或隔膜材料,消除或减少离子或pH值区域的多根并合,大幅提高致动器材料的反应,精确度,时间和体积变化量,并且改善电极材料的范围和装置内阴极和阳极的电极配置。
溶液中带有多孔膜的电极可以方便地通过电荷或离子分离调节聚合物致动器周围的pH值。电解质可以是水溶液或者非水溶液。聚合物致动器,可配置电解液的pH值或化学变化引起的电极电势差扩大或缩小。聚合物致动器可以配置为根据两极间电势差引起的电解质中pH值或化学成分变化而膨胀或收缩。
致动器组件还可提供一个柔性密封外壳,来密封电极的进口和出口点。在可选的实施方式中,组件提供了第二个聚合物致动器,从而每个致动器都靠近一个电极,并且两个致动器都设置为在电势差作用在电极上时同时膨胀或收缩。
聚合物致动器和与聚合物致动器接触的电极,可以封装在一个由与多孔膜相同材料制成的柔性容器或袋内,电极的一部分在柔性容器的外面。柔性容器外部的电极部分则通过多孔膜材料与电解质绝缘,以在电势差作用在电极上时促进驱动。柔性容器或袋,或柔性容器或袋的至少一部分优选采用弹性材料制成。另外还需要可以让电解质或溶液透过的刚性结构,例如多孔的,环绕在聚合物致动器材料的周围,至少部分地环绕,以便控制致动的方向。
接触驱动刺激的聚合物致动器的表面积可以通过把聚合物致动器材料粉碎或研磨成更小的颗粒或微粒来增大。致动材料的微粒可形成含有电解质的浆液。微粒可以被封闭在一个柔性的多孔外壳中,外壳的外表面与电极接触,或让电极穿透外壳与微粒和微粒周围的电解质直接接触。这个柔性外壳可以包含,至少部分地包含在一个多孔的刚性容器里,这样可以允许在电解质流体流过刚性容器时控制驱动的行为。
致动器组件还可能包括气体吸收剂材料,如活性炭。可选地,电解质或溶液中产生的气体可以收集在柔性密封外壳外部的一个存储区域内。存储区域与电解质是流体连通的,以选择性的让气体通过,而不需将电解质迁移到存储区域内。
致动器组件中的聚合物致动器可以作为压板或活塞。此外,致动器组件中的电极可以配置为允许一个更复杂系统中的一系列致动器电连通性的串联。组件还可能包括一个可编程控制器和在电极上产生电势差以运转可编程控制器的电源。一个或多个传感器可以把反馈传递给控制器,以使致动器组件进行更多的自动操作。按所需配置的致动器组件或多个致动器组件,可用于泵送液体。
本发明在另一方面,提供了包括外壳,第一电极、第二电极和电解质的聚合物致动器组件。电极用膜隔开,以在第一和第二电极之间施加电压时保持围绕各自电极的电解质之间的pH值差异。组件可包括多个配置在电极附近来对电解质内的pH值改变做出反应的聚合物致动器。
通过将致动材料粉碎或研磨成颗粒可增加聚合物致动器的表面积。多孔容器是一种聚合物袋,致动材料的颗粒在袋内形成带有电解质的浆液。
在本发明的另一方面,聚合物致动器部件包括致动聚合物,这种聚合物可以对与疏水聚合物的交联刺激做出反应而增大体积。致动聚合物和疏水聚合物包括乙醚环氧化物和NH反应物,优选的NH成分对于两种聚合物都很常用。致动聚合物中的环氧化物是一种亲水的双氧化物,如聚乙二醇二缩水甘油醚。疏水聚合物的中的环氧化物是疏水性的双环氧化物,如新戊二醇二缩水甘油醚或聚丙二醇二缩水甘油醚。NH反应物可以是一种聚醚胺,如Huntsman公司的JEFF AMINE? T-403。疏水性聚合物还可包括聚乙烯亚胺和水,以减少聚合反应时间。
环氧化物对NH反应剂的比例在没有树状大分子的致动器聚合物中通常是大约1:2到1:10之间,最佳值约为1:2.85,疏水性聚合物中环氧化物对NH反应剂的比例通常是大概1:1.5到1:3,优选大约是1:2.0。纳入树状大分子后的环氧化物对NH反应剂的比例显著不同,取决于每个树状大分子上的NH位点的数量,其范围可以每个第1代分子中4个NH单位到每个第10代分子中超过5000个。结合了树状大分子的聚合物会有较大的环氧化物对NH反应剂的比例,可以很容易地达到1:4到1比数千NH单位。
本发明的复合水凝胶材料可用于生产一种用疏水性聚合物密封在一个限定体积中的致动器聚合物,或是一种通过疏水性聚合物与外界环境隔离的致动器聚合物。此复合水凝胶材料可以用作传感器材料结构,凝胶电解质材料,选择性离子渗透膜,液体过滤和处理部件,伤口护理膜或酸清除材料,以及其他本领域技术人员所认识到的其他应用。
