Rational design of solid materials: A case study of lithium-ion conductors

In the absence of a reliable method for a priori prediction of structure and properties of inorganic solid materials, an experimental approach involving a systematic study of composition, structure and properties combined with chemical intuition based on previous experience is likely to be a viable alternative to the problem of rational design of inorganic materials. The approach is illustrated by taking perovskite lithium-ion conductors as an example.

Structural, dielectric and optical properties of lithium borate-bismuth tungstate glass-ceramicsc

Glasses in the system (1 - x)Li2B4O7-xBi(2)WO(6) (0.1 less than or equal to x less than or equal to 0.35) were prepared by splat quenching technique. Powder X-ray diffraction (XRD) and differential thermal analysis (DTA) were employed to characterize the as-quenched glasses. High-resolution transmission electron microscopy (HR TEM) revealed the presence of fine, nearly spherical crystallites of Bi2WO6 varying from 1.5 to 20 nm in size, depending on x in the as-quenched glasses. The glasses (corresponding to x = 0.3) heat-treated at 723 K for 6 h gave rise to a clear crystalline phase of Bi2WO6 embedded in the Li2B4O7 glass matrix, as observed by X-ray studies. The dielectric constants of the as-quenched glasses as well as the glass-ceramics decreased with increase in frequency (40Hz-100 kHz) at 300 K, and the value obtained for the glass-ceramic (x = 0.2) is in agreement with the values predicted using Maxwell's model and the logarithmic mixture rule. The dielectric constants for both the as-quenched glass and the glass-ceramic increased with increase in temperature (300 - 873 K) and exhibited anomalies close to the onset of the crystallization temperature of the host glass matrix. The optical transmission properties:of these glass-ceramics were found to be compositional dependant. (C) 2000 Elsevier Science Ltd.

Studies on the Effect of Li2SO4 on the Structure of Lithium Borate Glasses

Thermal and spectroscopic investigations have been carried out on a number of glasses with a wide range of compositions in the pseudoternary glass system, Li2SO4-Li2O-B2O3, to understand the role of sulfate ions in modifying the borate glass structure. Both nuclear magnetic resonance (NMR) and infrared (IR) spectroscopic results indicate that four-coordinate boron atoms are retained in the glass structure to a greater extent in sulfate-containing glasses than in pure lithium borate glasses. There seems to be some evidence for the existence of sulfoborate-type units in Raman spectra in the region of 800-960 cm(-1). These conclusions are supported by the observed behavior of glass transition temperatures and molar volumes. The possibility of formation of sulfoborate-type units is discussed from bonding and thermodynamic points of view.

The molecular dynamics study of lithium ion conduction in phosphate glasses and the role of non-bridging oxygen

Molecular dynamics (MD) simulation of lithium phosphate (Li2O-P2O5) glasses with varying Li2O content has been carried out. Two different P-O distances corresponding to phosphorus coordination with bridging oxygen (BO) and non-bridging oxygen (NBO) were identified in the simulated glasses. NBO-BO interconversion or bond switching was noted, which results in a dynamic equilibration of the tetrahedral phosphate units (P-n, n = 1,3 indicates the number of bridging oxygen atoms in the coordination of phosphorus). The NBO-BO bond switching is mildly activated with an effective activation barrier of 0.03-0.05 eV. Lithium ion jumps do not appear to be strongly coupled to bond switching. But the number of Li+ ions coordinated to an optimum number of NBOs and the number of Li+ ions jumping out of their sites appear to be correlated. Detailed analysis was made of the dynamics of P-n species and new insights have been obtained regarding ion migration in network-modified phosphate glasses.

Characterization of lithium borate–bismuth tungstate glasses and glass-ceramics by impedance spectroscopy

Transparent glasses in the system (1−x)Li2B4O7–xBi2WO6 (0≤x≤0.35) were prepared via melt quenching technique. Differential thermal analysis was employed to characterize the as-quenched glasses. Glass-ceramics with high optical transparency were obtained by controlled heat-treatment of the glasses at 720 K for 6 h. The amorphous nature of the as-quenched glass and crystallinity of glass-ceramics were confirmed by X-ray powder diffraction studies. High resolution transmission electron microscopy (HRTEM) shows the presence of nearly spherical nanocrystallites of Bi2WO6 in Li2B4O7 glass matrix. Capacitance and dielectric loss measurements were carried out as a function of temperature (300–870 K) in the frequency range 100 Hz–40 MHz. Impedance spectroscopy employed to rationalize the electrical behavior of glasses and glass-ceramics suggest the coexistence of electronic and ionic conduction in these materials. The thermal activation energies for the electronic conduction and ionic conduction were also estimated based on the Arrhenius plots.

