Experimental and first‐principles study of Ti–C–O system: Interplay of thermodynamic and structural properties

The thermodynamic properties and vacancy formation mechanism of Ti–C–O system were investigated by means of empirical calorimetry method and first‐principles calculations. The heat of combustion of titanium oxycarbides (TiC_1?xO_x, 0≤x≤1) solid solution were first measured by burning the materials in oxygen bomb calorimeter through sophisticated design experimental environment. The mixing enthalpy of the reaction (1?x)TiC + xTiO=TiC_1?xO_x was further calculated based on the measured data. Mixing enthalpy was also calculated via efficient first‐principles method based on the density functional theory. The vacancies in TiC_1?xO_x were described as two kinds of models that are disordered and segregated vacancies in titanium oxycarbides solid solution. The calculation results with segregation model show good agreement with the calorimetric results. The heat capacity values were further calculated to deduce the mixing and formation Gibbs free energy. The additive law of the heat capacity and entropy means that the structure of titanium oxycarbides tends to be in order, and this result shows a good agreement with the segregated model in TiC_1?xO_x. These results are explained on the basis of the interplay between thermodynamic and structural properties, which offered the important theoretic foundation for the novel titanium production process.     

Borate melt structure: Temperature‐dependent B–O bond lengths and coordination numbers from high‐energy X‐ray diffraction

Borate melts containing <20 mol% Na₂O have been studied using high‐energy synchrotron X‐ray diffraction. Temperature dependencies of the mean B–O bond lengths are shown to vary strongly with soda content, by comparison to previous measurements on liquid B₂O₃ and Na₂B₄O₇. Whereas in liquid B₂O₃ linear thermal expansion of the BØ₃ units is observed, with coefficient α_BO = 3.7(2) × 10^?6 K^?1, this expansion is apparently slightly suppressed in melts containing <20 mol% Na₂O, and is dramatically reversed at the diborate composition. These effects are interpreted in terms of changes in the mean B–O coordination number, where the reaction BØ₄^? + BØ₃ ? BØ₃ + BØ₂O^? shifts to the right with increasing temperature. The empirical bond‐valence relationship is used to convert measured bond lengths, r_BO, to coordination numbers, n_BO, including a correction for the expected thermal expansion. This method is more accurate and precise than direct determination of n_BO from peak areas in the radial distribution functions. Gradients of Δn_BO/ΔT = ?3.4(3) × 10^?4 K^?1 close to the diborate composition, and Δn_BO/ΔT = ?0.3(1) × 10^?4 K^?1 for a 13(3) mol% Na₂O melt are observed, in reasonable agreement with Raman spectroscopic observations and thermodynamic modeling, with some quantitative differences. These observations go toward explaining isothermal viscosity maxima and changes in fragility across the sodium borate system.     

Rubber–clay nanocomposite by solution blending

Ethylene vinyl acetate rubber (45% vinyl acetate content, EVA‐45) and organomodified clay (12Me‐MMT) composites were prepared by solution blending of the rubber and the clay. A combination of X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy studies showed that the composites obtained are on the nanometer scale. The measurements of the dynamic mechanical properties for different compositions over a temperature range (?100 to +100°C) showed that the storage moduli of these rubber–clay nanocomposites are higher above the glass to rubber transition temperature compared to the neat rubber. The tensile strength of the nanocomposites is about 1.6 times higher than that of the EVA‐45. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2216–2220, 2003     

Synthesis,structural characterization,and photoluminescence properties of TTB‐type PbTa2O6:Eu3+ phosphor

Undoped and Eu³⁺‐doped tetragonal tungsten bronze (TTB) PbTa₂O₆ phosphors were synthesized by using solid‐state reaction method. Synthesized samples were characterized by XRD, SEM‐EDS, and photoluminescence analyses. XRD results revealed TTB‐type crystal structure with single phase up to 10 mol% Eu³⁺ doping concentration. In SEM‐EDS analyses, elemental composition of Pb decreased with the increasing concentration of Eu³⁺. Emissions at the excitation wavelength of 398.5 nm were observed at 593.2 and 618.8 nm due to ⁵D₀→⁷F₁ transitions and ⁵D₀→⁷F₂ transitions, respectively. Emission increased with the increasing Eu³⁺ doping concentration up to 10 mol% and not observed concentration quenching.     

