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.     

酞菁钴/铁纳米填充母粒组成的磁流变液性能

采用有机/无机原位（insitu）复合方法制备得出酞菁钴/铁纳米填充母粒,与甲基硅油组成磁流变液（MRS）。MRS的附加动态剪切应力（Δτ)与分散介质浓度、外加磁场强度呈正比例关系;剪切速率对Δτ的影响表明磁致流变为链状结构特征;Δτ对温度不敏感;MRS对外加磁场有可逆的开/关变化特征,无记忆效应,磁流变响应时间小于0.1s。     

Electrorheological suspensions of laponite in oil: rheometry studies

We have studied the effect of an external direct current (DC) electric field ( approximately 1 kV/mm) on the rheological properties of colloidal suspensions consisting of aggregates of laponite particles in a silicone oil. Microscopy observations show that, under application of an electric field greater than a triggering electric field Ec approximately 0.6 kV/mm, laponite aggregates assemble into chain- and/or columnlike structures in the oil. Without an applied electric field, the steady-state shear behavior of such suspensions is Newtonian-like. Under application of an electric field larger than Ec, it changes dramatically as a result of the changes in the microstructure: a significant yield stress is measured, and under continuous shear the fluid is shear-thinning. The rheological properties, in particular the dynamic and static shear stress, were studied as a function of particle volume fraction for various strengths (including null) of the applied electric field. The flow curves at constant shear rate can be scaled with respect to both the particle fraction and electric field strength onto a master curve. This scaling is consistent with simple scaling arguments. The shape of the master curve accounts for the system's complexity; it approaches a standard power-law model at high Mason numbers. Both dynamic and static yield stresses are observed to depend on the particle fraction Phi and electric field E as PhibetaEalpha, with alpha approximately 1.85 and beta approximately 1 and 1.70 for the dynamic and static yield stresses, respectively. The yield stress was also determined as the critical stress at which there occurs a bifurcation in the rheological behavior of suspensions that are submitted to a constant shear stress; a scaling law with alpha approximately 1.84 and beta approximately 1.70 was obtained. The effectiveness of the latter technique confirms that such electrorheological (ER) fluids can be studied in the framework of thixotropic fluids. The method is very reproducible; we suggest that it could be used routinely for studying ER fluids. The measured overall yield stress behavior of the suspensions may be explained in terms of standard conduction models for electrorheological systems. Interesting prospects include using such systems for guided self-assembly of clay nanoparticles.     

The transformation of 1,2,4-trimethylbenzene A probe reaction to monitor external surface modifications of HZSM-5?

The transformation of 1,2,4-trimethylbenzene is proposed as a new probe reaction to monitor the catalytic effects of inertisation of the external surface of HZSM-5. The external surface has been modified by coating ZSM-5 crystallites with an inert silicalite shell. At 723 K and a WHSV of 0.6 h⁻¹ it has been shown that the isomerisation products 1,2,3-trimethylbenzene and 1,3,5-trimethylbenzene reflect changes in external activity. The disproportionation products, 1,2,4,5-tetramethylbenzene and 1,2,3,5-tetramethylbenzene together are shown to indicate changes in overall activity and shape selective properties of the catalyst sample. The results correlate with those observed for the reaction of 1,3,5-triisopropylbenzene and n-hexane cracking.     

Conformations of polymer chains in voids with an external electric field by Green's function methods

The statistical conformations of a length of polymer chain, such as DNA, trapped in a void within a gel under the influence of an external electric field, have been studied by the method of Green's functions. Based upon a rectangular box approximation for the void shape, the method gives an explicit analytical expression for the end-to-end distance (R_x) as a function of applied field strength, number of chain segments coiled within the void, and size of a chain segment. Results of calculations show that the field compresses the entrained coil into more compact configurations, as would be expected. Such compression is believed to affect the electrophoretic mobility of a long chain molecule like DNA in a dilute gel. © 1995 John Wiley & Sons, Inc.     

