Ionic transport properties of PVdF-HFP-MMT intercalated nanocomposite electrolytes based on ionic liquid, 1-butyl-3-methylimidazolium bromide

Ionic conductivity and transport properties of polyvinylidenefluoride–co-hexafluoropropylene– montmorillonite intercalated nanocomposite electrolytes based on ionic liquid 1-butyl-3-methylimidazolium bromide have been studied for various concentrations of montmorillonite clay. Ionic conductivity of the order of 10^?3?S?cm^?1 at room temperature with thermal stability up to about 235 °C has been obtained for the electrolyte system. The electrolyte system has superior properties at 5 wt% of clay loading with highly amorphous morphology as seen from selected area electron diffraction micrograph. Scanning electron microscope studies show that the electrolyte system has highly porous morphology and the ionic liquid is trapped in the pores. Dielectric properties of the electrolyte system have been studied to investigate the relaxation processes occurring in the system. Variation of real part of dielectric permittivity with frequency shows two relaxation processes occurring in the system, slow at low frequency and fast at high frequency. Kohlrausch exponential parameter has been calculated from modulus formalism, and the values show that the distribution of conductivity relaxation times becomes narrower with increasing clay loading.     

Shear‐Enhanced Nucleation of Isotactic Polypropylene in Limited Space

The nucleation rate was measured by directly counting the number of nuclei, which were developed while an isotactic polypropylene melt was flowing under shear in a thin film. The nucleation rate was enhanced with an increased rate of shear, e.g., by a factor of 10 larger at the rate of shear of 14 s^?1 compared with the quiescent state, at 134°C. The ratio of the shear‐enhanced nucleation rate to the nucleation rate in the quiescent state was larger at a higher temperature of crystallization, i.e., about 10 times at 134°C to 590 times at 140°C. The increase of the nucleation rate under shear flow was explained by a reduction of the lateral and end (fold) surface free energies; the product σ _s ² σ _e decreased to 3.2×10^?7 for the sheared melt, from 6.0×10^?7 (J m^?2)³ for the isotropic state. The free energy reduction was caused by transition of the nucleus formation mode from three‐dimensional folded chain nuclei to two‐dimensional bundle nuclei, in which chains lie down on the glass substrate, aligning parallel to the flow direction.     

The dependence of muon intensity on the geomagnetic latitude

The vertical momentum spectrum of cosmic-ray muons has been determined by a counter controlled neon-hodoscope in the spectral region (0.2–3) Bev/c at geomagnetic latitude 12 °N. The observed spectrum agrees satisfactorily with the calculated spectrum of Olbert for muon momentum above 1.8 Bev/c. Below about 1.8 Bev/c, the measured spectrum exceeds slightly the theoretical spectrum of Olbert, calculated for the same geomagnetic latitude. The measured spectrum agrees with the experimental spectrum of Allkofer at 9 °N, but is somewhat below the spectrum obtained by Hayman in the low momentum region at 57.5 °N. This shows that there exists a latitude dependence of the low momentum muon spectrum. The estimated integral intensity of muon of momentum ≧320 Mev/c is found to be 7.3×10^?3 cm^?2 sec^?1 str^?1 which agrees with the value of other investigators^1–9.     

Shock-wave compression of x-cut quartz as determined by electrical response measurements

The mechanical response of x-cut quartz in the vicinity of the Hugoniot elastic limit is determined from measurements of the piezoelectric current from samples impact loaded from 26 to 130 kbar. The Hugoniot elastic limit is determined to be 60_?1·5⁺³ kbar at a compression of 0·066_?0·002^+0·004 This Hugoniot elastic limit corresponds to a shear strength of 5·5 per cent of the C₄₄ shear modulus. For stresses well above the Hugoniot elastic limit the electrical current measurements show that the material exhibits a substantial reduction of shear strength. The pressure derivative of the bulk modulus is determined to be 4·5, substantially less than the ultrasonic value. The experimental records show evidence for a time delay for reduction of shear strength which varies from about 10^?7 sec immediately above the 60 kbar Hugoniot elastic limit to about 10^?8 sec for stresses well above the Hugoniot elastic limit. The measurements also show stress relaxation below the Hugoniot elastic limit between 40 and 60 kbar.     