Microfocus small‐angle X‐ray scattering investigation of the skin–core microstructure of lyocell cellulose fibers

Skin–core microstructures in hydrated lyocell cellulose fibers were investigated using microfocus small‐angle X‐ray scattering (SAXS). Both single fibers and fiber cross sections were observed. In all the fibers studied, a thin skin layer was observed in which the voids were smaller in cross section and better oriented than those in the core. The division between skin and core may not be sharp. A draw ratio of 0.80 gave fibers with voids that were shorter, larger in cross section, and more misoriented than the fibers produced with a draw ratio of 1.68. In contrast, there was little difference in void structure between samples coagulated in water and in 25% amine oxide aqueous solution. The results are explained in the context of the spinodal decomposition, which is thought to occur during coagulation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2799–2816, 2002; DOI 10.1002/app.10256     

Controllable Formation of the Crystalline Phases in Ge–Ga–S Chalcogenide Glass‐Ceramics

We prepared chemically stoichiometric, S‐poor and S‐rich Ge–Ga–S glasses and annealed them at a temperature that was 20°C higher than its respective glass transition temperature. We aimed at tuning the formation of the different crystals in chalcogenide glass‐ceramics. Through systematic characterization of the structure using X‐ray diffraction and Raman scattering spectra, we found that, GeS₂ and GeS crystals only can be created in S‐rich and S‐poor glass‐ceramics, respectively, while all GeS, Ga₂S₃, and GeS₂ crystals exist in chemically stoichiometric glass‐ceramics. Moreover, we demonstrated the homogeneous distribution of the crystals can be formed in the S‐rich glass‐ceramics from the surface to the interior via composition designing. The present approach blazes a new path to control the growth of the different crystals in chalcogenide glass‐ceramics.     

Phase equilibria study and thermodynamic description of the BaO‐CaO‐Al2O3 system

A combined experimental investigation and thermodynamic assessment was performed for the BaO‐CaO‐Al₂O₃ system. By using a high‐temperature equilibration/quenching technique and scanning electron microscopy, electron probe microanalysis, and X‐ray powder diffraction analysis, the phase equilibria at 1500°C and phase stability of BaCa₂Al₈O₁₅ phase were determined. An extensive literature survey was conducted for the experimental and thermodynamic modeling data of the BaO‐CaO‐Al₂O₃ system. According to the literature data and the present measurements, a thermodynamic assessment was made in order to obtain a set of self‐consistent thermodynamic parameters to describe the BaO‐CaO‐Al₂O₃ system. Based on the thermodynamic parameters acquired in this work, isothermal sections at 1100°C, 1250°C, 1400°C, 1475°C, and 1500°C and the BaO·Al₂O₃‐CaO·Al₂O₃ and BaO·6Al₂O₃‐CaO·6Al₂O₃ joints were calculated and compared with the available experimental data.     

Thermodynamic study of a water–dimethylformamide–polyacrylonitrile ternary system

Experimental cloud‐point data were obtained by cloud‐point titration. The phase diagram for a ternary system of water–dimethylformamide–polyacrylonitrile was determined by numerical calculation on the basis of the extended Flory–Huggins theory and was found to agree well with the cloud‐point data. To construct the theoretical phase diagram, three binary interaction parameters were obtained with different methods. The ternary phase diagram was used to investigate the mechanism of fiber formation. The skin–core structure and fingerlike pores in polyacrylonitrile fiber may be effectively eliminated if the composition of the spinning solution is properly chosen, and consequently, homogeneous polyacrylonitrile fiber with a bicontinuous structure and good mechanical properties can be obtained through the spinning process. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Three‐dimensional mapping of crystalline ceramic waste form materials