Complex Reconfiguration of DNA Nanostructures

Nucleic acids have been used to create diverse synthetic structural and dynamic systems. Toehold‐mediated strand displacement has enabled the construction of sophisticated circuits, motors, and molecular computers. Yet it remains challenging to demonstrate complex structural reconfiguration in which a structure changes from a starting shape to another arbitrarily prescribed shape. To address this challenge, we have developed a general structural‐reconfiguration method that utilizes the modularly interconnected architecture of single‐stranded DNA tile and brick structures. The removal of one component strand reveals a newly exposed toehold on a neighboring strand, thus enabling us to remove regions of connected component strands without the need to modify the strands with predesigned external toeholds. By using this method, we reconfigured a two‐dimensional rectangular DNA canvas into diverse prescribed shapes. We also used this method to reconfigure a three‐dimensional DNA cuboid.     

Shape changing hydrogels and their applications as soft actuators

In nature, plants or animals change their geometric shapes and hence realize different functions or movements. Inspired by the shape changes of plants and animals, several hydrogels that can change their geometric shapes upon external stimuli have been developed. This article provides a brief overview of shape changing hydrogels. First, two strategies to realize the shape changes of hydrogels, that is, preparing hydrogels with inhomogeneous structures and applying inhomogeneous stimuli onto homogeneous hydrogels, are discussed. Then, external stimuli that can actuate the shape changes of the stimuli-responsive hydrogels are presented. The applications of shape changing hydrogels such as soft machines, soft robotics, drug carriers, microfluidic valves, and sensors have been provided in third part. Finally, we offer our perspective on open challenges and future areas of interest for the shape changing hydrogel actuators. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1314–1324     

Hemodynamics and Wall Shear Stress of Blood Vessels in Aortic Coarctation with Computational Fluid Dynamics Simulation

The purpose of this study was to identify the characteristics of blood flow in aortic coarctation based on stenotic shape structure, stenosis rate, and the distribution of the wall load delivered into the blood vessels and to predict the impact on aneurysm formation and rupture of blood vessels by using a computational fluid dynamics modeling method. It was applied on the blood flow in abdominal aortic blood vessels in which stenosis occurred by using the commercial finite element software ADINA on fluid-solid interactions. The results of modeling, with an increasing stenosis rate and Reynolds number, showed the pressure drop was increased and the velocity was greatly changed. When the stenosis rate was the same, the pressure drop and the velocity change were larger in the stenosis with a symmetric structure than in the stenosis with an asymmetric one. Maximal changes in wall shear stress were observed in the area before stenosis and minimal changes were shown in stenosis areas. The minimal shear stress occurred at different locations depending on the stenosis shape models. With an increasing stenosis rate and Reynolds number, the maximal wall shear stress was increased and the minimal wall shear stress was decreased. Through such studies, it is thought that the characteristics of blood flow in the abdominal aorta where a stenosis is formed will be helpful in understanding the mechanism of growth of atherosclerosis and the occurrence and rupture of the abdominal aortic flow.     

Study of stress-induced changes in poly(ethylene terephthalate) through Fourier transform infrared spectroscopy

The molecular level changes resulting from an external stress applied onto a highly uniaxially oriented poly(ethylene terephthalate) film has been studied. For this purpose, a new technique - Fourier Transform Infrared Spectroscopy - has been employed. Stress-induced differences are visible in a number of bands within the IR spectra of stressed PETP films. From the assignments of these IR bands, it is inferred how external stresses applied on the polymer films are actually transmitted to the molecular level. The intermicrofibrillar chains are the first to be stressed followed by stress transmission on the crystalline regions. These stresses are also responsible for stretching the backbone bonds, for transforming gauche conformations (predominantly present in the amorphous regions) of the ethylene glycol linkages to the trans, and for modifying the interchain interactions.     

