聚合物形状记忆材料的研究进展

聚合物形状记忆材料作为一种重要的刺激响应材料,近10年内得到了快速的发展,出现了新的分类方向,机理解释、转变结构和应用。在航空航天、传感制动和生物医药等领域展现了优越的性能,研究成果受到了学术和工业上的极大重视,成为当今最富有活力的研究领域之一。本文全面总结了近期国内外学者对聚合物形状记忆材料的研究进展,阐述了聚合物形状记忆材料的记忆机理及分类和功能应用,并探讨了未来的研究前景和方向,以期为聚合物形状记忆材料的研究提供参考。     

可生物降解交联聚合物的研究进展

交联聚合物具有稳定的三维网络结构,可以提高药物缓释载体的尺寸稳定性。本文综述了可生物降解交联聚合物的研究进展,主要介绍了可生物降解交联聚合物的制备方法,包括交联剂交联、辐照交联、光致交联以及过氧化物交联在制备可生物降解交联聚合物中的应用,详细介绍了交联剂的种类及结构对交联效果的影响、交联后聚合物性能的变化等。最后总结了可生物降解交联聚合物在组织工程支架、药物缓释材料、神经再生修复材料以及形状记忆材料等生物医用领域的应用。     

形状记忆聚合物变形模式研究进展

近年来,形状记忆聚合物（SMP）的发展取得了明显进步,其自身的优势也得到了充分的展示.形状记忆聚合物是一种刺激响应智能材料,在特定的外部刺激条件下可以根据预先设计的方式改变形状.形状记忆聚合物具有密度低、变形量大、驱动方式丰富、生物相容性好等一系列优势,使其在航空航天、生物医学、仿生工程、电子元件、智能机器人等领域有着巨大的应用潜力.为了更好地适应不同应用和不同领域的需求,形状记忆聚合物的变形模式也在不断地创新,本综述介绍了形状记忆聚合物不同的变形方式及其相关应用的进展,并对形状记忆聚合物面临的挑战和其潜在的研究方向进行了展望.     

结晶行为对无定型/结晶聚合物共混体系形状记忆性能影响的研究进展

形状记忆聚合物因其具有质轻、低耗、形变量大、回复率高、形状可调、刺激方式多样等众多优点而受到广泛关注。相较于其它类型的形状记忆聚合物而言,共混型形状记忆聚合物的制备则更为简单方便。目前最常见的共混型形状记忆材料是无定型/结晶聚合物体系,其中结晶聚合物的结晶行为是影响整个体系形状记忆性能的关键。本文结合了该领域的研究现状,就结晶度、晶体尺寸以及晶体取向对共混体系形状记忆性能影响的研究进展进行了综述。     

高温形状记忆聚合物研究进展

形状记忆聚合物因质量轻、形变量大、性能可控、结构设计性强等优点,其相关的基础前沿研究和潜在的应用开发一直是研究者不断探索的焦点。为满足复杂环境领域（高低温、强辐射、真空等）对形状记忆聚合物的应用需求,近年来研究者开展了高温形状记忆聚合物的研究,并取得了阶段性的研究成果。本文总结了近年来高温形状记忆聚合物的最新研究进展,并对其类型、机制、调控方法及典型应用进行了阐述和分析,最后对高温形状记忆聚合物的未来发展趋势及挑战进行了总结和展望。     

生物降解聚合物的研究和产业化进展及展望

结合作者等近十年来在生物降解聚合物领域的研究和产业化工作,本文概述了聚乳酸、聚氨基酸、聚对二氧六环酮及其它生物降解聚合物的合成进展,综述了可生物降解温度敏感水凝胶、形状记忆高分子材料的研究概况,阐述了可生物降解聚合物在生物活性大分子控释体系、超细纤维组织工程支架上的应用研究,介绍了可生物降解聚合物在食品包装、纺织和汽车电子等方面的应用,总结了可生物降解聚合物、医疗器械、药物制剂和组织工程等领域产业化近况.最后展望了生物降解聚合物的研究、应用和产业化前景.     