This work demonstrates the use of synchrotron‐based, transmission X‐ray microscopy (TXM) and scanning electron microscopy to image the 3‐D morphologies and spatial distributions of Ga‐doped phases within model, single‐ and two‐phase waste form material systems. Gallium doping levels consistent with those commonly used for nuclear waste immobilization (e.g., Ba_1.04Cs_0.24Ga_2.32Ti_5.68O₁₆) could be readily imaged. The analysis suggests that a minority phase with different stoichiometry/composition from the primary hollandite phase can be formed by the solid‐state ceramic processing route with varying morphology (globular vs. cylindrical) as a function of Cs content. The results presented in this work represent a crucial step in developing the tools necessary to gain an improved understanding of the microstructural and chemical properties of waste form materials that influence their resistance to aqueous corrosion. This understanding will aid in the future design of higher durability waste form materials.     

Photoluminescence characterization and heat treatment effect on luminescence behavior of BaTa2O6:Dy3+ phosphor

Undoped and Dy³⁺‐doped barium tantalate phosphors were synthesized by the solid‐state reaction method at 1425°C. Also, 10 mol% Dy³⁺‐doped BaTa₂O₆ was sintered between 1150 and 1425°C in order to determine temperature effect on structural and luminescence properties. Afterwards, they were characterized by XRD, SEM‐EDS and photoluminescence (PL) analyses. PL spectra exhibited the excitation peaks between 300 and 440 nm. Two typical emissions were observed at 486.2 nm (blue) and 577.7 nm (yellow) due to the ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions, respectively. Emission intensities increased with increasing doping concentration of Dy³⁺ up to 10 mol% and then decreased due to the concentration quenching effect. Moreover, depending on the increase in heat treatment temperature, the intensity of emission reached maximum at 1425°C. The calculated CIE chromaticity coordinates of phosphors located in the white light region.     

High quality factor microwave dielectric ceramics in the (Mg1/3Nb2/3)O2–ZrO2–TiO2 ternary system

Novel high quality factor microwave dielectric ceramics (1?x)ZrTiO₄?x(Mg_1/3Nb_2/3)TiO₄ (0.325≤x≤0.4) and (ZrTi)_1?y(Mg_1/3Nb_2/3)_yO₄ (0.2≤y≤0.5) with the addition of 0.5 wt% MnCO₃ in the (Mg_1/3Nb_2/3)O₂–ZrO₂–TiO₂ ternary system were prepared, using solid‐state reaction method. The relationship between the structure and microwave dielectric properties of the ceramics was studied. The XRD patterns of the sintered samples reveal the main phase belonged to α‐PbO₂‐type structure. Raman spectroscopy and infrared reflectivity (IR) spectra were employed to evaluate phonon modes of ceramics. The 0.65ZrTiO₄?0.35(Mg_1/3Nb_2/3)TiO₄?0.5 wt% MnCO₃ ceramic can be well densified at 1240°C for 2 hours and exhibits good microwave dielectric properties with a relative permittivity (ε_r) of 42.5, a quality factor (Q×f) value of 43 520 GHz (at 5.9 Ghz) and temperature coefficient of resonant frequency (τ_f) value of ?5ppm/°C. Furthermore, the (ZrTi)_0.7(Mg_1/3Nb_2/3)_0.3O₄?0.5 wt% MnCO₃ ceramic sintered at 1260°C for 2 hours possesses a ε_r of 31.8, a Q×f value of 35 640 GHz (at 6.3 GHz) and a near zero τ_f value of ?5.9 ppm/°C. The results demonstrated that the (Mg_1/3Nb_2/3)O₂–ZrO₂–TiO₂ ternary system with excellent properties was a promising material for microwave electronic device applications.     

