On the solubility of lanthanum oxide in molten alkali fluorides

The solubilities of lanthanum oxide in LiF, NaF, KF and eutectic melt LiF-NaF-KF (46.5 mole% LiF; 11.5 mole% NaF and 42.0 mole% KF) were measured in order to find the suitable electrolyte for electrodeposition of lanthanum. Solidus-liquidus lines were obtained by the method of thermal analysis. The solubility of lanthanum oxide in alkali fluorides is rather low and decreases in the order LiF>NaF>KF. It was found that lanthanum oxide reacts with the components of the melt. LaOF and alkali metal oxide are formed during dissolution of La₂O₃ in the melt.     

Hydrothermal synthesis of zinc silicates from borosilicate glasses and from mixtures of zinc oxide and silica

The formation of sauconite and hemimorphite from glasses and oxide precursors in aqueous solution at 150–200°C is described. A tentative schematic stability diagram for a portion of the system Na₂O-ZnO-SiO₂-H₂O at 150°C is presented. The relevance of this work to the use of a sodium zinc borosilicate glass as a matrix for the immobilization of nuclear fuel reprocessing wastes is discussed briefly.     

Effect of silver on phase separation and crystallization of niobium oxide containing glasses

Effect of silver introduction in sodium phosphate and sodium borophosphate glasses containing large amount of niobium oxide have been investigated using differential scanning calorimetry and XRD. Same sodium niobate phase in the Nb₂O₅-NaNbO₃ based solid solution have been observed following two heat treatments designed for nucleation and growth of the crystalline phase. Silver introduction in the glass composition is clearly responsible for increasing the crystallization rate. Its effect after nucleation and crystallization treatments has been shown. Phase metastable separation is occurring during heat treatment with formation of a phosphate rich and niobium rich phase. Crystallization effect on optical transparency of glasses and on Raman scattering response have been investigated.     

Cerium influence on the thermal properties and structure of high-alkaline borosilicate glasses

Journal of Thermal Analysis and Calorimetry - The influence of cerium oxide on the thermal properties and the glass structure has been studied for the...     

Formation of quantum-size PbTe microcrystals in sol-gel derived silica and borosilicate glasses

PbTe-doped silica and borosilicate glasses with the particle size ranging from 2 to 15 nm were prepared by the sol-gel method. Under a reducing H₂ gas atmosphere, PbTe microcrystalline phase was produced at a temperature of about 400°C via the initial Te crystalline phase formed at a low temperature, around 300°C. In borosilicate glasses, PbTe microcrystals were found to have a higher growth rate than in silica glasses. The absorption edge was shifted from the infrared to near visible range with a decrease in particle size due to the quantum-size confinement effect.     

电感耦合等离子体原子发射光谱法测定钼镧合金中镧元素

采用盐酸-硝酸溶解钼镧合金样品,建立电感耦合等离子体原子发射光谱法（ICP-AES）测定钼镧合金中镧元素的分析方法,给出影响测量结果的不确定度分量。选择379.478nm为镧的分析谱线,通过基体匹配法消除基体钼的干扰。在优化条件下对钼镧合金样品进行测定,线性相关系数在0.999以上,定量下限为0.048%,测定结果的相对标准偏差（RSD,n=11）小于3%,回收率为93.00%~105.00%。该方法快速、准确,可以满足实际生产中钼镧合金样品的测定要求。     

Spectroscopic ellipsometry study of CVD molybdenum oxide films: effect of temperature

The optical properties of CVD MoO₃ films were studied by ellipsometry in the spectral range 280–820 nm. The films were deposited on silicon substrates by pyrolytic decomposition at atmospheric pressure of Mo(CO)₆ at 150 and 200 °C. To optimize the film structure, annealing was performed at temperatures of 300 and 400 °C. The refractive index for as-deposited MoO₃ films varies within 1.8–2.2 and the optical band gap energies in the range 2.87–2.98 eV. After annealing, the latter values slightly increase to 2.85–3.05 eV, depending on the annealing temperature. The band gap energies are typical for a polycrystalline material. Peaks in the spectral dependence of the absorption coefficient were observed. Their position and intensity are found to be affected by the process temperature. Electronic Publication     

Avrami exponent of crystallization in tellurite glasses

Nucleation process and crystal growth for three samples of the (20-x)Li₂O–80TeO₂–xWO₃ glass system were studied using X-ray diffraction and differential scanning calorimetry techniques. X-ray diffraction data confirmed the amorphous characteristic of the as-quenched samples and indicated the growth of crystalline phases formed due to the thermal treatment for annealed samples. These results reveal the presence of three distinct γ-TeO₂, α-TeO₂ and α-Li₂Te₂O₅ crystalline phases in the TL sample, and two distinct α-TeO₂ and γ-TeO₂ crystalline phases in the TLW5 and TLW10 samples. The activation energy and the Avrami exponent were determined from DSC measurements. The activation energy values X-ray diffraction data of the TLW10 glass sample suggest that γ-TeO₂ phase occur before the α-TeO₂. The results obtained for the Avrami exponent point to that the nucleation process is volumetric and that the crystal growth is two or three-dimensional.     

Study of glassy microporous filters in the sodium borosilicate glasses with appropriate carriers

Summary DúThe aim of this work is to prepare a porous filter composed of two porous layers: macro-porous carrier and micro-porous sodium borosilicate (NBS) glass with TiO₂ additive (NBST glass), a Vycor-type glass. In the present work we prepared the macroporous support from the same material (NBST glass) as the upper microporous layer and then by sintering both parts to produce the required composite. This work introduces the results of experiments in the preparation of micro-porous filter on NBST glass base, laid on macro-porous carrier. After sintering of scrap NBST glass, porous samples were prepared to be used as carriers for micro-porous samples of phase-separated NBST glass. In other cases, the following carrier materials were used: a) frita SIMAX, b) Al₂O₃. The properties of the NBST glass and the changes in the glass structure with temperature were studied in order to determine the optimal sintering temperature of the prepared glasses. For the development of the sintered glasses, valuable information was obtained from heating microscopy (HM) and scanning electron microscopy (SEM) studies. The combination of the HM and SEM results with the measurements of the micro-hardness and density directed to the further study of the phase separated NBST glasses.     