本发明的另一个方面提供了一种聚合物致动器的材料,由一种包括亲水性醚和,疏水性醚的醚反应物和与环氧化物的醚反应物进行聚合反应而制成。材料的致驱动速度或材料的弹性可以通过主导醚反应物对次要醚反应物的比例来进行调整。在这方面,环氧化物对NH反应物的最优优选比例通常是大约1:2.5到1:3,更优选约为1:2.85。亲水醚对疏水醚的比例大约为100:1到1:100之间,通常约为99:1。
在另一个方面,本发明提供了对聚合物致动器电极的改进。通过但不限于在电极上应用或附着活性炭层,可以让电极有双倍的层容量或电荷存储,此电极需要在聚合物致动器中的电极和电解质交界处控制气体的产生。在这一方面中,本发明为激活聚合物致动器提供了一种装置,包括一个或多个聚合物致动器,每个致动器有一个或多个双层电容器电极。聚合物致动器可被电激活或化学激活。双层电容器电极插在电解质中,电解质可以是水溶液,也可以是非水溶液。电极可连接到放电电路和控制器,其中控制器被配置用来在预定的时间或当系统中电荷积累达到特定的量时打开和关闭放电电路。
附图说明
本发明的许多方面通过参考附图可以更好地被理解。附图上的部元件并不一定按比例缩放,强调的重点是清楚地表明本发明的原理。此外,附图中同样的附图标记在几幅图指定相应的零件,其中:
图1A和IB描绘了根据本发明一个方面的激活前和激活后的示例性复合环氧聚合物致动器部件;
图1C描述了按照本发明的复合环氧聚合物致动器部件的示例性阵列;
图2A以示意图的形式描绘了本发明的一个示例性致动器组件;
图2B以示意图的形式描绘了本发明的另一个示例性致动器组件,除其他部分外,还包括多个驱动区域;
图2C 以示意图的形式描绘了本发明的另一个示例性致动器组件,除其他部分外,还包括致动器组件的每个电极周围的氢化物材料;
图3A以示意图的形式以描绘了本发明的示例性致动器组件,除其他部分外,还包括气体吸收剂材料;
图3B以示意图的形式以描绘了示例性致动器组件,除其他部分外,还包括一个单独的室,用于隔绝致动器中可能产生的气体;
图4根据本发明的一个方面,以示意图的形式描绘了一种致动器组件,包括双层电容器电极。
具体实施方式
在下面的描述中,表示方向或几何的术语,如“上部”,“下部”,“侧面”,只参照附图中描绘的图的方向来使用。这些都不表示或限制于根据引力参照系确定的方向,只是用来区分彼此相对的方向。由于本发明的部件可以在许多不同的方向配置,方向术语用于说明图形目的,并不表示限制。可以理解,在不偏离本发明的范围的情况下,可以采用其他实施方式,也可在结构或逻辑上有所变化。
为了说明的简洁性,不同实施方式中的细节,如电源到电极的电流或布线路径信息等已忽略,因为这些路径的各种方法在现有技术中都是已知的。 “电解质”一词指的是并包括所有水性,非水性,聚合物和固体电解质,包括那些在现有技术中已知众所周知的。 “电极”一词是指通常用于电化学系统的阳极和阴极,电极是以现有技术中已知的材料制成,如金属、碳、石墨、氧化物或导电聚合物或这些材料的组合制成。 “隔膜”一词是指任何纳米,、微观或宏观的多孔材料,可以使得指定的离子通过或比含有离子的周围媒质更地穿过。 “离子”一词是指离子和离子种类以及阴离子、阳离子、电子、质子和这些离子的浓度值。 “外壳”一词是指设备装置的外表部分,可以用柔性材料、刚性材料、弹性材料、非弹性材料或这些材料的组合制成,例如橡胶、硅胶树脂、聚氨酯,金属化聚合物薄膜和其他现有技术上已知的塑料或聚合物。外壳被配置为允许内部零件运动和膨胀,也可以让允许电解质灌装填充到设备装置中,起到容器和屏障的作用以阻止任何电解质的泄漏或蒸发,如果需要的话,允许电极进出外壳并与电源电气接触,如果需要的话,也能排出产生的任何有害气体。
