Extraction of europium and electrodeposition of Al–Li–Eu alloy from Eu2O3 assisted by AlCl3 in LiCl–KCl melt

The work presents an electrochemical study on preparation of Al–Li–Eu alloys on a tungsten electrode in molten LiCl–KCl–AlCl₃–Eu₂O₃ system at 753 K and 953 K. Gibbs energy shows that AlCl₃ can chloridize Eu₂O₃, with a discharge in the form of Eu(III) ions on the cathode. The electrochemical behavior of Al(III), Li(I) and Eu(III) and alloy formation processes were investigated by cyclic voltammetry, square wave voltammetry, and chronopotentiometry. Cyclic voltammetry indicated that the underpotential deposition of europium on pre-deposited Al forms two Al–Eu intermetallic compounds at electrode potentials around ?2.00 V and ?2.34 V, respectively. And the underpotential deposition of lithium on Al surface at about ?2.24 V leads to a formation of Al–Li alloy. X-ray diffraction (XRD) indicated that Al–Li–Eu alloys with different phases were obtained via galvanostatic electrolysis. The microstructure and micro-zone chemical analysis of Al–Li–Eu alloy were characterized by scanning electron microscopy (SEM) with energy dispersive spectrometry (EDS), respectively. The analysis of EDS showed that element Eu mainly distributes on needle-like precipitate, and not homogeneously in the Al–Li–Eu alloy. Composition of the alloys was analyzed by inductive coupled plasma analysis, and current efficiency was also determined with respect to the alloy composition.     

Effect of Li2O on melt crystallization of CaO–SiO2–CaF2 based glasses

This paper presents the effects of Li₂O on the kinetics and structural aspects of the Cuspidine (Ca₄Si₂F₂O₇) crystallization behavior of CaO–SiO₂–CaF₂ glass (basicity 1.7). In order to elucidate the crystallization characteristics during differential scanning calorimetry (DSC) measurements, the kinetic parameters have been determined using the Johnson-Mehl-Avrami-Kolmogorov (JMAK) equation. The crystallization rate constant and negative activation energy thus calculated indicated that the limiting step of crystallization was nucleation. Also, Raman spectroscopy and Solid-state MAS NMR spectroscopy analyses indicated that lithium could interact with fluorine, thereby disturbing the interaction between calcium and fluorine. This retards Cuspidine nucleation at the initial stage of melt crystallization. These findings on CaO–SiO₂–CaF₂-based glass lubricants can be used to optimize essential properties such as viscosity and crystallization temperature during continuous casting of steels.     

Electrochemistry of molten LiCl–KCl–CrCl3 and LiCl–KCl–CrCl2 mixtures

Chemical reactions during dissolution of CrCl3 or CrCl2 in molten LiCl–KCL eutectic have been demonstrated to occur, but the nature of the reactions is not yet well understood. Reduction of CrCl3 to chromium metal occurs through two well-characterized electrochemical steps, at approximately +0.1 and –0.9 V vs Ag/AgCl. Each step was studied in the 0.025–0.085 molar CrCl3 concentration range, at various temperatures between 375 and 550 °C. The Cr(iii)/Cr(ii) electron transfer step exhibited reversible behaviour under all the experimental conditions studied. In contrast, the Cr(ii)/Cr(0) step could involve Cr(ii) adsorbed species and initial chromium electrocrystallization phenomena, mainly depending on the nature of the substrate.     

Crystallisation and characterisation of dielectric glass ceramics in Li2O–Al2O3–SiO2 system

Abstract

Glass ceramics in the Li₂O–Al₂O₃–SiO₂ system have been synthesised to produce bulk materials grown in a glass phase via quenching followed by controlled crystallisation. The crystallisation and microstructure of Li₂O–Al₂O₃–SiO₂ (LAS) glass–ceramic with nucleating agents (B₂O₃ and/or P₂O₅) are investigated by differential thermal analysis, X-ray diffraction and scanning electron microscopy and the effects of B₂O₃ and P₂O₅ on the crystallisation of LAS glass are also analysed. The introduction of both B₂O₃ and P₂O₅ promotes the crystallisation of LAS glass by decreasing the crystallisation temperature and adjusting the crystallisation kinetic parameters, allows a direct formation of β spodumene phase and as a result, increases the crystallinity of the LAS glass ceramic. Microstructural observations show that the randomly oriented, nanometre sized crystalline is found with residual glass concentrated at crystallite boundaries. Furthermore, it is interesting that codoping of B₂O₃ and P₂O₅ creates not much effect on the crystallisation temperature. The dielectric properties of the glass–ceramics formed through controlled crystallisation have a strong dependence on the phases that are developed during heat treatment. The dielectric constant is continuously increased and the dielectric loss is decreased with addition of additives where mobile alkali metal ions (e.g. Li⁺) are incorporated in a crystal phase and minimise the residual glass phase.     

