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。     

聚合物反应加工过程中的原位合金化

用反应加工方法将具有不同性能的高分子材料通过共价键或离子键组装在一起,制备具有各共混组分优良性能的新型高分子合金材料,是当前高分子材料科学发展较快的领域之一.本文分别就聚合物/聚合物共混体系和聚合物/可聚合性单体共混体系原位合金化问题进行了讨论,简要概括了国内外该领域研究取得的最新成果.     

光致感应型形状记忆和形状改变高分子材料

光致形状记忆高分子材料是一类在室温、一定波长的光照条件下发生形变后,再次成型得到二次形状,通过另一波长光刺激手段的处理,又可使其发生形状回复,从而"记忆"初始形状的新型功能高分子材料。该类材料具有非接触性、瞬时性、精确性和清洁性等特点。这些独特的优点使得该类材料越来越受到研究者的关注。本文主要集中对近年来光诱导的形状记忆和形状改变高分子材料的研究现状进行简要的论述,重点是光化学反应型材料,如含肉桂酸基和偶氮苯基系列材料,分别介绍了这些材料的分类、特性、工作原理及潜在的应用。最后对光致型形状记忆高分子材料的存在问题、发展方向和应用前景进行了展望。     

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.     

共混型高分子梯度材料的研究进展

共混型高分子梯度材料具有综合性能好、制备更简便等优点,近年来备受研究者的关注.本文综述了近十年来共混型高分子梯度材料的研究进展.介绍了在溶液体系、熔融体系、乳液体系中通过共混方法构筑高分子梯度材料的制备方法,如溶解扩散法、电场诱导法、温度梯度法等.对在不同共混体系中预测聚合物组分的分散相或组成形成梯度变化的相关理论进行了评述,分析了影响梯度相结构形成的各种因素,并进一步分析了共混型高分子梯度材料的发展方向和研究重点.     

基于聚乳酸的可降解形状记忆高分子的研究进展

综述了基于聚乳酸的可生物降解的形状记忆高分子材料的研究情况。首先介绍了形状记忆高分子材料的记忆效应、记忆机理,然后讨论了基于聚乳酸的三种类型的形状记忆高分子材料：单组份的聚乳酸类、聚乳酸共聚物类以及聚乳酸与无机物的复合材料,分别介绍了各种类型的形状记忆高分子材料的形状记忆性能和生物降解性能。最后,讨论了聚乳酸类记忆材料的应用情况,并对其研究前景和发展趋势进行了展望。     

光致型形状记忆高分子材料

形状记忆高分子材料是当前的研究热点之一,其中光致型形状记忆高分子材料凭借其独特的优势受到研究者的广泛关注。本文综述了光致型形状记忆高分子材料的研究进展,分别介绍了该类材料的特性、分类、工作机理、应用研究和发展趋势。根据不同的形状记忆机理将该类材料分为光化学反应型和光热效应型,并重点对这两种类型的形状记忆高分子材料进行了描述。最后,对光致型形状记忆高分子材料的存在问题、发展方向和应用前景进行了展望。     

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。     

碳纳米管的加入对聚偏氟乙烯/丙烯酸酯共混物形状记忆性能的影响

利用聚偏氟乙烯(PVDF)微小结晶的物理交联点作用,制备了形状记忆性能优异的聚偏氟乙烯/丙烯酸酯聚合物(PVDF/ACM)共混材料。为提高其形状回复应力,又将碳纳米管(CNT)引入该共混体系中,系统研究了PVDF/ACM/CNT三元体系纳米复合材料的制备、结构及性能。结果表明,碳纳米管在PVDF/ACM体系中分散均匀;在基本保持其形状记忆性能的前提下,加入质量分数为4%的CNT,材料在25℃时的储能模量由2000 MPa提高至3130 MPa。     

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.     

Ternary Flexible Electro‐resistive Memory Device based on Small Molecules

Flexible memory devices have continued to attract more attention due to the increasing requirement for miniaturization, flexibility, and portability for further electronic applications. However, all reported flexible memory devices have binary memory characteristics, which cannot meet the demand of ever‐growing information explosion. Organic resistive switching random access memory (RRAM) has plenty of advantages such as simple structure, facile processing, low power consumption, high packaging density, as well as the ability to store multiple states per bit (multilevel). In this study, we report a small molecule‐based flexible ternary memory device for the first time. The flexible device maintains its ternary memory behavior under different bending conditions and within 500 bending cycles. The length of the alkyl chains in the molecular backbone play a significant role in molecular stacking, thus guaranteeing satisfactory memory and mechanical properties.     