如图所示,致动器100部分地是由聚合物致动材料组成的。在一个示范示例性实施方式中这些聚合物致动器是由对离子或pH值有响应的基于聚合物的环氧聚合物水凝胶组形成的。这种聚合物的例子在在2007年7月10日提交,并于2008年7月3日发表公开的申请号为WO2008/079440 A2的共同拥有W1POWIPO专利申请号WO2008/079440 A2中有说明,该专利申请的标题名称为 “超弹性环氧水凝胶”。其它的聚合物致动器的例子,可能包括含有具有离子官能团的聚合物,如羧酸甲酸,磷酸,磺酸,伯胺,仲胺,叔胺,还有和铵,丙烯酸,甲基丙烯酸,乙烯基乙酸,马来酸,偏kurir基氧乙基磷酸,乙烯基磺酸,苯乙烯磺酸,乙烯基吡啶,乙烯基苯胺,乙烯基咪唑,氨乙基丙烯酸酯,甲氨基乙基丙烯酸酯,二甲氨基丙烯酸乙酯,乙氨基丙烯酸乙酯,乙基甲氨基丙烯酸乙酯,二乙氨基丙烯酸乙酯,氨乙基甲基丙烯酸甲酯,甲氨基甲基丙烯酸乙酯,二甲氨基甲基丙烯酸乙酯,乙氨基甲基丙烯酸乙酯,乙基甲氨基甲基丙烯酸乙酯, 二乙氨基甲基丙烯酸乙酯,氨丙基丙烯酸酯,甲基氨丙基丙烯酸酯,二甲氨基丙基丙烯酸酯,乙氨基丙基丙烯酸酯,乙基甲氨基丙基丙烯酸酯, 二乙氨基丙基丙烯酸酯,氨丙基甲基丙烯酸酯,甲氨基丙基甲基丙烯酸酯,二甲氨基丙基甲基丙烯酸酯,乙氨基丙基甲基丙烯酸酯,乙基甲氨基丙基甲基丙烯酸甲酯;聚合物,如二乙氨基丙基甲基丙烯酸酯,二甲氨基乙基丙烯酰胺,二甲氨基丙基丙烯酰胺,和αkurir基氧乙基三甲基铵盐,所用的都已有描述出来都被报道使用,这些例子仅作为参考,并不作为对本发明范围的限制。
本发明的某一方面包括疏水材料与智能水凝胶聚合物通过交联组成的新的致动聚合物,利用多个双环氧化物或者聚环氧化物作为交联机制,在分子水平上把材料粘附在一起。复合材料还可以通过使用单一的双环氧化物或聚环氧化物形成,然后通过具有不同的功能或高分子链和主链的聚胺成分,例如EFF AMINE?来交联材料的不同层。
以前提交的PCT/US2007/073188(整体包括于此),描述了用一种聚胺与缩水甘油醚反应而形成的独特的环氧水凝胶聚合物。产生的聚合物是一种超弹性水凝胶,适用于多种应用。环氧树脂环氧水凝胶可通过混合一定比例的 “醚反应物”,如聚乙二醇二缩水甘油醚和聚乙二醇胺以及水,致使使得这些材料发生水性聚合反应来进行生产。特别优选的是聚乙二醇胺,例如可从Huntsman公司在购买的商标名为JEFF AMINE?品牌下的,和其他聚醚胺作为 “环氧”的成分,这些成分与各种醚反应,形成环氧水凝胶。聚乙二醇胺所包含连接在聚醚主链的末端的主要氨基伯胺连接在聚醚主链的末端。因此,它们是“聚醚胺”。聚醚的主链基于环氧丙烷(PO),或是环氧乙烷(EO),或是混合环氧丙烷/环氧乙烷,或可包含其他主链片段以及通过阻碍伯胺或通过仲胺的官能度提供多样的反应。
在本发明的一个实施方式中,水凝胶聚合物致动器的亲水变体基于JEFF AMINE? T-403和聚乙二醇二缩水甘油醚与凝胶的疏水变体交联,其通过改变二缩水甘油醚(醚反应物)组分,并保持不变的环氧物JEFF AMINE? T-403组分实现。
由图1A可见,简单的气缸10由一半亲水致动器材料12和一半非驱动疏水材料14组成,两者可在分子水平上交联,该气缸可铸造。致动器材料12先放入模具或铸件进行部分地加工处理。然后,第二个材料放入模具,这两种材料都可以进行整体地加工处理。双环氧化物对NH的比例是可变的,新戊二醇二缩水甘油醚和聚丙二醇二缩水甘油醚都可以替代致动器材料中使用的聚乙二醇二缩水甘油醚。用JEFF AMINE ?T-403和新戊二醇二缩水甘油醚的混合物可以得到对于致动器应用具有疏水性能优势的聚合物。在这种方式下,两种或多种以上环氧聚合物可附着在一起,即使它们性能差异很大。
