Small activation entropy bestows high-stability of nanoconfined D-mannitol

It has been a long-standing puzzling problem that some glasses exhibit higher glass transition temperatures(denoting high stability) but lower activation energy for relaxations(denoting low stability). In this paper, the relaxation kinetics of the nanoconfined D-mannitol(DM) glass was studied systematically using a high-precision and high-rate nanocalorimeter.The nanoconfined DM exhibits enhanced thermal stability compared to the free DM. For example, the critical cooling rate for glass formation decreases from 200 K/s to below 1 K/s; the Tg increases by about 20 K–50 K. The relaxation kinetics is analyzed based on the absolute reaction rate theory. It is found that, even though the activation energy E~*decreases,the activation entropy S~*decreases much more for the nanoconfined glass that yields a large activation free energy G~*and higher thermal stability. These results suggest that the activation entropy may provide new insights in understanding the abnormal kinetics of nanoconfined glassy systems.     

Effects of top confinement and diluents on morphology in crystallization of poly(l‐lactic acid) interacting with poly(ethylene oxide)

Effects of top confinement and diluent poly(ethylene oxide) (PEO) on poly(l ‐lactic acid) (PLLA) crystal morphology have been investigated. When crystallized at 120 °C, uncovered neat PLLA sample exhibits higher growth rate ringless spherulites; while the covered sample exhibits lower growth rate ring‐banded spherulites. As PEO is introduced into PLLA, the morphology also undergoes significant changes. For the same T_c,PLLA = 120 °C, the PEO/PLLA blend with PEO composition greater than 25% exhibits ring‐banded patterns even in uncovered sample. However, in much greater PEO composition (>80 wt %), uncovered samples exhibit ring bands diverging into dendritic patterns, while top covered samples tend to maintain the spiral ring‐band patterns. Both PEO inclusion in PLLA and top cover on films impose growth kinetic alterations. Additionally, the top glass cover tends to prevent the lower surface tension PLLA to be accumulated on the surface, resulting in the formation of ring‐band pattern. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1160–1170     

Ion transport in polymerized lyotropic liquid crystals containing ionic liquid

In this work, we investigate the effect of morphology and segmental dynamics on ion transport in polymerized lyotropic liquid crystals (polyLLCs) containing 1-butyl-3-methylimidazolium tetrafluoroborate as ionic liquid (IL). We demonstrate that two important factors, which affect ion conduction in polyLLCs, are grain size and chain density at the interface. The polyLLC with large grain size (70 nm) shows significant reduction in ion conductivity (one order of magnitude) compared to its homopolymer/IL mixture. However, the polyLLC with small grain size (20 nm) has little difference in ion conductivity compared to its homopolymer/IL mixture. It is observed that decreasing the chain density enhances the interaction of IL with polymer chains and consequently slows the relaxation of polymer chains. In addition, comparing the dynamics of polymer chains in mixtures of homopolymer/IL and templated LLC mesophases shows that the confinement in LLC structure prolongs the relaxation of polymer chains.     

Heavy-Atom Tunneling in Semibullvalenes: How Driving Force,Substituents, and Environment Influence the Tunneling Rates

The Cope rearrangement of selectively deuterated isotopomers of 1,5-dimethylsemibullvalene 2 a and 3,7-dicyano-1,5-dimethylsemibullvalene 2 b were studied in cryogenic matrices. In both semibullvalenes the Cope rearrangement is governed by heavy-atom tunneling. The driving force for the rearrangements is the small difference in the zero-point vibrational energies of the isotopomers. To evaluate the effect of the driving force on the tunneling probability in 2 a and 2 b , two different pairs of isotopomers were studied for each of the semibullvalenes. The reaction rates for the rearrangement of 2 b in cryogenic matrices were found to be smaller than the ones of 2 a under similar conditions, whereas differences in the driving force do not influence the rates. Small curvature tunneling (SCT) calculations suggest that the reduced tunneling rate of 2 b compared to that of 2 a results from a change in the shape of the potential energy barrier. The tunneling probability of the semibullvalenes strongly depends on the matrix environment; however, for 2 a in a qualitatively different way than for 2 b .     

