Synthesis and characterization of Na2O–CaO–SiO2 glass–ceramic

The Na₂O–CaO–SiO₂ ternary glass–ceramic with the composition of 49 mass% Na₂O, 20 mass% CaO, and 31 mass% SiO₂ was prepared by the conventional method. The ternary glass–ceramic was characterized using X-ray diffraction (XRD), differential thermal analysis (DTA), thermogravimetric analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy techniques. The Na₂CaSiO₄ phase, having the cubic crystal system, with the crystallite size of 25.14 nm and lattice parameter of 0.7506 nm was determined from the XRD pattern. The activation energy of the glass–ceramic calculated from the DTA curves was found to be 162.02 kJ mol^?1. The Avrami exponent was found to be ~2 indicating a one-dimensional growth process. The mass loss percent from ambient temperature to 1,173 K is less than 1 %. The density was calculated to be 2,723 kg m^?3. The fine-grained microstructure with the particle sizes less than 1 μm was confirmed by the scanning electron microscope micrograph.     

Kinetics of nonisothermal crystallization of Cs2O–Fe2O3–P2O5 glasses

The crystallization kinetics of Cs₂O–Fe₂O₃–P₂O₅ glasses containing 12.5–27 mol% Cs₂O were studied by using differential scanning calorimetry under nonisothermal conditions. Strong dependence of activation energy with temperature was observed, indicating the complex nature of the crystallization process. The various crystallization products were identified by X-ray diffraction technique. CsFeP₂O₇ was found to be the major crystalline phase in all cases. The overall activation energy obtained by classical model-free kinetic method was compared with that of isoconversional method; and from the results, the dependence of activation energy on extent of reaction and average temperature was delineated.     

Preparation and electrocatalytic performance of Fe–N–C for electroreduction of H2O2

Fe–N–C catalysts were prepared through metal-assisted polymerization method. Effects of carbon treatment, Fe loading, nitrogen source, and calcination temperature on the catalytic performance of the Fe–N–C for H₂O₂ electroreduction were measured by voltammetry and chronoamperometry. The Fe–N–C catalyst shows optimal performance when prepared with pretreated active carbon, 0.2 wt.% Fe, paranitroaniline (4-NA) and one-time calcination. The Fe–N–C catalyst displayed good performance and stability for electroreduction of H₂O₂ in alkaline solution. An Al–H₂O₂ semi-fuel cell was set up with Fe–N–C catalyst as cathode and Al as anode. The cell exhibits an open-circuit voltage of 1.3 V and its power density reached 51.4 mW cm⁻² at 65 mA cm⁻².     

Thermal stability of Li2O–SiO2–TiO2 gels evaluated by the induction period of crystallization

To evaluate the thermal stability of materials, various criteria have been used. Not only the simple parameters, as characteristic temperatures, but also the combined criteria E/RT _p , k _f (T) and criterion based on the length of induction period of crystallization have been taken into account. Four gels with the composition Li₂O–2SiO₂–nTiO₂ (n = 0.00, 0.03, 0.062, and 0.1) were prepared and the validity of the criteria was tested by applying them to these gels. The results indicate that thermal stability of the studied gels decrease with amount of TiO₂.     

Direct crystallization of silicate–phosphate glasses of NaCaPO4–SiO2 system

The subject of the study was silicate–phosphate glasses of NaCaPO₄–SiO₂ system which are precursors of glass–crystalline materials. Glass–crystalline materials of NaCaPO₄–SiO₂ system obtained via crystallization of glasses belong to a group of the so-called bioactive materials. In order to obtain glass–crystalline materials with pre-established parameters, it is necessary to conduct crystallization of glasses at specific conditions. In order to design direct crystallization process properly, it is necessary to know the structure and microstructure of the glassy precursor. Microscopic investigation showed that liquation takes place in all the studied glasses. Based on DSC examinations, it has been found out that crystallization of the glasses of NaCaPO₄–SiO₂ system is a multistep process. The presence of several clearly separated exothermic peaks in DSC curves of investigated glasses makes it possible to crystallize only the separated phase with the matrix remaining amorphous or vice versa. Conducted detailed X-ray and spectroscopic studies of the materials obtained by heating in a gradient furnace (in the temperature specified on the basis of DSC) showed that separated phase and matrix crystallizes separately. Therefore, bioactive glass–crystalline materials can be obtained due to the existence of the phase separation phenomenon and pre-established sizes of the crystalline phase.     

