Responsive Gels with the Polymer Containing Alternating Naphthalene Diimide and Fluorinated Alkyl Chains: Gel Formation and Responsiveness as Well as Electrical Conductivity of Polymer Thin Films

A new electroactive polymer 1 with alternating NDI (naphthalene diimide) moieties and fluorinated alkyl chains was prepared and characterized. Gels of polymer 1 were formed in several solvents. Interestingly, gels of polymer 1 exhibited responsiveness toward N₂H₄, F^? and CN^?. Absorption and ESR spectroscopic studies revealed that such responsiveness is owing to the reduction of NDI moieties into the respective NDI^.?. In addition, thin films of polymer 1 were easily prepared with spin‐coating technique and the electrical conductivity of thin films reached 52.4 S/m after exposure to N₂H₄ vapor.     

Isobaric expansion coefficient and isothermal compressibility for a finite-size ideal Fermi gas system

Due to quantum size effects (QSEs), the isobaric thermal expansion coefficient and isothermal compressibility well defined for macroscopic systems are invalid for finite-size systems. The two parameters are redefined and calculated for a finite-size ideal Fermi gas confined in a rectangular container. It is found that the isobaric thermal expansion coefficient and isothermal compressibility are generally anisotropic, i.e., they are generally different in different directions. Moreover, it is found the thermal expansion coefficient may be negative in some directions under the condition that the pressures in all directions are kept constant.     

Defect Chemistry of Singly and Doubly Doped Ceria: Correlation between Ion Transport and Energetics

Earlier studies have shown a strong correlation between the enthalpy of formation, ΔH_f,ox, and the ionic conductivity, σ_i, near room temperature in doped ceria systems, which are promising solid electrolytes for intermediate‐temperature solid oxide fuel cells (IT‐SOFCs). The present work demonstrates that this correlation holds at the operating temperature of IT‐SOFCs, 600–700 °C. Solid solutions of Ce_1?xNd_xO_2?0.5x, Ce_1?xSm_xO_2?0.5x, and Ce_1?xSm_0.5xNd_0.5xO_2?0.5x are studied. The ΔH_f,ox at 702 °C is determined by considering the excess heat content between 25 and 702 °C combined with the value of ΔH_f,ox at 25 °C. Both σ_i and ΔH_f,ox show maxima at x=0.15 and 0.20 for the singly and doubly doped ceria, respectively, suggesting that the number of mobile oxygen vacancies in these solid solutions reaches a maximum near those compositions. An increase in temperature results in a shift of the maximum in both ΔH_f,ox and σ_i towards higher concentrations. This shift results from a gradual increase in dissociation of the defect associates.     

Identification of radical structures on 1‐pentamethylbenzyl‐3‐ethylimidazoliumsilver(I)bromide and 1,3‐bis(pentamethylbenzyl)‐4,5‐dimethylbenzimidazoliumsilver(I)bromide exposed to gamma rays: an EPR study

1‐Pentamethylbenzyl‐3‐ethylimidazoliumsilver(I)bromide and 1,3‐bis(pentamethylbenzyl)‐4,5dimethylbenzimidazoliumsilver(I)bromide and their Ag⁺ complexes were synthesized and their polycrystal forms were produced by recrystallization in dichloromethane/Et₂O solvent system. Structural determinations were carried out by ¹H NMR and ¹³C NMR with a Varian 400 NMR system using tetramethylsilane as internal standard and CDCl₃ as solvent. The disappearance of acidic N‐heterocyclic carbene proton showed the formation of Ag(I) complexes. Also, elemental analyses were carried out. Electron paramagnetic resonance (EPR) measurements were performed to determine the formed radical structure on the samples irradiated at the room temperature for 72 h by using ⁶⁰Co‐source with dose rate of 0.680 kGy. The EPR measurements were carried out in the temperature range of 200 K–450 K. Identical radicals were determined on the irradiated compounds. It was observed that the shapes of the spectra of the samples were independent of the temperature but, the resonance line intensities changed linearly with the temperature. Also, it was detected that the free radical on the 1‐pentamethylbenzyl‐3‐ethylimidazoliumsilver(I)bromide is not stable compared to that on the 1,3‐bis(pentamethylbenzyl)‐4,5dimethylbenzimidazoliumsilver(I)bromide. Copyright © 2016 John Wiley & Sons, Ltd.     