在一个特定的实施方式中,疏水聚合物14连接在致动器材料12上。图1C的疏水聚合物14连接在致动器的亲水材料12上,致动器材料12上有可定址的电极6和7,电极通过电路连接在一个或多个控制器传感器和电源上。JEFF AMINE? T -403中可添加多种不同的化学物质,以制成一种既具有疏水性能又有能力和之前递交的PCT/US2007/073188中所描述的致动器凝胶结合的聚合物。例如,新戊二醇二缩水甘油醚可添加到JEFF AMINE? T -403中,环氧化物/NH反应物配比的比例为1比:2.85,与标准的致动器凝胶配方中环氧化物/ NH反应物配比的比例相同。为了促进聚合反应,环氧化物与NH反应物的比例可能需要下调。新戊二醇二缩水甘油醚和JEFF AMINE? T-403的混合物按照具有环氧化物/NH反应物的比例为1比:1.7、1.8、1.9和2.0进行混合,这些比例被证实经过在60℃加热5小时,并在常温下进一步固化72小时后,均可成功聚合。按这些比率产生的聚合物由于其疏水性,放在水中存储三个星期后,膨胀率最高约为8 - 10%。此外,随着环氧化物对NH反应物的配比比例增加,由此产生的聚合物弹性也有所增加。因此,具有环氧化物/NH的比例为1:2.0的JEFF AMINE? T-403与新戊二醇二缩水甘油醚的混合物,展现出与致动器聚合物12之间优异的附着力,不仅是在固化后,还有通过水合作用时。
如果需要的话,可以增加疏水性和减少聚合所需的时间。聚(丙二醇)缩水甘油醚(PPGDGE)可以添加到新戊二醇二缩水甘油醚和JEFF AMINE? T-403的混合物中,保持环氧化物和NH反应物的比例为1:2.0或更多。合成了具有10%,26%和50%的PPGDGE的聚合物,并将其储存在水中,以测试它们的疏水性或抗膨胀能力。所有的凝胶在水中储存两周后都膨胀12%至15%。此外,令人惊讶的是,与基础成分新戊二醇二缩水甘油醚和JEFF AMINE? T-403相比,PPGDGE的添加导致聚合物的弹性下降。
为了缩短凝胶的固化时间,可以把聚乙烯亚胺(分子量1300)添加到基础成分新戊二醇二缩水甘油醚和JEFF AMINE? T-403的凝胶中。添加10%和15%的聚乙烯亚胺和10%的水,可以让凝胶的聚合反应更加迅速。凝胶经过60℃下加热5小时后完全地聚合,并不需要在室温下进一步固化以降低凝胶的粘性。
聚合更快的优势可能伴随有疏水性的下降。试验发现这些包含聚乙烯亚胺的凝胶在水中存储两周后会膨胀23%至32%。因此,具有疏水性增加和聚合反应时间减少的聚合物是可能的,但可能会伴随有性能折衷,特别是在所得聚合物的疏水性方面。
与环氧化物对NH反应物的比例相比,高分子链的长度和胺的比例对环氧化物/NH反应物的比例也可能减少亲水致动器凝胶的聚合反应时间。例如,使用聚乙烯亚胺(支化聚合物,与类似Epomin SP-012类似)对不同成分组成进行了评估,聚乙烯亚胺为低摩尔浓度,质量百分比为50%,在水溶液中分子量为2000和1300。生成的凝胶可以在室温下聚合反应约40分钟,环氧化物对NH的比例为1:7或更高。这些凝胶比较脆而且硬,显示出正常范围水合率,约400%与我们的标准凝胶配方一致。
对亲水致动器聚合物和疏水聚合物组成的新型复合致动器结构的初始致动测试,如图IB所示,成功地表明在1mA的正向电流作用下每个致动器部分都膨胀了100%。因此,采用这种经检验的复合聚合物可以有效地构造可寻址的定位蠕动式的泵机制,或图1C所示的致动器阵列。同样,经检验的聚合物被证明是快速化学反应水凝胶,能够在各种应用中使用。包括这些聚合物的材料,可以以多层次和形状进行铸造,有利于特定用途和应用。
在本发明的另一个实施方式中,两种或更多的双环氧化物结合成一种单一的聚合物致动器组合物,而这种致动器材料的性能可以根据功能主导的双环氧化物对功能次要的双环氧化物的比例进行调整。功能主导的双环氧化物对功能次要的双环氧化物的比例可以变化以有利地改变材料的驱动速度或柔韧度。在一个特定的实施方式中,把1%的新戊二醇二缩水甘油醚加入到前文PCT/US2007/073188提到的JEFF AMINE? T403和PEGDE的配方中,可以制成速度更快的致动器。这并不是要限制通过交联功能层制成的复合组件的使用或所用的材料。
复合水凝胶材料可以用作传感器材料结构,凝胶电解质材料,选择性离子渗透膜,液体过滤和治疗、伤口护理膜,致动器或者甚至酸清除材料。这个过程也可被用来密封复合结构的外层或不同层,例如致动器,从而有效地把所含的电解质密封在聚合物内或周围,以防止蒸发。此外,内部材料可以通过使用所述的复合水凝胶的通过紫外线曝光保护,来防护来自外界环境的侵害。上述实施方式只是本发明的复合凝胶的可能应用的几个例子,并不意味着限制本发明的范围。