The Slow Molecular Mobility in Semicrystalline Poly(Ethylene Oxide)

The thermally stimulated depolarization current (TSDC) technique has been used to study the slow molecular mobility in the amorphous part of the semicrystalline polymer, poly(ethylene oxide) (PEO). Experiments were carried out in the temperature range that includes the glassy state, the glass transformation region and the rubber state. The dipole moments in the polymeric main chain originated a broad and low intensity secondary relaxation in the temperature region from ?130°C up to the glass transition region; the activation energy of the motional modes of this secondary relaxation was in the range between 35 and 100 kJ mol^?1. The glass transition temperature of the PEO, provided by the TSDC technique, was T_g = ?53°C, and the fragility index was found to be m = 43. A strong relaxation above T_g was observed, whose molecular origin was discussed. The thermal behavior of the PEO was also characterized by differential scanning calorimetry.     

Exfoliation process of graphite via intercalation compounds with sulfuric acid

Exfoliation process of graphite via its residue compound from intercalation compound with sulfuric acid was discussed by measuring exfoliation volume and pore sizes among and inside their worm-like particles. Exfoliation process was found to divide into three steps, below 650, 650–800 °C and above 800 °C. Below 650 °C, exfoliation of graphite flakes to form worm-like particles occurred rapidly and so exfoliation volume increased. Above 650 °C, increase in exfoliation volume, i.e. decrease in bulk density, became more rapid, but the growth of pores inside the particles was not so much pronounced. Above 800 °C, the increasing rate in exfoliation volume seemed to become slow, change in bulk density looking small, but pores inside the particles grew more. Exfoliated graphite prepared at 1000 °C had the exfoliation volume of about 0.15 m³/kg (bulk density of about 7 kg/m³), which is composed of large spaces with the cross-sectional area of more than 8000 μm² and worm-like particles containing ellipsoidal pores with averaged cross-sectional area of about 320 μm² and sizes of about 31×11 μm².     

Preparation of Li1.5Al0.5Ti1.5(PO4)3 solid electrolyte via a co-precipitation method

The co-precipitation method can make the materials react uniformly at molecular level and has the advantages of lower polycrystalline synthesized temperature and shorter sintering time. Therefore, it is expected that the mass production of Li_1.5Al_0.5Ti_1.5(PO₄)₃ (LATP) solid electrolyte would be possible by application of the co-precipitation method for LATP preparation. In this study, an application of the co-precipitation method for a preparation of LATP solid electrolyte is attempted. Crystallized LATP powder is obtained by heating precipitant containing Li, Al, Ti, and PO₄ at 800 °C for 30 min. The LATP bulk sintered pellet is successfully prepared using the crystallized LATP powder by calcinating at 1,050 °C. The cross-sectional SEM images show that many crystal grains exist, and the grains are in good contact with each other, i.e., there is no void space. All diffraction peaks of the pellet are attributed to LATP in XRD pattern. The sintered pellet is obtained by calcinating at 1,050 °C, which is more than 150 °C lower than that of conventional method. The LATP solid electrolyte shows a good conductivity which is 1.4?×?10^?3 S cm^?1 for bulk and 1.5?×?10^?4 S cm^?1 for total conductivities, respectively.     

Phase velocity and attenuation of 9 GHz hypersound in polycrystalline nickel films as a function of quartz-substrate temperature

Using a movable narrow beam of 9 GHz hypersound and wedge-shaped evaporated Ni films, the phase velocity and attenuation of longitudinal as well as of transverse hypersound was determined at a temperature of 2 K by multiple-beam interferometry in these Ni films. They were evaporated onto a quartz substrate at substrate temperatures ranging from 50°C to 500°C. The macroscopic moduliK (bulk modulus) andG (shear modulus) can be obtained from the measured phase velocities. WhereasK appears independent on substrate temperature and agrees within experimental error with theoretical prediction deduced from known elastic constants of the crystallites, the observed shear modulusG possesses at a substrate temperature of 50°C only 2/3 of the predicted value and increases with substrate temperature by reaching the theoretical value at about 300°C.     