Calibration Curve with Improved Limit of Detection for Cadmium in Soil: An Approach to Minimize the Matrix Effect in Laser-Induced Breakdown Spectroscopic Analysis

The present article describes a working or combined calibration curve in laser-induced breakdown spectroscopic analysis, which is the cumulative result of the calibration curves obtained from neutral and singly ionized atomic emission spectral lines. This working calibration curve reduces the effect of change in matrix between different zone soils and certified soil samples because it includes both the species' (neutral and singly ionized) concentration of the element of interest. The limit of detection using a working calibration curve is found better as compared to its constituent calibration curves (i.e., individual calibration curves). The quantitative results obtained using the working calibration curve is in better agreement with the result of inductively coupled plasma–atomic emission spectroscopy as compared to the result obtained using its constituent calibration curves.     

Temperature memory effect and its stability revealed via differential scanning calorimetry in ethylene‐vinyl acetate within glass transition range

In this article, we reveal the temperature memory effect (TME) in a commercial thermoplastic polymer, namely ethylene‐vinyl acetate (EVA), within its glass transition range via a series of differential scanning calorimeter (DSC) tests. In addition, we investigate the influence of heating holding time and also compare the observed TME in current study with that of shape memory alloys (SMAs). It is concluded that the TME via DSC (without any macroscopic shape change) is achievable within the glass transition range of a polymer. Conversely, although the observed TME shares the many similar features as those in SMAs, due to the nature of micro‐Brownian motion in the glass transition of polymers, the resulted TME is strongly affected by the heating holding time. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1731–1737     

Periodic solutions to a class of biological diffusion models with hysteresis effect

This paper is concerned with a class of biological models which consists of a nonlinear diffusion equation and a hysteresis operator describing the relationship between some variables of the equations. By the viscosity approach, we show the existence of periodic solutions of the problem under consideration. More precisely, with the help of the subdifferential operator theory and Leray–Schauder theorem, we show the existence of periodic solutions to the approximation problem and then obtain the solution of the original problem by using a passage-to-limit procedure.     

DC conductivity of new single and mixed alkali oxyfluorovanadate glasses

New glasses have been prepared according to these formulas (70-x)V₂O₅-30BaF₂-xAF, where AF=LiF or NaF and (60-x)V₂O₅-30BaF₂-10LiF-xAF, where AF=NaF and x=10, 15, 20, 25 and 30 mol%. Density of the glasses was measured and molar volume calculated and they correlated with the AF content. The dc conductivity has been measured in the temperature range from 302 to 453 K. The dc conductivity increases with temperature and V₂O₅ content, while it decreases with the alkali fluoride content. Conductivity has been correlated with the calculated polaron distance, R, and glass transition temperature, T_g. The activation energy, W, increases with the increase in the alkali fluoride, while it decreases with the V₂O₅ content. Some parameters like polaron distance, R, polaron radius, r_p, ion concentrations, n(V), n(Li) or n(Na), hopping energy, W_H, density of localized states at Fermi level, N(E_F), polaron coupling constant, γ_p, polaron band width, J, hopping mobility, μ, and carrier density for electronic conduction, N_c, were calculated to explain the conduction mechanism and behavior of the present glasses.     

Thermoacoustic Emission from Carbon Nanotubes Imaged by Atomic Force Microscopy

The thermoacoustic effect of isolated single‐wall carbon nanotubes aligned between electrodes is experimentally observed for the first time by imaging the emitted acoustic wave using an atomic force microscopy‐based technique specifically developed for the task. The capability of such a technique for single‐point thermoacoustic measurements is first verified on carbon nanotubes layers with two electrodes for injecting alternate electric current. The technique is then demonstrated to allow the acquisition, simultaneously with the topography, of images reflecting the pressure of the acoustic wave at fixed distance from the sample. Such a capability is used to collect images reflecting the amplitude of acoustic waves generated by isolated nanotubes and nanotube bundles by the thermoacoustic effect.     

Cross‐linked poly(aryl ether sulfone) membranes for direct methanol fuel cell applications

Partially sulfonated poly(aryl ether sulfone) (PESS) was synthesized and methacrylated via reaction with glycidyl methacrylate (PESSGMA) and cross‐linked via radical polymerization with styrene and vinyl‐phosphonic acid (VPA). The chemical structures of the synthesized pre‐polymers were characterized via FTIR and ¹H NMR spectroscopic methods and molecular weight was determined via GPC. Membranes of these polymers were prepared via solution casting method. The crosslinking of the PESS polymer reduced IEC, proton conductivity, swelling in water, and methanol permeability of the membranes while increasing the modulus and the glass transition temperature. However, the introduction of the VPA comonomer increased the proton conductivity while maintaining excellent resistance to methanol cross‐over, which was significantly higher as compared with both PESS and the commercial Nafion membranes. Membranes of PESSGMA copolymers incorporating VPA, exhibited proton conductivity values at 60 °C in the range of 16–32 mS cm⁻¹ and methanol permeability values in the range of 6.52 × 10⁻⁹ – 1.92 × 10⁻⁸ cm² s⁻¹. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 558–575