Effect of lithium ion irradiation on the transport and optical properties of Bridgman grown n-type InSb single crystals

Single crystal (100) wafers of n-InSb were implanted with 50 MeV Li3+ ions at various fluences ranging from 10(10) to 10(14) ions/cm(2) at room temperature. Investigations of the optical, electrical, and structural properties of the as-grown, irradiated, annealed wafers were carried out by infrared and Raman spectroscopies, Hall measurements, and high resolution x-ray diffraction (HRXRD). In the case of samples irradiated with an ion fluence of 1.6x10(14) ions/cm(2), electrical measurements at 80 K reveal that there is a decrease in carrier concentration from 8.5x10(15) (for unirradiated) to 1.1x10(15)/cm(3) and an increase in mobility from 5.4x10(4) to 1.67x10(5) cm(2)/V s. The change in carrier concentration is attributed to the creation of electron trap centers induced by ion beam irradiation and the increase in mobility to the formation of electrical inactive complexes. Nevertheless, even with the irradiation at 1.6x10(14) ions/cm(2) fluence the crystalline quality remains largely unaffected, as is seen from HRXRD and Raman studies. (C) 2001 American Institute of Physics.

Probing the mobility of lithium in LISICON: Li+/H+ exchange studies in Li2ZnGeO4 and Li2+2xZn1-xGeO4

We investigated Li+/H+ exchange in the lithium ion conductors (LISICONS) [ Li2+2xZn1-xGeO4; x = 0.5 ( I) and x = 0.75 (II)] and their parent, gamma-Li2ZnGeO4. Facile exchange of approximately 2x lithium ions per formula unit occurs with both the LISICONS in dilute acetic acid, while the parent material does not exhibit an obvious Li+/H+ exchange under the same conditions. The results can be understood in terms of lithium ion distribution in the crystal structures: the parent Li2ZnGeO4, where all the lithium ions form part of the tetrahedral framework structure, does not exhibit a ready Li+/H+ exchange; LISICONS, where lithium ions are distributed between framework ( tetrahedral) and nonframework sites, undergo a facile Li+/H+ exchange of the nonframework site lithium ions. Accordingly, Li+/H+ exchange in dilute aqueous acetic acid provides a convenient probe to distinguish between the mobile and the immobile lithium ions in lithium ion conductors.

A LOWER INITIAL ABUNDANCE OF SHORT-LIVED Ca-41 IN THE EARLY SOLAR SYSTEM AND ITS IMPLICATIONS FOR SOLAR SYSTEM FORMATION

The short-lived radionuclide Ca-41 plays an important role in constraining the immediate astrophysical environment and the formation timescale of the nascent solar system due to its extremely short half-life (0.1 Myr). Nearly 20 years ago, the initial ratio of Ca-41/Ca-40 in the solar system was determined to be (1.41 +/- 0.14) x 10(-8), primarily based on two Ca-Al-rich Inclusions (CAIs) from the CV chondrite Efremovka. With an advanced analytical technique for isotopic measurements, we reanalyzed the potassium isotopic compositions of the two Efremovka CAIs and inferred the initial ratios of Ca-41/Ca-40 to be (2.6 +/- 0.9) x 10(-9) and (1.4 +/- 0.6) x 10(-9) (2 sigma), a factor of 7-10 lower than the previously inferred value. Considering possible thermal processing that led to lower Al-26/Al-27 ratios in the two CAIs, we propose that the true solar system initial value of Ca-41/Ca-40 should have been similar to 4.2 x 10(-9). Synchronicity could have existed between Al-26 and Ca-41, indicating a uniform distribution of the two radionuclides at the time of CAI formation. The new initial Ca-41 abundance is 4-16 times lower than the calculated value for steady-state galactic nucleosynthesis. Therefore, Ca-41 could have originated as part of molecular cloud materials with a free decay time of 0.2-0.4 Myr. Alternative possibilities, such as a last-minute input from a stellar source and early solar system irradiation, could not be definitively ruled out. This underscores the need for more data from diverse CAIs to determine the true astrophysical origin of Ca-41.

Synthesis and antioxidant activity study of pyrazoline carrying an arylfuran/arylthiophene moiety

A novel series of N-acetyl-3-aryl-5-(5-(p/o-nitrophenyl)-2-furyl//thienyl)-substituted pyrazolines (3a-o) were synthesized by the reaction of 1-aryl-3-(5-(p/o-nitrophenyl)-2-furyl/thienyl)-2-propene-1-ones with hydrazine hydrate in acetic acid medium. The structures of the newly synthesized compounds were established by IR, H-1-NMR, mass spectra and a single-crystal X-ray study. The antioxidant activities of the synthesized compounds were determined using the DPPH scavenging assay. The compounds 3a, 3f, 3h and 3o showed moderate activity.