Redox behavior of molybdenum and tungsten in phosphate glasses

In this work, vitreous samples were prepared in the binary system (100 - x)NaPO3-xMO3 with M = Mo and W and x varying from 10 to 60. The transmittance properties in the UV, visible, and near-infrared were monitored as a function of MO3 concentration. In both cases, an increase in the amount of transition metal results in an intense and broad absorption band in the visible and near-infrared attributed to metal reduction under synthesis conditions. It was shown that this large absorption can be partially or totally removed using specific oxidizing agents or by improving synthesis parameters such as melting temperature or cooling rate of the melt. In addition, structural investigations by Raman and X-ray absorption spectroscopy suggest that reduction only occurs when the metal cation is in octahedral geometry and that the transmittance improvement is not related with any structural changes. These results were explained in terms of thermodynamic equilibrium of redox species in the melt and allowed to obtain for the first time transparent and chemically stable glasses containing high concentrations of MO3 with transition metals in octahedral geometry inside the glass network.     

Mechanism of RuO2 crystallization in borosilicate glass: an original in situ ESEM approach

Ruthenium, a fission product arising from the reprocessing of spent uranium oxide (UOX) fuel, crystallizes in the form of acicular RuO(2) particles in high-level waste containment glass matrices. These particles are responsible for significant modifications in the physicochemical behavior of the glass in the liquid state, and their formation mechanisms are a subject of investigation. The chemical reactions responsible for the crystallization of RuO(2) particles with acicular or polyhedral shape in simplified radioactive waste containment glass are described. In situ high-temperature environmental scanning electron microscopy (ESEM) is used to follow changes in morphology and composition of the ruthenium compounds formed by reactions at high temperature between a simplified RuO(2)-NaNO(3) precursor and a sodium borosilicate glass (SiO(2)-B(2)O(3)-Na(2)O). The key parameter in the formation of acicular or polyhedral RuO(2) crystals is the chemistry of the ruthenium compound under oxidized conditions (Ru(IV), Ru(V)). The precipitation of needle-shaped RuO(2) crystals in the melt might be associated with the formation of an intermediate Ru compound (Na(3)Ru(V)O(4)) before dissolution in the melt, allowing Ru concentration gradients. The formation of polyhedral crystals is the result of the direct incorporation of RuO(2) crystals in the melt followed by an Ostwald ripening mechanism.     

Surface and bulk crystallization in non-isothermal devitrification of glasses

The surface and bulk crystallization of Li₂O · 2 SiO₂ glass has been studied by differential thermal analysis and the influence of the specific surface area of the sample and the nucleation heat treatment on the crystallization kinetics is pointed out. The kinetic parameters were also evaluated from the DTA curves and related to the crystallization mechanism. The results agree well with the isothermal data reported in the literature.     

Understanding cellulose dissolution: effect of the cation and anion structure of ionic liquids on the solubility of cellulose

The effect of ionic liquids (ILs) on the solubility of cellulose was investigated by changing their anions and cations. The structural variation included 11 kinds of cations in combination with 4 kinds of anions. The interaction between the IL and cellobiose, the repeating unit of cellulose, was clarified through nuclear magnetic resonance (NMR) spectroscopy. The reason for different dissolving capabilities of various ILs was revealed. The hydrogen bonding interaction between the IL and hydroxyl was the major force for cellulose dissolution. Both the anion and cation in the IL formed hydrogen bonds with cellulose. Anions associated with hydrogen atoms of hydroxyls, and cations favored the formation of hydrogen bonds with oxygen atoms of hydroxyls by utilizing activated protons in imidazolium ring. Weakening of either the hydrogen bonding interaction between the anion and cellulose, or that between the cation and cellulose, or both, decreases the capability of ILs to dissolve cellulose.     

Formation of borosilicate glasses from silicon alkoxides and metaborate esters in dry non-aqueous solvents

The reaction of metaborate esters (RO)₃B₃O₃ [R = Me, Et, ClCH₂CH₂–, Cl₃CCH₂–, ClCH₂CH₂CH₂–, (ClCH₂)₂CH–] with Si(OR)₄ (R = Me, Et), either neat or in dry propan-2-one or dry THF at room temperature, led to gels which when dried and heated in air for 20 mins at 600°C afforded borosilicate glasses in high ceramic yields. The dried gels and glasses were characterized by elemental analysis, TGA, IR, and powder XRD, and solid-state MAS ²⁹Si and ¹¹B NMR. The gelling reaction was investigated by solution ¹¹B and ²⁹Si NMR. These NMR studies indicated B–O–Si reaction intermediates and a mechanism involving alkoxy exchange and various condensation/elimination reactions of the borosilicate esters have been proposed.     

Synergism between molybdenum and lanthanum in the disproportionation of hydrogen peroxide into singlet oxygen

The catalytic disproportionation of hydrogen peroxide into singlet molecular oxygen was studied using the combined action of lanthanum(III) and molybdenum(VI). A synergistic effect was observed between both metals, resulting in a strong acceleration of the H2O2 disproportionation. An optimum in the catalytic activity was found at La/Mo and La/NaOH molar ratios of 4/1 and 1/3, respectively.