Decay of electrical conductivity in p-toluene sulfonate doped polypyrrole films

Long term performance of conductivity of p-toluene sulfonic acid (pTSA) doped electrochemically synthesized polypyrrole (PPy) films was estimated from accelerated aging studies between 80 °C and 120 °C. Conductivity decay experiments indicated that overall aging behavior of PPy films deviated from first order kinetics at prolonged aging times at elevated temperatures. However, an approximate value for the activation energy of the conductivity decay of PPy was calculated as E=47.4 kJ/mol, enabling an estimate of a rate constant of k=8.35×10⁻⁶/min at 20 °C. The rate of decrease of conductivity was not only temperature dependent but also influenced by the dopant concentration. A concentration of 0.005 M pTSA in the electrolyte resulted in a conductive film and when this film was exposed to 120 °C for a period of 40 h, the conductivity decayed to about 1/20 of its original value. The concentration of pTSA was increased to 0.05 mol/l and when the resulting film was aged in the same way, it showed a decrease in the conductivity to about 1/3 of its original value. Both microwave transmission and dc conductivity data revealed that highly doped films were considerably more electrically stable than lightly doped films. The dopant had a preserving effect on the electrical properties of PPy.

Synthesis, characterization and analytical modelling of mechanical behavior of a conducting polymer actuator

Electrochemical synthesis of a tri-layer polypyrrole based actuator optimized for performance was reported. The 0.05 M pyrrole and 0.05 M tetrabutylammonium hexaflurophosphate in propylene carbonate (PC) yielded the optimum performance and stability. The force produced ranged from 0.2 to 0.4mN. Cyclic deflection tests on PC based actuators for 3 hours indicated that the displacement decreased by 60%. PC based actuator had a longer operating time, exceeding 3 hours, compared to acetonitrile based actuators. A triple-layer model of the polymer actuator was developed based on the classic bending beam theory by considering strain electrode material. A tri-layer actuator was fabricated [4, 6], by initially sputter coating a PVDF film with approximately 100nm of gold layer, resulting in a conductive film with a surface resistance of 8-10Ω. The PVDF film was about ~145µm thick had an approximate pore size of 45μm. A solution containing 0.05M distilled pyrrole monomer, 0.05M (TBAPF6) and 1% (w/w) distilled water in PC (propylene carbonate) solution was purged with nitrogen for 15 minutes. The continuity between PPy and PVDF. Results predicted by the model were in good agreement with the experimental data.

Direct current electric potential in an anisotropic half-space with vertical contact containing a conductive 3D body

Detailed studies of anomalous conductors in otherwise homogeneous media have been modelled. Vertical contacts form common geometries in galvanic studies when describing geological formations with different electrical conductivities on either side. However, previous studies of vertical discontinuities have been mainly concerned with isotropic environments. In this paper, we deal with the effect on the electric potentials, such as mise-`a-la-masse anomalies, due to a conductor near a vertical contact between two anisotropic regions. We also demonstrate the interactive effects when the conductive body is placed across the vertical contact. This problem is normally very difficult to solve by the traditional numerical methods. The integral equations for the electric potential in anisotropic half-spaces are established. Green’s function is obtained using the reflection and transmission image method in which five images are needed to fit the boundary conditions on the vertical interface and the air-earth surface. The effects of the anisotropy of the environments and the conductive body on the electric potential are illustrated with the aid of several numerical examples.

Ion exchange, anisotropic structure and thermal stability of polypyrrole films

The thermal stability of electrochemically prepared polypyrrole (PPy) films with p-toluene sulfonate (pTS) or perchlorate (CIOP₄⁻) counter ion (PPy/pTS and PPy/ClO₄⁻) is improved by simple treatment with aqueous sulfuric acid, sodium sulfate or sodium bisulfate. The degree of stabilization achieved depends on the solution, temperature and duration of treatment. PPy/pTS is easily stabilized and thick films (43μm) retain 90 % of the initial conductivity after long period (300 h) at 150 °C, while thinner films (12 μm) retain slightly less (70 %). A model for the conductivity decay has been proposed. Although the mechanism for improved stability is not yet clear it is apparent that the level of ion exchange and the original polymer microstructure are important. The early stages of ion exchange are not symmetrical and diffusion is facilitated at the electrode side of the film. Furthermore, X-ray diffraction shows no evidence of morphological change after treatment of thick PPy/pTS but in thin PPy/pTS and PPy/ClO₄⁻ films an additional peak is indicative of more ordered structure following treatment. These observation may imply that there is a higher density of crosslinks and branching at the growth side than at the electrode side of the film.

Proton conductive composite membranes

In this work we investigated the synthesis of composite organic and inorganic membranes for proton conduction. Particles derived from metal alkoxides (M(OR)n) sol-gel processes (Ti, Zr, W with phosphoric acid) were embedded in polymeric matrices of poly-vinyl alcohol, (3-glycidoxypropyl)-trimethoxysilane and ethylene glycol. The structure of the composite membranes was complex as several IR peaks were convoluted, indicating the assignment of several functional groups. However, the peaks assigned to OH groups reduced in intensity in the composite membranes, indicating that cross-linking of hydroxyl groups in the organic and inorganic phases of the membrane may have occurred. The particles allowed for re-arrangement of the polymer matrix, as crystallinity was reduced compared to a polymer blank membrane. The composite membrane process resulted in homogeneous dispersion of nanoparticles into the polymer film. Proton conduction of the inorganic phase was mainly dominated by titania. Binary mixtures of titania phosphate (sample name TiP) resulted in proton conduction of 7.15 × 10−2 S.cm−1, one order of magnitude higher than zirconia phosphate (ZrP). The addition of Zr and W to TiP forming ternary or quaternary phases also led to lower proton conduction as compared to TiP. Similar trends were also observed for the composite membranes, though the TiP composite membrane proton conduction reduced after several hours of testing at 50°C, which was mainly attributed to acid leaching.

Automatic cast listing in feature-length films with Anisotropic Manifold Space

Our goal is to automatically determine the cast of a feature-length film. This is challenging because the cast size is not known, with appearance changes of faces caused by extrinsic imaging factors (illumination, pose, expression) often greater than due to differing identities. The main contribution of this paper is an algorithm for clustering over face appearance manifolds. Specifically: (i) we develop a novel algorithm for exploiting coherence of dissimilarities between manifolds, (ii) we show how to estimate the optimal dataset-specific discriminant manifold starting from a generic one, and (iii) we describe a fully automatic, practical system based on the proposed algorithm. The performance of the system is evaluated on well-known featurelength films and situation comedies on which it is shown to produce good results.

A highly conductive porous graphene electrode prepared via in situ reduction of graphene oxide using Cu nanoparticles for the fabrication of high performance supercapacitors

Herein, a new graphene/Cu nanoparticle composite was prepared via the in situ reduction of GO in the presence of Cu nanoparticles which was then utilized as a sacrificing template for the formation of flexible and porous graphene capacitor electrodes by the dissolution of the intercalated Cu nanoparticle in a mixed solution of FeCl3 and HCl. The porous RGO electrode was characterized by atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). The as-prepared graphene/Cu nanoparticle composite and the pure graphene film after removal of Cu nanoparticles possessed high conductivity of 3.1 × 10³ S m^-1 and 436 S m^-1 respectively. The porous RGO can be used as the electrode for the fabrication of supercapacitors with high gravimetric specific capacitances up to 146 F g^-1, good rate capability and satisfactory electrochemical stability. This environmentally friendly and efficient approach to fabricating porous graphene nanostructures could have enormous potential applications in the field of energy storage and nanotechnology.