形状记忆高分子材料

作为一种新型的功能材料,形状记忆高分子不仅具有形变量大、赋形容易、形状恢复温度便于调整、加工方便的优点,而且种类丰富、质轻价廉.按形状记忆的方式,它可分为热致感应型、光致感应型和化学物质感应型等,能满足不同的应用需求.     

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.     

Local structure and influence of bonding on the phase-change behavior of the chalcogenide compounds K1−xRbxSb5S8

KSb₅S₈ and its solid solution analogs with Rb and Tl were found to exhibit a reversible and tunable glass→crystal→glass phase transition. Selected members of this series were analyzed by differential scanning calorimetry to measure the effect of the substitution on the thermal properties. The solid solutions K_1−xRb_xSb₅S₈ exhibited clear deviations in melting and crystallization behavior and temperatures from the parent structure. The crystallization process of the glassy KSb₅S₈ as a function of temperature could clearly be followed with Raman spectroscopy. The thermal conductivity of both glassy and crystalline KSb₅S₈ at room temperature is ∼0.40 W/m K, among the lowest known values for any dense solid-state material. Electronic band structure calculations carried out on KSb₅S₈ and TlSb₅S₈ show the presence of large indirect band-gaps and confirm the coexistence of covalent Sb-S bonding and predominantly ionic K(Tl)?S bonding. Pair distribution function analyses based on total X-ray scattering data on both crystalline and glassy K_1−xRb_xSb₅S₈ showed that the basic structure-defining unit is the same and it involves a distorted polyhedron of “SbS₇” fragment of ∼7 Å diameter. The similarity of local structure between the glassy and crystalline phases accounts for the facile crystallization rate in this system.     

聚合物电存储材料及其双电极型存储器件

随着信息产业的高速发展,传统的存储技术已不能完全满足人们的需求。因此,对聚合物电存储材料与器件的研究应运而生。相对于传统的无机存储材料,基于聚合物的电存储材料与器件具有易加工、低成本、稳定性好、低功耗、可实现三维堆积以及高存储密度等优点,极有可能取代传统的无机半导体器件,显示出广阔的发展前景。本文介绍了聚合物电存储器件的一些基本原理及基本概念,并对存储器件几种主要的作用机制做了归纳; 根据器件的易失性与否,描述了闪存、一次写入多次读取及动态随机存储器件三类存储器件的存储特点,总结了聚合物电双稳材料及其在三类存储器件中应用的研究进展,探讨了这一研究领域需要解决的一些关键问题,最后展望了聚合物电存储材料与器件的研究和发展方向。     

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.     

形状记忆聚合物及其应用

形状记忆材料可对热、化学、机械、光、磁或电等外加刺激的触发作出响应,从而改变自身的技术参数。形状记忆聚合物作为一类重要的形状记忆材料,在航空航天、生物医学、电力电子、包装、智能控制系统等领域具有广泛的应用。分析了形状记忆聚合物的形状记忆机理,并介绍了几类常见的形状记忆聚合物及其在各领域中的应用,最后提出了形状记忆材料研究中的一些不足及解决措施。     

Shape memory hybrid based on polyvinyl alcohol and 0D silver nanoparticles

Shape memory hybrids (SMH) have drawn significant attention because they allow an easy alternative for the design of shape memory materials with tailored properties or features. In this work, a shape memory hybrid was made, based on polyvinyl alcohol (PVA) as the elastic domain and 0D silver nanoparticles (Agnps) as the transition domain, a dissolution method of mixing both components, and evaporation of water afterward allowed the formation of films of the hybrid material. Two different size distributions of silver nanoparticles were used (13.7 ± 2.6 and 67.9 ± 14.1 nm), in order to study the effect of the size on the shape memory effect (SME) of the final SMH, under temperature stimuli. The materials obtained were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy, infrared spectroscopy (IR), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) techniques. The crystallinity of PVA was slightly altered with the addition of Agnps. Finally, the shape memory effect was tested on both hybrid materials, resulting in a better response to temperature for the SMH prepared with Agnps of 68 nm, also the shape recovery time can be tuned varying both the increase of temperature and the size distribution of Agnps used.