CN114214842B - 一种具有光电刺激响应双程形状记忆纤维及其制备方法 - Google Patents
一种具有光电刺激响应双程形状记忆纤维及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种具有光电刺激响应双程形状记忆纤维及其制备方法,属于高分子、金属科学技术领域。该结构以光响应形状记忆聚合物SMP作为包裹料,以形状记忆合金SMA作为芯料,当光照射到SMP时,使其发生形状回复,并带动SMA卷曲变形。对SMA进行通电加热,使其形状回复,同时热能使SMP变软,并跟随SMA展开变形。通过对所述纤维结构进行光照和通电,可实现功能性的选择和大型可延展性设备的携带,与普通的形状记忆材料相比,该构造具有刚度大,质量体积小,可重复展开和折叠,易于控制等优点。
Description
技术领域
本发明涉及一种具有光电刺激响应双程形状记忆纤维及其制备方法,属于高分子、金属科学技术领域。
背景技术
形状记忆聚合物(Shape Memory Polymer,SMP)是一类既能在外界作用(温度、力等)下改变形状并保持临时形状、又能在外界刺激作用(热、光、磁等)下由临时形状逐渐回复到初始形状的高分子材料。SMP材料具有变形大、成本低、密度小、制备简单、组分易调控和易于成型等优点,因而成为近年来智能材料尤其是形状记忆材料领域的研究热点。
近年来,随着科学技术和制造业水平的发展与提高,SMP独特的形状记忆效应和可调谐弹性模量为基于SMP的柔性光/电子器件的研究和应用开辟了新的领域。SMP及其复合材料的新功能和新特性赋予了柔性光/电子器件更多的功能,从而实现一些新的应用。除此之外,4D打印技术的发展为制备具有刺激响应型的复杂三维智能结构件提供了更多的可行性。
众多国内外研究学者都对形状记忆复合材料做了大量的研究使SMP复合材料得到了前所未有的发展,然而关于SMP复合材料在实际中的应用依然还有很多问题需要解决。首先,在特定的应用环境中要求形状记忆复合材料具有全方位的性能,这就需要对SMP复合材料的性能和结构进行大量的研究,如增强材料和聚合物基体的界面结合情况以及对性能的影响等问题;其次,SMP复合材料的回复应力很低,这在很大程度上限制了其应用,虽然形变回复应力可以通过与其他材料共混得到一定程度的改善,但这种方法会导致形变回复率和形变应变降低;最后,大多数形状记忆效应的研究只是简单的形状收缩或者弯曲过程,双程或者多程形状记忆效应的研究仍在初始阶段,而具有可控的回复速度、更高的回复程度、准确的回复形状和较高的回复力的研究亟待解决。
发明内容
[技术问题]
依靠SMP形状记忆效应驱动的弹性基体可实现重复展开和折叠,但SMP相变产生的驱动力较小,限制了弹性基体的模量,导致主动器刚度小,不满足可展开结构的工作需求。
[技术方案]
基于上述技术问题,本发明将形状记忆聚合物(Shape Memory Polymer,SMP)与形状记忆合金(Shape Memory Alloy,SMA)构成一个组合纤维结构,本发明以SMP作为包裹料,SMA作为芯料,采用SMP充当弹性基体,弯曲折叠由SMP驱动,展开由SMA驱动。当温度大于玻璃化转变温度(Tg)时弹性模量较小,可满足SMA驱动力限制;当温度小于Tg时弹性模量较大,通过材料设计使展开锁定后的温度低于SMP的Tg点,可达到提高刚度的目的。由此构造出刚度大、质量体积比小、可重复展开和折叠的SMA-SMP双程记忆纤维材料。
本发明利用光致型SMP在光照的刺激下与记忆金属在电的刺激下能够从变形态逐渐回复到初始态的特殊性能,设计了具有双程形状记忆效应的组合纤维结构。在光和电的配合下,该结构可以实现在光电控制下完成折叠展开过程。与普通的形状记忆材料相比,该构造具有刚度大,质量体积小,可重复展开和折叠,易于控制等优点。
本发明首先提供了一种具有光电刺激响应双程形状记忆纤维,所述具有光电刺激响应双程形状记忆纤维包括芯料以及包裹在芯料外层的包裹料,其中,所述芯料为SMA,所述包裹料为SMP。
在本发明的一种实施方式中,所述形状记忆合金包括Au-Cd、Ag-Cd、Cu-Zn、Cu-Zn-Al、Cu-Zn-Sn、Cu-Zn-Si、Cu-Sn、Cu-Zn-Ga、In-Ti、Au-Cu-Zn、Ni-Al、Fe-Pt、Ti-Ni、Ti-Ni-Pd、Ti-Nb、U-Nb或Fe-Mn-Si的任一种或几种。