Influence of SrO content on microstructure and crystallization of glazes in the SiO2–Al2O3–CaO–MgO–K2O system

The effect of the SrO addition on the microstructure and structure of the glazes from the SiO₂–Al₂O₃–CaO–MgO–K₂O system was investigated in this study. The results were obtained by testing the ability of the frits crystallization, the stability of the crystallizing phases during the single-step fast-firing cycle depending on their chemical composition and the effect of addition of strontium oxide. Differential scanning calorimetry (DSC) curves showed that all glazes crystallized, and diopside and anorthite were mainly identified as dominant phases in the obtained glazes, while the size and amount of each depended on the amount of SrO introduced. The thermal characteristic of the frits was carried out using DSC, and crystalline phases were determined by X-ray diffractometry. The glaze microstructure was investigated by scanning electron microscopy and transmission electron microscopy. Additional information on the microstructure of frits was derived from spectroscopic studies in the mid-infrared range.

     

Crystallization behaviour of TiO2–ZrO2 composite nanoparticles

Nano-composite TiO₂?CZrO₂ materials were prepared via sol?Cgel processes by hydrolysis of mixtures of titanium- and zirconium-containing alkoxides with TiO₂:ZrO₂ ratios of 1:2, 1:1, 2:1, and 10:1. Precipitated powders were dried at room temperature and annealed in ambient air at temperatures between 350 and 500?°C for 4?h. Pure TiO₂ and ZrO₂ powders were synthesized for comparison. Samples were characterized with X-ray diffraction (XRD) and X-ray absorption near edge fine structure (XANES). The detailed analysis of those data provides the crystalline and amorphous phase composition as well as the crystallite particle size. According to XRD and XANES analysis, only the two pure oxide samples and one of the composite samples with a composition TiO₂:ZrO₂?=?10:1, crystallized. Both titania containing powders, the pure TiO₂ and the TiO₂:ZrO₂?=?10:1 composite, were found to crystallize in the anatase structure. ZrO₂ was found to stay amorphous in the composites but crystalline in the pure oxide. In the crystallized composite TiO₂:ZrO₂?=?10:1 sample, the concentration of the amorphous phase remains larger than in pure TiO₂ samples, but the crystallite size was found to be nearly constant with increasing annealing temperature in contrast to the increasing particle size of pure TiO₂-samples. Pure TiO₂ precipitates are amorphous directly after preparation, however they crystallize after 6?month storage at ambient conditions by aging. Such an aging was not observed for the TiO₂:ZrO₂ composites.     

Electronic Energy Structure of a Series of Chalcopyrite-Like Compounds AgGaS2–CdGa2S4–InPS4

The effect of pseudovacancies on the density of electronic states of valence electrons in AgGaS₂, CdGa₂S₄, and InPS₄ is studied both experimentally, by means of X-ray spectroscopy, and theoretically, by calculating the partial densities of electronic states using the local coherent potential. The compounds under study are the derivatives of the sphalerite structural type (doubled cell) with gradually increasing deficiency of metals from to and further to , where is a vacancy. The environment of the metal atoms remains tetrahedral, while that of the sulfur atoms changes with increasing number of vacancies from four (AgGaS₂) to three (CdGa₂S₄) and two (InPS₄). For the compounds under study, SK and PK X-ray emission and absorption spectra were recorded at a resolution of about 0.2 eV, and the local partial densities of states were calculated for all components of the compounds. The theoretical curves practically coincide in shape and energy position of fine structure elements with the corresponding experimental curves. This allowed reliable conclusions about the energy positions of electronic states at the top of the valence band and about the dependence of the SK emission and absorption spectra in the series of compounds under study on variation of the crystal structure and on the chemical composition of the nearest surroundings of sulfur atoms.     

Impedance spectroscopy of V2O5–Bi2O3–BaTiO3 glass–ceramics

The glasses within composition as: (80 − x)V₂O₅/20Bi₂O₃/xBaTiO₃ with x = 2.5, 5, 7.5 and 10 mol% have been prepared. The glass transition (T_g) increases with increasing BaTiO₃ content. Synthesized glasses ceramic containing BaTi₄O₉, Ba₃TiV₄O₁₅ nanoparticles of the order of 25–35 nm and 30–46 nm, respectively were estimated using XRD. The dielectric properties over wide ranges of frequencies and temperatures were investigated as a function of BaTiO₃ content by impedance spectroscopy measurements. The hopping frequency, ω_h, dielectric constant, ε′, activation energies for the DC conduction, E_σ, the relaxation process, E_c, and stretched exponential parameter β of the glasses samples have been estimated. The, ω_h, β, decrease from 51.63 to 0.31 × 10⁶ (s⁻¹), 0.84 to 0.79 with increasing BaTiO₃ respectively. Otherwise, the E_σ, increase from 0.279 to 0.306 eV with increasing BaTiO₃. The value of dielectric constant equal 9.5·10³ for the 2.5BaTiO₃/77.5V₂O₅/20Bi₂O₃ glasses-ceramic at 330 K for 1 KHz which is ten times larger than that of same glasses composition. Finally the relaxation properties of the investigated glasses are presented in the electric modulus formalism, where the relaxation time and the respective activation energy were determined.     

