Anisotropic surface melting in lyotropic cubic crystals

From experiments with metal crystals, in the vicinity of their crystal/liquid/vapor triple points, it is known that melting of crystals starts on their surfaces and is anisotropic. Recently, we have shown that anisotropic surface melting occurs also in lyotropic systems. In our previous paper (Eur. Phys. J. E 19, 223 (2006)), we have focused on the case of poor faceting at the Pn3m/L1 interface in C12EO2/water binary mixtures. There anisotropic melting occurs in the vicinity of a Pn3m/L3/L1 triple point. In the present paper, we focus on the opposite case of a rich devil's-staircase-type faceting at Ia3d/vapor interfaces in monoolein/water and phytantriol/water mixtures. We show that anisotropic surface melting takes place in these systems in a narrow humidity range close to the Ia3d-L2 transition. As whole (hkl) sets of facets disappear one after another when the transition is approached, surface melting occurs in a facet-by-facet type.     

Light Diffraction of Aligned Polymer Fibers Periodically Dispersed by Phase Separation of Liquid Crystal and Polymer

We have confirmed light diffraction of aligned polymer fibers obtained by a phase separation of an anisotropic-phase solution of liquid crystal and polymer. He—Ne laser light passing through the polymer fibers was scattered in the axis vertical to the fibers, and had two peaks of light intensity symmetrical to the center of the transmitting laser spot. The two peaks were found to be caused by light diffraction due to the periodic polymer-fiber dispersion because the peaks corresponded to values calculated by intervals between the fibers. The periodical fiber networks are considered to be formed by anisotropic spinodal decomposition. This effect can be used to measure the dispersion order of the polymer fibers. © 2004 The Optical Society of Japan     

金属Al表面熔化各向异性的分子动力学模拟

采用嵌入原子势,使用分子动力学方法对金属Al不同低指数晶面的表面熔化现象分别进行了模拟.分析了熔化过程中样品结构组态的变化.模拟结果表明对于不同的自由表面,表面熔化呈现出明显的各向异性行为.Al（110）面在低于熔点的温度之下发生预熔化;（111）与（001）面都出现过热现象.与（111）面不同,（001）面发生过热现象时表面原子层为类液层,而（111）面仍然保持很好的晶格结构,即预熔化的Al（001）面在高于熔点的温度下,仍可以在很长的时间内处于相对稳定的亚稳态.由模拟得到Al的热力学熔点为950 K左右,与实验值基本符合. 关键词： 分子动力学 表面熔化 过热     

Crystallization of a flexible-chain polymer in melt in the presence of double-stranded DNA

The behavior of a mixture of short fragments of double-stranded DNA and a flexible-chain polymer is addressed. The role of the DNA double helix in the formation of the crystalline phase in the flexible-chain polymer’s melt is examined. It is shown that the presence of DNA rigid fragments in melt results in increase in the melting temperature. A shift of the melting temperature of a perfect crystal with respect to the pure melt of polymer is calculated.     

Thermal and optical properties of electron beam irradiated cellulose triacetate

Samples from Cellulose triacetate (CTA) sheets were irradiated with electron beam in the dose range 10–200 kGy. Non-isothermal studies were carried out using thermogravimetric analysis (TGA) to obtain the activation energy of thermal decomposition for CTA polymer. The CTA samples decompose in one main break down stage. The results indicate that the irradiation by electron beam in the dose range 80–200 kGy increases the thermal stability of the polymer samples. Also, the variation of melting temperatures with the electron dose has been determined using differential thermal analysis (DTA). The CTA polymer is characterized by the appearance of one endothermic peak due to melting. It is found that the irradiation in the dose range 10–80 kGy causes defects generation that splits the crystals depressing the melting temperature, while at higher doses (80–200 kGy), the thickness of crystalline structure (lamellae) is increased, thus the melting temperature increases. In addition, the transmission of these samples in the wavelength range 200–2500 nm, as well as any color changes, were studied. The color intensity ΔE* was greatly increased on increasing the electron beam dose, and accompanied by a significant increase in the blue color component.      

Photo-orientation at liquid crystal—polymer interfaces

It is suggested that liquid crystal—polymer interfaces are coupled systems, in which the components mutually influence the orientational state of each other. The photo-orientation process at liquid crystal-polymer interfaces provides a striking example of such a coupling. Experiments show that the anisotropic structure generated by polarised light at a polymer surface is strongly affected by the phase of the liquid crystal covering the polymer. Photo-orientation is significantly more efficient when the liquid crystal is in the isotropic phase than when it exhibits orientational order. The observations are interpreted by assuming that in the smectic and nematic phases the liquid crystal stabilises to a large extent polymer chain-segments aligned parallel to the director, while it blocks the photo-induced formation of chain-segments in the perpendicular direction. Other situations, in which the coupling between the liquid crystal and the polymer can be important, are also discussed briefly.     