An Ultra-Microporous Metal–Organic Framework with Exceptional Xe Capacity

Molecular confinement plays a significant effect on trapped gas and solvent molecules. A fundamental understanding of gas adsorption within the porous confinement provides information necessary to design a material with improved selectivity. In this regard, metal–organic framework (MOF) adsorbents are ideal candidate materials to study confinement effects for weakly interacting gas molecules, such as noble gases. Among the noble gases, xenon (Xe) has practical applications in the medical, automotive and aerospace industries. In this Communication, we report an ultra-microporous nickel-isonicotinate MOF with exceptional Xe uptake and selectivity compared to all benchmark MOF and porous organic cage materials. The selectivity arises because of the near perfect fit of the atomic Xe inside the porous confinement. Notably, at low partial pressure, the Ni–MOF interacts very strongly with Xe compared to the closely related Krypton gas (Kr) and more polarizable CO₂. Further ¹²⁹Xe NMR suggests a broad isotropic chemical shift due to the reduced motion as a result of confinement.     

Numerical Simulation of the Distribution Function and Free Energy of a Single Wormlike Polymer Confined between Hard Walls

We focus on the distribution and free energy of a wormlike polymer confined between two parallel hard walls.The variation in the distribution and free energy of the wormlike chain as the spacing between the walls decreases(or as the total contour length of the wormlike chain increases or as the persistence length of the chain increases)is simulated.The main reason for these changes is a degradation of the long wormlike chain into a Gaussian long chain under weak confinement.     

Confined crystallization of polymers within anodic aluminum oxide templates

In this article, a review of recent literature on confined crystallization within nanoporous anodic aluminum oxide (AAO) templates is presented. For almost all infiltrated polymeric materials, crystal orientation within the nanopores is a function of pore diameter. T_c and T_m usually decrease and are a function of pore size. When no pore interconnection remains, the crystallization occur at large supercoolings in heterogeneity free environments. Hence, the nucleation mechanism changes from heterogeneous to surface or homogeneous nucleation. The crystallization kinetics of infiltrated polymers should be close to first order, since in confined environments nucleation is the determining step of the overall crystallization and Avrami indexes (n) of ～1 (or lower in some cases) should be obtained. Examples are provided where these conditions have been met and first order kinetics (n = 1) were measured as opposed to higher orders (n = 3?4) for the same polymer in the bulk. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1179–1194     

Spherical confinement of coulombic systems inside an impenetrable box: H atom and the Hulthén potential

The generalized pseudospectral method is used to study spherical confinement in two simple Coulombic systems: (i) well celebrated and heavily studied H atom (ii) relatively less explored Hulthén potential. In both instances, arbitrary cavity size as well as low and higher states are considered. Apart from bound state eigenvalues, eigenfunctions, expectation values, quite accurate estimates of the critical cage radius for H atom for all the 55 states corresponding to , are also examined. Some of the latter are better than previously reported values. Degeneracy and energy ordering under the isotropic confinement situation are discussed as well. The method produces consistently high‐quality results for both potentials for small as well as large cavity size. For the H atom, present results are comparable to best theoretical values, while for the latter, this work gives considerably better estimates than all existing work so far. © 2014 Wiley Periodicals, Inc.     

量子受限效应和对称性效应对硅光子晶体禁带的影响

光子晶体不仅可以用来调控自发辐射, 还可以用来控制光的传输和局域. 采用平面波展开法进行模拟计算, 分析硅背景下的二维正方、三角晶格光子晶体散射基元的形状和空间取向对光子禁带的影响. 计算结果表明: 对称性和量子受限效应之间的竞争是导致光子晶体禁带宽度发生变化的原因.     

黑腔冷冻靶传热与自然对流的数值模拟研究

惯性约束聚变的设计要求在靶丸内形成均匀光滑的氘氚冰层, 靶丸周围的热环境对冰层的质量特别是低阶粗糙度有很大的影响. 本文对自主研发的黑腔冷冻靶实验装置中的热物理问题展开了数值模拟, 重点考察了黑腔冷冻靶的传热和流体力学特性. 通过参数分析得到了自然对流对靶丸温度均匀性产生影响的临界条件. 比较了黑腔不同布置朝向时的流场和温度分布, 结果显示黑腔水平布置时自然对流更加强烈, 造成的靶丸温度不均匀性也更大. 在此基础上, 讨论了消除自然对流影响的可能性, 结果发现仅当黑腔垂直布置时利用黑腔分区方法能够消除对流效应对靶丸温度不均匀性的影响而黑腔水平布置时不能消除. 研究结论对于实验中冷冻靶结构的设计、改进和实验的开展等具有指导意义.