Liquid–vapor phase equilibria of three-component systems of propanol-2–propanoic acid esters

The boiling points of solutions of three-component systems formed by propanol-2 and propanoic acid esters are measured at different pressures by means of ebulliometry. The coefficients of the activity of the solutions’ components are measured using Wilson and nonrandom two-liquid (NRTL) equations. The results from calculations are in line with the experimental data.

     

Effect of zinc oxide on microhardness and sintering behavior of MgO–Al2O3–SiO2 glass–ceramic system

Glass–ceramic in the MgO–Al₂O₃–SiO₂ system with crystallization ability of gahnite (ZnO·Al₂O₃) and mullite were synthesized. It was found that the glass–ceramic containing gahnite phase had desirable mechanical behavior and reached to an acceptable hardness and density. The compositions were designed based on magnesium oxide replacement (from MgO–Al₂O₃–SiO₂ glass–ceramic system) with zinc oxide. Glass–ceramics were characterized by DTA, X-ray diffraction and scanning electron microscopy. Heat treatment at 1100 °C cause form gahnite crystals in glass–ceramic. Microhardness increased with increasing gahnite crystals. To achieve good mechanical properties, the initially formed high gahnite phase must transform.     

Structural studies of copper-containing multicomponent glasses from the SiO2–P2O5–K2O–CaO–MgO system

Multicomponent glasses from the SiO₂–P₂O₅–K₂O–MgO–CaO–CuO system acting as slow release fertilizers were synthesized by the melt-quenching technique. The influence of CuO and P₂O₅ addition on the structure of glasses was evaluated by FTIR, Raman, ³¹P, and ²⁹Si MAS NMR spectroscopies. The studies showed that the Cu²⁺ ions displacing Ca²⁺ ions and Mg²⁺ ions in the structure of glass prefer to associate with the phosphorus Q¹ species, forming the Q⁰ species with chemically stable POCu bonds. This is accompanied by the reduction of the degree of polymerization of the phospho-oxygen sub-network, with a simultaneous increased degree of polymerization of the silico-oxygen sub-network of the silicate–phosphate glasses.     

Crystallization, mechanical properties and in vitro bioactivity of sol–gel derived Na2O–CaO–SiO2–P2O5 glass–ceramics by partial substitution of CaF2 for CaO

The partial substitution of CaF₂ for CaO in the Na₂O–CaO–SiO₂–P₂O₅ system was conducted by the sol–gel method and a comparison of the glass–ceramic properties was reported. Based on thermogravimetric and differential thermal analysis, the gels were sintered with a suitable heat treatment procedure. The glass–ceramic properties were characterized by X-ray diffraction, fourier-transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectrometer and so on, and the bioactivity of the glass–ceramic was evaluated by in vitro assays in simulated body fluid. Results indicate that with the partial substitution of CaF₂ for CaO in glass composition, the volume density, apparent porosity, bending strength and microhardness of the glass–ceramics have been significantly improved. Furthermore, CaF₂ promotes glass crystallization which does not inhibit the glass–ceramic bioactivity.     

Microcalorimetric Evaluation of Precipitation in Cu–2Be–0.2Mg

Beryllium precipitation from the Cu-rich matrix in a Cu–2 mass% Be–0.2 mass% Mg alloy homogenized and quenched from 1073 K was studied by differential scanning calorimetry (DSC). The DSC traces showed two main exothermic effects, A and B, each comprising two subeffects: A₁ and A₂ , and B₁ and B₂ respectively. Effects A₁ and A₂ correspond to the precipitation of GP zones and subsequent overlapping and independent precipitation of the phase. Only at very low heating rates can be inherited from GP zones. Effects B₁ and B₂ correspond to heat evolved during transitions to the states with and phases, respectively. Heat effect A can be quantitatively described in terms of solid solubilities before and after precipitation, and of the precipitation heats of the phases involved. The heat content of the combined GP zone/ phase precipitation effect was proportional to the number of beryllium atoms precipitated, yielding an average value of 21 kJ mol^–1 beryllium for beryllium precipitation. It was shown that the phase arises from the combined transition from states with GP zones and phases, whereas arises from the transition of states with and phases. The apparent activation energies associated with GP zones and , and phases are 1.16±0.08, 1.18±0.07, 1.37±0.08 and 1.74±0.09 eV, respectively. These values are discussed in terms of the mobility of dissolved atoms related to the concentrations of excess vacancies and solute-vacancy complexes, and the direction of plate-like precipitate growth (either normal or perpendicular to the plate). It is inferred that the main roles of magnesium are to decrease the amount and rate of GP formation, to enhance the volume fraction of and to suppress the discontinuous precipitation of .This revised version was published online in November 2005 with corrections to the Cover Date.     