Surfactant‐modified feldspar: Isotherm,kinetic, and thermodynamic of binary system dye removal

In this article, surface modification of feldspar using hexadecyltrimethyl ammonium bromide (HDTMA) and its dye removal ability in single and binary systems was studied. Acid Black 1 (AB1) and Acid Red 14 (AR14) were used as model dyes. The monocomponent Langmuir isotherm model was applied to experimental data and the isotherm constants were calculated for both dyes. The monolayer coverage capacities of surfactant‐modified feldspar (HDTMA‐feldspar) for AB1 and AR14 dyes in single solution system were found as 6.369 mg/g and 3.984 mg/g, respectively. It was observed that the equilibrium uptake amounts of AB1 and AR14 dye in binary mixture onto sorbent decreased with increasing concentrations of the other dye resulting in their antagonistic effect. Equilibrium adsorption for binary systems was analyzed by using the Extended Langmuir and Jain and Snoeyink Modified Extended Langmuir models. The rate of kinetic processes of single and binary dye systems onto adsorbent was described by using two kinetics adsorption models. The pseudo‐second‐order model was the best choice among the kinetic models to describe the adsorption behavior of single and binary dyes onto HDTMA‐feldspar. Thermodynamic parameters showed that dye adsorption on HDTMA‐feldspar were exothermic and unspontaneous in nature. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

X‐ray diffraction characterization of the structure of zein–Oleic acid films

Wide‐angle (WAXS) and small‐angle X‐ray scattering (SAXS) studies of dry granular zein, zein fibers, zein–oleic acid resin, and zein–oleic acid films are reported. WAXS patterns showed two diffuse rings for these samples indicative of noncrystalline structures. Measured d‐spacings of ∼ 4.6 Å and ∼ 10.5 Å were found for zein–oleic acid resins and films, consistent with the presence of α‐helical segments. The granular zein and zein fibers had ∼ 4.6‐Å and ∼ 9.5‐Å spacings. Neither the films nor the fibers showed evidence of orientation of the molecular axes. SAXS studies of zein–oleic acid films indicated that the structure of the films was affected by preparation method. Biaxially drawn resin films showed periodicities of ∼ 170 Å along the film surface direction and ∼ 135 Å in the thickness direction, while the cast films had weaker intensity periodicities of ca. 80 Å for all beam directions; a weak, diffuse 45‐Å spacing was also observed for both samples. The 170‐Å periodicity was present in the resin before deformation and following uniaxial deformation. No SAXS periodicity was observed for the granular zein or zein fibers. Several structural models are presented for the resin films that are consistent with reports in the literature that zein, in solution, consist of prism‐like particles consisting of four or more molecules. ? 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1267‐1281, 1999     

Experimental investigation of the LiAlSi2O6‐MgSiO3 and LiAlSi2O6‐CaMgSi2O6 isopleths at 1 atm

The phase diagrams of the LiAlSi₂O₆‐MgSiO₃ and LiAlSi₂O₆‐CaMgSi₂O₆ isopleths were experimentally investigated at 1 atm using the quenching method and differential scanning calorimetry and the phases produced were characterized with the help of X‐ray diffraction and electron probe microanalysis. With the help of thermodynamic optimization, the phase diagrams of both systems were more accurately reported. No detectable solubility of Li₂O in diopside and enstatite was found. However, both systems are not simple binary eutectic systems because their phase equilibria are somewhat complex due to the presence of some β‐spodumene solid solution. In the β‐spodumene solid solution, no notable solubility of MgO and CaO was detected; evidence of significant solubility of SiO₂ was confirmed.     

Adhesion properties of phosphate‐ and siloxane‐containing polyurethane dispersions to steel: An analysis of the metal–coating interface

Polyurethane dispersions containing phosphate and siloxane groups in the main chain were investigated as possible self‐assembling metal coatings. Improved adhesion of the polymer to the metal was observed because of the formation of an insoluble metal phosphate layer at the metal–coating interface. The neutralizing amine of the dispersions affected the formation of this metal phosphate, and the metal phosphate formation was dependent on the curing temperature and boiling point of the amine used for neutralization. A crosscut comparative study of adhesion proved that the phosphate‐containing coatings had better adhesion because of the formation of ionic bonds at the metal–coating interface. A solid‐state adhesion prediction method based on thermodynamic considerations was used. The results of the solid‐state adhesion method correlated well with that obtained from the crosscut adhesion test method. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 900–907, 2003     