Stress‐Induced Stabilization of Crystals in Shape Memory Natural Rubber

In contrast to all known shape memory polymers, the melting temperature of crystals in shape memory natural rubber (SMNR) can be greatly manipulated by the application of external mechanical stress. As shown previously, stress perpendicular to the prior programming direction decreases the melting temperature by up to 40 K. In this study, we investigated the influence of mechanical stress parallel to prior stretching direction during programming on the stability of the elongation‐stabilizing crystals. It was found that parallel stress stabilizes the crystals, which is indicated by linear increase of the trigger temperature by up to 17 K. The crystal melting temperature can be increased up to 126.5 °C under constrained conditions as shown by X‐ray diffraction measurements.     

Highly Elastic Organic Crystals for Flexible Optical Waveguides

The study of elastic organic single crystals (EOSCs) has emerged as a cutting‐edge research of crystal engineering. Although a few EOSCs have been reported recently, those suitable for optical/optoelectronic applications have not been realized. Here, we report an elastic crystal of a Schiff base, (E)‐1‐(4‐(dimethylamino)phenyl)iminomethyl‐2‐hydroxyl‐naphthalene. The crystal is highly bendable under external stress and able to regain immediately its original straight shape when the stress is released. It displays bright orange–red emission with a high fluorescence quantum yield of 0.43. Intriguingly, it can serve as a low‐loss optical waveguide even at the highly bent state. Our result highlights the feature and utility of “elasticity” of organic crystals.     

Molecular mobility of poly(methyl methacrylate) glass during uniaxial tensile creep deformation

An optical photobleaching method has been used to measure the segmental dynamics of a poly(methyl methacrylate) (PMMA) glass during uniaxial creep deformation at temperatures between T_g ? 9 K and T_g ? 20 K. Up to 1000‐fold increases in mobility are observed during deformation, supporting the view that enhanced segmental mobility allows flow in polymer glasses. Although the Eyring model describes this mobility enhancement well at low stress, it fails to capture the dramatic mobility enhancement after flow onset, where in addition the shape of the relaxation time distribution narrows significantly. Regions of lower mobility accelerate their dynamics more in response to an external stress than do regions of high mobility. Thus, local environments in the sample become more dynamically homogeneous during flow. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1713–1727, 2009     

Radiation Chemical Studies of Protein Reactions: Effect of Amino Acids,Proteins, Vitamins,Chelating Agents,S-Containing Compounds,and Temperature on Viscosity

Amino acids, proteins, vitamins, chelating agents, and S-containing compounds were found to protect the shape of the external envelope of the protein molecule from radiation damage. The behavior of the viscosity change closely resembles that found with sodium glutamate and sodium benzoate, as shown by a similar dependence on the concentration. Protein irradiated by γ-rays showed the effect of temperature on changes in the shape of the external envelope of the protein molecule. The behavior of the viscosity change was studied.     

Effect of filler morphology and surface chemistry on the rheological properties of filled polypropylenes

The effect of filler size, shape and surface chemistry is investigated for mineral-filled polypropylene. Viscosity, first normal stress difference and dynamic properties are all considered. It is shown that, other things being equal, viscosity decreases as filler size increases, the filler surface is made hydrophobic or the shape of the filler is changed from ‘blocky’ to ‘platey’. The first normal stress difference is found to be relatively insensitive to such changes.     

Stress memory polymers

Like shape memory polymers, a novel phenomenon of stress memory was shown in which the stress of a material can respond to an external stimulus. This concept was further enlightened by a switch‐spring‐frame model that would eliminate the limitation of existing models which overlooked the stimulus responsive nature of such polymers. The discovery being reported in this article was stemmed from a real case study into shape memory polymer fibers in compression stocking for varicose veins. The breakthrough of stress memory enabled researchers to develop applications needing stimuli‐responsive forces, which can broaden the horizon of such smart polymers in emerging smart products in many multidisciplinary fields such as sensors, stress garments, and massage devices, electronic skins, and artificial muscles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 893–898     

