A Molecular Dynamics study of the influence of side-chain length and spacing on lithium mobility in non-crystalline LiPF6·PEOx; x = 10 and 30

Molecular Dynamics (MD) simulation techniques have been used to investigate systematically how the length and spacing of poly(ethylene oxide) (PEO) side-chains along a PEO backbone influence ion mobility for two different salt concentrations. This is of fundamental relevance to the design of new polymer electrolytes for battery applications. The salt used has been LiPF₆ in concentrations corresponding to Li:EO ratios of 1:30 and 1:10. The MD box contained PEO backbones of 89–343 EO units to which 3, 6, 7, 8, 9 and 15 EO unit side-chains were added. The selected spacings along the backbone between the PEO side-chains attachment points were 5, 10, 15, 20 and 50 EO units. The backbone and all side-chains were methoxy end-capped, and the simulations were all made at 293 K. Ion mobilities have been estimated from the variation of mean-square-displacement with time, and have been analysed in relation to chain dynamics, cross-linking and ion pairing. Comparisons are also made with the results of simulated PEO systems without side-chains and/or without salt. It is found that, at a higher concentration, many short side-chains give the highest ion mobility, while the mobility is highest for side-chain lengths of 7–9 EO units at the lower concentration.     

Spectroscopic studies on conjugated polymers in mesoporous channels: influence of polymer side-chain length

The influence of mesoporous environment on the conjugated polymers was studied by UV-Vis absorption and Photoluminescence spectroscopy. The applied polymers were three novel poly(p-phenylenevinylene) derivatives (DDMA-PPV). These polymers have dibenzothiophen-5,5-dioxide units in their backbones, but are different from each other in the length of alkoxy side-chains. The polymers were incorporated into the mesoporous channels of SBA-15 by sorption from their dilute solutions. The confined polymers exhibited different trends in the shifts of the absorption onsets and the emission peaks depending on the length of the side-chains. The polymer with shorter side-chain showed red-shifts in both the absorption and emission spectra, whereas the polymer with longer side-chain showed blue-shifts. These phenomena were caused by the combined influences from the electronic confinement and the conformation distortion. Moreover, these trends were enhanced when the polymers were loaded in amine-modified SBA-15.     

Polarisation-sensitive optical elements in azobenzene polyesters and peptides

In this article, we describe fabrication of polarisation holographic optical elements in azobenzene polyesters. Both liquid crystalline and amorphous side-chain polyesters have been utilised. Diffractive optical elements such as lenses and gratings that are sensitive to the polarisation of the incident light have been fabricated with polarisation holography. Computer-generated optical elements and patterns have also been written with a single polarised laser beam. Recording of polarisation defects enabling easy visualisation is also shown to be feasible in azobenzene polyesters.     

Preparation of Main-Chain Thermotropic Polyesters With Two Types of Mesogens Connected Alternatively by Aliphatic Spacers

A homologous series of main-chain thermotropic polyesters (PBTn, n = 2, 4, 6) containing biphenyl and triad aromatic ester mesogenic units interconnected by n-methylene spacers in the main chain were prepared from terephthaloyl bis(4-oxybenzoyl chloride) (TOBC) and 4,4′-bis(ω-hydroxyalkyloxy)biphenyls (n-BP, n = 2, 4, 6) by solution polycondensation. The chemical structures of the monomers and PBTn were characterized by spectroscopic techniques and elemental analysis. The solubility, supermolecular structures, thermal and liquid crystalline properties of PBTn were investigated by differential scanning calorimetry (DSC), polarizing microscopy (PLM), small-angle X-ray scattering (SAXS), thermogravimetric analyses (TGA), and wide-angle X-ray diffraction (WAXD), and they were found to be closely dependent on the length of the methylene spacers. The increasing methylene units led to improved solubility, broader liquid crystalline range, reduced mesophase-isotropic transition point, higher thermal stability, and decreasing crystallinity. The decomposition temperatures (5% mass loss) of the polymers were above 380°C in nitrogen atmosphere and only PBT4 and PBT6 exhibited smectic mesophases as well as high viscosity in the mesophase.     

