Applications of Oligomers for Nanostructured Conducting Polymers

This Feature Article provides an overview of the distinctive nanostructures that aniline oligomers form and the applications of these oligomers for shaping the nanoscale morphologies and chirality of conducting polymers. We focus on the synthetic methods for achieving such goals and highlight the underlying mechanisms. The clear advantages of each method and their possible drawbacks are discussed. Assembly and applications of these novel organic (semi)conducting nanomaterials are also outlined. We conclude this article with our perspective on the main challenges, new opportunities, and future directions for this nascent yet vibrant field of research.

     

Direct observations of La ordering and domain structures in La0.61Li0.17TiO3 by high resolution electron microscopy

La_0.61Li_0.17TiO₃ microstructures have been studied by high resolution electron microscopy. A local lattice distortion occurs in the vicinity of the domain boundary region due to the twin with an angle of 89°. The average domain size of La_0.61Li_0.17TiO₃ is greater than 20 nm. The domain size and structures of La_0.61Li_0.17TiO₃ differ greatly from those of La-poor compounds, such as La_0.55Li_0.35TiO₃. At a nanoscopic level, microdomains of 20–100 nm in size construct a two-dimensional structure in La-rich compounds, while microdomains of 5–10 nm in size construct a three-dimensional structure in La-poor compounds. In addition, the Li-ion conduction mechanisms for La-rich and La-poor compounds are two- and three-dimensional, respectively.     

Substitution and proton doping effect on SrZrO3 behaviour: high‐pressure Raman study

The high‐pressure Raman studies of pure, Yb‐modified, protonated and non‐protonated SrZrO₃ dense ceramics were performed between 0.1 and 40 GPa using a diamond anvil cell. Lanthanide‐modified, protonated SrZrO₃ perovskites are potential materials for electrolytic membrane in fuel cells and electrolysers working at medium temperature. The comparison of the Raman spectra shows important differences in the pressure behaviour between the pure and Yb‐modified SrZrO₃ ceramics. SrZrO₃ exhibits a rigid structure without any structural modification, whereas for both SrZr_0.93 Yb_0.07 O_2.965 and SrZr_0.93 Yb_0.07 O_2.962 H_0.003 a sequence of structural modifications at 10, 20 and 35 GPa is revealed. The character of these structural modifications is very similar to that observed as a function of the temperature (orthorhombic Pnma 750 °C → pseudo‐tetragonal Imma 840 °C → tetragonal I4/mcm 1070 °C → cubic Pm3m), which suggests that they can be considered as the phase transitions. Despite the low level of proton content (0.3% mole/mole), significant difference between protonated and non‐protonated compounds is observed for the 700–750 cm⁻¹ doublet assigned to the Zr O octahedron stretching mode, perturbed by an oxygen atom vacancy and/or neighbouring Yb ion. The location of proton is discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

The relation between crystal structure and the formation and mobility of protonic charge carriers in perovskite-type oxides: A case study of Y-doped BaCeO3 and SrCeO3

Proton conductivity phenomena in 10% Y-doped barium and strontium cerate are investigated experimentally and by quantum molecular dynamics simulations. In particular the impact of deviations from the cubic perovskite structure on the formation and mobility of protonic charge carriers is investigated. For Y: SrCeO₃, which shows a larger deviation from the ideal cubic perovskite structure, the concentration and mobility of protonic defects is significantly lower than for Y: BaCeO₃. The first is due to the decay of the oxygen position into two sites, only one of which is involved in the formation of protonic defects. The symmetry reduction also leads to the formation of different one-dimensional proton diffusion paths, and unfavourable jumps between such paths are supposed to control the macroscopic proton diffusion coefficient in Y: SrCeO₃. The analysis suggests the formation of strong but transient hydrogen bonds and inter-octa-hedra proton transfer between vertices for SrCeO₃ in contrast to just intra-octahedra proton transfer for BaCeO₃. Whereas for BaCeO₃ the proton transfer step is identified to be rate-limiting at T= 1000 K, for SrCeO₃ both proton transfer and reorientation are found to be of similar magnitude.     