在一种应用中,本发明涉及对一种聚合物致动器的改进,包括增加有效表面积以增加聚合物致动器的膨胀率的大小和可重复性。这已经通过增加聚合物的实际表面积和有效表面积,改进电极和采用减排气体的方法而得以实现。本发明的改进,已证明可以让体积膨胀率相对于现有技术的方法提高400%,同时减少不确定性。
图2A以示意图的方式描述了根据本发明的致动器组件100的一个示例性实施方式。致动器组件100包括聚合物致动器材料113和相关电极组,该电机组包括顶部电极106和底部电极108。底部电极与金属氢化物材料110接触。电极组和聚合物致动器113装在外壳114内。外壳114可由折痕,褶皱或边上的其他附加材料构成,以适应致动器材料的高膨胀率,以及提供储藏容器或区域来收集产生出的额外气体,而不影响致动器组件的膨胀率。电解质112也可包含在外壳114内,并与电极组(106,108)和致动器113接触。致动器113是一个经过研磨水合环氧凝胶,把凝胶装入一个柔性的多孔袋116中而成的聚合的聚合物致动器。致动器113,也可以由两个或多个上述的双环氧化物组成,以改变致动器材料的性能。袋116用编织的聚丙烯网116制成,厚度0.006”,孔径150微米并且进行了热密封。配置中可以使用一个或多个袋,以在容量和强度方面获得优势。多孔隔膜115在保持连续电解质112的情况下,隔开了电极108和相对电极106间的pH梯度。
聚合物致动器113可随电解质112的变化膨胀和收缩。聚合物致动器113有多种类型可用,包括“酸响应”聚合物致动器和“碱响应”聚合物致动器。“酸响应”聚合物致动器会因聚合物致动器113周围的电解质112的pH值降低而膨胀。这可以通过施加电极106相对电极108的正偏压而实现。施加正偏压,导致电流从电极106流向电极108,并导致致动器113周围的电解质112中的阳离子(H +)浓度增加。在水溶液中设置的电极之间施加的电压,由于电极反应消耗氢离子和/或氢氧根离子,或由于电极表面出现双电荷层而产生浓度梯度,从而改变在电极附近的pH值。因此,致动器113周围的电解质变得酸性更强(pH值降低),而导致致动器113膨胀。
由于固态聚合物凝胶块的膨胀速度受到电解质或溶剂通过聚合物扩散的能力的限制,致动器的驱动速度可以通过增加聚合物致动器材料与电解质接触的表面积来提高。如果电偏压反转,阳离子反向流动,并且致动器113周围的电解质112碱性增强(或酸性减弱),这将导致致动器113出现相反的效果。
“碱响应”聚合物致动器113也可以使用。在这种情况下,施加电极106相对电极108的负偏压会导致聚合物致动器周围的电解质112的 pH值增加,这将反过来导致碱响应聚合物致动器113膨胀。在这种情况下,金属氢化物110会在水性电解质溶液中接触电极 106,取决于电解质、电化学反应和在运行过程中产生的气体类型。当聚合物致动器113膨胀时,它会导致整个致动器组件100膨胀。
图2B以示意图的形式描述了致动器组件的一种替代设计120,其同时利用酸响应和碱响应致动器。致动器组件120包括酸响应致动器铸造凝胶123A,碱响应聚合物致动器铸造凝胶123B,顶部电极128,穿出外壳与金属氢化物121接触的底部电极126,全装在外壳124内。顶部电极128和酸响应感致动器123A周围是电解质122A;底部电极126和碱响应致动器123B周围是底部电解质122B。多孔隔膜125把顶部电解质122和底部电解质122B分隔开,同时允许离子在电解质之间流动。
当正偏压电流施加在顶部电极128和底部电极126之间时,顶部电解质122A的pH值会降低,而底部电解质122B的pH值则增加。顶部电解质122A pH值的降低(酸性增强)会导致酸响应聚合物材料123A膨胀,底部电解质122B pH值升高(碱性增强),会导致碱响应聚合物材料123B膨胀。两层致动器可以让整个致动器组件120获得的总位移加倍。据预测,用酸响应和碱响应聚合物致动器交替叠加而成的聚合物致动器附加层,可用于进一步提高致动器组件120的最大总膨胀量。