Bioactivity investigation of glass and glass ceramics in Li2O–SiO2–CaO–P2O5–CaF2 system

Abstract

Glass samples in Li₂O–SiO₂–CaO–P₂O₅–CaF₂ system with different contents of P₂O₅, CaO and CaF₂ in relative ratios responded to fluoroapatite (FA) composition (referred to P₂O₅ addition) have been prepared and heat treated at 550 and 750°C to obtain glass ceramics. Bioactivity of all samples has been proved in vitro by the presence of new layer of apatite-like phases formed after soaking in simulated body fluid (SBF). The development and the apatitic character of created layers have been demonstrated by Fourier transform infrared analysis. Scanning electron microscopy and electron probe microanalysis have demonstrated that the density and the thickness of new layer depend on P₂O₅ content, crystallisation temperature and immersion time. The bioactivity has been enhanced by P₂O₅ addition as well in the case of the base glasses as in the case of glass ceramics. The additional heat treatment appeared to inhibit the bioactive behaviour, though the longer SBF acting leads to the additional formation of apatite-like layer. The mechanical properties, expressed as Vicker hardness, have been found higher and increasing with P₂O₅ in glass ceramics treated at 750°C comparatively with base glass samples and the highest value of 7˙37 GPa has been achieved by 14 wt-%P₂O₅ addition. The same content of P₂O₅ in glass ceramics heat treated at 550°C resulted in a decrease in hardness to a minimum value from all samples. The increase and decrease in hardness responded to development and suppression of crystallisation respectively. The inhibition of crystallisation has been affected by the presence of 'amorphous' FA according to X-ray diffraction and differential thermal analysis results.     

Crystallization behavior and melt structure of typical CaO–SiO2 and CaO–Al2O3-Based mold fluxes

Crystallization behavior and melt structure of two typical mold fluxes A (CaO–SiO₂-based) and B (CaO–Al₂O₃-based) for casting high-aluminum steel were investigated using double hot thermocouple technology (DHTT), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The results suggest that the crystallization temperature of Flux B is higher, and its crystallization incubation time is shorter compared with Flux A. The precipitated phase in Flux A is CaSiO₃, whereas BaAl₂O₄ and Ca₂Al₂SiO₇ form in Flux B. The structure analyses suggest that the degree of polymerization of Flux A is larger than that of Flux B. In addition, the major structural units of Flux A are Si–O–Si, Q₀^Si, Q₁^Si, Q₂^Si and Q₃^Si, but those of Flux B are mainly aluminate (Al–O–Al, Al–O^-), aluminosilicate (Al–O–Si) and silicate units (Q₀^Si, Q₁^Si, Q₂^Si and Q₃^Si). These different melt structures are the main reasons why the precipitated phases in these two mold fluxes are different, and the crystallization ability of Flux A is weaker than Flux B.     

Lithium concentration effect on crystallization kinetics and spectral properties of Cr-doped Li2O–K2O–Al2O3–B2O3 glass-ceramics

Alkali-aluminaborate glass-ceramics doped with Cr ions are synthesized by volume crystallization. According to non-isothermal DSC method three parallel processes occur in material: 2D Avrami-Yerofeev nucleation, 2D and 3D crystallization. During the heat treatment, the LiAl₇B₄O₁₇ crystalline phase is formed. With Li₂O content rising crystallinity of the material increases from 27 to 69% and the crystalline field strength Dq/B of Cr³⁺ increases from 2.25 to 3.55. The photoluminescence spectra possess intense bands at 685, 700, and 715 nm for glass with 6.8 mol.% Li₂O and higher and its decay kinetics is described by the sum of two exponentials. The maximum luminescence QY obtained is 50% at 16.1 mol.% Li₂O. The highest conversion efficiency of the 532 nm LED luminescence obtained by glass-ceramics with chromium is 10%. Thus, Cr-doped alkali-alumina-borate glass-ceramics are a promising material for use in the design of radiation sources for the red and NIR spectral regions.     

