Dielectric relaxation studies of poly(propylene glycol) confined in vermiculite clay

The molecular dynamics of oligomeric poly(propylene glycol) (PPG) liquids (M(w)=1200, 2000 and 4000 g/mol) confined in a two-dimensional layer-structured Na-vermiculite clay has been studied by broadband dielectric spectroscopy. In addition to the alpha-relaxation, the normal mode relaxation process was studied for all samples both in bulk and confinement. For the normal mode process the relaxation rate in the clay is drastically shifted to lower frequencies compared to that of the bulk material in contrast to the alpha-process whose relaxation time is only slightly affected by the confinement. Also the temperature dependence of the relaxation time for the normal mode process is strongly affected by the confinement. Moreover, in the clay the intensity of the normal mode is stronger than that of the alpha-process, in contrast to the bulk samples where the opposite is observed.     

Spin charge carrier dynamics in poly(bis-alkylthioacetylene)

Initial and laser-irradiated poly(bis-alkylthioacetylene) (PATAC) samples were investigated by electron paramagnetic resonance (EPR) at X-band (9.6 GHz), Q-band (37 GHz), and D-band (140 GHz) in a wide temperature range. Two types of paramagnetic centers were proved to exist in laser-modified polymer, namely, localized and mobile polarons with the concentration ratio and susceptibility depending on the irradiation dose and temperature. Superslow torsion motion of the polymer chains was studied by the saturation transfer method at D-band EPR. Additional information on the polymer chain segment dynamics was obtained by the spin probe method at X-band EPR. Spin-spin and spin-lattice relaxation times were measured separately by the steady-state saturation method at D-band EPR. Intrachain and interchain spin diffusion coefficients and conductivity arising from the polaron dynamics were calculated. It was shown that the polaron dynamics in laser-modified polymer is affected by the spin-spin interaction. The interchain charge transfer is stimulated by torsion motion of the polymer chains, whereas the total conductivity of irradiated PATAC is determined mainly by the dynamic of diamagnetic charge carriers. Magnetic, relaxation and dynamics parameters of PATAC were also shown to change during polymer storage.     

Zinc oxide nanoparticles reinforced conducting poly(aniline-co-p-phenylenediamine) nanocomposite

Zinc oxide (ZnO) nanoparticles were synthesized by thermal decomposition method and formation of composite with conducting copolymer via in situ chemical oxidative polymerization. Transmission electron microscopy showed that the nanoparticles with an average diameter of 15–25?nm were dispersed in the copolymer matrix. The comonomer molecules were adsorbed on the surface of ZnO particles and then polymerized to form core–shell nanocomposite. The obtained nanocomposite showed a significant improvement in the thermal behavior as indicated by thermogravimetric analysis. The nanocomposite was also confirmed by Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, and X-ray diffraction. Room temperature conductivity of nanocomposite was higher than the value obtained for the pure copolymer. Photocatalytic activity of the nanocomposite was evaluated by measuring the degradation of methylene blue dye under UV irradiation.     

Interfacial relaxation in fiber textures based on poly(dodecanamide)

The electrical relaxation in composite textures based on poly(dodecanamide) filled with polyamide fibers has been investigated using dielectric relaxation and thermally stimulated current measurements over wide ranges of frequencies and temperatures. The mechanisms of electrical relaxation in the range of the structural transition and at interfaces in the composite are established.     