致动器组件130的一种可替代的实施方式如图2C所示,且包括图2A所示的带有顶部电极136,以及与顶部电极136接触的金属氢化物材料131A,还有底部电极138的致动器组件的相同的实施方式。
致动器组件130的一种可替代的实施方式如图2C所示,且包括图2A所示的带有作为铸造凝胶的复合物致动器材料的致动器组件的相同的实施方式,在相同的配置中也可使用多个致动器材料模件或袋,对于描绘的所有配置同样如此,图2C也示出了顶部电极136,与电极136接触的金属氢化物131A,以及底部电极138。
另一种聚合物致动器组件的实施方式如图3A所示,其中顶部电极206靠近气体吸附剂材料215,如活性炭,这样的材料可以在潮湿情况下吸附气体,例如氧气。气体吸附材料与电解质212接触,吸附从电极206产生并穿过电解质212的气体。底部电极208与金属氢化物材料210接触。电极组和作为铸造凝胶的致动器材料213都包含在外壳214内。外壳214内装有与电极组和致动器材料213接触的电解质212。多孔隔膜215把电极208和周围的电解质212分隔开。利用与图2A描述的相同类型的驱动机制和响应方式,聚合物致动器213会根据电解质212的变化而膨胀或收缩。
而另一个优选的聚合物致动器组件的实施方式如图3B所示,其中致动器材料230是装在多孔柔性袋223中的聚合物微粒,然后聚合物微粒容纳袋223装在牢固的多孔结构 229中,这样可以帮助容纳并引导柔性袋223在聚合材料230致动器做出驱动响应时向一个方向膨胀,可以提高推动的效率以及增加板228在因聚合材料230膨胀而随之膨胀的柔性袋223的推动下移动的距离。顶部电极206插入聚合物微粒230之间的微粒袋223中,以最大化接触。
组件224开孔至另一个气体吸收材料227中,例如“Oxisorb”液态氧吸收剂。气体吸收剂227通过疏水隔膜材料226与电解质分隔开,这样可以限制电解质液体,却让气体渗透通过。在排气孔也可以不用吸收剂227,使得仅把气体容纳在分离的隔间中,使气体不会影响聚合材料的驱动。隔膜材料226与电解质222接触,收集电极206产生并穿过222电解质迁移的气体。底部电极208与金属氢化物材料221接触,这样可以使气体吸附到金属氢化物材料221上。电极组(206,208)和聚合物致动器223都容纳在与电解质222接触的外壳224中。多孔膜225可以把电极208同周围的电解质222分隔开。
所有图中都显示了电源101和控制器103,用于控制致动器组件的运动、速度和力。在图3B的实施方式中,也示出了与传感器105的交互作用,以进行反馈并自动化控制致动器组件。
在各种分析科学和方法,如HPLC或其他色谱的方法中有许多已知的减排气体的材料和技术,本文描述的所有实施方式是为了示出利用了减排气体的材料、部件和技术作为组件一部分的可能的致动器组件配置,而不是以任何方式限制本发明的范围。
在本发明的另一方面,具有双层电容或电荷存储的电极被用于控制致动器中气体的生成。例如,伪电容型电极可用于控制气体生成。
根据本发明,电流建立一个电荷层,而不是在电解质和电极表面界面生成气体。这个过程一直持续直到电极完全充电,此时,电荷分散,气体产生。
正如图4所示的例子中所见,致动器组件容纳在柔性的非渗透的外壳材料302中,例如(但不局限于)金属化聚乙烯薄膜。外壳包含电解质308,聚合物致动器材料301,容纳聚合物的半多孔容器303,接触或靠近聚合物304的电极,位于电极之间的半多孔隔膜或板305,碳聚四氟乙烯电容层涂层306,与放电电路309电气连接的相反电极307,控制器和电源。
在本发明所示方面的一个实施例中,在充电周期中的预定时间为电极放电。在这个实施例中,气体产生的点是预定时间的函数,而不是电容内的能量积累率的函数。一旦发生放电,充电过程会重新启动,从而通过利用充放电循环使电极不产生气体。