Dual effect of ZrO2 on phase separation and crystallization in Li2O–Al2O3–SiO2–P2O5 glasses

ZrO₂ is an effective nucleation agent for low-expansion lithium–aluminum silicate (LAS) glass–ceramic (GC) with high Al₂O₃ content. However, the effect of ZrO₂ is still not fully understood in LAS glasses with low contents of Al₂O₃ and P₂O₅. In this work, the effect of ZrO₂ on the phase separation and crystallization of Li₂O–Al₂O₃–SiO₂–P₂O₅ glasses were investigated. The results revealed that ZrO₂ significantly increased T_g and the crystallization temperature of Li₂SiO₃ and Li₂Si₂O₅ crystals. Li₃PO₄ crystals precipitated preferentially in the glass containing 3.6-mol% ZrO₂, wherein Zr was stable in the network and no precipitation of ZrO₂ nanocrystals was observed. Moreover, the separation of phosphate-rich phases in the as-quenched glasses increased with the addition of ZrO₂. The findings of the study revealed a dual role of ZrO₂. First, ZrO₂ acted as a glass network former rather than a nucleation agent, increasing glass viscosity and the nucleation barrier of Li₂SiO₃ through its strong network connectivity. Second, as Zr preferentially combined with non-bridging oxygen to form Si–O–Zr linkages, a sufficient amount of charge-balancing Li⁺ ions existed in the network, which promoted the separation of phosphate-rich phases. It indicated that the incorporation of ZrO₂ contributes to the activation of the nucleation role of P₂O₅, thus contributing to the formation of nanocrystals and fine microstructure of GCs.     

Comparative Characteristics of the Li–Fe–O and Li–Fe–Р–O Powders Obtained by Pyrolytic Extraction

Theoretical Foundations of Chemical Engineering - The structural and optical properties of lithium–iron oxide and lithium–iron–phosphorus oxide obtained by pyrolytic extraction...     

Effect of SiC nanowires on the thermal shock resistance of joint between carbon/carbon composites and Li2O–Al2O3–SiO2 glass ceramics

In order to improve the bonding property of joint between SiC modified carbon/carbon (C/C) composites and Li₂O–Al₂O₃–SiO₂ (LAS) glass ceramics, SiC nanowires were attempted as the reinforcement materials in the interface region of SiC transition layer and Li₂O–MgO–Al₂O₃–SiO₂ (LMAS) gradient joining interlayer. The C/C–LAS joint with SiC nanowire-reinforced interface layer was prepared by a three-step technique of pack cementation, in situ reaction and hot-pressing. The microstructure and thermal shock resistance of the as-prepared joints were examined. The average shear strength of the joined samples with SiC nanowires increased from 24.9 MPa to 31.6 MPa after 40 thermal cycles between 1000 °C and room temperature, while that of the joined samples without SiC nanowires dropped from 21.4 MPa to 8.3 MPa. The increase of thermal shock resistance of the C/C–LAS joints was mainly attributed to the toughening mechanism of SiC nanowires by pullout, bridging and crack deflection.     

Electrodeposition of cohesive carbon films on aluminum in a LiCl–KCl–K2CO3 melt

Electrodeposition of carbon on an aluminum electrode was studied in a LiCl–KCl–K₂CO₃ melt. A cyclic voltammogram for an aluminum electrode indicates that the cathodic current is due to the reduction of CO₃^2– ions. Carbon films on aluminum substrates were obtained by potentiostatic electrolysis, and the cohesiveness of the films depended on the potential. SEM observations showed that the morphology of the deposited carbon film depends on the electrolytic conditions. Raman spectroscopy, XPS and XAES measurement showed that the film consisted of carbon in the sp² state.     

