Molecular dynamic study of dielectric polarization and ferroelectricity in a model polar polymer

Molecular dynamics simulations are used to explore the polarization response of a lamellar crystal consisting of folded chains of a highly simplified model polar polymer. The system is based on a united atom model of polyethylene with constrained bond lengths and bond angles, and it is endowed with artificial partial charges placed on the united atoms to give it a simple polar character. Simulations performed with various temperatures, electric field directions, and electric field application histories reveal a complicated sequence of reorientation processes, including pronounced ferroelectric behavior. The sequence includes a weak, temperature‐independent prompt response, and a slow‐rising delay regime with stretched exponential behavior and thermally‐activated reorientation parameters consistent with trans‐gauche (TG) barrier crossings in the amorphous phase. When the delay regime has progressed sufficiently, a primary large‐amplitude response due to organized rotation of large subsegments in the crystalline phase occurs in a rapid manner that requires relatively few TG barrier crossings. A final, extremely slow rise in residual polarization completes the sequence. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 740–759     

The First One‐Pot Synthesis of Metal–Organic Frameworks Functionalised with Two Transition‐Metal Complexes

The synthesis of a metal–organic framework (UiO‐67) functionalised simultaneously with two different transition metal complexes (Ir and Pd or Rh) through a one‐pot procedure is reported for the first time. This has been achieved by an iterative modification of the synthesis parameters combined with characterisation of the resulting materials using different techniques, including X‐ray absorption spectroscopy (XAS). The method also allows the first synthesis of UiO‐67 with a very wide range of loadings (from 4 to 43 mol %) of an iridium complex ([IrCp*(bpydc)(Cl)Cl]^2?; bpydc=2,2′‐bipyridine‐5,5′‐dicarboxylate, Cp*=pentamethylcyclopentadienyl) through a pre‐functionalisation methodology.     

Tailorable PC71BM Isomers: Using the Most Prevalent Electron Acceptor to Obtain High‐Performance Polymer Solar Cells

Despite being widely used as electron acceptor in polymer solar cells, commercially available PC₇₁BM (phenyl‐C₇₁‐butyric acid methyl ester) usually has a “random” composition of mixed regioisomers or stereoisomers. Here PC₇₁BM has been isolated into three typical isomers, α‐, β₁‐ and β₂‐PC₇₁BM, to establish the isomer‐dependent photovoltaic performance on changing the ternary composition of α‐, β₁‐ and β₂‐PC₇₁BM. Mixing the isomers in a ratio of α/β₁/β₂=8:1:1 resulted in the best power conversion efficiency (PCE) of 7.67 % for the polymer solar cells with PTB7:PC₇₁BM as photoactive layer (PTB7=poly[[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]]). The three typical PC₇₁BM isomers, even though sharing similar LUMO energy levels and light absorption, render starkly different photovoltaic performances with average‐performing PCE of 1.28–7.44 % due to diverse self‐aggregation of individual or mixed PC₇₁BM isomers in the otherwise same polymer solar cells.     

Breaking and Making of Carbon–Carbon Bonds by Lanthanides and Third‐Row Transition Metals

Carbon‐atom extrusion from the ipso‐position of a halobenzene ring (C₆H₅X; X=F, Cl, Br, I) and its coupling with a methylene ligand to produce acetylene is not confined to [LaCH₂]⁺; also, the third‐row transition‐metal complexes [MCH₂]⁺, M=Hf, Ta, W, Re, and Os, bring about this unusual transformation. However, substrates with substituents X=CN, NO₂, OCH₃, and CF₃ are either not reactive at all or give rise to different products when reacted with [LaCH₂]⁺. In the thermal gas‐phase processes of atomic Ln⁺ with C₇H₇Cl substrates, only those lanthanides with a promotion energy small enough to attain a 4fⁿ5d¹6s¹ configuration are reactive and form both [LnCl]⁺ and [LnC₅H₅Cl]⁺. Branching ratios and the reaction efficiencies of the various processes seem to correlate with molecular properties, like the bond‐dissociation energies of the C?X or M⁺?X bonds or the promotion energies of lanthanides.     

基于DIS数字信息化系统对透光物质透光性能的研究

采用DIS数字信息化系统,对不同浓度的蓝墨水溶液在激光光源照射下的透射平均照度及照度分布图像进行实验研究,得到了平均照度值随溶液浓度变化的规律。对不同颜色塑料膜片对白炽灯光源透过照度值及照度分布图像进行实验研究得到及其相关之规律。     

Porous shape memory polymers: Design and applications

Porous shape memory polymers (SMPs) exhibit geometric and volumetric shape change when actuated by an external stimulus and can be fabricated as foams, scaffolds, meshes, and other polymeric substrates that possess porous three-dimensional macrostructures. These materials have applications in multiple industries such as textiles, biomedical devices, tissue engineering, and aerospace. This review article examines recent developments in porous SMPs, with a focus on fabrication methods, methods of characterization, modes of actuation, and applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1300–1318     

Cold,warm, and hot programming of shape memory polymers

In this article, programming is classified as hot, warm, and cold, based on the temperature zone within which the programming is conducted. The strain and stress locking and releasing mechanisms are discussed within the thermodynamics framework. A new formula is developed for quantifying the strain recovery ratio of cold-programmed SMPs. Stress fixity ratio and stress recovery ratio are also defined based on the understanding of stress locking and recovery mechanisms. State-of-the-art literature on warm and cold programming is reviewed. Well-controlled programming as well as free strain recovery test and constrained stress recovery test are conducted, in order to validate the memory mechanisms discussed in this study. It is found that, while programming temperature has an insignificant effect on the final free shape recovery, it has a significant effect on the stress recovery. The recovery stress programmed by cold programming may be lower, equal to, or higher than that by hot programming, due to the different stress locking mechanisms and other factors such as damage during the thermomechanical cycle. Cold, Warm, and Hot Programming of Shape Memory Polymers © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1319–1339     

Optical analysis of polymer powder materials for Selective Laser Sintering

This study increases the basic understanding of optical material properties of polymer powders used in selective laser sintering (SLS). Therefore, different polymer powder materials were analyzed regarding their optical material properties with an integration spheres measurement setup. By the measurements a direct connection between the absorption behavior of the solid material and the overall optical material characteristics of the same material in powdery form could be shown. The results were used to develop an advanced explanation model for the optical material properties of powders. At present, existing explanation models only consider the occurring of multiple reflections in the gaps between the particles to explain the overall optical material properties of powder materials. Thus, by also considering the absorption behavior of the single particles, the basic understanding of the beam-matter interaction and their effect on the optical material properties of powder materials can be expanded.     

New Penta(tetrathiafulvalenyl)[60]fullerenes for Supramolecular Materials

New penta(organo)fullerenes donor–acceptor systems bearing five tetrathiafulvalene recognition units have been synthesized to promote self‐assemblies similar in appearance to shuttlecocks nested into each other thanks to the conical host cavity created around the fullerene together with the π–π and electronic interactions.     

Intermolecular Stetter reaction of aromatic aldehydes with (E)-(2-nitrovinyl)cyclohexane induced by N-heterocyclic carbene and thiourea

Intermolecular Stetter reaction of aromatic aldehydes with (E)-(2-nitrovinyl)cyclohexane catalyzed by thiazolium A has been developed. The reaction rate and efficiency are profoundly impacted by the presence of thiourea B. The reaction affords moderate to good yields of the Stetter product. Some factors influencing yield were discussed.