Twin roller quenching technique and preparation of glasses of high melting ionic solids

A rapid quenching technique with a quenching rate of roughly 106°C/sec has been developed to prepare glassy samples of ABO3 type materials. Glasses of potassium lithium niobate have been prepared by this technique. These glasses have been characterized by x-ray diffraction, electron diffraction and differential scanning calorimetry techniques to assess the quality of the obtained glasses.

Ionic conductivity and dielectric measurements in single crystal β---AgI

Ionic conductivity measurements have been made on pure, copper-doped and cadmium-doped single crystals. Dielectric measurements in the frequency range 30Hz–100Hz showed that there was no anomalously to be (0.64 ± 0.02) eV and migration energies for silver ion intersitials and vacancies in the c direction to be (0.41 ± 0.02) eV and (0.50 ± 0.02) eV respectively. ESR measurements have shown that copper exists as Cu+ in these crystals. Dielectric measurements in the frequency range (OHz–100KHz showed that there was no anomalously high value for ε as reported earlier.

Green synthesis of ZnO nanoparticles in a room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Nanoparticles of ZnO with the wurtzite structure have been successfully synthesized via a microwave through the decomposition of zinc acetate dihydrate in an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, as a solvent. Fundamental characterizations including X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were conducted for the ZnO nanostructures.

Dispersion interactions in room-temperature ionic liquids: Results from a non-empirical density functional

The role of dispersion or van de Waals (VDW) interactions in imidazolium-based room-temperature ionic liquids is studied within the framework of density functional theory, using a recently developed non-empirical functional [M. Dion, H. Rydberg, E. Schroder, D. C. Langreth, and B. I. Lundqvist, Phys. Rev. Lett. 92, 246401 (2004)], as efficiently implemented in the SIESTA code [G. Roman-Perez and J. M. Soler, Phys. Rev. Lett. 103, 096102 (2009)]. We present results for the equilibrium structure and lattice parameters of several crystalline phases, finding a general improvement with respect to both the local density (LDA) and the generalized gradient approximations (GGA). Similar to other systems characterized by VDW bonding, such as rare gas and benzene dimers as well as solid argon, equilibrium distances and volumes are consistently overestimated by approximate to 7%, compared to -11% within LDA and 11% within GGA. The intramolecular geometries are retained, while the intermolecular distances and orientations are significantly improved relative to LDA and GGA. The quality is superior to that achieved with tailor-made empirical VDW corrections ad hoc [M. G. Del Popolo, C. Pinilla, and P. Ballone, J. Chem. Phys. 126, 144705 (2007)]. We also analyse the performance of an optimized version of this non-empirical functional, where the screening properties of the exchange have been tuned to reproduce high-level quantum chemical calculations [J. Klimes, D. Bowler, and A. Michaelides, J. Phys.: Condens. Matter 22, 074203 (2010)]. The results for solids are even better with volumes and geometries reproduced within 2% of experimental data. We provide some insight into the issue of polymorphism of [bmim][Cl] crystals, and we present results for the geometry and energetics of [bmim][Tf] and [mmim][Cl] neutral and charged clusters, which validate the use of empirical force fields. (C) 2011 American Institute of Physics. [doi:10.1063/1.3652897]

On conduction mechanism in paramagnetic phase of Gd based manganites

Materials belonging to the family of manganites are technologically important since they exhibit colossal magneto resistance. A proper understanding of the transport properties is very vital in tailoring the properties. A heavy rare earth doped manganite like Gd0·7Sr0·3MnO3 is purported to be exhibiting unusual properties because of smaller ionic radius of Gd. Gd0·7Sr0·3MnO3 is prepared by a wet solid state reaction method. The conduction mechanism in such a compound has been elucidated by subjecting the material to low temperature d.c. conductivity measurement. It has been found that the low band width material follows a variable range hopping (VRH) model followed by a small polaron hopping (SPH) model. The results are presented here

Characterization of anodic silicon oxide films grown in room temperature ionic liquids

The electroformation of silicon oxide was performed in two room temperature ionic liquids (RTIL), 1-butyl-3-methyl-imidazolium bis(trifluoromethane sulfonyl) imide (BMITFSI) and N-n-butyl-N-methylpiperidinium bis(trifluoromethane sulfonyl) imide (BMPTFSI). This phenomenon was studied by electrochemical techniques and it was observed that the oxide growth follows a high-field mechanism. X-ray Photoelectron Spectroscopy experiments have shown that a non-stoichiometric oxide film was formed, related to the low water content present in both RTILs (< 30 ppm). The roughness values obtained by using AFM technique of the silicon surface after etching with HF was 1.5 nm (RMS). The electrochemical impedance spectroscopy at low frequencies range was interpreted as a resistance in parallel with a CPE element, the capacitance obtained was associated with the dielectric nature of the oxide formed and the resistance was interpreted considering the chemical dissolution of the oxide by the presence of the TFSI anion. The CPE element was associated with the surface roughness and the very thin oxide film obtained. (C) 2007 Elsevier Ltd. All rights reserved.

Transport properties in ionic liquids and ionic liquid mixtures : the challenges of NMR pulsed field gradient diffusion measurements

Pulsed field gradient NMR is a powerful method for the measurement of diffusion coefficients in liquids and solids and has begun to attract much attention in the ionic liquids field. However, aspects of the methodology as traditionally applied to solutions may not be uniformly applicable in these more viscous and chemically complex systems. In this paper we present data which shows that the Pulsed Gradient Spin Echo (PGSE) method in particular suffers from intrinsic internal gradients and can produce apparent diffusion coefficients which vary by as much as 20% for different ¹H nuclei within a given moleculean obvious anomaly. In contrast, we show that the Pulsed Gradient Stimulated Echo method does not suffer from this problem to the same extent and produces self-consistent data to a high degree of accuracy (better than 1%). This level of significance has allowed the detection, in this work, of subtle mixing effects in [C₃mpyr][NTf₂] and [C₄mpyr][NTf₂] mixtures.