为了制造这类电极,需要把特氟隆(聚四氟乙烯)水乳液,例如杜邦公司制造的,与高表面积炭或其他高表面积材料,如活性炭;还有氧化物,如金属氧化物;以及其他材料,如金属氢化物混合。这些材料可以单独使用也可混合在一起,以得到一个所需的电极气体减排的效果曲线。高表面积材料与乳液混合,压制或涂到电极上,并烘烤至正确的处理温度使得混合物一起结合到电极上,这个过程在电池和电容器制造的技术领域中是众所周知的。电极基质上可以用固态金属(例如但不仅限于低成本的铝或不锈钢箔)穿孔、膨胀或电镀,就像本领域中众所周知的那样。
应当强调的是,本发明的上述实施方式,特别是,任何“优选”的实施方式,只是实施的可能例子,仅是为了更清楚地了解本发明的原理。上述的实施方式可以在没有大幅偏离发明的精神和原则的前提下进行许多变化和修改。所有这些修改和变化都意味着包括在此处本发明的范围内,为以下的权利要求所保护。
Claims (51)
1.一种致动器组件,包括阳极和阴极,电解质以及与阳极或阴极接触的体积变化的聚合物致动器,其中电极由多孔膜彼此分隔,该多孔膜有利于通过电荷或离子分离调节pH值。
2.根据权利要求1所述的致动器组件,还包括接触并覆盖一个或多个电极表面的金属氢化物材料。
3.根据权利要求2所述的致动器组件,还包括一种密封的柔性外壳,封闭有电解质,阳极,阴极,和体积变化的聚合物致动器,电极的密封入口或出口,其中体积变化的聚合物致动器配置为可响应电势差引起的电解质中pH值或化学变化而膨胀或收缩。
4.根据权利要求3所述的致动器组件,还包括第二体积变化聚合物致动器,其中每个体积变化聚合物致动器都与一个电极相邻,并以多孔薄膜彼此隔开;而且其中体积变化聚合物致动器配置为在施加电势差时同时膨胀或收缩。
5.根据权利要求3所述的致动器组件,其中体积变化聚合物致动器和接触聚合物致动器的电极被密封在一个用与多孔膜相同材料制成的柔性容器或袋内;而且其中电极伸出柔性容器的部分保持与电解质连续地绝缘。
6.根据权利要求5所述的致动器组件,其中柔性的容器或袋,或柔性容器或袋的一部分,是由弹性材料制成的。
7.根据权利要求3所述的致动器组件,还包括一种至少部分包围着体积改变聚合物致动器材料的刚性结构,以促进驱动的方向;其中刚性结构可以让电解质透过。
8.根据权利要求7所述的致动器组件,其中至少有一部分刚性结构是多孔的。
9.根据权利要求3所述的致动器组件,其中体积变化聚合物致动器包括一种致动材料的微粒,这种致动材料的微粒和电解质形成浆液,而且其中致动器组件还包括一个具有内部和外部的柔性多孔壳,其中致动材料微粒都容纳在壳内部。
10.根据权利要求9所述的致动器组件,其中一个电极与壳外部的表面接触。
11.根据权利要求9所述的致动器组件,其中一个电极与壳内部的聚合物致动器微粒接触。
12.根据权利要求9所述的致动器组件,其中壳容纳在一个刚性多孔容器内,电解质可以透过容器流到壳内的致动材料上。
13.根据权利要求3所述的致动器组件,还包括气体吸收剂。
14.根据权利要求3所述的致动器组件,还包括一个在密封柔性外壳外的存储区域,此区域与密封柔性外壳内的电解质保持流体连接。
15.根据权利要求1所述的致动器组件,其中致动器组件的电极配置为允许致动器组件与至少一个其他致动器组件串联的电气连接。
16.根据权利要求1所述的致动器组件,其中电解质包括水性溶液。
17.根据权利要求1所述的致动器组件,其中电解质包括非水性溶液。
18.根据权利要求1所述的致动器组件,其中聚合物致动器驱动压板或活塞。
19.根据权利要求18所述的致动器组件,其中压板或活塞要泵送流体。
20.根据权利要求1所述的致动器组件,还包括电源和可编程控制器。
21.根据权利要求20所述的致动器组件,还包括一个或多个把反馈传递给控制器的传感器。
22.一种聚合物致动器组件,包括:
外壳;
与电解质的第一部分接触的第一电极;
与电解质的第二部分接触的第二电极;
分隔电解质的第一部分和第二部分的薄膜,以在第一和第二电极之间施加电压时,在电解质第一和第二部分之间产生pH值差;
多个聚合物致动器,其设置在电解质的第一部分中,并配置为根据电解质的第一部分中的pH值改变而改变体积。
