Fabrication of a high lithium ion conducting lithium borosilicate glass

A lithium ion conducting glass, Li₂O-B₂O₃-SiO₂, is fabricated by the conventional melt and quenching technique from a mixture of Li₂CO₃, B₂O₃ and SiO₂ powders. It appears that B₂O₃ decreases the crystallization tendency of the Li₂O-SiO₂ binary glass, resulting in an expanded glass forming region in the Li₂O-B₂O₃-SiO₂ ternary glass. The maximum conductivity is 2 × 10^− 6 S cm^− 1 at 25 °C for the 50Li₂O-38B₂O₃-12SiO₂ glass sample. The observed high conductivity is due to the mixed former effect. The conductivity strongly depends on the Li₂O content, but not on K (SiO₂/B₂O₃) in the Li₂O-B₂O₃-SiO₂ ternary glass.     

Aggregation of Anthraquinone Dye Molecules in a Nematic Liquid Crystal

We report an experimental evidence that molecules of anthraquinone dye aggregate in an anisotropic solvent, a nematic liquid crystal (NLC). We observe strong nonlinear dependencies of the dielectric permittivity and anisotropy of light absorption on the dye concentration c. Moreover, the data suggest that the aggregates are linear, but, in contrast to the isotropic case, their formation in a NLC undergoes two different concentration regimes with a well pronounced crossover. These effects are explained by the interplay between the aggregates’ lengths and their orientational ordering due to the interaction with the nematic director.     

Crystallization of lithium metasilicate from lithium disilicate glass

The crystallization behavior of lithium disilicate glass powder heated in molten LiNO₃ salt was investigated using X-ray diffraction techniques. Heat treatment at 500°C with LiNO₃ molten salt caused a lithium metasilicate, Li₂SiO₃, crystal phase to appear after 5–96 h. By contrast, glass powder heat-treated in air at 500°C remained amorphous after 5 h and turned into lithium disilicate, Li₂Si₂O₅, crystal after 40 h. Qualitatively similar results were obtained at 400°C. Glass powder heat-treated at 575°C in both molten salt and in air turned into lithium disilicate crystal. Metasilicate crystallization occurs with LiNO₃ molten salt at 500 and 400°C due to the incorporation of lithium into the sample glass powder from the melt during crystallization. An increase in lithium content in the sample after molten salt heat treatment was confirmed by chemical analysis using dc plasma emission spectroscopy.     

Structure and lithium ion diffusion in lithium silicate glasses and at their interfaces with lithium lanthanum titanate crystals

Solid state lithium ion electrolytes are important to the development of next generation safer and high power density lithium ion batteries. Lithium containing glasses such as lithium silicate glasses have been widely studied due to their high ionic conductivity. Recently, lithium silicate glasses were introduced in polycrystalline lithium lanthanum titanate (LLT) ceramics as intergranular thin films between the crystalline grains to achieve higher lithium ion conductivities in these solid state electrolytes. In this work, we present investigations of the structure and diffusion behavior of lithium silicate glasses and their interfaces with LLT crystals using molecular dynamics simulations. The short and medium range structures of the lithium silicate glasses were characterized and the ceramic/glass interface models were obtained using MD simulations. Lithium ion diffusion behaviors in the glass and across the glass/ceramic interfaces, as well as the effect of atomic structure on diffusion behaviors, were investigated. It was found that there existed a minor segregation of lithium ions at the glass/crystal interface. The interface lithium ion diffusion energy barrier was found to be dominated by the glass phase.     

Bidomain structures formed in lithium niobate and lithium tantalate single crystals by light annealing

The bidomain structures produced by light external heating in z-cut lithium niobate and lithium tantalate single crystals are formed and studied. Interdomain regions about 200 and 40 μm wide in, respectively, LiNbO₃ and LiTaO₃ bidomain crystals are visualized and studied by optical microscopy and piezoresponse force microscopy. Extended chains and lines of domains in the form of thin layers with a width less than 10 μm in volume, which penetrate the interdomain region and spread over distances of up to 1 mm, are found.     

Structure and properties of lithium thio-boro-germanate glasses

Structural studies of the ternary xLi₂S + (1 − x)[0.5B₂S₃ + 0.5GeS₂] glasses using IR, Raman, and ¹¹B NMR show that the Li₂S is not shared proportionately between the GeS₂ and B₂S₃ sub-networks of the glass. The IR spectra indicate that the B₂S₃ glass network is under-doped in comparison to the corresponding composition in the xLi₂S + (1 − x)B₂S₃ binary system. Additionally, the Raman spectra show that the GeS₂ glass network is over-modified. Surprisingly, however, the ¹¹Boron static NMR gives evidence that ∼80% of the boron atoms are in tetrahedral coordinated. A super macro tetrahedron, B₁₀S₁₈⁻⁶ is proposed as one of the structures in these glasses in which can account for the apparent low fraction of Li₂S present in the B₂S₃ sub-network while at the same time enabling the high fraction of tetrahedral borons in the glass.     