苯乙烯基形状记忆聚合物热力学行为的有限元分析

对苯乙烯基形状记忆聚合物进行了拉伸实验研究,测定了该材料在25℃、30℃、40℃和50℃时的弹性模量和屈服极限.根据实验结果,建立了苯乙烯基形状记忆聚合物的材料参数方程,描述了苯乙烯基形状记忆聚合物在玻璃体转化过程中,材料参数和温度的关系.在假设形状记忆聚合物为各向同性材料的基础上,将Tobushi等建立的热力学本构方程从一维扩展到三维.基于有限元分析软件ABAQUS的二次开发功能,针对上述本构方程和材料参数方程,编写了可供ABAQUS调用的UMAT函数,并对苯乙烯基形状记忆聚合物实现形状记忆效应的高温变形、应力冻结和形状恢复等热力学过程,进行了有限元数值模拟分析.     

新型光驱动形状记忆有序多孔膜的设计及构筑

长期以来,设计和制备微纳米尺寸的有序多孔结构是材料科学领域的重要研究课题。聚合物有序多孔膜因兼具高度规则的孔结构和聚合物的多功能性,在工程技术和科学研究领域受到广泛关注。有序多孔膜的孔隙大小、形状及可重复使用等性质对其功能化和潜在应用具有重要影响。形状记忆特性是一种独特的环境响应特性。形状记忆材料能够记忆初始形状,并且在形变后能够在外界刺激下回复其初始形状。将形状记忆特性引入到有序多孔膜中,可实现多孔膜孔形状、尺寸的有效调控,并提高薄膜的可重复使用性,但由于多孔膜孔结构难以实现均匀形变,形状记忆有序多孔膜鲜有报道。华东理工大学林绍梁课题组在光驱动形状记忆多孔膜的设计和制备方面取得了一些新进展。     

智能高分子材料

本文介绍了形状记忆树脂、高分子凝胶、本征导电聚合物、高分子复合材料、高分子薄膜、超分子聚合物、液晶聚合物等智能高分子材料的一般概念及其应用的一些方面。     

双向形状记忆结晶聚合物及其复合材料的研究进展

形状记忆聚合物是一种典型的智能材料,具有质轻、形变量大、可对多种刺激进行响应等优点.根据形状记忆过程的可逆性进行分类,形状记忆效应可以分为2种:单向与双向形状记忆效应.与不可逆的单向形状记忆过程相比,双向形状记忆过程是可逆的,样品不需要使用者进行再次变形,就可以在原始形状与临时形状之间进行可逆转换,因此其具有极高的实用价值与广阔的应用前景,受到各国研究人员的广泛关注,成为当前的研究热点之一.本文总结了近年来所研究的双向形状记忆结晶聚合物及其复合材料,包括恒外力条件下(外力≠0)的准双向形状记忆结晶聚合物,无外力条件下的双向形状记忆结晶聚合物及其复合材料.具体来说,前者包括在恒外力作用下的化学或物理交联的结晶聚合物.后者包括双层或核-壳聚合物复合材料、由分步交联得到的双网络交联结晶聚合物、化学交联的双组分结晶聚合物、具有较宽熔融转变的化学交联结晶聚合物与物理交联的结晶聚合物.重点关注了这些材料的制备方法、影响因素及相应的双向形状记忆机理,并对其研究前景进行了展望.     

Thermosetting Shape Memory Polymers and Composites Based on Polybenzoxazine Blends,Alloys and Copolymers

When dealing with smart polymers, in particular with shape memory polymers, the polymer type and composition specify the overall material properties and in particular the extent of the shape memory effect. Polybenzoxazines as a polymer with high potential for structural applications represent a promising component for materials with both shape memory effect and structurally interesting material properties. This minireview gives insight into how the shape memory effect, in particular the shape recovery event, is influenced by internal factors such as polymer structure, morphology and external factors such as filler addition.     

Automatic equipment with improved performances (ATD and DSC) in shape memory alloys studies

We describe an experimental set-up of high resolution thermal analysis (HRTA) activated by Peltier effect and computer-controlled by the signal processing that allows a high resolution programming of the temperature and a reproducibility better than ±0.01 deg.The basic equipment is suitable for studying the behaviour of the shape memory alloys (i.e. Cu based alloys). We also describe the applications of the system, which allows to build up a calorimetric system (heat flux or conduction calorimetry) (resolution 1.5 W) or a stress-strain-temperature system of 20 N of maximum charge (resolution around 1 mN and 0.1 m.CICYT projects MAT89-407-C03-01 and PETRI-90 are gratefully acknowledged. H. T. acknowledges the DGICYT (sabbatic program) for financial aid in international cooperation. The enlightening discussions with Dr. F. C. Lovey (Centro Atomico Bariloche - Argentina) are also acknowledged.     