Coverage of foreign atoms on surfaces as a function of adsorption,sputtering, and diffusion rates

During sputtering of a surface the coverage of foreign atoms may be changed by diffusion from the bulk to the surface and by adsorption from the gas phase. Assuming sufficiently high negative surface segregation enthalpy i.e. high ratios of surface to bulk concentration in equilibrium, simple expressions of the coverage time function for finite and semi-infinite samples are derived. The equations were applied to experimental results of oxygen coverage on a niobium surface where the three processes mentioned above were active. From the comparison with these results the diffusion coefficients of O in Nb D = 2 × 10^?13 m²/s at 520°C and D = 9 × 10^?13 m²/s at 600°C were evaluated.     

Low-temperature sintering effects on NASICON-structured LiSn<Subscript>2</Subscript>P<Subscript>3</Subscript>O<Subscript>12</Subscript> solid electrolytes prepared via citric acid-assisted sol-gel method

LiSn₂P₃O₁₂ with sodium (Na) super ionic conductor (NASICON)-type rhombohedral structure was successfully obtained at low sintering temperature, 600 °C via citric acid-assisted sol-gel method. However, when the sintering temperature increased to 650 °C, triclinic structure coexisted with the rhombohedral structure as confirmed by X-ray diffraction analysis. Conductivity–temperature dependence of all samples were studied using impedance spectroscopy in the temperature range 30 to 500 °C, and bulk, grain boundary and total conductivity increased as the temperature increased. The highest bulk conductivity found was 3.64?×?10^?5 S/cm at 500 °C for LiSn₂P₃O₁₂ sample sintered at 650 °C, and the lowest bulk activation energy at low temperature was 0.008 eV, showing that sintering temperature affect the conductivity value. The voltage stability window for LiSn₂P₃O₁₂ sample sintered at 600 °C at ambient temperature was up to 4.4 V. These results indicated the suitability of the LiSn₂P₃O₁₂ to be exploiting further for potential applications as solid electrolytes in electrochemical devices.     

Effects of anisotropy,order parameter,and viscosity on translational self-diffusion in nematic liquid crystals

A theory developed for the translational diffusion in nematic liquids crystals shows a dependence on the viscosities, order parameter, and molecular structure. Theoretical results for self-diffusion in p-azoxyanisole at 125°C are D^{∥ = 4.3 × 10?6, D⊥ = 3.1 × 10?6 c2/s}, andD^∥/D^⊥ = 1.4.     

Electrical characterization of gadolinia-doped ceria films grown by pulsed laser deposition

Electrical characterization of 10 mol% gadolinia doped ceria (CGO10) films of different thicknesses prepared on MgO(100) substrates by pulsed laser deposition is presented. Dense, polycrystalline and textured films characterized by fine grains (grain sizes < 18 nm and < 64 nm for a 20-nm and a 435-nm film, respectively) are obtained in the deposition process. Grain growth is observed under thermal cycling between 300 and 800°C, as indicated by X-ray-based grain-size analysis. However, the conductivity is insensitive to this microstructural evolution but is found to be dependent on the sample thickness. The conductivity of the nanocrystalline films is lower (7.0×10^?4  S/cm for the 20-nm film and 3.6×10^?3  S/cm for the 435-nm film, both at 500°C) than that of microcrystalline, bulk samples ( $6\times 10^{-3}$  S/cm at 500°C). The activation energy for the conduction is found to be 0.83 eV for the bulk material, while values of 1.06 and 0.80 eV are obtained for the 20-nm film and the 435-nm film, respectively. The study shows that the ionic conductivity prevails in a broad range of oxygen partial pressures, for example down to about 10 ^?26  atm at 500°C.     