Enhanced Aggregation of Tin(IV)Porphyrins in a Polyfluorinated Surfactant-Clay Hybrid Environment

Abstract

Tetra-(4-sulfonatophenyl)porphyrinatotin(IV) aggregated efficiently in a clay (saponite) layer intercalated with a polyfluorinated surfactant, but no aggregation was observed in a hydrocarbon type surfactant-clay hybrid environment. Germanium(IV) porphyrins remained as monomers even in the polyfluorinated environment.     

Stability of lithium silicate gels

Lithium silicate gels with 15 mol% Li₂O were prepared by combining a lithium nitrate solution with partially hydrolyzed tetraethyl orthosilicate (TEOS). Using low pH and high water levels, samples were cast, gelled, and dried to form cylinders 30 mm in length and 5 mm in diameter in about a week. The dried gels had a uniform lithium content throughout. Lithium disilicate crystals and quartz crystals appeared in samples heated above 600°C.     

Nanoparticle Aggregation and Fractal Growth in Fluid Smectic Membranes

We observe directly the diffusion and aggregation of buckyball clusters dispersed in thin, freely-suspended films of smectic liquid crystal using reflected light microscopy. The buckyballs at early times are barely resolvable, nanoscale clusters, which diffuse stochastically in the film. Clusters eventually coalesce to form micron-scale, fractal aggregates whose effective radius increases approximately linearly with time, so that after several days, millimeter-size fractals extend across the entire film. The measured fractal dimension of these final networks suggests that the aggregation of the buckyball clusters in the film is a diffusion-limited process.     

Thermoluminescence of X-irradiated glassy and devitrified lithium disilicates

Thermoluminescence of X-irradiated glasses and crystals of lithium disilicate has been measured in the temperature range from room temperature to 400°C. The difference in thermoluminescence between them was explained in terms of the varying degree of overlapping of trap levels. The variations of some TL peak intensity ratios with irradiation or decay time were discussed. The origin of TL in glasses and also in crystals was attributed to trapped excitons.     

Aggregation model for the gelation of a sol starting from the processing conditions

A stochastic computational model for the gelation of a sol is explained and tested for the case of neutral silica aerogels. The computational model produces the final structure of the sol after gelation, using two of the several physical phenomena occurring during gelation of sols. Diffusion, represented by Brownian motion, is modeled by a random walk, and chemical reactions are incorporated through a stochastic aggregation model using a probability function; the latter determined in terms of the processing conditions based on the knowledge of the cluster formation energies. The two phenomena are coupled by a Monte Carlo simulation. The analysis of the connected structure and its functionality is demonstrated for neutral silica aerogels. It is shown how the gelation process can be controlled to obtain different structures for different application requirements. The only parameters required by the model are the density and the processing conditions. The results of the model show that those parameters strongly affect the structure of the generated samples. Therefore, processing conditions could be selected to produce aerogels with structures tailored to specific applications, which would constitute a major achievement in aerogel fabrication.     

Further investigations of the effect of replacing lithium by sodium on lithium silicate scintillating glass efficiency

Ce³⁺ doped lithium (⁶Li) silicate glasses are thermal neutron detectors. Prior work showed that when sodium (Na) is substituted for Li the scintillation efficiency, under beta particle stimulation, increased and then decreased as the sodium (Na) content was increased. When all the ⁶Li was replaced by Na no scintillation was observed. Raman spectra, acquired using a visible excitation source, provided no evidence of anomalous behavior. SEM microscopy did show some phase separation, but there was no obvious correlation with the scintillation efficiency. We have reexamined these glass samples using deep UV Raman excitation which reduces fluorescence interference. The newly acquired spectra show evidence of phase separation in the glasses. Specifically we see a peak at 800 cm^? 1 Raman shift which can be assigned to a vitreous silica moiety that results from phase separation. There is a strong correlation between this peak's area, the scintillation efficiency, and the Na content. The observed trend suggests that phase separation enhances scintillation and addition of Na reduces the amount of phase separation. We also see evidence of at least two defect structures that can be tentatively assigned to a three-membered ring structure and an oxygen vacancy. The latter is fairly strongly correlated with enhanced scintillation efficiency.     

