Ionic conductivity of PVdF-co-HFP/LiClO4 in terms of free volume defects probed by positron annihilation lifetime spectroscopy

ABSTRACT

Polymers based on ionic conducting materials have important interest because of their potential applications in polymer electrolytes and membranes for fuel cell application. PVdF-co-HFP poly(viniliden-co-hexafluoropropylene) was chosen as a polymer matrix because of its high ionic conductivity and better mechanical properties. Polymer matrix composites were prepared with various amounts of LiClO₄ salt by a solution casting method. The sample-ionic conductivity measurements were recorded by AC impedance analyzer at different frequencies from 0.1?Hz to 20?MHz and at different temperatures from 273 to 373?K.

The changes of nanoscopic free volume and free volume fraction in these materials were investigated in terms of temperature from 273 to 373?K using Positron Annihilation Lifetime Spectroscopy (PALS) and Simha-Somcynsky (SS) Hole Theory. The free volume had a bump at about 3% in weight percentage of the salt and there is a slight increase after 10%. The effects of weight percentages of LiClO₄ and temperature were investigated. The mechanism of the ac ionic conductivity was presented in terms of the free volume models, however thermo-occupancy function justifies the best accurate representation of the data.     

Sputtering of SiC with low energy He and Ar ions under grazing incidence

The effect of low energy sputtering under grazing incidence upon the surface composition of SiC was investigated by Auger electron spectroscopy. The energy of the sputtering projectiles (He, Ar) varied from 200 to 1500?eV. Peak shifts to the higher energies with increasing argon ion energy were observed for all silicon and carbon Auger transitions. These shifts were explained by enhanced damage of the surface region within the sampling depth of the Auger electrons. The insensitivity of the Auger peak position to the energy of helium ions indicates that the damage state in the surface region does not change with the increasing energy of helium ions. An increase of the carbon concentration with the decrease of the argon energy was observed. The experiments were accompanied by dynamic Monte Carlo simulations by the TRIDYN code.     

Influence of gamma radiation on morphology structure,electrochemical corrosion behavior and hardness of Ni–Cr based alloys

This study evaluates the effects of gamma radiation on structure, electrochemical corrosion behavior and Vickers hardness of commercial dental Nikkeli–Kromi–Polttosekoitus [Ni_65.2Cr_22.5Mo_9.5X_2.8 (X=Nb, Si, Fe and Mn)] alloy. The corrosion rate of Ni_65.2Cr_22.5Mo_9.5X_2.8 (X=Nb, Si, Fe and Mn) alloy with 0.5 M HCl is increased with increasing the exposure rate of gamma radiation. The corrosion resistance of Ni_65.2Cr_22.5Mo_9.5X_2.8 (X=Nb, Si, Fe and Mn) is varied and reaches a minimum value at 30 KGy. The corrosion potential value also is varied and reaches its highest value at 30 KGy. The Vickers hardness value of Ni_65.2Cr_22.5Mo_9.5X_2.8 (X=Nb, Si, Fe and Mn) alloy is decreased by increasing the gamma radiation dose. Also it is obvious from our results that the effects of gamma radiation at the surface are much higher as compared with deeper parts and the structure of the alloy is changed due to its exposure to gamma radiation.     

Thermal noise as a spectroscopic tool to determine transport properties

The utilization of thermal fluctuations or Johnson/Nyquist noise as a spectroscopic method to determine transport properties in conductors or semiconductors is developed. The autocorrelation function is obtained from power spectral density measurements thus enabling electronic transport property calculation through the Green–Kubo formalism. This experimental approach is distinct from traditional numerical methods such as molecular dynamics simulations, which have been used to extract the autocorrelation function and directly related physics only. This work reports multi-transport property measurements consisting of the electronic relaxation time, resistivity, mobility, diffusion coefficient, electronic contribution to thermal conductivity and Lorenz number from experimental data. Double validation of the experiment was accomplished through the use of a standard reference material and a standard measurement method, i.e. four-probe collinear resistivity technique. Thermal noise measurements resulted in a 1.1 and 5% agreement with the reference material and four-probe values, respectively. Additional measurements were also taken on nanoscale Au and Cu thin films. Specifically, the validated spectroscopic methodology was applied to 30 nm Au and Cu thin films to obtain transport property data that was again compared to four-probe resistivity measurements. Comparative analysis of the resistivity data showed agreement within 13.6 and 4.8% for the Au and Cu samples, respectively, thus lending further credibility to the experimental method and theory.     