Energy-savvy solid-state and sonochemical synthesis of lithium sodium titanate as an anode active material for Li-ion batteries

Lithium sodium titanate insertion-type anode has been synthesized by classical solid-state (dry) and an alternate solution-assisted (wet) sonochemical synthesis routes. Successful synthesis of the target compound has been realized using simple Na- and Li-hydroxide salts along with titania. In contrast to the previous reports, these energy-savvy synthesis routes can yield the final product by calcination at 650 -750 degrees C for limited duration of 1-10 h. Owing to the restricted calcination duration (dry route for 1-2 h and wet route for 1-5 h), they yield homogeneous nanoscale lithium sodium titanate particles. Sono-chemical synthesis reduces the lithium sodium titanate particle size down to 80-100 nm vis-a-vis solid-state method delivering larger (200-500 nm) particles. Independent of the synthetic methods, the end products deliver reversible electrochemical performance with reversible capacity exceeding 80 mAh.g(-1) acting as a 1.3 V anode for Li-ion batteries. (C) 2015 Elsevier B.V. All rights reserved.

Structural evolution and second harmonic properties of lithium niobate-tantalate nanocrystals embedded in a borate glass

Nano-crystals of LiNbxTa1 (-) O-x(3) were evolved by subjecting melt-quenched 1.5Li(2)O-2B(2)O(3)-xNb(2)O(5)-(1 - x)Ta2O5 glasses (where x = 0, 0.25, 0.5, 0.75 and 1.00) to a controlled 3-h isothermal heat treatment between 530 and 560 degrees C. Detailed X-ray diffraction and Raman spectral studies confirmed the formation of nano-crystalline LiNbxTa1 (-) O-x(3) along with a minor phase of ferroelectric and non-linear optic Li2B4O7. The sizes of the nanocrystals evolved in the glass were in the range of 19-37 nm for x = 0-0.75 and 23-45 nm for x = 1.00. Electron microscopic studies confirmed a transformation of the morphology of the nano-crystallites from dendritic star-shaped spherulites for x = 0 to rod-shaped structures for x = 1.00 brought about by a coalescence of crystallites. Broad Maker-fringe patterns (recorded at 532 nm) were obtained by subjecting the heat-treated glass plates to 1064 nm fundamental radiation. However, an effective second order non-linear optic coefficient, d(eff), of 0.45 pm/V, which is nearly 1.2 times the d(36) of KDP single crystal, was obtained for a 560 degrees C/3 h heat-treated glass of the representative composition x = 0.50 comprising 37 nm sized crystallites. (C) 2015 Elsevier B.V. All rights reserved.

Structural evolution and second harmonic properties of lithium niobate-tantalate nanocrystals embedded in a borate glass

Nano-crystals of LiNbxTa1 (-) O-x(3) were evolved by subjecting melt-quenched 1.5Li(2)O-2B(2)O(3)-xNb(2)O(5)-(1 - x)Ta2O5 glasses (where x = 0, 0.25, 0.5, 0.75 and 1.00) to a controlled 3-h isothermal heat treatment between 530 and 560 degrees C. Detailed X-ray diffraction and Raman spectral studies confirmed the formation of nano-crystalline LiNbxTa1 (-) O-x(3) along with a minor phase of ferroelectric and non-linear optic Li2B4O7. The sizes of the nanocrystals evolved in the glass were in the range of 19-37 nm for x = 0-0.75 and 23-45 nm for x = 1.00. Electron microscopic studies confirmed a transformation of the morphology of the nano-crystallites from dendritic star-shaped spherulites for x = 0 to rod-shaped structures for x = 1.00 brought about by a coalescence of crystallites. Broad Maker-fringe patterns (recorded at 532 nm) were obtained by subjecting the heat-treated glass plates to 1064 nm fundamental radiation. However, an effective second order non-linear optic coefficient, d(eff), of 0.45 pm/V, which is nearly 1.2 times the d(36) of KDP single crystal, was obtained for a 560 degrees C/3 h heat-treated glass of the representative composition x = 0.50 comprising 37 nm sized crystallites. (C) 2015 Elsevier B.V. All rights reserved.

Population Characteristics of Largemouth Bass Associated with Changes in Abundance of Submersed Aquatic Vegetation in Lake Seminole, Georgia

Population characteristics of largemouth bass ( Micropterus salmoides L.) including growth, body condition (relative weight), survival, and egg production were examined in relation to abundance of submersed aquatic vegetation (SAV) coverage (primarily hydrilla [ Hydrilla verticillata L.f. Royle]) in three embayments of Lake Seminole, GA, and compared to a previous study conducted in 1998. (PDF has 8 pages.)