Charge transport in a mixed ionically/electronically conducting, cationic, polyacetylene ionomer between ion-blocking electrodes

The electrical behavior of the cationic, polyacetylene-based, conjugated ionomer, poly[(2-cyclooctatetraenylethyl)trimethylammonium trifluoromethanesulfonate], sandwiched between gold electrodes is reported. The steady-state current of this mixed ionically/electronically conducting system is assigned to be unipolar diffusive hole transport for voltages below approximately 1.4 V, giving way to bipolar migratory transport above approximately 1.4 V. In the low-voltage regime, a non-Faradaically controlled doping model is proposed where p-doping at the anode is balanced by the charging of an ionic double layer at the cathode. In the high-voltage regime, n- and p-type regions extend from the electrodes as the voltage becomes sufficient to drive disproportionation and the electric field required by the redistribution of ions begins to substantially influence carrier transport. The assignment of a transport mechanism is primarily based on analyzing the decay of the steady-state system under short-circuit and open-circuit conditions. First, it is shown that the power describing the power-law decay of the short-circuit current is characteristic of the steady-state carrier profile. Second, it is argued that a component of the time-dependent, open-circuit voltage decaying more rapidly than the time scale for ion motion is indicative of a substantial migratory component to steady-state transport, as observed in the high-voltage regime. The hole and electron mobilities are estimated to be on the order of 10(-7)-10(-6) cm(2) V(-1) s(-1).     

A direct hydrogen-1 and phosphorus-31 nuclear magnetic resonance cation solvation study of Al(ClO4)3, Ga(ClO4)3, In(ClO4)3, UO2(ClO4)2, and UO2(NO3)2 in water-acetone-dimethylsulfoxide and water-acetone-hexamethylphosphoramide mixtures

A competitive solvation study of Al(ClO₄)₃, Ga(ClO₄)₃, In(ClO₄)₃, UO₂(ClO₄)₂, and UO₂(NO₃)₂ in water-acetone-dimethylsulfoxide (DMSO) and water-acetone-hexamethylphosphoramide (HMPT) mixtures has been carried out by direct H¹ and P³¹ nuclear magnetic resonance (NMR) techniques. At low temperature, proton and ligand exchange are slow enough in these systems to permit the observation of signals for bulk and coordinated molecules of water and the organic bases (DMSO and HMPT). Both DMSO and HMPT compete effectively with water for coordination sites in the Al³⁺, Ga³⁺, and In³⁺ systems, with steric effects dominating the HMPT results. Both Al³⁺ and In³⁺ are able to bind a maximum of two to three HMPT molecules, for example. In contrast, UO²⁺ is solvated selectively by the organic molecules to the allowed maximum of 4 molecules per cation. H¹ and P³¹ NMR spectral results support the formation of only the mono-, tri-, and tetra-HMPT solvation complexes.     

Analysis of impact-excited HeI states by applying magnetic and electric depolarization techniques

The magnetic depolarization of the impact radiation at λ(4¹ D?2¹ P)=492 nm and λ(3¹ D?2¹ P) = 668 nm as well as the splitting of the magnetic depolarisation signals in electric fields were investigated for 10–25 keV H ₂ ⁺ (D ₂ ⁺ )-He collisions (only 492 nm line) and for 5-22.5 keV He-He collisions (both lines). The results are compared with analogous measurements for He⁺- He and Ne⁺ - He collisions and the dynamics of the excitation process are qualitatively discussed. In particular, we emphasize the importance of inertia for the evolution of the electron cloud during the final phase of the collision process.     

Polymerization of w/o microemulsions for the preparation of transparent SiO2/PMMA nanocomposites

Reverse w/o microemulsions composed of methyl methacrylate (MMA) forming the oil phase, nonionic surfactants, and water are used for the synthesis of transparent SiO2/PMMA nanocomposites. An inorganic precursor, tetraethoxysilane (Si(OEt)(4), TEOS), is hydrolyzed in the reverse micelles containing aqueous ammonia. During the hydrolysis of TEOS, polymerization of the continuous MMA phase is initiated using AIBN (azobisisobutyronitrile), and after thermal polymerization at 333 K for 12 h, solid blocks of PMMA are obtained in which nanometer-sized silica particles are trapped in the solid polymer matrix. According to small-angle X-ray and dynamic light scattering experiments, the water droplets in MMA microemulsions are 12 nm (R(W) = 13) in diameter, whereas after polymerization of the microemulsion, the SiO2 particles in the transparent SiO2/PMMA composites are 26 nm in diameter. Transmission electron micrographs demonstrate a low degree of agglomeration in the composites. In comparison with materials generated from micelle-free solutions, the particle size distribution is narrow. The reverse micelle-mediated approach produces composites of high transparency comparable with that of pure PMMA.