Triple shape memory effect in multiple crystalline polyurethanes

Remembering more than one permanent shape is an attractive research topic for shape memory materials (SMMs). In this paper, multiple crystalline shape memory polyurethanes (SMPUs) are prepared with PCL10000 and PTMG2900 by a three‐step polymerization method. DSC and WAXD results show that the obtained polyurethane contains, simultaneously and independently, two kinds of crystals. In addition, it is confirmed through DMA analysis that reversible soft phase and hard domains are formed in the PCL‐PTMG based SMPU system; and two‐step modulus decreases at low temperature range can be obtained in the SMPU with suitable mass proportion of PCL to PTMG, e.g., 1:7. Thus, shape memory effect (SME) can be achieved in this system. Moreover, it is found that the PTMG soft segment dominates the shape memory effect when the PCL mass is lower than that of PTMG; while the PCL soft segment dominates the SME when PCL mass is higher than that of PTMG; and a two‐step programing shape recovery can be achieved when the mass proportion of PCL/PTMG reaches a balance value, e.g., 3:5. Copyright © 2009 John Wiley & Sons, Ltd.     

Shape memory fiber spun with segmented polyurethane ionomer

The effect of cationic groups within hard segments on shape memory polyurethane (SMPU) fibers was studied and the cyclic tensile testing was conducted to assess the shape memory effect. Mechanical properties, hard segment crystallization, and dynamic mechanical properties of SMPU ionomer fibers composed of 1,4‐butanediol (BDO), N‐methyldiethanolamine (NMDA), 4,4′‐methylenebis(phenyl isocyanate) (MDI), and poly(butylene adipate)diol (PBA) were investigated using a universal tensile tester, differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). The results demonstrate that only 2 wt% NMDA can significantly change the glass transition temperature of the soft segment phase. DSC shows that the ionic group within hard segments can facilitate the crystallization of hard segments in unsteamed SMPU ionomer fibers. But for steamed fiber specimens, this effect is insignificant. Moreover, the ionic groups in hard segments with different hard segment contents (HSC) have different effects. In unsteamed fibers with 64 wt% HSC, 2 wt% NMDA increases the glass transition of soft segments from 63.5 to 70.6°C. However, in fibers with 55 wt% HSC, the glass transition temperature is lowered from 46.7 to 33.5°C. The post‐treatment, high‐pressure steaming is an effective way to remove the internal stress and subsequently improve the dimensional stability of SMPU ionomer fibers. Copyright © 2008 John Wiley & Sons, Ltd.     

Two-way shape memory behavior of styrene-based bilayer shape memory polymer plate

In this work, a bilayer shape memory polymer (SMP) composite plate with two-way shape memory behavior is simulated, in which two types of styrene-based SMPs with well-separated glass transition temperatures are assembled in parallel. The finite element (FE) software ABAQUS is selected to exhibit the two-way shape memory effect during the shape recovery step and the Generalized Maxwell Model with the WLF equation is applied to characterize the temperature-dependent properties of the SMP bilayer plates. The effect factors of axial predeformation, thermal expansion coefficient and plate thickness are all considered for the two-way shape memory behavior of the styrene-based bilayer SMP plate. After that, a smart gripper composed of four SMP composite plates is proposed to realize grabbing and releasing functions for one-step and staged heating recovery. The FE results provide some necessary theoretical guidelines for future soft smart structural designs and optimization.     

Revealing Triple‐Shape Memory Effect by Polymer Bilayers

Bilayer polymers that consist of two epoxy dual‐shape memory polymers of well‐separated glass transition temperatures have been synthesized. These bilayer epoxy samples exhibit a triple‐shape memory effect (TSME) with shape fixities tailorable by changing the ratio between the two layers. The triple‐shape fixities of the bilayer epoxy polymers can be explained by the balance of stress between the two layers. Based on this work, it is believed that the following three molecular design criterions should be considered in designing triple‐shape memory polymers with optimum TSME: 1) well‐separated thermal transitions, 2) a strong interface, and 3) an appropriate balance of moduli and relative ratios between the layers (or microphases).