Electrical,structural, and morphological studies of honeycomb-like microporous zinc-ion conducting poly (vinyl chloride)/poly (ethyl methacrylate) blend-based polymer electrolytes

Solid polymer electrolytes (SPEs) based on poly (vinyl chloride)/poly (ethyl methacrylate) [PVC/PEMA] blend complexed with zinc triflate [Zn(CF₃SO₃)₂] salt have been prepared using solution casting technique. Thin film samples containing various blend ratios of PVC/PEMA with fixed composition of salt have been examined by means of complex impedance analysis, and as a consequence, the typical composition corresponding to PVC (30 wt%)/PEMA (70 wt%) has been identified as the optimized blend exhibiting the highest room temperature ionic conductivity of 10^?8 Scm^?1. The ionic conductivity of the optimized blend was further enhanced from 10^?8 to 10^?6 Scm^?1 by adding the chosen salt in different weight percentages at 301 K. The occurrence of complexation of the polymer blend and an evidence of interaction of cations, namely Zn²⁺ ions with the polymer blend, have been confirmed by Attenuated total reflectance-Fourier transformed infrared (ATR-FTIR) spectroscopy measurement studies. The efficacy of ion-polymer interactions was estimated by means of an evaluation of transport number data pertaining to Zn²⁺ ions which was found to be 0.56. The apparent changes resulting in the structural properties of these polymer electrolytes possessing a honeycomb-like microporous structure were identified using X-ray diffraction (XRD) and scanning electron microscopic (SEM) studies. Such promising features of the present polymer blend electrolyte system appear to suggest possible fabrication of new rechargeable zinc batteries involving improved device characteristics.     

Spin relaxation in the quasi-one-dimensional conductor Rb2Pt(CN)4(FHF)0.4

We analyze the electron paramagnetic resonance linewidth in Rb₂Pt(CN)₄(FHF)_0.4 as a function of temperature. Above 60 K, the results are interpreted as a superposition of spin-phonon and spin-spin relaxation effects. The dominant contribution to the relaxation rate l/T₂ has a dipolar origin in contrast to the spin-phonon origin observed in K₂Pt(CN)₄Br_0.3 · H₂O. This difference could arise from different anisotropy ratios of the transfer integrals. The influence of the interchain coupling is also discussed.     

Spin resonance of tetramethyltetrathiafulvalene tetracyanoquinodimethane: a comparison with tetrathiafulvalene tetracyanoquinodimethane

Electron spin resonance spectra and linewidth studies of two different phases of tetramethyltetrathiafulvalene (TMTTF) tetracyanoquinodimethane (TCNO) are presented. The linewidth of the solution grown 1:1 phase (TMTTF)(TCNQ), which is the structural analog to tetrathiafulvalene- tetracyanoquinodimethane (TTF) (TCNQ), is shown to have a similar temperature dependence to that of (TTF) (TCNQ) in contrast with earlier reports. The vapor grown phase, identified by X-ray studies as (TMTTF)_1.66 (TCNQ)₂, is shown to have different magnetic and electronic properties. These results are discussed and compared with earlier spin resonance reports on (TMTTF) (TCNQ).     

Proton conducting polymer electrolytes on the basis of poly(vinylphosphonic acid) and imidazole

Anhydrous proton conducting polymer electrolytes have been prepared by doping of poly(vinylphosphonic acid) (PVPA) with imidazole (Im) in with various stoichiometric ratios, x, to form PVPA x Im where x is the number of moles of Im per moles of polymer repeat unit. Polymer electrolytes, PVPA x Im (with x=0.5, x=1 and x=2) can be cast into transparent, homogeneous films. FT-IR results indicate the transfer of acidic protons to imidazole units to form imidazolium ions. Thermogravimetric analysis illustrates that these blends are thermally stable up to about 150 °C. The glass transition temperatures of the blends were detected via differential scanning calorimetry. DC conductivity increases with doping ratio of Im reaching ∼5×10⁻³ S/cm for x=2 at 130 °C.     

Spin relaxation studies of the muonium substituted ethyl radical in the gas phase

This short communication draws attention to the power of μSR and related measurements in providing an unusually complete characterisation of muonium substituted organic radicals in the gas phase. Spectroscopic information is available from muon spin rotation and muon level crossing resonance, giving all the nuclear hyperfine coupling constants, just as in the liquid phase. In addition, measurements of the relaxation time of the muon Zeeman energy become possible; these are potentially informative on the molecular collision dynamics. Demonstration results are presented in summary for the muonium substituted ethyl radical, ĊH₂CH₂Mu, in ethene gas.     