Electrochemical behaviour of LaCl3 at tungsten and aluminium cathodes in LiCl–KCl eutectic melt

The electrochemical behaviour of lanthanum was studied at inert tungsten electrode and reactive aluminium electrode in LiCl–KCl eutectic melt in the temperature range 698–798 K using transient electrochemical techniques. Reduction of La(III) to La(0) at the tungsten electrode takes place in a single step. The reduction shows quasi-reversible behaviour for polarization rates, 25 ≤ ν ≤ 150 mV s^?1 and is predominantly controlled by charge transfer of La(III) ions for scan rates higher than 75 mV s^?1. The heterogenous rate constant of the process was estimated from impedance spectroscopy and from the semi-integrals of the cyclic voltammograms. The redox potential of the La(III)/La couple at the Al electrode was observed to be more positive than that at the inert electrode. This potential shift is due to the lowering of the activity of La in the metal phase caused by the formation of the intermetallic compound Al₁₁La₃. Thermodynamic properties such as Gibbs energy of formation of Al₁₁La₃, excess Gibbs energy and the activity coefficient of La in Al were calculated from the open circuit potential measurement.     

The role of K2O on sintering and crystallization of glass powder compacts in the Li2O–K2O–Al2O3–SiO2 system

The effects of K₂O content on sintering and crystallization of glass powder compacts in the Li₂O–K₂O–Al₂O₃–SiO₂ system were investigated. Glasses featuring SiO₂/Li₂O molar ratios of 2.69–3.13, far beyond the lithium disilicate (LD-Li₂Si₂O₅) stoichiometry, were produced by conventional melt-quenching technique. The sintering and crystallization behaviour of glass powders was explored using hot stage microscopy (HSM), scanning electron microscopy (SEM), differential thermal (DTA) and X-ray diffraction (XRD) analyses. Increasing K₂O content at the expense of SiO₂ was shown to lower the temperature of maximum shrinkage, eventually resulting in early densification of the glass-powder compacts. Lithium metasilicate was the main crystalline phase formed upon heat treating the glass powders with higher amounts of K₂O. In contrast, lithium disilicate predominantly crystallized from the compositions with lower K₂O contents resulting in strong glass–ceramics with high chemical and electrical resistance. The total content of K₂O should be kept below 4.63 mol% for obtaining LD-based glass–ceramics.     

Phase formation in porous liquid phase sintered silicon carbide: Part III: Interaction between Al2O3–Y2O3 and SiC

The structure and phase formation of porous liquid phase sintered silicon carbide (porous LPS-SiC), containing yttria and alumina additives have been studied. The present paper is focused on the system Y–Al–Si–C–O. The systems Al–Si–C–O and Y–Si–C–O have been studied in previous papers [J. Eur. Ceram. Soc. (in press) parts I and II].The reaction products of the interaction of Al₂O₃/Y₂O₃ with SiC and resulting microstructures were analysed by model experiments. The influences of different sintering atmospheres, namely argon and Ar/CO and different temperatures have been investigated. Thermodynamic calculations and sintering experiments reveal that silicides or carbides can be formed in addition to stable oxides. The main parameters controlling the formation of the different reaction products are the free carbon content, the oxygen activity and the temperature.Using CO containing atmospheres, the decomposition of the oxide additives can be effectively suppressed and stable porous LPS-SiC can be produced.     

Dy3+ doped LiCl–CaO–Bi2O3–B2O3 glasses for WLED applications

Dy³⁺ doped calcium bismuth borate glasses were synthesized in the composition range of xLiCl-(30 − x)CaO-20Bi₂O₃-50B₂O₃ + 1 mol% Dy₂O₃ (x = 0, 2, 5, 7, 10 and 15 mol%, LC0, LC2, LC5, LC7, LC10 and LC15 respectively) using conventional melt-quench technique. Broad XRD profiles confirmed non-crystalline nature of synthesized compositions. The compositional dependencies of structural changes (using FTIR spectra), thermal behavior (using DSC thermographs) and optical band gap (using UV–Vis–NIR spectra) were discussed. Photoluminescence (PL) excitation spectra recorded at 577 nm yielded six different excitation peaks belonging to Dy³⁺ ions. The PL emission spectra recorded at 451 nm were analyzed to extract different light emission parameters viz. Y/B ratio, color coordinates, correlated color temperature (CCT) following CIE 1931 chromaticity diagram. The emission colors were found to lie in white light region and lies very close to standard white light emission. The CCT of sample LC10 (5335 K) is closest to CCT of standard white light (5615 K) which depicted the optimized concentration of LiCl for application of these glasses in WLED application.     