First-principles study of structural,elastic, electronic and thermodynamic properties of topological insulator Bi2Se3 under pressure

The structural, elastic, electronic and thermodynamic properties of the rhombohedral topological insulator Bi₂Se₃ are investigated by the generalized gradient approximation (GGA) with the Wu–Cohen (WC) exchange-correlation functional. The calculated lattice constants agree well with the available experimental and other theoretical data. Our GGA calculations indicate that Bi₂Se₃ is a 3D topological insulator with a band gap of 0.287 eV, which are well consistent with the experimental value of 0.3 eV. The pressure dependence of the elastic constants C_ij, bulk modulus B, shear modulus G, Young’s modulus E, and Poisson’s ratio σ of Bi₂Se₃ are also obtained successfully. The bulk modulus obtained from elastic constants is 53.5 GPa, which agrees well with the experimental value of 53 GPa. We also investigate the shear sound velocity V_S, longitudinal sound velocity V_L, and Debye temperature Θ_E from our elastic constants, as well as the thermodynamic properties from quasi-harmonic Debye model. We obtain that the heat capacity C_v and the thermal expansion coefficient α at 0 GPa and 300 K are 120.78 J mol^?1 K^?1 and 4.70 × 10^?5 K^?1, respectively.     

Diffusion von Protonen (Tritonen) in Eiskristallen

The diffusion coefficient of tritons in ice crystals has been measured at different temperatures between 0°C and ?35°C. The applied method excludes any surface diffusion. The absolute value of the diffusion coefficient at ?7°C was determined as 2·10^?11 cm²/sec (±10%) and the activation energy as 13,5 kcal/mole (±8%). The activation energy of proton (triton)-diffusion is therefore consistent with the activation energy found for the dielectric and mechanical relaxation of protons in ice. The importance of this consistency relative to the diffusion mechanism is discussed.     

Study of the paraelectric behavior of OH− ions in alkali halides with optical and caloric methods II.: Dynamics of the dipole alignment

The relaxation behavior of OH^? dipole centers in ten alkali halides was studied with electro-optical and electro-caloric methods as a function of applied field, temperature and host lattice system. The reorientation kinetics of the 〈100〉 oriented OH^? dipoles can be fitted successfully to a phonon-assisted (90°) orientational tunneling model. Below 5°K the observed time dependence of the optical dichroism and the T^?1 dependence of the relaxation time gives clear evidence for the predominance of one-phonon processes, while above 5°K the T^?4 dependence indicates multi-phonon processes. It could be demonstrated that in the one-phonon region of the dipole relaxation a population inversion among the dipole levels (with subsequent phonon emission) can be achieved after a fast reversal of the field polarity. An attempt is made to discuss the observed strong variation of the relaxation time (12 orders of magnitude) with the host lattice in terms of a tunneling matrix element renormalized due to the anisotropic lattice distortion around the defect.     

Equilibrium molecular dynamics calculation of the bulk viscosity of liquid water

Twenty independent equilibrium molecular dynamics simulations were performed in NVE ensemble to calculate the bulk viscosity of water at a temperature of 303 K and a density of 0.999 gcm^?3. The energy of each simulation with a production time of 200ps was conserved within 1 part in 10⁴. By stopping the velocity-scaling procedure at a proper step, the energies of independent simulations were specified precisely. This caused the simulations of different start configurations to sample the same NVE ensemble. The shear viscosity of SPC/E water obtained in the present study was 6.5±0.4 × 10^?4 Pas, which is in close agreement with a previous calculation in the NVT ensemble (Balasubramanian, S., Mundy, C. J., and Klein, M. L., 1996, J. clzern. Phys., 105, 11 190). The bulk viscosity was 15.5 ± 1.6 × 10^?4 Pas, which is 27% smaller than the experimental value. Thus, like its behaviour in predicting the shear viscosity, the SPC/E model also underestimates the bulk viscosity of real water.     