On crystallization and phase separation phenomena in PEN/PHBA copolyesters

Two different etching techniques that reveal the semicrystalline morphology of polyesters have been developed and applied to an analysis of the phase structure of copolyesters made by reacting poly(hydroxybenzoic acid) (PHBA), and poly(ethylene naphtha-lene-dicarboxylate) (PEN). One technique is based on oxidation with acidic permanganate solutions and is used to study the macroscopic distribution of different phases. The other is based on sa-ponification with alkaline reagents and reveals more detailed structure within the various phases. Etching and electron microscopic examinations have been carried out for three different PEN-co-PHBA compositions. Three different types of solid phase are revealed: (1) a phase rich in PEN; (2) a phase containing roughly equal proportions of the two components, liquid crystalline at high temperatures; (3) a solid phase of crystalline HBA-rich molecules, which segregate into laminar regions. These observations are consistent with the previously published thermal, x-ray, and dynamic mechanical analyses of these materials.     

SrTiO3基片的晶体质量及表面粗糙结构的X射线研究

用X射线双晶衍射摇摆曲线以及双晶X射线形貌对两个SrTiO₃基片的单晶质量进行了对比研究，并用X射线掠入射镜面反射及漫散射研究了它们的表面粗糙结构．结果表明，两个SrTiO₃基片中都存在镶嵌缺陷，其中一个样品的晶体质量相对较高．两个样品的表面粗糙结构相差很大，包括均方根粗糙度σ和横向相关长度ξ．σ分别为（0.5±0.1）和（1.3±0.1）nm，ξ分别为（1200±200）和（300±20）nm．样品的表面粗糙将增加Ｘ射线的漫散射强度而降低镜面反射的强度．晶体质 关键词：     

Local atomic order and optical properties in amorphous and laser-crystallized GeTe

In this work we study the role of short-range order changes upon amorphization on the optical properties of GeTe – a prototype phase change material employed for optical data storage. It is found that the profound change in the absorption is due to changes in the matrix elements of the optical transitions. The importance of the local distortions in the crystalline phase for the optical absorption are revealed as well. Modifying the degree of the distortions has a significant impact on the optical properties of the crystalline state and should therefore become a promising instrument to improve material properties for storage applications.Furthermore we study the effect of electron–electron and electron–hole interactions on the optical properties. This is achieved by evaluating many-body effects in the crystalline phase through a GW correction of eigenvalues and the solution of the Bethe–Salpeter equation. To cite this article: W. Wełnic et al., C. R. Physique 10 (2009).     

XRD study on the effect of the deposition condition on pulsed laser deposition of ZnO films

Using a pulsed laser deposition (PLD) process on a ZnO target in an oxygen atmosphere, thin films of this material have been deposited on Si(111) substrates. An Nd: YAG pulsed laser with a wavelength of 1064 nm was used as the laser source. The influences of the deposition temperature, laser energy, annealing temperature and focus lens position on the crystallinity of ZnO films were analyzed by X-ray diffraction. The results show that the ZnO thin films obtained at the deposition temperature of 400°C and the laser energy of 250 mJ have the best crystalline quality in our experimental conditions. The ZnO thin films fabricated at substrate temperature 400°C were annealed at the temperatures from 400°C to 800°C in an atmosphere of N₂. The results show that crystalline quality has been improved by annealing, the optimum temperature being 600°C. The position of the focusing lens has a strong influence on pulsed laser deposition of the ZnO thin films and the optimum position is 59.5 cm from the target surface for optics with a focal length of 70 cm.      

Comparative study on the hydrogen storage capacity of crystalline and amorphous nanomaterials of MoO<Subscript>3</Subscript>: effect of a catalytic Pd capping

Hydrogen storage capacities were investigated for two forms of MoO₃ nanomaterial, amorphous of low crystallinity, and other highly crystalline, using the quartz crystal microbalance technique. Effect of a catalytic Pd capping on the nanomaterials was evaluated. MoO₃ materials were grown using the gas condensation method, and both the amorphous and crystalline samples were composed of orthorhombic phases with Mo⁶⁺ oxidation state. For 4-min measurements, uncapped amorphous MoO₃ achieved a higher storage capacity than its crystalline counterpart, while Pd-capped samples exhibited lower values due to slower kinetics. Then, Pd-capped samples were measured using longer H2 exposure times of 30 min, finding that Pd-capped crystalline MoO₃ sample exhibited higher hydrogen storage capacity than its amorphous counterpart. Pd capping was found to affect the hydrogenation of the underlying oxide layer, mainly due to differences in long-range order and layered structure between crystalline and amorphous MoO₃ samples.     

