Polymer 4D printing: Advanced shape-change and beyond

4D printing is an exciting branch of additive manufacturing. It relies on established 3D printing techniques to fabricate objects in much the same way. However, structures which fall into the 4D printed category have the ability to change with time, hence the “extra dimension.” The common perception of 4D printed objects is that of macroscopic single-material structures limited to point-to-point shape change only, in response to either heat or water. However, in the area of polymer 4D printing, recent advancements challenge this understanding. A host of new polymeric materials have been designed which display a variety of wonderful effects brought about by unconventional stimuli, and advanced additive manufacturing techniques have been developed to accommodate them. As a result, the horizons of polymer 4D printing have been broadened beyond what was initially thought possible. In this review, we showcase the many studies which evolve the very definition of polymer 4D printing, and reveal emerging areas of research integral to its advancement.     

Synthesis of self‐healing polyurethane urea‐based supramolecular materials

Supramolecular polyurethane ureas are expected to have superior mechanical properties primarily due to the reversible, noncovalent interactions such as hydrogen bonding interactions. We synthesized polyurethane prepolymers from small molecular weight of poly(tetramethylene ether)glycol and isophorone diisocyanates, which were end capped with propylamine to synthesize polyurethane ureas with high contents of urea and urethane groups for hydrogen‐bonding formations to facilitate self‐healing. The effects of polyurethane urea molecular weight (3000 ≤ M_n ≤ 9000), crosslinking, and cutting direction were studied in terms of thermal, mechanical, and morphological properties with an emphasis on the self‐healing efficiency. It was found that the thermal self‐healability was more pronounced as the molecular weight of polyurethane urea decreased, showing a maximum of more than 96% with 3000 M_n when the sample was cut along the stretch direction. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 468–474     

Ionic conductivity of multiarm star polymer/LiClO4 electrolytes

A series of polymer electrolytes based on multiarm polymers and lithium salt complexes were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and impedance measurement. The relationships of conductivity with salt concentration, temperature, and arm numbers are discussed. It is suggested that the star polymer has a higher solvency and ion transfer ability on lithium salts than on linear polymers. The conductivity maximum appeared at a higher salt concentration ([EO]/[Li] = 4). Impedance measurement suggested that the optimum conductivity was 2 × 10^?4 s · cm^?1. The conductivity increased with temperature and the dependence of ionic conductivity on temperature fits the Arrhenius equation. Among the studied systems, the star polymer with a five arm number performs better than other structures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4195–4198, 2004     

A fractal model of reinforcement of elastoplastic nanocomposites

Within the framework of fractal analysis and percolation theory, an alternative model of reinforcement of filled polymers is offered. Practically, this model can be used only to describe the reinforcement of nanocomposites, because, according to the treatment considered, a pronounced reinforcement can be reached only at ratios of filler particle diameter to the statistical segment length of about 10 and less. A theoretical calculation showed a good qualitative and quantitative agreement with experiments. The type of reinforcement mechanism of composites is determined by the type of the space (fractal or Euclidean) in which the structure of the polymeric matrix is formed. __________ Translated from Mekhanika Kompozitnykh Materialov, Vol. 42, No. 6, pp. 797–802, November–Decem ber, 2006.     

Dual effects of fullerene doped to holographic polymer dispersed liquid crystals

Doping of conductive fullerene particles to the formulation of conventional holographic polymer dispersed liquid crystal‐induced dual effects of reducing both droplet coalescence and operating voltage. Fullerene induced an induction period which otherwise does not exist, followed by a gradual increase of diffraction efficiency to a saturation value being increased with increasing fullerene content. The increased diffraction efficiency was caused by the decreased droplet coalescence which was due to the hindered migration of LC by the fullerene particles. On the other hand, doped fullerene particles augmented the conductivity of polymer phase and hence the local electrical field imposed on LC droplet, which overcome the threshold for driving and reduced operating voltage and response times. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5590–5596, 2007     

The influence of hard‐segments on two‐phase structure and shape memory properties of PCL‐based segmented polyurethanes