Effect of different plasticizers on the secondary relaxation of poly(vinyl chloride)

Samples of poly(vinyl chloride) plasticized with variable amounts of either dibutyl phthalate (DPB) or dicyclohexyl phthalate (DCHP) were investigated by dynamic-mechanical measurements in the β relaxation temperature range. In this range of temperature, a superposition of the relaxation due to the cyclohexyl group with the PVC β peak was found for the samples plasticized with DCHP. By studying the dependence of the activation energy and of the peak broadness on the DCHP concentration it was possible to show that the PVC β relaxation is reduced to zero at the critical plasticizer weight fraction W₁ = 0.2. For the PVC-DBP series the β peak disappears at the same plasticizer content. These results strengthen the hypothesis that the β peak of PVC is due to a kind of cooperative motion since 1 mole of plasticizer for every 20 repeating units of the polymer is sufficient to suppress the PVC β relaxation.     

Proton conducting composite membranes based on poly(1-vinyl-1,2,4-triazole) and nitrilotri (methyl triphosphonic acid)

Polymer electrolyte composite membranes based on poly(1-vinyl-1,2,4-triazole) (PVTRI) and nitrilotri(methyl triphosphonic acid) (TPA) were investigated. PVTRI was produced by free radical polymerization of 1-vinyl-1,2,4-triazole. The polymer PVTRI was doped with TPA at various molar ratios x=0.125, x=0.25, and x=0.5. The proton transfer from TPA to the triazole rings was proved with Fourier-transform infrared spectroscopy (FT-IR). Thermogravimetry (TG) analysis showed that the samples are thermally stable up to approximately 250 °C. DSC results illustrated the homogeneity of the materials as well as the softening effect of the dopant. Cyclic voltammetry results illustrated that the electrochemical stability domain of the dopant extends over 1.5 V. The maximum proton conductivity has been measured for PVTRITPA-0.25 as 8.5×10⁻⁴ S cm⁻¹ at 150 °C.     

Spin transport and relaxation in graphene

We review our recent work on spin injection, transport and relaxation in graphene. The spin injection and transport in single layer graphene (SLG) were investigated using nonlocal magnetoresistance (MR) measurements. Spin injection was performed using either transparent contacts (Co/SLG) or tunneling contacts (Co/MgO/SLG). With tunneling contacts, the nonlocal MR was increased by a factor of ∼1000 and the spin injection/detection efficiency was greatly enhanced from ∼1% (transparent contacts) to ∼30%. Spin relaxation was investigated on graphene spin valves using nonlocal Hanle measurements. For transparent contacts, the spin lifetime was in the range of 50-100 ps. The effects of surface chemical doping showed that for spin lifetimes in the order of 100 ps, charged impurity scattering (Au) was not the dominant mechanism for spin relaxation. While using tunneling contacts to suppress the contact-induced spin relaxation, we observed the spin lifetimes as long as 771 ps at room temperature, 1.2 ns at 4 K in SLG, and 6.2 ns at 20 K in bilayer graphene (BLG). Furthermore, contrasting spin relaxation behaviors were observed in SLG and BLG. We found that Elliot-Yafet spin relaxation dominated in SLG at low temperatures whereas Dyakonov-Perel spin relaxation dominated in BLG at low temperatures. Gate tunable spin transport was studied using the SLG property of gate tunable conductivity and incorporating different types of contacts (transparent and tunneling contacts). Consistent with theoretical predictions, the nonlocal MR was proportional to the SLG conductivity for transparent contacts and varied inversely with the SLG conductivity for tunneling contacts. Finally, bipolar spin transport in SLG was studied and an electron-hole asymmetry was observed for SLG spin valves with transparent contacts, in which nonlocal MR was roughly independent of DC bias current for electrons, but varied significantly with DC bias current for holes. These results are very important for the use of graphene for spin-based logic and information storage applications.     