The effect of box shape on the dynamic properties of proteins simulated under periodic boundary conditions

The effect of the box shape on the dynamic behavior of proteins simulated under periodic boundary conditions is evaluated. In particular, the influence of simulation boxes defined by the near-densest lattice packing (NDLP) in conjunction with rotational constraints is compared to that of standard box types without these constraints. Three different proteins of varying size, shape, and secondary structure content were examined in the study. The statistical significance of differences in RMSD, radius of gyration, solvent-accessible surface, number of hydrogen bonds, and secondary structure content between proteins, box types, and the application or not of rotational constraints has been assessed. Furthermore, the differences in the collective modes for each protein between different boxes and the application or not of rotational constraints have been examined. In total 105 simulations were performed, and the results compared using a three-way multivariate analysis of variance (MANOVA) for properties derived from the trajectories and a three-way univariate analysis of variance (ANOVA) for collective modes. It is shown that application of roto-translational constraints does not have a statistically significant effect on the results obtained from the different simulations. However, the choice of simulation box was found to have a small (5-10%), but statistically significant effect on the behavior of two of the three proteins included in the study.     

Control and optical mapping of mechanical transitions in polymer networks and DNA-based soft materials

Complex mechanical changes in response to an external trigger are pervasive in natural soft materials and often sought for applications. Be it the reversible stiffening of sea cucumber, the failure of a polymeric or colloidal gel under load, or the dissolution of a biosensing hydrogel upon target binding, mechanical transitions are typically enabled, and critically affected, by heterogeneous structures and reversible bonds. New possibilities to monitor evolving properties and to gain access to stress propagation with temporal and spatial resolution are being disclosed by mechanochromic molecules and molecular complexes, which transduce a mechanical stress into a light signal and act as built-in stress reporters. I will review recent strategies and identify future directions for the design of mechanically responsive soft networks and for their optical mapping, focusing particular attention on the emerging class of hydrogels based on DNA self-assembly.     

Shape memory poly(ester urethane) with improved hydrolytic stability

In two hydrolytic degradation studies the tensile (mechanical) and functional (thermo-mechanical) properties of a hydrolysis-stabilized shape memory poly(ester urethane) and its non-stabilized analog were investigated. Hydrolytic degradation was enforced by specimen immersion in de-ionized water at 80 °C. Significant differences in the fundamental shape memory parameters were monitored as function of aging time for the stabilized and non-stabilized polymer. This included the ability to recover strain (shape recoverability) and stress (stress recoverability) on heating after shape programming. Hydrolysis-related mechanical and functional changes were correlated with morphological ones, detected by differential scanning calorimetry (DSC). The shape memory poly(ester urethane), which was protected by a carbodiimide-based hydrolysis stabilizer, revealed significantly improved resistance towards hydrolysis with respect to various mechanical and shape memory parameters.     

Faceting of nanocrystals during chemical transformation: from solid silver spheres to hollow gold octahedra

We demonstrate that performing a replacement reaction on single crystalline Ag nanospheres of approximately 10 nm in diameter in an organic solvent produces hollow Au nanocrystals with an octahedral shape. Different from those Au shells made by starting with Ag particles about 1 order of magnitude larger, which largely reproduce that of the sacrificial Ag counterparts, the hollow nanocrystals obtained in this work show significant changes in the external morphology from the spherical Ag precursors. This evolution of a faceted external morphology during chemical transformation is made possible by the enhanced role of surface effects in our smaller nanocrystals. The competition between the Au atom deposition and Ag atom dissolution on various nanocrystal surfaces is believed to determine the final octahedral shape of the hollow Au nanocrystals. Simultaneous achievement of surface-mediated shape control and a hollow morphology in a one-pot, single-step synthetic procedure in this study promises an avenue to finer tuning of particle morphology, and thus physical properties such as surface plasmon resonance.