Poly(ε‐caprolactone)‐based segmented polyurethanes (PCLUs) were prepared from poly(ε‐caprolactone) diol, diisocyanates (DI), and 1,4‐butanediol. The DIs used were 4,4′‐diphenylmethane diisocyanate (MDI), 2,4‐toluenediisocyanate (TDI), isophorone diisocyanate (IPDI), and hexamethylene diisocyanate (HDI). Differential scanning calorimetry, small‐angle X‐ray scattering, and dynamic mechanical analysis were employed to characterize the two‐phase structures of all PCLUs. It was found that HDI‐ and MDI‐based PCLUs had higher degree of microphase separation than did IPDI‐ and TDI‐based PCLUs, which was primarily due to the crystallization of HDI‐ and MDI‐based hard‐segments. As a result, the HDI‐based PCLU exhibited the highest recovery force up to 6 MPa and slowest stress relaxation with increasing temperature. Besides, it was found that the partial damage in hard‐segment domains during the sample deformation was responsible for the incomplete shape‐recovery of PCLUs after the first deformation, but the damage did not develop during the subsequent deformation. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 557–570, 2007     

Divinylsiloxane‐bisbenzocyclobutene‐based polymer modified with polystyrene–polybutadiene–polystyrene triblock copolymers

Divinylsiloxane‐bisbenzocyclobutene (DVS‐bisBCB) polymer has very low dielectric constant and dissipation factor, good thermal stability, and high chemical resistance. The fracture toughness of the thermoset polymer is moderate due to its high crosslink density. A thermoplastic elastomer, polystyrene–polybutadiene–polystyrene triblock copolymer, was incorporated into the matrix to enhance its toughness. The cured thermoset matrix showed different morphology when the elastomer was added to the B‐staged prepolymer or when the elastomer was B‐staged with the DVS‐bisBCB monomer. Small and uniformly distributed elastomer domains were detected by transmission electron micrographs (TEM) in the former case, but TEM did not detect a separate domain in the latter case. A high percentage of the polystyrene–polybutadiene–polystyrene triblock copolymer could be incorporated into the DVS‐bisBCB thermoset matrix by B‐staging the triblock copolymer with the BCB monomer. The elastomer increased the fracture toughness of DVS‐bisBCB polymer as indicated by enhanced elongation at break and increased K1c values obtained by the modified edge‐lift‐off test. Elastomer modified DVS‐bisBCB maintained excellent electrical properties, high T_g and good thermal stability, but showed higher coefficient of linear thermal expansion values. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1591–1599, 2006     

聚丙烯/POE共混组成对材料断裂行为的影响

采用基本断裂功(EWF)方法对聚丙烯(PP)/聚烯烃弹性体(POE)共混物的注射双边缺口拉伸试样的断裂行为进行了研究,比较了不同POE含量对共混物各断裂参数的影响.结果表明,PP和用量为5phr POE的共混物都可完全满足EWF方法的要求,共混物的断裂韧性-比基本断裂功we,较PP有显著提高;POE用量为10phr以上的共混物则出现明显的成颈现象而限制了EWF方法的应用;PP和各种POE用量的共混物都得到了其屈服所需要的比基本断裂功we,y和比塑性功β′wp,y.     

一种新型的侧链型聚氨酯高分子钌聚合物的合成

通过分子设计,将带有-OH端基的钌(Ⅱ)联吡啶配合物[Ru(bpy)2L]PF6{L=希夫碱4-[(N甲-基-N羟-乙基)氨基]苯甲醛缩肼基硫代甲酸甲酯}与甲苯-2,4异-氰酸酯、丙烯酸羟乙酯发生共聚合反应,合成了新的侧链型聚氨酯高分子钌聚合物(4)。4的结构经红外光谱和差热分析表征。     

Kinetics of formation of a linear polymer-polymer network system in the presence of 3d metal chelates

For semi-interpenetrating polymer networks (semi-IPNs) based on an incompatible polyurethane network/linear polymethylmethacrylate pair formed in situ in the presence of 3d metal chelates, we have studied the effect of the system composition on the kinetics of formation of the components and the nature of complex formation between the metal compound and the polymer matrix. The ratio of the system components has been shown to have an effect on the selection of the macroligand in formation of complexes of the metal chelate with the polar groups of the semi-IPN, where the general character of the kinetic behavior for the formation of the network and the linear polymer is preserved. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 6, pp. 351–356, November–December, 2006.