Electron resonance spectra of NCS and vibronically-excited NCO in the gas phase

Near 25 °C, ab initio calculations of the zero-density viscosity of helium gas η _He have an uncertainty of approximately 0.001%, which is 1/40th of the uncertainty of the best measurements. The uncertainties of the published calculations for neon and argon are probably much larger. This paper presents new measurements of the viscosities of neon, argon, and krypton at 25 °C made with a capillary viscometer that was calibrated with helium. The resulting viscosity ratios are η _Ne/η _He?=?1.59836?±?0.00037, η _Ar/η _He?=?1.13763?±?0.00030, and η _Kr/η _He?=?1.27520?±?0.00040. The argon ratio agrees with a recent, unpublished calculation to within the combined uncertainty (measurement plus calculation) of 0.032%. The neon ratio is smaller than the calculated value by 0.13%.     

Relaxation phenomena and nuclear magnetic resonance of116In(T 1/2=14s) produced by capture of polarized neutrons in the indium III–V compounds

Polarized¹¹⁶In nuclei have been produced by capture of polarized thermal neutrons in several In compounds. At temperaturesT below 77 °K and magnetic field strengthsH ₀ of several kOe, asymmetries of a few percent of the β^? decay of the¹¹⁶In ground state could be observed in polycrystalline InP, InAs and InSb, thus indicating the nuclear polarization. Nuclear magnetic resonance signals have been measured with the result for the magnetic moment μ _i (¹¹⁶In)=2.7723 (10) nm (uncorrected). β^? decay asymmetry and spin lattice relaxation timeT ₁ have been studied as a function ofH ₀ andT. The effect ofH ₀ is to decouple the hyperfine interaction caused by the capture-γ recoil process. However,H ₀ has no influence uponT ₁, which demonstrates the absence of nuclear relaxation due to paramagnetic impurities.T ₁ is determined by quadrupolar relaxation. A quadrupole momentQ(¹¹⁶In)=0.09 (2) b was calculated by comparison of the¹¹⁶In relaxation rates with those of the stable¹¹⁵In isotope in the same compounds. Above 30 °K the temperature dependence of 1/T ₁ agrees with a recent theoretical investigation. Below 30 °K the relaxation rate shows an anomalous behaviour, which can be explained by resonance modes due to recoil lattice defects.     

Ionic conductivity studies on LiSmO<Subscript>2</Subscript> by impedance spectroscopy

Lithium samarium oxide has been prepared by solid-state reaction method and characterized by X-ray diffraction (XRD) and impedance spectroscopy. XRD pattern of the sample reveals the formation of the sample. The conductivity studies, dielectric studies, and modulus analysis of the samples have been carried out for different temperatures. The bulk conductivity of the sample has been found to be 1.21 × 10⁻⁵ Scm⁻¹ at 420 °C. The temperature variation of the direct current conductivity obeys the Arrhenius relation. The modulus analysis of the sample indicates the non-Debye nature of the sample which corresponds to long-time slow polarization and relaxation of hopping charges.     

Measurements of the complex shear modulus of polymers under hydrostatic pressure usina the quartz resonator method

Abstract

The quartz resonator method measures the complex shear modulus or compliance of viscoelastic materials in the frequency range from 50 kHz to 140 MHz at temperatures between ?150°C and 300°C and pressures up to 1 GPa. This method can be applied to viscous fluids or polymer melts -even in their glassy or seminystalline regime.

The phase diagram of poly(diethylsiloxane) PDES (a mesophase polymer) was determined for two samples with different molecular weight at pressures up to 400 MPa and temperatures between 20°C and 100°C. Phase transitions are indicated by a sharp bend in the shear compliance although the volume effect of the mesophase-isotropic transition vanishes around 80 MPa.

The pressure dependence of the glass relaxation process (in PVAc), was studied by measuring the change of the complex shear modulus with pressure at constant temperatures between 95°C and 145°C and pressures up to 600 MPa. Additionally to the relaxation process, also the pressure dependence of the real part of the shear modulus in the glassy region can be determined for testing the dislocation concept in the meandermodell by W. Pechhold.