23.根据权利要求20所述的聚合物致动器,其中至少一个聚合物致动器包括容纳在多孔容器内的聚合物致动材料的颗粒。
24.根据权利要求23所述的聚合物致动器,其中多孔容器是聚合物袋。
25.根据权利要求23所述的聚合物致动器,其中聚合物致动材料的颗粒包括具有电解质的浆液。
26.一种聚合物致动器部件包括一种受到刺激后体积增大,与疏水聚合物交联的致动聚合物。
27.根据权利要求26所述的聚合物致动器部件,其中致动聚合物和疏水聚合物包括NH反应物和环氧化物。
28.根据权利要求27所述的聚合物致动器部件,其中致动聚合物内的NH反应物与疏水聚合物中的NH反应物包括相同的NH反应物。
29.根据权利要求27所述的聚合物致动器部件,其中致动聚合物中的环氧化物包括聚乙二醇二缩水甘油醚。
30.根据权利要求27所述的聚合物致动器部件,其中疏水聚合物中的环氧化物包括新戊二醇二缩水甘油醚或聚丙二醇二缩水甘油醚。
31.根据权利要求27所述的聚合物致动器部件,其中疏水聚合物中的NH反应物包括聚醚胺。
32.根据权利要求27所述的聚合物致动器部件,其中致动器聚合物中的NH反应物包括聚醚胺。
33.根据权利要求28所述的聚合物致动器部件,其中NH反应物包括聚醚胺。
34.根据权利要求33所述的聚合物致动器部件,其中聚醚胺包括聚乙二醇胺。
35.根据权利要求27所述的聚合物致动器部件,其中疏水聚合物中环氧化物对NH反应物的比例是1:1.5到1:4之间。
36.根据权利要求27所述的聚合物致动器部件,其中疏水聚合物中的环氧化物对NH反应物的比例为1:2.0。
37.根据权利要求26所述的聚合物致动器部件,其中疏水聚合物包括聚乙烯胺和水。
38.一种聚合物致动器材料,包括NH反应物和环氧化物,其中环氧化物包括亲水醚或疏水醚。
39.根据权利要求38所述的聚合物致动器材料,其中环氧化物对NH反应物的比例是1:2.85。
40.根据权利要求38所述的聚合物致动器材料,其中亲水醚对疏水醚的比例为99:1。
41.根据权利要求35所述的聚合物致动器材料,其中疏水聚合物用于保护亲水聚合物免受外部环境影响。
42.根据权利要求35所述的聚合物致动器材料,其中疏水聚合物将致动器聚合物密封在限定的体积中。
43.一种激活聚合物致动器的装置,包括一个或多个聚合物致动器,每个致动器有一个或多个双层电容器电极。
44.根据权利要求43所述的装置,其中聚合物致动器通过电激活。
45.根据权利要求43所述的装置,其中聚合物致动器通过化学方法激活。
46.根据权利要求43所述的装置,其中一个或多个双层电容器电极位于非水性电解质中。
47.根据权利要求43所述的装置,其中一个或多个双层电容器电极在水性电解质中。
48.根据权利要求43所述的装置,其中双电层电容器电极连接到放电电路,其中放电电路与控制器电接触。
49.根据权利要求48所述的装置,其中放电电路包括存储装置,用于存储和重复利用电荷。
50.根据权利要求43所述的装置,其中控制器被配置为在预定时间或当系统积累到指定的电荷量时打开和关闭放电电路。
51.根据权利要求43所述的装置,其中聚合物致动器串联起来形成了一个泵。
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Also Published As
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EP2531549A1 (en) | 2012-12-12 |
US20120029430A1 (en) | 2012-02-02 |
JP5895313B2 (ja) | 2016-03-30 |
WO2011094747A1 (en) | 2011-08-04 |
JP2013519344A (ja) | 2013-05-23 |
US20170069824A1 (en) | 2017-03-09 |
US9500186B2 (en) | 2016-11-22 |
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