Mechanical properties of single crystalline and glassy lithium triborate

Mechanical properties of LiB₃O₅ single crystal plates with different orientation as well as of glass with the same composition have been investigated. The nano‐ (H) and microhardness (H_M), the reduced Young's modulus (E_r) and the crack behaviour of the samples were studied. Both hardness and Young's modulus of glass appeared smaller in comparison to corresponding single crystal data (H ∼ 7 – 8 GPa, H_M ∼ 6 GPa, E_r ∼ 70 – 80 GPa for glass and H ∼ 10 – 15 GPa, H_M ∼ 6 –11 GPa, E_r ∼ 93 – 155 GPa for single crystal). H, E_r, and the plane of crack propagation proved orientation‐dependent. Cracks in the glass sample were not observed up to 0.49 N microindentation load, whereas for the single crystal the cracks appeared already at 0.098N. In single crystals the observed cleavage planes {211} and/or {412} are oriented nearly parallel to planes of B‐O rings. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Piezo-optic surfaces of lithium niobate crystals

A method of construction of the spatial distribution of the piezo-optic effect in crystals is proposed. A particular case of this method is the known technique of construction of indicator surfaces of the piezo-optic effect. The essence of the proposed method consists in determining the difference in the radius vectors of the optical indicatrix perturbed by stress and the free optical indicatrix. It is shown that this difference in the radius vectors is mathematically identical to the law of transformation of the piezo-optic tensor during the rotation of the coordinate system.     

Growth and characterization of glycine lithium sulphate single crystal

Single crystal of glycine lithium sulphate, a nonlinear optical material, was grown from aqua solution by temperature reduction method. The solubility and metastable zonewidth of glycine lithium sulphate were estimated using aqueous solution. The cell parameters of the grown crystal were estimated by single crystal X‐ ray diffraction analysis. The presence of functional groups was identified from FTIR spectrum. Thermal analysis was performed to study the thermal stability of the grown crystal. The transmission and absorption spectra of this crystal show that the lower cut off wavelength lies at 330 nm. Powder Second Harmonic Generation efficiency of the grown crystal measured by Kurtz technique is 0.75 times that of potassium dihydrogen orthophosphate. Vickers microhardness study was carried out on the well developed (011) face of the grown crystal. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural and optical properties of lithium barium bismuthate glasses

Structural and optical properties of some ion-conducting lithium barium bismuthate glasses have been studied. The structure of these glasses has been explored from the compositional variation of the density, the molar volume and the glass transition temperature. The density and the molar volume decrease with the increase of lithium ion content in these glasses keeping the barium content fixed. The optical studies in the ultraviolet–visible (UV–VIS) and infrared (IR) regions for all these glasses show a sharp cut-off and a large transmitting window, which make them appealing candidates for the different spectral devices.     

The preparation and properties of cerium-activated lithium glass scintillators

We report the preparation of cerium activated lithium glass scintillators for thermal neutron detection and their properties. The technological requirements and appropriate compositions are proposed, by which high detection efficiency of lithium glass scintillators for thermal neutrons can be obtained. When used as neutron detectors, the ⁶Li glass ST-602 affords excellent pulse height discrimination against gamma radiation, particularly in the case of thin ⁶Li glass.     

Amorphous phase separation and crystallization in a lithium silicate glass prepared by the sol-gel method

A 10Li₂O---90SiO₂ (mol%) gel-glass has been prepared by using tetramethyl orthosilicate and lithium iso-propoxide as starting materials. The phase separation and crystallization behaviour was compared with the corresponding conventionally melted glass using DTA, X-ray diffraction and TEM. The same crystallization phase was found in both the gel glass and melted glass upon heating above 650°C. However, the rate of crystallization in the gel-glass was higher than in the melted glass. TEM revealed amorphous phase separation in the gel glass and melted glass. However, the morphologies were different, an interconnected microstructure being observed in the gel glass and a droplet structure in the melted glass. These differences can be partly attributed to differences in OH content. Other potential influencing factors are also considered. After 650°C for 2 h lithium disilicate crystals were observed in the volume of the gel glass by TEM. As the crystals grew they absorbed Li₂O from the surrounding lithia-rich amorphous phase so that silica-rich (lithia depleted) diffusion zones formed around them.     

Stoichiometry and point defects in lithium niobate crystals

Investigations of the OH⁻ ion incorporation into LiNbO₃ crystals and the comparison of calculated and measured densities show that undoped congruent lithium niobate crystals contain Li⁺ and O^{− −} ion vavancies O and Li⁺. If really present, stacking faults are of inferior importance. The good agreement of the absorption edges of stoichiometric and of 2.7 mol% MgO containing congruent lithium niobate crystals is explained by the occupance of all oxygen sites within these crystals.