Performance of ferrite fillers on electrical behavior of polymer nanocomposite electrolyte

Dispersal of nanofillers in polymer electrolytes have shown to improve the ionic properties of Polyethylene oxide (PEO)-based polymer electrolytes in recent times. The effects of different nanoferrite fillers (i.e., Al–Zn ferrite, Mg–Zn ferrite, and Zn ferrite) on the electrical transport properties have been studied here on the composite polymer electrolyte system. The interaction of salt/filler with electrolyte has been investigated by XRD studies. SEM image and infrared spectral studies give an indication of nanocomposite formation. In conductivity studies, all electrolyte systems are seen to follow universal power law. Composition dependence (with ferrite filler) gives the maximum conductivity in [93PEO–7NH₄SCN]: X ferrite (where X?=?2% in Al–Zn ferrite, 1% Mg–Zn ferrite, and 1% Zn ferrite) system.     

Effect of temperature and high pressure on Mn2+ EPR spectra in K3H(SO4)2 fast-proton conductor

The linewidth ΔH _pp and spin-Hamiltonian parameters under temperature and high hydrostatic pressure by X-band continuous wave electron paramagnetic resonance in the K₃H(SO₄)₂ crystal were studied. Spin-Hamiltonian parameters, direction cosines and coordination of Mn²⁺ ion were determined at room temperature. The pressure at 300?MPa leads to the change of hydrogen bond potential and the transition from double well to single well potential moves about 10?K towards a higher temperature.     

Laser‐Triggered Proton Acceleration From Micro‐Structured thin Targets

By using relativistic massively parallel PIC code MANDOR, which features arbitrary target design including 3D micro‐structuring, a study of ion acceleration in short laser pulse interaction with different thin targets has been performed. Based on 3D simulation results it has been shown that micro‐structures on the front surface of thin plane targets increase a number and energy of hot electrons in comparison with that for the case of pure plain foils of optimal thickness. As a result, the energy of accelerated ions also increases up to 50%. However, the efficiency of ion acceleration from structured target reduces with laser pulse intensity increase, so that for laser pulses of ultra‐relativistic intensity a positive role of surface micro‐structuring diminishes. We have also studied to which extent a sub‐ps imperfection of the laser pulse shape, which smoothes the surface micro‐structures suppresses high‐energy ion generation. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Irradiation effect on the activation energy of thermal decomposition of polymers

The present work looks into the aspect of thermal modifications induced in polymers by proton irradiation. The kinetics of thermal decomposition of polymers is investigated by using the thermogravimetric (TG) technique. It has been observed that the degradation of polymers is a multi-step process that involves sequential and competing processes, and obeys the Arrhenius kinetics which allows us to connect the rate constant with the absolute temperature and the activation energy. The activation energy of thermal decomposition has been calculated from the TG curves, and its variation with different irradiation doses has been derived.     

EXAFS studies of ceramic proton conductors

Abstract

We report the results of EXAFS studies of rare earth doped SrCeO₃ and BaCeO₃, two systems that are important proton-conducting oxides. Using Gd doped SrCeO₃ as an example we outline the strategy of the measurements and the way they are compared with parallel atomistic simulations.     

Impact of proton irradiation with different fluences on the characteristics of InP/InGaAs heterostructure

ABSTRACT

The effect of traps to C–V and I–V plots of InP/InGaAs heterostructure with 3?MeV proton irradiation at different fluences has been discussed. After proton irradiation, the total reverse capacitance increases, which does not only include the variation of the depletion region width, but also the charging and discharging effect of traps. The total actual traps density N_SS of InP/InGaAs heterostructure could reach 13 orders of trap density, which is from the peak under reverse bias. The forward current is dominated by recombination current at low voltage and by the tunneling current at high voltage. The tunneling current and trap-assisted tunneling current are dominant in the reverse current.