Preparation and characterization of a lithium ion conducting electrolyte based on poly(trimethylene carbonate)

In this paper, the results of preliminary studies of two new solvent-free polymer electrolytes based on poly(trimethylene carbonate), p(TMC), with lithium trifluoromethanesulphonate, (triflate), and lithium perchlorate are described. Thin films of these electrolytes were obtained by evaporation of solvent from homogeneous mixtures of known masses of host polymer and salt. Electrolytes with compositions of n between 1.5 and 85, where n represents the molar ratio of (O=COCH₂CH₂CH₂O) units per lithium ion, have been prepared. These solvent-free electrolytes were characterized by measurements of total ionic conductivity, differential scanning calorimetry (DSC) and thermogravimetry (TGA). As expected from previous studies with these salts in poly(ethylene oxide), PEO, the triflate-based system showed superior thermal stability but with a lower total ionic conductivity than that of the perchlorate-containing electrolyte. The highest conductivity (approximately 3×10⁻⁴ Ω⁻¹ cm⁻¹) was found at 95°C with the electrolyte composition of (TMC)₂LiClO₄.     

Spin relaxation times in disordered graphene

We consider two mechanisms of spin relaxation in disordered graphene. i) Spin relaxation due to curvature spin orbit coupling caused by ripples. ii) Spin relaxation due to the interaction of the electronic spin with localized magnetic moments at the edges. We obtain analytical expressions for the spin relaxation times τ_SO and τ_J due to both mechanisms and estimate their values for realistic parameters of graphene samples. We obtain that spin relaxation originating from these mechanisms is very weak and spin coherence is expected in disordered graphene up to samples of length .     

Dielectric relaxation study of poly(ethylene glycols) using TDR technique

Temperature dependent dielectric relaxation and thermodynamic properties of polyethylene glycols HO[CH₂CH₂O)_nH with number average molecular weight 200 (n = 4), 300 (n = 7), 400 (n = 9) and 600 (n = 14) g mol^− 1 have been studied using Time Domain Reflectometry (TDR) in the frequency range 10 MHz to 20 GHz. The frequency dependence of the complex dielectric permittivity is analyzed by the Havriliak-Negami expression. The static permittivity ε₀, high frequency limiting static permittivity ε_∞, average relaxation time τ₀ and thermodynamic energy parameters such as free energy, enthalpy of activation and entropy of activation have been determined. The average free energy of activation ΔF_τ for PEG molecules was found to be in the range 4-5 kcal mol^− 1. The values of entropy ΔS_τ for PEG-200, PEG-400 and PEG-600 molecules were found to be positive while entropy ΔS_τ for PEG-300 molecules was found negative, which confirms that the configuration of PEG-300 involved in the dipolar orientation has an activated state, which is more ordered than the normal state compared to PEG-200, PEG-400 and PEG-600 molecules.     

Structural and ionic conductivity studies of solid polymer electrolytes based on poly (vinylchloride) and poly (methylmethacrylate) blends

Thin film of poly (vinylchloride) and poly (methylmethacrylate) blend polymer electrolytes plasticized with a combination of DBP and Li₂SO₄ salts have been prepared by solution casting technique. The prepared films were subjected to a.c. impedance measurements as a function of temperature ranging from 304–373 K. The maximum conductivity at 304 K was found to be 1.24 × 10⁻⁸ S·cm⁻¹ for PVC-PMMA-Li₂SO₄-DBP (7.5-17.5-5-70 mole-%). Temperature dependence studies on the ionic conductivity in the PVC-PMMA-Li₂SO₄-DBP system suggest that the ion conduction follows the Williams-Landel-Ferry (WLF) mechanism, which is further confirmed by Vogel-Tamman-Fulcher (VTF) plots. XRD, FTIR, SEM and thermal studies revealed complex formation in.     

Assignment of bis(methylenedithio)tetrathiafulvalene vibrational spectra

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 52, No. 4, pp. 622–627, April, 1990.