Interactions of gamma rays with undoped and Mn-doped sodium phosphate glasses

Ultraviolet and visible spectroscopic measurements were used to investigate prepared undoped and Mn-doped sodium phosphate glasses before and after successive gamma irradiation. The effects of both glass composition and MnO₂ content on the generation of radiation-induced defects were investigated. Undoped sodium phosphate glass shows strong UV absorption, which is attributed to the presence of trace iron impurities present in the raw materials. Mn-doped glasses reveal an additional visible broad band centered at about 500 nm due to Mn³⁺, which has recently been related to the ⁵E_g →⁵T_2g transition. The radiation-induced bands are correlated with the generation of liberated electron–hole pairs during the process of gamma irradiation and the possibility of photochemical reactions especially with trace iron impurities and manganese ions. The intensity and the position of the induced bands are observed to depend on the type and composition of glass, concentration of the dopant and also on the irradiation dose. Manganese ions when present in relatively higher content have been found to show a shielding behavior towards the effects of progressive gamma irradiation causing a retardation of the growth of the induced defects. Infrared and Raman spectra of the undoped and Mn-doped glasses were measured to investigate the structural phosphate groups present and the effect of MnO₂ on the network structure. An ESR investigation was carried out to confirm the state of manganese ions in the prepared sodium phosphate glasses.     

The measurement of solid–liquid interfacial energy in colloidal suspensions using grain boundary grooves

Interfacial energy is a fundamental physiochemical property of any multi-phase system. Among the most direct approaches for determining solid–liquid interfacial energy is a technique based on measuring the shape of grain boundary grooves in specimens subjected to a linear temperature gradient. This technique was adapted to crystallizing colloids in a gravitational field. Such colloids exhibit a freezing–melting phase transition and are important not only as self-assembling precursors to photonic crystals, but also as physical models of atomic and molecular systems. The grain boundary groove technique was tested using suspensions of sterically stabilized poly(methyl methacrylate) spheres, which have been shown to closely approximate the hard sphere potential. Whereas isotropic models did not fit grain boundary groove data well, the capillary vector model, which is suitable for both isotropic and anisotropic surface energies, produced γ₁₁₀?=?0.58?±?0.05 k _B T/σ². This value of interfacial energy is in agreement with many of the published values for hard spheres, supporting the validity of our grain boundary groove technique adaptations to colloidal systems in a gravitational field. Finally, kinks observed in groove profiles suggest a minimum anisotropy parameter of ε?=?0.029 for hard spheres.     

Growth of tertiary dendritic arms during the transient directional solidification of hypoeutectic Pb–Sb alloys

Despite the importance of a complete characterization of dendritic patterns in castings, the availability of studies on the development of tertiary dendrite arms is scarce in the literature. In the present study, the tip cooling rate, local solidification time, primary and tertiary dendrite arm spacings have been determined in Pb–Sb alloys castings directionally solidified under unsteady-state heat flow conditions. The alloys compositions experimentally examined are widely used in the as-cast condition for the manufacture of positive and negative grids of lead-acid batteries. The initial growth of tertiary dendritic arms from the secondary branches was found to occur only for a Pb–3.5 wt% Sb alloy at cooling rates in the range 0.4–0.2?K/s, with no evidence of this spacing pattern for Pb–Sb alloys having lower solute content. Tertiary dendritic branches have been observed along the entire casting lengths for alloys of the Pb–Sb hypoeutectic range having compositions higher than 4.0 wt% Sb. It is shown that a power function experimental law with a characteristic ?0.55 exponent is able to characterize the tertiary spacing evolution with the solidification cooling rate for alloys compositions ≥4.0 wt% Sb. The only exception was the Pb–3.5 wt% Sb alloy for which λ ₃ exhibited significant lower values when compared with the experimental values obtained for the other Pb–Sb alloys for a same solidification cooling rate.     

Thermal stability and UV–Vis-NIR spectroscopy of a new erbium-doped fluorotellurite glass

A new transparent bulk glass from the system 76TeO₂?·?10ZnO?·?9.0PbO?·?1.0PbF₂?·?3.0Na₂O doped with Er³⁺ (TZPPN doped with Er³⁺) has been prepared using the conventional melt-quenching method. Results of differential thermal analysis (DTA) measurements indicate good thermal stability of this glass. The refractive indices at different wavelengths, the optical energy gap, the Sellmeier gap energy and the dispersion energy have been estimated. The Judd–Ofelt parameters, Ω _t (t?=?2,?4,?6) of Er³⁺ were evaluated from optical absorption spectra. Electric dipole, magnetic dipole type transition probabilities, spectroscopic quality factors, branching ratio and radiative lifetimes of several excited states of Er³⁺ have been predicted using intensity Judd–Ofelt parameters. The spectroscopic properties indicate that TZPPN glass doped with Er³⁺ is a promising candidate for laser applications and may be suitable for upconversion fibre optical devices.