Effect of electrodeposition modes on ruthenium oxide electrodes for supercapacitors

With developments in energy storage devices, supercapacitors are gaining more attraction because of their potential to excel batteries shortly. In this work, ruthenium oxide (RuO₂) has been deposited on stainless steel and studied the influence of surface modification of solid electrodes on capacitance properties. Hydrous ruthenium oxide was plated by different modes such as potential sweep method (cyclic voltammetric), constant potential method (chronoamperometry) and optimised potential pulse method using a recently reported precursor material namely ruthenium nitrosylsulfate (RuNS). The structural information and morphology of electrodeposits were characterised by X-ray diffractometer and scanning electron microscope respectively. The XRD studies indicate a poor crystalline state for RuO₂ in all the modes of deposition but can contribute to a higher surface area when compared to a highly crystalline form. The SEM analysis revealed the formation of surface modification concerning the change of potential mode. Mud-cracked morphology, spherical particles and dendrimeric morphology observed on chronoamperometry, potential pulse and cyclic voltammetry respectively. Electrochemical studies were also conducted on the samples to assess their performance for supercapacitor applications. The spherical particles of hydrous RuO₂ show high performance of capacitance behaviour 1180 F/g in 0.5 M H₂SO₄ at the scan rate of 5 mV/s. Dendrimeric morphology and mud-cracked morphology shows 573 F/g and 546 F/g respectively in same 0.5 M H₂SO₄ at the scan rate of 5 mV/s. The studies reveal that RuO₂ electrodes can be exploited for their outstanding capacitive behaviour by properly controlling the morphology of the deposits.     

激发频率对高氢稀释下纳米晶硅薄膜生长特性的影响

利用等离子体增强化学气相沉积技术,在高氢稀释条件下,研究不同激发频率对纳米晶硅薄膜生长特性的影响.剖面透射电子显微镜(TEM)分析结果显示,不同激发频率下制备的纳米晶硅薄膜晶化区均呈锥状结构生长,但13.56 MHz激发频率下制备的纳米晶硅薄膜最初生长阶段存在非晶态孵化层,即纳米晶硅薄膜的形成经历了由非晶态孵化层到晶态结构层的转变.而高激发频率(40.68 MHz)下硅纳米晶则能直接在非晶态衬底上生长形成.Raman谱和红外吸收谱测量结果表明高激发频率(40.68 MHz)下制备的纳米晶硅薄膜不但具有较高     

Screening of an Electric Field and the Quasi-Static Capacitance of an Induced Charge in Semiconductors with Hopping Conductivity

Expressions for the screening length of an external electrostatic field in a crystalline semiconductor are derived in the Debye–Hückel and Mott–Schottky approximations taking into account electron (hole) hopping via hydrogen-like donors (acceptors). The feasibility of determining the Debye–Hückel screening length from measurements of a quasi-static capacitance with low and high degrees of basic dopant compensation has been demonstrated even in a strong field, that is, in the Mott–Schottky approximation. To measure the capacitance, the electric signal frequency must be much less than the average frequency of electron hopping via donors.     

Influence of molecular-substrate interaction on the self-assembly of discotic liquid crystals

We compare by scanning tunnelling microscopy the structure of hexakis-2,3,6,7,10,11-alkyloxytriphenylene self-assembled at the liquid-solid interface with either gold (1 1 1) or graphite (HOPG) as the substrate. The symmetry-breaking transition previously observed on graphite, when the length of the side-chains is increased, is observed to take place also on gold. However, it corresponds to a more drastic reduction of symmetry and is associated to a decrease of the molecular area. We interpret this change in terms of a variation in the adsorption energy of the conjugated core with the substrate.     

Study of Friction between Liquid Crystals and Crystalline Surfaces by Molecular Dynamic Simulations

The lubrication characteristics of liquid crystal (LC) molecules sheared between two crystalline surfaces obtained from molecular dynamics (MD) simulations are reported in this article. We consider a coarse-grained rigid bead-necklace model of the LC molecules confined between two atomic surfaces subject to different shearing velocities. A systematic study shows that the slip length of LC lubrication changes significantly as a function of the LC-surface interaction energy, which can be well described though a theoretical curve. The slip length increases as shear rate increases at high LC-surface interaction energy. However, this trend can not be observed for low interaction energy. The orientation of the LC molecules near the surface is found to be guided by the atomics surfaces. The influence of temperature on the lubrication characteristics is also discussed in this article.     