在本发明的一种实施方式中,所述形状记忆聚合物为光致型形状记忆聚合物。
在本发明的一种实施方式中,所述光致型形状记忆聚合物包括含有N-取代肉桂酰胺光敏结构单元的热塑性聚氨酯类多嵌段共聚物,交联的聚丙烯酸乙酯,偶氮苯侧链的聚乙烯醇单分子聚合物等的一种或几种。
工作原理如下:在空间利用方面,该结构在正常情况下有两种工作状态:收缩状态和展开状态。收缩状态的实现是通过光照照射光响应SMP,使其发生形状回复,并带动SMA弯曲变形。因此该设计要求既能节约空间,又能考虑到形状记忆聚合物材料的柔韧性,即形状记忆聚合物材料在弯曲成一定夹角时不会发生断裂。展开状态的实现是通过对SMA通电加热,SMA形状回复,同时热使SMP变软,并跟随SMA展开变形。该设计充分展现了记忆合金的记忆效应和伪弹性,由于采用SMP充当弹性基体,该过程产生的耗散能将大大减少。本发明通过光照实现本发明纤维结构的收缩状态,又能通过利用通电实现本发明纤维结构的展开状态,即可以完全用外界刺激实现双程形状记忆功能,无需使用人工外力,可重复展开和折叠,易于控制。
本发明还提供了上述具有光电刺激响应双程形状记忆纤维的制备方法,包括以下步骤:
将SMA在外力作用下通过压轮,使其横截面积被压缩,以获得所要求的横截面积形状和尺寸;通过包覆工艺,将对应光响应SMP包覆到SMA外,即可制备得到上述具有光电刺激响应双程形状记忆纤维。
在本发明的一种实施方式中,为了提高柔韧度和整体度,让两根以上的SMA单线,交织在一起作为芯料。
在本发明的一种实施方式中,所述具有光电刺激响应双程形状记忆纤维的驱动过程包括:对光响应SMA-SMP组合纤维进行光照处理使其形状回复,并带动SMA卷曲变形;对SMA-SMP组合纤维进行通电,使SMA加热并带动处于高弹态下的SMP展开变形,实现光电刺激条件下的双程形状记忆效应。
本发明还提供了包含上述具有光电刺激响应双程形状记忆纤维的柔性电子器件或设备。
本发明还提供了上述具有光电刺激响应双程形状记忆纤维在高分子等领域的应用。
本发明相对于现有技术,具有以下的优点和效果:
本发明以具有形状记忆效应的物质作为结构材料,同时也是实现其转变的功能材料,将形状记忆聚合物与记忆合金构成一个组合纤维结构,使其具有展开和折叠的功能。它有以下优势:(1)形状记忆聚合物材料的密度一般较低,因而能在很大程度上降低材料的质量;(2)在光电控制下,以形状记忆聚合物和形状记忆合金相互作用下完成形状转变,控制更加精确,提高了驱动力,降低了能耗损失。
附图说明
图1组合纤维结构折叠-展开过程示意图,a表示展开状态,b表示收缩状态,c表示再次展开状态。
具体实施方式
下面结合实施例对本发明作进一步的描述,但本发明的实施方式不限于此。
实施例1
一种具有光电刺激响应双程形状记忆纤维,所述具有光电刺激响应双程形状记忆纤维包括芯料以及包裹在芯料外层的包裹料,其中,所述芯料为形状记忆合金,所述包裹料为形状记忆聚合物。
进一步的,所述形状记忆合金包括Au-Cd、Ag-Cd、Cu-Zn、Cu-Zn-Al、Cu-Zn-Sn、Cu-Zn-Si、Cu-Sn、Cu-Zn-Ga、In-Ti、Au-Cu-Zn、Ni-Al、Fe-Pt、Ti-Ni、Ti-Ni-Pd、Ti-Nb、U-Nb或Fe-Mn-Si的任一种或几种;所述形状记忆聚合物为光致型形状记忆聚合物,包括含有N-取代肉桂酰胺光敏结构单元的热塑性聚氨酯类多嵌段共聚物,交联的聚丙烯酸乙酯,偶氮苯侧链的聚乙烯醇单分子聚合物等的一种或几种。
进一步的,上述具有光电刺激响应双程形状记忆纤维通过以下方法制备得到,且使用过程如下:
第一步,将SMA在外力作用下通过压轮,使其横截面积被压缩,以获得所要求的横截面积形状和尺寸;
第二步,为了提高柔韧度和整体度,让两根以上的单线,按着规定交织在一起;
第三步,采用专用的设备,通过包覆工艺,将对应光响应SMP包覆到SMA外制备得到具有光电刺激响应双程形状记忆纤维;
第四步,对光响应SMA-SMP组合纤维进行光照处理使其形状回复,并带动SMA卷曲变形;
第五步,对SMA-SMP组合纤维进行通电,使SMA加热并带动处于高弹态下的SMP展开变形,实现光电刺激条件下的双程形状记忆效应。
本发明上述具有光电刺激响应双程形状记忆纤维的工作原理如下:
