Photoinduced electron transport process in electrochemical cell I. Phenomenological description

The process of electron transport plays an essential role in the fundamental phenomena of life like photosynthesis, respiration and vision as well as in photoelectronic devices. However, the molecular mechanisms of the electron way and factors governing the transport rate in such systems are still unclear. Several groups have reported theoretical approaches for searching the mechanisms by using statistical mechanics, coherent dynamics and quantum mechanics. The current density vector inside the semiconducting layer is determined. In this paper we consider the problem of transport of electron promoted in the electrochemical cell constructed of two electrodes with the dye molecules immersed in. We describe the process of electron promotion by refractive light wave on the vacuum–semiconductor boundary as well as on the semiconducting electrode and the dye molecule layer in terms of extended phenomenological electrodynamics formalism. The results of our theoretical model show that such a theoretical approach will give more information on the mechanism of electron transport and will give insight in the determination of some electric features of materials.     

Phenomenological description of the crystal-liquid crystal phase diagram

A new Landau-type phenomenological free energy function to describe the phase diagram of uniaxial anisotropic materials is proposed. The resulting phase diagram includes crystalline, smectic A, nematic and isotropic states, as well as a theoretically possible plastic solid state. Depending on the parameters of the free energy, smectic A phase may or may not be present for a given material. The obtained topologies of the temperature-pressure phase diagram qualitatively agree with results from computer simulations of model liquid crystalline materials.     

Charge transport properties in carbon black/polymer composites

The charge transport properties of polymer matrix–carbon black composites are investigated in this study. Direct current conductivity is examined with varying parameters: the temperature and the conductive filler content. Conductivity data are analyzed by means of percolation theory, and both percolation threshold and critical exponent are determined at each of the examined temperatures. The temperature dependence of conductivity and the agreement of experimental results with the variable range hopping model reveal hopping conduction as the predominant transport mechanism, below and in the vicinity of the critical concentration of carbon black particles. At higher concentrations, the contribution of hopping transport to the overall conductivity is reduced and a balance between hopping and conduction via geometrical contact occurs. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2535–2545, 2007     

Characterization and electrical transport properties of polyaniline and multiwall carbon nanotube composites

Polyaniline/multiwalled carbon nanotube (PANI/MWNT) composites were prepared by in situ polymerization. Scanning electron microscope, X‐ray diffraction, Fourier transform infrared, Uv‐Visible spectroscopy, Fluorescence spectrophotometry were done to characterize the PANI/MWNT composites. Thermal stability was measured by thermogravimetry analysis. The thermal stability of PANI/MWNT composites becomes higher than PANI. Electrical transport properties of different PANI/MWNT composites were investigated in the temperature range 77 ≤ T ≤ 300 K with and without magnetic field up to 1 T. The dc resistivity of PANI/MWNT composites shows different behavior compared to the sample without MWNT. The room temperature dc magnetoconductivity of the samples is negative; however, its sign changes to positive by lowering the temperature, which has been explained by hopping type charge transport. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1767–1775, 2010     

Electrical transport properties of poly(aniline-co-p-phenylenediamine) and its composites with incorporated silver particles

Statistical copolymers of aniline and p-phenylenediamine, poly(aniline-co-p-phenylenediamine)s, were synthesised by oxidative polymerisation using various oxidants, ammonium peroxydisulphate or silver nitrate. Depending on the choice of oxidant, copolymers or composites with silver particles were obtained. Different molar concentrations of p-phenylenediamine in the reaction mixture provided materials of different conductivities. The influence of both the copolymer composition and the presence of discrete silver particles on the electric and dielectric properties of the system was studied. The results showed a decrease in the conductivity of copolymers and their composites with the silver content compared with the content of standard polyaniline salt. The reduction in conductivity was described in terms of the decreased density of hopping centres due to defects in the copolymer structure. The dielectric relaxations observed were described in terms of their activation energies and were linked to the corresponding conduction mechanism.     

Synergistic effects on polyurethane/lead zirconate titanate/carbon black three-phase composites

Synergistic processes in hybrid composites have frequently been described in the literature over the past few years, opening doors to new studies and applications for this type of material. In this study, three-phase composites were obtained using polyurethane (PU) as the matrix, lead zirconate titanate (PZT) as the ferroelectric ceramic and carbon black (CB) as the conductive phase. The discussion is primarily focused on a comparison of the electrical, thermal and dielectric properties of three-phase composites with those of PU_CB and PU_PZT biphasic composites. The study describes a synergistic effect between the PU/PZT/CB phases involved in the generation of charges between the particles, implying better homogeneity of the composites as well as influence over the PU crystallization. The PU_CB conductivity profile showed a phenomenon of multi-step percolation thresholds attributed to the molecular structure and repulsive surface charge of CB particles. The surface charge phenomenon restricted the percolation curve analysis of the three-phase composites by means of classic percolation theory, shown by distortion of the critical exponents. The dielectric constant three-phase composites increased gradually as a function of CB in accordance with the percolation profile.     

The properties of silica-gelatin composites

Silica-gelatin composites with various silica-to-gelatin ratios were obtained. The influence of high-dispersity silica on the swelling of composites in water and desorption of pyridoxine and thiamine vitamins incorporated into the material was studied. The addition of silica to gelatin was shown to increase the time of the dissolution of the materials in aqueous medium and decelerate the desorption of vitamins.     