Sintering behavior and microwave dielectric properties of 0.67CaTiO3–0.33LaAlO3 ceramics modified by B2O3–Li2O–Al2O3 and CeO2

A low temperature sintering method was used to avoid the relatively high sintering temperatures typically required to prepare 0.67CaTiO₃–0.33LaAlO₃ (CTLA) ceramics. Additionally, CeO₂ was introduced into the CTLA ceramics as an oxygen-storage material to improve their microwave dielectric properties. 0.67CaTiO₃–0.33LaAlO₃ ceramics co-doped with B₂O₃–Li₂O–Al₂O₃ and CeO₂ were prepared by a conventional two-step solid-state reaction process. The sintering behavior, crystal structure, surface morphology, and microwave dielectric proprieties of the prepared ceramic samples were studied, and the reaction mechanism of CeO₂ was elucidated. CTLA+0.05 wt% BLA+3 wt% CeO₂ ceramics sintered at 1360 °C for 4 h exhibited the optimal microwave dielectric properties: dielectric constant (ε_r)=45.02, quality factor (Q×f)=43102 GHz, and temperature coefficient of resonant frequency (τ_f)=2.1 ppm/°C. The successful preparation of high-performance microwave dielectric ceramics provides a direction for the future development and commercialization of CTLA ceramics.     

Catalytic behavior of V2O5 in rechargeable Li–O2 batteries

The possibility of using vanadium pentoxide (V₂O₅) as a catalyst in rechargeable lithium–oxygen (Li–O₂) batteries was studied. A V₂O₅-carbon composite was cast onto Ni foam to form a cathode. Electrochemical cells designed based on the flat cell manufactured by Hohsen Corporation were fabricated. The initial discharge capacity was 715 mA?h?g^?1, and the maximum discharge capacity reached 2,260 mA?h?g^?1 during the twelfth cycle. The cell had high capacity retention during cycling (1.24?% during cycles 2–8). V₂O₅ acted as a catalyst as well as an active material, improving the specific capacity and capacity retention of the non-aqueous Li–O₂ cell more effectively than do other materials.     

Energy Transfer and Spectroscopic Investigation of Dy2O3 Doped Li2O–BaO–GdF3–SiO2 for White Light LED

Glass Physics and Chemistry - LGFDy glasses doped with Dy2O3 (0.1, 0.5, 1.0, 1.5 and 2.0 mol %) were synthesised by conventional melt quenching method and various properties are studied by...     

Quantitative prediction of the structure and properties of Li2O–Ta2O5–SiO2 glasses via phase diagram approach

Tantalum silicate glasses serve as laser host materials to take advantage of their high refractive index and the ability to tailor their physical properties in the design of high-performance photonic and photoelectric components. However, successful attainment of feature control in tantalum-doped materials remains a longstanding problem due to the limited understanding of local structure around the tantalum ions, a problem that lies at the heart of predicting the micro- and macroscopic properties of these glasses. Herein, we present a novel approach for predicting the local structural environments in tantalum silicate glass based on a phase diagram approach. The phase relations and glass formation region of Li₂O–Ta₂O₅–SiO₂ ternary systems are explored to calculate the structure and additive physical properties of lithium tantalum silicate glasses. These measured and calculated results are in good quantitative agreement, indicating that the phase diagram approach can be applied broadly to Li₂O–Ta₂O₅–SiO₂ ternary glass systems. Using the phase diagram approach, the local structure of tantalum can be directly obtained. Each Ta atom is surrounded by six atoms, and its polyhedron, the TaO₆ octahedron, bonds through oxygen to Li and Ta. As a network modifier, Ta⁵⁺ depolymerizes the silicate glass structure by modulating the local structure of lithium atoms in Li₂O–Ta₂O₅–SiO₂ ternary glass system. The compositional dependence of structure in lithium tantalum silicate glasses is quantitatively determined based on the structure of the nearest neighbor congruent compound through the lever rule. These findings offer a precise prediction of tantalum silicate glass properties with quantitative control over local structural environment of the disordered materials.