聚合物网络稳定铁电液晶中的条纹织构的研究

对聚合物网络稳定的铁电液晶体系进行了研究.实验表明,在聚合物网络单体聚合过程中施加低频交变电场，在偏光显微镜下观察到均匀的液晶分子排列出现一新的条纹织构.从体系自由能的角度对条纹织构给出合理的解释. 关键词：     

Facile Fabrication of Anisotropic Colloidal Particles with Controlled Shapes and Shape Dependence of Their Elastic Properties

A facile technique with only one step for fabrication of anisotropic colloidal particles at the air/water interface is demonstrated. Anisotropic colloidal particles with controlled shapes can be easily obtained by tuning the incubation time in solvent vapor at room temperature. The formation of separate anisotropic particles is attributed to the lateral stretch on the particles by the interfacial forces and repulsion among the neighboring particles by the generation of the polymer solution flows. To further explain the proposed formation mechanism of the colloidal particles with shape anisotropy, an in situ experiment is designed for direct observation of the arrangement change of the colloidal particles. This fabrication technique is general and applicable to polymer colloidal particles with various initial sizes ranging from microscale to nanoscale. Moreover, the elastic properties of the anisotropic colloidal particles are measured which exhibit a prominent change with different shapes and the change trend of the elastic moduli is similar for particles with different original sizes. This work provides a versatile approach for fabrication of anisotropic colloidal particles with tunable shapes and sizes and establishes the interplay between particle shape and elastic property, which is much valuable for further research on the effect of particle parameters on drug delivery process.     

On the Mechanisms of Recrystallization After Melting in Semicrystalline Polymers: The Effect of the Initial Melt State

The mechanisms of recrystallization after melting during a heating scan of syndiotactic polypropylene (sPP) and isotactic polystyrene (iPS) were studied. This was done by monitoring the structure evolution during the recrystallization process and its changes during a subsequent heating scan via time- and temperature-dependent SAXS measurements, respectively. The results of this study showed that the sPP samples exhibited a recrystallization mechanism similar to the multistage route found upon initial crystallization of semicrystalline polymers from an entangled melt. Meanwhile, a different recrystallization mechanism was shown by the iPS samples. In this case, the recrystallization process proceeded as a direct growth into the melt in a one-step process. This is the first time we observed such a mechanism that resembles the picture presented by the classical models for crystallization from an entangled polymer melt. The reason for such different mechanisms may be related to the initial melt state prior to crystallization. It seems as though when crystallization sets in in an entangled polymer melt, it follows the multistage route, whereas if the melt is locally disentangled, it proceeds by a direct growth mechanism.     

各向异性表面张力对定向凝固中共晶生长形态稳定性的影响

研究各向异性表面张力对定向凝固中共晶生长形态稳定性的影响.应用多重变量展开法导出了共晶界面表达式和扰动振幅的变化率满足的色散关系.结果表明,共晶生长系统有两种整体不稳定性机理:由非震荡导致的"交换稳定性"机理和由震荡导致的"整体波动不稳定性"机理.震荡有四种典型模式,即:反对称-反对称(AA-),对称-反对称(SA-)、反对称-对称(AS-)和对称-对称(SS-)模式.稳定性分析表明:共晶界面形态稳定性取决于Peclet数ε的某一个临界值ε_*,当ε大于临界值ε_*时,共晶界面形态不稳定;当ε小于临界值ε_*时,共晶界面形态稳定.随着各向异性表面张力增大,对应于AA-,SA-和SS-模式的临界值ε_(aa*),ε_(sa*)和ε_(ss*)随之减小,表明各向异性表面张力减小这三种模式的稳定性区域;然而,随着各向异性表面张力增大,对应于AS-模式的临界值ε_(as*)随之增大,表明各向异性表面张力增大AS-模式的稳定性区域.     

Effect of ethylene carbonate concentration on structural and electrical properties of PEO–PMMA polymer blends

Polyethylene oxide–polymethyl methacrylate (PEO–PMMA) polymer blend electrolyte system complexed with silver salt having different ethylene carbonate (EC) concentrations was prepared using solution cast technique. Complex formation and change in structural and microstructural properties have been studied by X-ray diffraction, Fourier transform infrared, and scanning electron microscopy analysis. The thermal properties of polymer films have been examined by the differential scanning calorimetry technique. Addition of plasticizer is observed to lower melting temperature. Electrical response of polymer films has been measured as a function of EC concentration and temperature using complex impedance spectroscopy. Complex impedance data are used to analyze the conductivity, permittivity, and modulus formalism to understand the conduction mechanism. The temperature dependence of electrical conductivity of polymer electrolytes shows a sudden rise at the melting temperature of PEO.     