Theoretical description of electron transport in homo-and molecularly doped polymers

The general aspects of electron transport in disordered organic media (polymers, organic glasses, molecularly doped polymers) are considered. A critical analysis of experimental results and their interpretation in terms of basic theoretical models and experimental methods used in research in this area is presented. Particular attention is given to the comparative analysis of the data obtained by the time-of-flight technique and in studying the radiation conductivity of polymers, in particular, to the possibility of describing the conductivity data in terms of the Gaussian disorder model.     

Novel syndiotactic polystyrene/BaTiO3-graphite nanosheets three-phase composites with high dielectric permittivity

Novel three-phase composites were prepared by embedding graphite nanosheets (GNs) and BaTiO₃ nanoparticles into syndiotactic polystyrene (sPS) matrix via a solution blending and flocculation method. The dependences of electric and dielectric properties of the resultant sPS/BaTiO₃-GNs composites on volume fractions of GNs (f_GNs) and frequency were investigated. The percolation theory was employed to explain the electric and dielectric behavior of sPS/BaTiO₃-GNs composite. It was found that the sPS/BaTiO₃-GNs composite showed an obvious insulator-conductor transition with a much low percolation threshold of f_GNs = 1.44 vol%. The dielectric permittivity of sPS/BaTiO₃-GNs composite reached as high as 51.8 at 100 Hz at percolation threshold, which was about 18 and 7 times higher than that of pure sPS and sPS/BaTiO₃ composite, respectively.     

Phenomenological study on heat and mass coupling mechanism of waxy crude oil pipeline transport process

Based on the phase equilibrium model of the paraffin wax precipitation in the process of oil pipeline transportation, theory and method of non-equilibrium thermodynamics were applied to obtain the linear phenomenological equations for the cross-interaction of heat and mass transfer during pipeline transport, which were derived from the irreversible entropy production rate equation. Then, the analysis of the irreversible heat flow and the mass flow were carried out, and the mathematical expressions of the phenomenological coefficient of liquid phase, the phenomenological coefficient of solid phase flow, and the heat flow phenomenological coefficient were obtained. Taking a waxy crude oil transportation pipeline in Daqing Oilfield as an example, based on the analysis of liquid–solid phase equilibrium, the irreversible linear phenomenological mechanism of heat and mass coupling in waxy crude oil pipeline transportation was analyzed in detail from three levels: phenomenological coefficients which reflect characteristic of the effect of force on flow in heat and mass transfer; thermodynamic forces which trigger heat and mass transfer; transmitted heat and mass flow density, providing a theoretical basis for the further study of the wax deposition in the process of pipeline transportation.     

Electrochemical properties of conducting polyethylene-polyacetylene composites

Production techniques, structure, and electrochemical properties of conducting thin-film materials consisting of a polyethylene (PE) substrate covered with a polyacetylene (PA) layer are studied. Properties of a free PA film are determined by the catalyst used in its synthesis. Properties of composites depend on the optimum selection of the PA/PE ratio (by weight), the catalyst used for polymerizing PA, and the PE structure. The capacity of composites is higher than that of free PA films. This points to the possible role of an increased transport of lithium cations at interfaces.     

The three-phase structure and mechanical properties of poly(ethylene terephthalate)

The relation between the mechanical properties and the microstructure of PET has been investigated, combining results from WAXS, SAXS, FTIR, DSC, and uniaxial compression tests. The rigid amorphous fraction in the PET was explicitly taken into consideration in interpreting structure–property relations. WAXS results prove that glass crystallized PET with a high volume fraction of rigid amorphous material and small crystal size, on uniaxial compression shows a considerable loss in crystalline fraction. FTIR results in combination with these WAXS results suggest that during this loss in crystallinity, short-range conformational order is retained, while long-range structural order is lost. At the same time, material with small crystals and a high amount of rigid amorphous material was found to show unexpectedly low yield stress. It is concluded that in the interpretation of these phenomena it is necessary to take the three-phase structure of PET, including the rigid amorphous fraction into account. This is expected to hold for other semicrystalline polymers, where a rigid amorphous fraction is prominent, such as PHB, PBT, PEN, PEEK, etc. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2092–2106, 2004     

Contribution of thermal analysis to the description of transport phenomena of pesticides

The vaporization enthalpies of two acetanilide pesticides, alachlor (2’,6’-diethyl-N-(methoxymethyl)-2-chloroacetanilide) and metolachlor (2-chloro-N-(2-ethyl-6-methylphenyl)-N-[(1S)-2-methoxy-1-methylethyl] acetamide), were determined by processing non-isothermal thermogravimetry data according to the Clausius-Clapeyron equation. The reliability of the procedure proposed was tested carrying out some experiments at different heating rates using acetanilide as a reference compound. A good agreement is found among the vaporization enthalpies derived from all the multi-heating rate experiments as well as with the one predicted from the vapor pressure data taken from literature. The vaporization temperatures (T _vap=470±2 K and T _vap=479±2 K) and enthalpies (Δ_vap H°(436 K)=85±1 kJ mol^–1 and Δ_vap H°(436 K)=70±1 kJ mol^–1) for alachlor and metolachlor, were selected, respectively.