晶体表面偏角对摇摆曲线及其半峰宽的影响

本文应用X射线衍射动力学理论,计算了晶体表面偏角对X射线双晶衍射摇摆曲线及其半峰宽的影响,得出当晶体表面向某一方向存在一定的偏角时,X射线的入射方向不同,将造成摇摆曲线位置的改变和半峰宽的变化,且其变化趋势随着入射角的变小而增大,随着入射角的减小,反射峰的半峰宽增大,并向高角方向漂移,采用掠入射的不对称衍射方式时,偏角的影响更为明显。 关键词：     

Controlling the micro/nanostructure of self-cleaning polymer coating

Polypropylene bio-mimic self-cleaning surfaces with porous micro-nano-binary morphology structures were prepared by a simple casting method. The influence of the cooling process and solvent composition on water contact angle, sliding angles and self-cleaning properties has been investigated. Detailed SEM morphology studies revealed that the polymer used in this work is commercial-grade granular low-density polyethylene (LDPE) forms petal-like crystalline, which are of micrometer scale in length and nanometer scale in thickness. The nano-crystallines on the surface represent a porous three-dimensional micro-nano-binary structure. It was found that a compromise to the film porosity and crystal nano structure is essential for achieving a satisfied self-cleaning surface. Under optimum condition, a water contact angle of 152.2°, and a sliding angle of 1.7° can be obtained using this simple method.     

Lipase-ultrasound assisted synthesis of polyesters

Poly (ethylene glutarate), poly (ethylene malonate) and poly (ethylene phthalate), were enzymatically synthesized by immobilized Candida antarctica lipase B in solvent free conditions. The synthesis of these polyesters was based on the ester-ester exchange reaction between ethylene glycol diacetate and di-ethyl glutarate, di-benzyl malonate, di-n-octyl phthalate to produce poly (ethylene glutarate), poly (ethylene malonate) and poly (ethylene phthalate), respectively. The effect of ultrasound and PET polymeric beads was evaluated and showed to improve the synthesis of all polyesters. Ultrasound, as a green solvent-free technology, showed high potentiality for the polyester synthesis intensification.     

硼对沉积本征微晶硅薄膜特性的影响

采用甚高频等离子体增强化学气相沉积(VHF-PECVD)技术制备了不同腔室环境下的微晶硅薄膜.对单室沉积掺杂层p材料后遗留在腔室中的硼对本征微晶i材料电学特性和结构特性的影响进行了详细研究.测试结果表明：单室沉积p层后的硼降低了微晶i层材料的暗电导,增加了材料的光敏性;由于硼对i层污染程度的不同,使得材料的激活能发生了变化;腔室中残余的硼也导致微晶硅薄膜的结晶状况恶化,同时弱化了材料的(220)择优取向.而在较高功率和较强氢稀释下制备的晶化率较高,(220)晶向明显择优的材料受硼污染影响相对减小. 关键词： 单室 甚高频等离子体增强化学气相沉积 微晶硅 硼     

Influence of feedbacks in the RF accelerating system and feeders between RF power generators and accelerating resonators on the in-phase dipole oscillations of bunches in cyclic accelerators

In cyclic accelerators, interaction of the beam with the RF accelerating system may generate inphase dipole oscillations of bunches, which govern the limiting current of charged particles in the accelerator. A method of calculating the influence of the parameters of the RF system on the limit current is suggested. It is shown that feedbacks stabilizing the performance of the RF system considerably influence the limiting current in the accelerator. Moreover, the length of feeders through which the power of RF generators is applied to accelerating resonators also has an effect on the limiting current. The efficiency of the method is demonstrated by calculating the limiting electron current in a Sibir’-2 storage ring installed at the Russian Research Centre Kurchatov Institute.     

Influence of pressure on the solid state phase transformation of Cu-Al-Bi alloy

The solid state phase transformation of Cu-Al-Bi alloy under high pressure was investigated by x-ray diffraction, energy dispersive spectroscopy and transmission electron microscopy. Experimental results show that the initial crystalline phase in the Cu-Al-Bi alloy annealed at 750℃ under the pressures in the range of 0-6 GPa is α-Cu solid solution (named as α-Cu phase below), and high pressure has a great influence on the crystallisation process of the Cu-Al-Bi alloy. The grain size of the α-Cu phase decreases with increasing pressure as the pressure is below about 3 GPa, and then increases (P 3 GPa). The mechanism for the effects of high pressure on the crystallisation process of the alloy has been discussed.