Raman spectroscopic study of CuO–V2O5–P2O5–CaO glass system

In order to evidence the structural changes induced by CuO and V₂O₅ in the phosphate glass network and their modifier or former role, x(CuO·V₂O₅)(100 − x)[P₂O₅·CaO] glass system was prepared and investigated using Raman spectroscopy (0 ≤ x ≤ 40 mol%).Raman spectra of the studied glasses present the specific bands of the phosphate glasses at low concentration of transition metal (TM) ions, but at higher concentration (x > 7 mol%) a strong depolymerization of the phosphate network appears; non-bridging oxygen atoms are involved in VOP and CuOP bonds and new short units are formed. For a high concentration of V₂O₅ (x > 10 mol%) the Raman bands of V₂O₅ prevail in the spectra; this fact suggests that vanadium oxide imposes its structural units in the network acting thus as a network glass former.2D correlation analysis was also applied for the concentration-dependent Raman spectra in order to verify the assignments of the vibration modes and to find correlations in the changes induced by TM ions content. 2D correlation maps indicate a good correlation between the bands at ∼705 cm⁻¹ assigned to POP stretching vibration and at ∼1175 cm⁻¹ assigned to PO₂ groups which suggest the depolymerization of the phosphate network. The correlation between the 1270 cm⁻¹ and 930 cm⁻¹ bands also suggests that V₂O₅ oxide is responsible for PO bonds breaking and POV formation.     

The effect of mechanical activation on the thermal reactions of P2O5–Al2O3–Fe2O3–Na2O phosphate glasses

The effect of mechanical activation on the structure and thermal reactions of glasses has been studied on the example of Na–Al–Fe phosphate glasses. These glasses are used in nuclear technology for immobilization of radioactive waste. The glasses were activated by grinding in a planetary mill. Mechanical activation causes a decrease of the T _g temperature as well as of the glass crystallization temperature. The type of crystalline phases formed and the quantitative proportions between them are changing. Analysis of inter-atomic interactions in the structure of glass was applied to explain the observed regularities governing the crystallization of the activated glasses.     

Cooling curve thermal analysis of Al–Mg2Si–Cu–xSr composite

Journal of Thermal Analysis and Calorimetry - In situ composites are today being considered for industrial use, owing to the fewer production steps involved, lower production cost, and better...     

Effect of TiO2 and SrO additions on some physical properties of 33Na2O–xSrO–xTiO2–(50 − 2x)B2O3–17P2O5 glasses

By means of the conventional quenching route, the glass series 33Na₂O–xSrO–xTiO₂–(50 ? 2x)B₂O₃–17P₂O₅ (x = 0–12.5 mol%) were prepared. The amorphous state of samples was verified by X-ray diffraction (XRD). Density, molar volume, micro-hardness, glass transition temperature (T _g), and crystallization temperature (T _c) parameters are determined for each glass. The results show that they depend strongly on the chemical compositions. The structure approach of the glasses is determined by Infrared spectroscopy (IR). This investigation highlights that the glassy-matrix contains various phosphate and borate structural units. The crystallization of the high-TiO₂ glasses by heat-treatments favors the formation of titanate phosphate Na₄TiO(PO₄)₂ or Sr_0.5Ti₂(PO₄)₃ along with Sr₃(PO₄)₂ inside the glass-matrix.     

Tandem intramolecular Diels–Alder/retro-Diels–Alder cycloaddition of 2H-chromen-2-one as dienes with the expulsion of CO_2

To study the intramolecular Diels-Alder cycloadditon of 2H-chromen-2-one as a diene, a series of chiral N-allyl-N-benzylamides that contain a 2H-chromen-2-one moiety were designed for the synthesis of benzo[f]isoindol-1-ones via an intramolecular Diels-Alder and a subsequent retro-Diels-Alder cycloaddition with the expulsion of CO₂. Both the yield (80%-89%) and absolute stereocontrol of the tandem reaction were high when an electron-withdrawing group was attached to the dienophile. The double bond in the styrene substructure remained in the products could be further derivatized by dihydroxylation.