On the concept of ionicity in ionic liquids

Ionic liquids are liquids comprised totally of ions. However, not all of the ions present appear to be available to participate in conduction processes, to a degree that is dependent on the nature of the ionic liquid and its structure. There is much interest in quantifying and understanding this ‘degree of ionicity’ phenomenon. In this paper we present transport data for a range of ionic liquids and evaluate the data firstly in terms of the Walden plot as an approximate and readily accessible approach to estimating ionicity. An adjusted Walden plot that makes explicit allowance for differences in ion sizes is shown to be an improvement to this approach for the series of ionic liquids described. In some cases, where diffusion measurements are possible, it is feasible to directly quantify ionicity via the Nernst–Einstein equation, confirming the validity of the adjusted Walden plot approach. Some of the ionic liquids studied exhibit ionicity values very close to ideal; this is discussed in terms of a model of a highly associated liquid in which the ion correlations have similar impact on both the diffusive and conductive motions. Ionicity, as defined, is thus a useful measure of adherence to the Nernst–Einstein equation, but is not necessarily a measure of ion availability in the chemical sense.

Recent progress in the development and use of organic ionic plastic crystal electrolytes

Significant progress has been made recently in the development of Organic Ionic Plastic Crystals (OIPCs), a unique family of solid state electrolytes with applications in electrochemical devices such as lithium batteries and dye-sensitised solar cells. The negligible volatility of OIPCs renders them more suitable than molecular species for long-term device use, while the high thermal and electrochemical stability of many OIPCs fulfils an essential requirement for solid state electrolytes for many device applications. However, the complex mechanisms of conduction through these materials, both in their pure state and in the presence of a small amount of a second component (such as lithium salts to enable their use in lithium batteries) are still not fully understood. At the same time, the range of anions and cations utilised in the synthesis of plastic crystal phases continues to increase. This perspective concentrates on recent research into both fundamental and device-oriented aspects of these materials. Important fundamental understanding of the physical properties and transport mechanisms of different OIPCs has been achieved through use of techniques including variable temperature solid-state NMR and crystallographic analysis, as well as detailed molecular dynamics simulations. In parallel, the applicability of these materials as electrolytes for dye-sensitised solar cells and lithium batteries is being more widely demonstrated. The possibility of using OIPCs as solid state electrolytes for fuel cells is also discussed.

Insight into local structure and molecular dynamics in organic solid-state ionic conductors

Elucidating the rate and geometry of molecular dynamics is particularly important for unravelling ion-conduction mechanisms in electrochemical materials. The local molecular motions in the plastic crystal 1-ethyl-1-methylpyrrolidinium tetrafluoroborate ([C2 mpyr][BF4 ]) are studied by a combination of quantum chemical calculations and advanced solid-state nuclear magnetic resonance spectroscopy. For the first time, a restricted puckering motion with a small fluctuation angle of 25° in the pyrrolidinium ring has been observed, even in the low-temperature phase (-45&thinsp;°C). This local molecular motion is deemed to be particularly important for the material to maintain its plasticity, and hence, its ion mobility at low temperatures.

A local-global scheme for tracking crack path in three-dimensional solids

This paper aims to contribute to the three-dimensional generalization of numerical prediction of crack propagation through the formulation of finite elements with embedded discontinuities. The analysis of crack propagation in two-dimensional problems yields lines of discontinuity that can be tracked in a relatively simple way through the sequential construction of straight line segments oriented according to the direction of failure within each finite element in the solid. In three-dimensional analysis, the construction of the discontinuity path is more complex because it requires the creation of plane surfaces within each element, which must be continuous between the elements. In the method proposed by Chaves (2003) the crack is determined by solving a problem analogous to the heat conduction problem, established from local failure orientations, based on the stress state of the mechanical problem. To minimize the computational effort, in this paper a new strategy is proposed whereby the analysis for tracking the discontinuity path is restricted to the domain formed by some elements near the crack surface that develops along the loading process. The proposed methodology is validated by performing three-dimensional analyses of basic problems of experimental fractures and comparing their results with those reported in the literature.

In situ MRI of operating solid-state Lithium metal cells based on ionic plastic crystal electrolytes

Solid-state ion conductors based on organic ionic plastic crystals (OIPCs) are a promising alternative to conventional liquid electrolytes in lithium battery applications. The OIPC-based electrolytes are safe (nonflammable) and flexible in terms of design and operating conditions. Magnetic resonance imaging (MRI) is a powerful noninvasive method enabling visualization of various chemical phenomena. Here, we report a first quantitative in situ MRI study of operating solid-state lithium cells. Lithium ion transfer into the OIPC matrix during the ongoing discharge of the anode results in partial liquefaction of the electrolyte at the metal interface. The developed liquid component enhances the ion transport across the interface and overall battery performance. Displacement of the liquefaction front is accompanied by a faster Li transfer through the grain boundaries and depletion at the cathode. The demonstrated solid-liquid hybrid properties, inherent in many OIPCs, combine benefits of highly conductive ionic liquids with safety and flexibility of solids.