Local structure of the MgxNixCoxCuxZnxO(x=0.2) entropy‐stabilized oxide: An EXAFS study

Entropy‐stabilized oxides (ESOs) provide an alternative route to novel materials discovery and synthesis. It is, however, a challenge to demonstrate that the constituent elements in an entropy‐stabilized crystal are homogeneously and randomly dispersed among a particular sublattice, resulting in a true solid solution with no evidence of local order or clustering. In this work, we present the application and analysis of extended X‐ray absorption fine structure (EXAFS) on the prototype ESO composition Mg_xNi_xCo_xCu_xZn_xO (x=0.2). In so doing, we can quantify the local atomic structure on an element‐by‐element basis. We conclude that local bond lengths between metal and oxygen vary around each absorbing cation, with notable distortion around the Cu–O polyhedra. By the second near neighbor (i.e., the cation‐cation pair), interatomic distances are uniform to the extent that the collected data can resolve. Crystal models that best fit the experimental scattering data include cations that are distributed randomly on an FCC sublattice with minimal positional disorder, with an interleaved FCC anion sublattice with oxygen ions displaced from the ideal locations to accommodate the distortions in the cation polyhedra. Density functional theory calculations of the ESO system yield a significant broadening in the positional distribution for the oxygen sublattice compared to that for the cation sublattice for all peaks, showing consistency with the conclusion from the experimental data that the distortion from an ideal rock salt structure occurs primarily through disorder in the oxygen sublattice.     

High‐temperature oxidation of aniline to highly ordered polyaniline–sulfate salt with a nanofiber morphology and its use as electrode materials in symmetric supercapacitors

In this study, for the first time, aniline was oxidized by ammonium persulfate (APS) at higher temperatures without any protic acid, and APS acted as an oxidizing agent and a protonating agent. During the oxidation of aniline by APS, sulfuric acid formation occurred, and the sulfuric acid was incorporated into polyaniline (PANI) as a dopant. PANI–sulfate samples were characterized by IR spectroscopy, X‐ray diffraction, and scanning electron microscopy techniques. In this methodology, a highly ordered PANI–sulfate salt (H₂SO₄) with a nanofiber morphology was synthesized. Interestingly, a PANI base was also obtained with a highly ordered structure with an agglomerated netlike nanofiber morphology. PANI–H₂SO₄ was used as an electrode material in a symmetric supercapacitor cell. Electrochemical characterization, including cyclic voltammetry (CV), charge–discharge (CD), and impedance analysis, was carried out on the supercapacitor cells. In this study, the maximum specific capacitance obtained was found to be 273 F/g at 1 mV/s. Scan rate from cyclic voltammetry and 103 F/g at 1 mA discharge current from CD measurement. Impedance measurement was carried out at 0.6 V, and it showed a specific capacitance of 73.2 F/g. The value of the specific capacitance and energy and power densities for the PANI–H₂SO₄ system were calculated from CD studies at a 5‐mA discharge rate and were found to be 43 F/g, 9.3 W h/kg, and 500 W/kg, respectively, with 98–100% coulombic efficiency. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Self‐assembling metal coatings from phosphated and siloxane‐modified polyurethane dispersions: An analysis of the coating–air interface

Polyurethane dispersion coatings containing phosphate and siloxane chains were evaluated for their self‐assembling properties for a single‐coating system. Dynamic contact angles (DCAs) and X‐ray photoelectron spectroscopy (XPS) were used to study the coating–air interface. The siloxane chains were the predominant species on the surfaces of the coatings. The wetting properties of the coating–air interface were reversed when the coated panels were immersed in an ionic solution, and the decrease in hydrophobicity was linear with time. Results from XPS and DCA analyses were similar. The self‐assembling properties of the coatings could be useful in the development of hydrophobic coatings from hydrophilic polymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 893–899, 2003