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1.
The structure and rotational barrier for the mesityl-silicon bond of 2,2-dimesityl-1,1,1,3,3,3-hexamethyltrisilane have been investigated by 1H- and 13C-variable temperature nuclear magnetic resonance (NMR) as well as by density functional theory structural calculations. The calculations show that the lowest energy structure has C2 symmetry with nonequivalent ortho methyl groups, consistent with the crystal structure and solution NMR. The nonequivalent ortho methyl groups exchange through a Cs transition state with a calculated relative free energy of 11.0 kcal mol−1. The barrier for this rotation found by dynamic NMR is 13.4 ± 0.2 kcal mol−1 at 298 K. 相似文献
2.
Physical aging in amorphous poly(ethylene furanoate): Enthalpic recovery,density, and oxygen transport considerations
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Steven K. Burgess Christopher R. Mubarak Robert M. Kriegel William J. Koros 《Journal of Polymer Science.Polymer Physics》2015,53(6):389-399
The current work utilizes three separate techniques to study the physical aging process in amorphous poly(ethylene furanoate) (PEF), which is a recently introduced engineering thermoplastic with enhanced properties compared to petroleum‐sourced poly(ethylene terephthalate). Differential scanning calorimetry aging experiments were conducted at multiple aging temperatures and times, and the resultant enthalpic recovery values compared to the theoretical maximum enthalpy loss evaluated from calculations involving extrapolation of the equilibrium liquid line. Density measurements reveal densification of the matrix for the aged versus unaged samples, and provide an estimate for the reduction in free volume for the aged samples. Complementary oxygen permeation and pressure‐decay sorption experiments provide independent verification of the free volume reduction mechanism for physical aging in glassy polymers. The current work provides the first detailed aging study for PEF. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 389–399 相似文献
3.
A. B. Mazo 《Fluid Dynamics》2002,37(6):913-918
Plane ideal incompressible flow in a rectangular channel partitioned by a thin permeable barrier (lattice) is considered. In flowing through the lattice the stream suddenly (jumpwise) changes direction and loses energy. The flow is assumed to be vortical; the vorticity is discontinuous on the lattice. A mathematical formulation of the problem for the stream function is proposed in the form of a nonlinear elliptic equation with coefficients discontinuous on the lattice line. A numerical solution is constructed using the finite-element iteration method. The results of the numerical simulation show how the flow velocity profile in the channel can be controlled by means of permeable barriers. 相似文献
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5.
As borders between different entities, lines are an important element of natural images. Indeed, the neurons of the mammalian
visual cortex are tuned to respond best to lines of a given orientation. This preferred orientation varies continuously across
most of the cortex, but also has vortex-like singularities known as pinwheels. In attempting to describe such patterns of
orientation preference, we are led to consider underlying rotation symmetries: Oriented segments in natural images tend to
be collinear; neurons are more likely to be connected if their preferred orientations are aligned to their topographic separation.
These are indications of a reduced symmetry requiring joint rotations of both orientation preference and the underlying topography.
This is verified by direct statistical tests in both natural images and in cortical maps. Using the statistics of natural
scenes we construct filters that are best suited to extracting information from such images, and find qualitative similarities
to mammalian vision.
PACS84.35+i 89.70.+c 87.57.Nk 相似文献
6.
在聚合物基体中掺入少量的层状硅酸盐所制备的聚合物/粘土纳米复合材料,其阻隔性能明显地优于纯聚合物及其传统的复合材料。实验及分析结果表明,聚合物/粘土纳米复合材料的微观结构和阻隔性能主要受控于粘土剥离后的径厚比.一简单的重整化群模型被用来评估粘土几何因素(诸如径厚比、取向、剥离程度等)对聚合物/粘土纳米复合材料阻隔性能的影响,所得到的逾渗阈值及最佳粘土含量与实验结果吻合。 相似文献
7.
通过系统研究A~190区超形变核中转动带的转动惯量、角动量顺排、旋称分裂随转动频率的变化规律, 结合我们用处理对力的粒子数守恒方法的计算结果, 对A~190区所有转动带的组态结构给出了一个整体的描述. 绝大多数超形变带都建立在强耦合轨道上, 例如中子[512]5/2, [624]9/2. 少数超形变带则建立在高j闯入轨道上, 即中子[761]3/2, [752]5/2. 根据我们提出的组态结构所进行的理论计算结果表明, A~190区所有转动带的一般行为、反常变化和带交叉都得到了满意的解释. 相似文献
8.
9.
Richard Kotek Kyeong Pang Ben Schmidt Alan Tonelli 《Journal of Polymer Science.Polymer Physics》2004,42(23):4247-4254
Poly(ethylene isophthalate) (PEI) was synthesized for this research with essentially a condensation polymerization of isophthalic acid and ethylene glycol catalyzed by zinc acetate and antimony trioxide. Several samples were obtained, and their characteristics were observed and compared with poly(ethylene terephthalate) (PET). The synthesized PEI samples were chemically identified by 1H NMR. Thermal analysis with differential scanning calorimetry (DSC) yielded results that indicate the samples were primarily amorphous, with a glass‐transition temperature of 55–60 °C. Molecular weights of these PEI samples were also obtained through intrinsic viscosity measurements (Mark–Houwink equation). Molecular weights varied with conditions of the polymerization, and the highest molecular weight achieved was 21,000 g/mol. Finally, the diffusion coefficient, solubility, and permeability of CO2 gas in PEI were measured and found to be substantially lower than in PET, as anticipated from their isomeric chemical structures. This is because in PET the phenyl rings are substituted in the para (1,4) positions, which allows for their facile flipping, effectively permitting gases to pass through. However, the meta‐substituted phenyl rings in PEI do not permit such ring flipping, and thus PEI may be more suitable for barrier applications. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4247–4254, 2004 相似文献
10.
Bakul C. Dave Xiankui Hu Yogeeswari Devaraj Shirshak K. Dhali 《Journal of Sol-Gel Science and Technology》2004,32(1-3):143-147
There is a current need for alternative coatings that can provide corrosion resistance to metals or alloy surfaces due to the environmental hazards posed by conventional coatings. Herein, we report on novel organically-modified sol–gel coatings for the protection of metal and alloy surfaces. The basic concept of chemical conversion of metal surfaces is based on deposition of a hydrophobic, nonporous sol–gel barrier layer for surface protection and corrosion prevention. The properties of these organosilica coatings can be tuned by varying the composition of precursors. The evaluation of hydrophobicity, adhesive strength, and anticorrosion properties of organically-modified sol–gel derived coatings suggests their potential utility as technologically-compatible alternatives to conventional coatings. 相似文献