     

CaractErisation Par DSC Des Sequences De Transformation Au Cours D'un Chauffage Lent Des Alliages Amf A Base De Cu–Al–Ni

Quenching of the eutectoidal composition of the shape memory alloys (SMA’s) allowed us to display the gradual transition of the martensitic structure as a function of the composition. Indeed, we have verified that for low Al and Ni percentages, the martensite structure obtained is β′, while, for high Al and Ni (Al<13.3 mass%) contents, the martensite structure is essentially of β₁′ type. Elsewhere, we have observed that a nickel addition (<4.3 mass%) operates simultaneously on the composition of the eutectoidal pointand the domain of the different martensitic structures types. During reheating of the quenched structure, the transformation sequences of the martensite to the parent phase (β1), then the decomposition of the later phase into the equilibrium phases, and finally, the redissolution of all phases to form the β phase at high temperature, are rather similar. This revised version was published online in August 2006 with corrections to the Cover Date.     

Shape memory effect and reversible phase crystallization process in SMPU ionomer

It is the first attempt to reveal the effect of reversible phase crystallization process on shape memory effect in shape memory polyurethane (PU) ionomer. Thereof the cyclic tensile testing was conducted with various cooling time to fix the temporary deformation for assessing shape memory function. The crystallization process of the reversible phase, poly (ε‐caprolactone) (PCL) in shape memory PU ionomers composed of different ionic group contents, 1,4‐butanediol, 4,4′‐methylenebis(phenyl isocyanate) and PCL, was investigated by using isothermal crystallization kinetics under the thermal routine similar to that for the cyclic tensile testing. The results demonstrate that the ionic groups within hard segments significantly slow down the crystal growth of the reversible phase. When the physical crosslink is strong enough, the crystallization rate would be a predominant factor determining the shape fixity ratio after various cooling time. Instead, when physical crosslink is weakening, the influence of crystallization rate is much less on the cooling time dependence of fixity. Copyright © 2007 John Wiley & Sons, Ltd.     

A hydrogel‐forming liquid crystalline elastomer exhibiting soft shape memory

Research in the field of liquid crystalline polymers has recently witnessed the introduction of liquid crystalline hydrogels. Here, we report the synthesis and characterization of a new liquid crystalline network featuring elastomeric softness, water‐swelling and shape memory characteristics. By comparing with a nonmesogenic network prepared using the same procedure, we reveal structure–property relationships of the liquid crystalline and crystalline polymer networks. Wide angle and small angle X‐ray scattering studies were used to examine the liquid crystalline ordering in both dry and hydrated states. Such ordering was found to be related to the observed shape memory and actuation (two‐way shape memory) properties and these phenomena are highlighted with demonstrations of shape change in response to heat and water stimuli. This study provides insight into the mechanisms affecting the shape evolution of water activated anisotropic liquid crystalline hydrogels and enables the future design of materials or devices for a variety of applications such as biomaterials interacting with body fluids in a hydrated state. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 38–52     

Investigation on Structures and Properties of Shape Memory Polyurethane/Silica Nanocomposites

In this study, high performance shape memory polyurethane (SMPU)/silica nanocomposites with different silica weight fraction including SMPU bulk, 3%, 4.5%, 6%, 7.5%, 10%, were prepared by sol‐gel process initiated by the solid acid catalyst of p‐toluenesulfonic acid (PTSA). Field emission scanning electron microscopy (FE‐SEM) and transmission electron microscopy (TEM) observation show that the silica nanoparticles are dispersed evenly in SMPU/silica nanocomposites. Tensile test and dynamic mechanical analysis (DMA) suggest that the mechanical properties and the glass transition temperature (T_g) of the nanocomposites were significantly influenced by silica weight fraction. Thermogravimetric analysis (TGA) was utilized to evaluate the thermal stability and determine the actual silica weight fraction. The TGA results indicate that the thermal stability can be enhanced with the hybridization of silica nanoparticles. Differential scanning calorimetry (DSC) was conducted to test the melting enthalpy (ΔH) and the results suggest that the ΔH was markedly improved for the SMPU/silica nanocomposites. Thermomechanical test was conducted to investigate the shape memory behavior and the results show that the shape fixity is improved by hybridization of silica and good shape recovery can be obtained with the increasing of cycle number for all the samples.