Vortex liquid crystals in anisotropic type II superconductors

In an isotropic type II superconductor in a moderate magnetic field, the transition to the normal state occurs by vortex lattice melting. In certain anisotropic cases, the vortices acquire elongated cross sections and interactions. Systems of anisotropic, interacting constituents generally exhibit liquid crystalline phases. We examine the possibility of a two step melting in homogeneous type II superconductors with anisotropic superfluid stiffness from a vortex lattice into first a vortex smectic and then a vortex nematic at high temperature and magnetic field. We find that fluctuations of the ordered phase favor an instability to an intermediate smectic-A in the absence of intrinsic pinning.     

Fluorescence of semiconductor nanorods in liquid-crystal composites

The fluorescence of CdSe/ZnS nanorods in liquid-crystal and anisotropic polymer composites is studied. A high degree of the fluorescence anisotropy is shown. It is found that a solubilizer strongly affects the CdSe/ZnS orientation, which opens new possibilities for creating electrically controlled liquid-crystal composites.     

Proof of gridlock in a polymer model

It has been suggested that some lattice models of polymers, especially ones that incorporate more realistic excluded volume interactions extending to further neighbors, may be subject to gridlock. A model is defined to have the property of gridlock if it cannot melt at any temperature unless a density decrease is allowed. Classical theories of polymer melting are incompatible with the property of gridlock. This paper proves rigorously that a two-dimensional square-lattice model of polymer chains that have nearest-neighbor excluded volume interactions (called the X1S model) has the gridlock property. The proof uses elementary concepts from graph theory. Also, different interpretations of the X1S model are given in terms of real polymers. This leads to a discussion of a number of different classes of melting depending upon whether the intramolecular rotameric energies and the attractive intermolecular energies are antagonistic to or supportive of the melting transition.     

Dislocation mediated melting of silicon-metal interfaces

It is known that the silicide formation between silicon and transition as well as noble metals occurs at 0.3–0.4 of the melting temperature of silicon. It is proposed that the chemical reaction is preceded by an interfacial melting process due to dislocation generation via the Kösterlitz-Thouless mechanism. The overall softening of the Debye temperature at the interface leads to the low temperature chemical reaction observed. A softening mechanism due to screening of the silicon lattice by the metal overlayer is suggested.     

Generating function of a thermoelectric field

It is shown that the state of a thermoelectric medium can be described by a single mathematical object — a generating function for a thermoelectric field. The relation between the generating function and the vector potential of the current density, the temperature distribution, and the potentials for uniform anisotropic and nonuniform isotropic media are considered.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fiziki, No. 5, pp. 21–24, May, 1986.     

Electro-optical properties of dilute solutions of flexible molecules ; the wormlike chain model

A theory of propagation and scattering of light in dilute solutions of flexible chain molecules is developed. The solvent is represented as a continuous isotropic dielectric medium. The polymer molecules are modelled as dielectric objects which may have an anisotropic dielectric tensor. The theory, applied to the wormlike chain model, represents the polymer molecules as flexible cylinders of constant cross section and with an isotropic internal dielectric constant. The increment in the refractive index of the solution and the isotropic and anisotropic light scattering intensities due to the presence of the chain molecules are derived. The numerical results of our model for the depolarization ratio as a function of the contour length and the persistence length of the polymer and of the refractive index of the solvent are presented and compared with the corresponding results for the popular bond additive approximation (BAA). It is found that the differences between our model and this approximation are due to the neglect of intramolecular dipole-induced dipole interactions in the BAA.     

Lamellar changes during heat treatment in isotactic polystyrene crystals

In the present investigation, the melting and thickening processes in lamellar crystals of isotactic polystyrene have been studied by transmission electron microscopy. It is shown that under properly chosen experimental conditions for the polymer, one can continuously follow the physical changes involved during the thickening as well as melting of lamellar crystals on heat treatment. The study of crystals grown at different temperatures reveals that melting of a single lamella starts at various areas. A commonly observed feature is the preferential melting of elastically bent parts of a lamella. It is indicated that the occurrence of melting in the various parts is due to a structural variation along the surface of lamellae resulting in a hindrance of the lamellar thickening process. At particular temperatures, melting of lamellar crystals is followed by recrystallization. The occurrence of a solid-stage thickening process is the major process so far observed during slow heat treatments. Considerable change in surface structure of the crystals grown at different temperatures is clearly reflected during the heat treatment. The rates of heating have marked influence on the resulting morphology of the crystalline superstructures.     

Dielectric properties of the P(VDF<Subscript>60</Subscript>/Tr<Subscript>40</Subscript>) copolymer in the porous glass matrix

The dielectric properties and electrical conductivity of the composite material, which was prepared by incorporating the P(VDF₆₀/Tr₄₀) copolymer into the porous glass matrix (the average pore diameter is approximately equal to 320 nm), and the bulk sample of the P(VDF₆₀/Tr₄₀) copolymer have been investigated in the temperature range 290–440 K. It is revealed that the incorporated material is characterized by an increase in the melting temperature and a considerable decrease in the temperature at which the ferroelectric phase formed in polymer inclusions becomes unstable. It is shown that charge transfer in the composite material occurs predominantly through channels filled with the polymer.