在空间利用方面,该结构在正常情况下有两种工作状态:收缩状态和展开状态。如图1a、b所示,收缩状态的实现是通过光照照射光响应SMP,使其发生形状回复,并带动SMA弯曲变形。因此该设计要求既能节约空间,又能考虑到形状记忆聚合物材料的柔韧性,即形状记忆聚合物材料在弯曲成一定夹角时不会发生断裂。如图1b、c所示,展开状态的实现是通过对SMA通电加热,SMA形状回复,同时热使SMP变软,并跟随SMA展开变形。该设计充分展现了记忆合金的记忆效应和伪弹性,由于采用SMP充当弹性基体,该过程产生的耗散能将大大减少。
实施例2
一种具有光电刺激响应双程形状记忆纤维,包括芯料以及包裹在芯料外层的包裹料形状记忆聚合物,其中,所述芯料为形状记忆合金Au-Cd,所述包裹料为交联的聚丙烯酸乙酯基SMP。制备方法如下:
第一步,将形状记忆合金Au-Cd在外力作用下通过压轮,使其横截面积被压缩,以获得所要求的横截面积形状和尺寸,将两根形状记忆合金交织在一起;
第二步通过包覆工艺,将对应光响应SMP包覆到SMA外制备得到具有光电刺激响应双程形状记忆纤维,即SMA-SMP组合纤维。
对光响应SMA-SMP组合纤维进行光照处理使其形状回复,并带动SMA卷曲变形,再对SMA-SMP组合纤维进行通电,使SMA加热并带动处于高弹态下的SMP展开变形,重复多次,实现了光电刺激条件下的双程形状记忆效应。
实施例3
一种具有光电刺激响应双程形状记忆纤维,包括芯料以及包裹在芯料外层的包裹料形状记忆聚合物,其中,所述芯料为形状记忆合金Cu-Zn-Al,所述包裹料为偶氮苯侧链的聚乙烯醇单分子SMP。制备方法如下:
第一步,将形状记忆合金Cu-Zn-Al在外力作用下通过压轮,使其横截面积被压缩,以获得所要求的横截面积形状和尺寸,将两根形状记忆合金交织在一起;
第二步通过包覆工艺,将对应光响应SMP包覆到SMA外制备得到具有光电刺激响应双程形状记忆纤维,即SMA-SMP组合纤维。
对光响应SMA-SMP组合纤维进行光照处理使其形状回复,并带动SMA卷曲变形,再对SMA-SMP组合纤维进行通电,使SMA加热并带动处于高弹态下的SMP展开变形,重复多次,实现了光电刺激条件下的双程形状记忆效应。
当选用上述其它形状记忆合金或其它形状记忆聚合物时,按照实施例2或3的方式也能够制备得到具有光电刺激条件下的双程形状记忆效应的SMA-SMP组合纤维。
虽然本发明已以较佳实施例公开如上,但其并非用以限定本发明,任何熟悉此技术的人,在不脱离本发明的精神和范围内,都可做各种的改动与修饰,因此本发明的保护范围应该以权利要求书所界定的为准。
Claims (6)
1.一种具有光电刺激响应双程形状记忆纤维,其特征在于,所述具有光电刺激响应双程形状记忆纤维包括芯料以及包裹在芯料外层的包裹料,其中,所述芯料为形状记忆合金SMA,所述包裹料为形状记忆聚合物SMP;
所述形状记忆合金SMA包括Au-Cd、Ag-Cd、Cu-Zn、Cu-Zn-Al、Cu-Zn-Sn、Cu-Zn-Si、Cu-Sn、Cu-Zn-Ga、In-Ti、Au-Cu-Zn、Ni-Al、Fe-Pt、Ti-Ni、Ti-Ni-Pd、Ti-Nb、U-Nb或Fe-Mn-Si的任一种或几种;
所述形状记忆聚合物SMP为光致型形状记忆聚合物;
所述光致型形状记忆聚合物包括含有N-取代肉桂酰胺光敏结构单元的热塑性聚氨酯类多嵌段共聚物,交联的聚丙烯酸乙酯,偶氮苯侧链的聚乙烯醇单分子聚合物的一种或几种;
所述具有光电刺激响应双程形状记忆纤维的驱动过程包括:
对光响应SMA-SMP组合纤维进行光照处理使其形状回复,并带动SMA卷曲变形;对SMA-SMP组合纤维进行通电,使SMA加热并带动处于高弹态下的SMP展开变形,实现光电刺激条件下的双程形状记忆效应。
2.权利要求1所述的一种具有光电刺激响应双程形状记忆纤维的制备方法,其特征在于,包括以下步骤:
将SMA在外力作用下通过压轮,使其横截面积被压缩,以获得所要求的横截面积形状和尺寸;通过包覆工艺,将对应光响应SMP包覆到SMA外,即可制备得到具有光电刺激响应双程形状记忆纤维,即SMA-SMP组合纤维。
3.根据权利要求2所述的制备方法,其特征在于,两根以上的SMA单线交织在一起作为芯料,以提高柔韧度和整体度。
4.包含权利要求1所述的一种具有光电刺激响应双程形状记忆纤维的柔性电子器件或设备。
5.权利要求1所述的一种具有光电刺激响应双程形状记忆纤维在高分子或电子电器领域的应用。
6.权利要求4所述的柔性电子器件或设备在电子电器领域的应用。
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