Crystalline Solution in the System MgO-Mg,SiO4,-MgAl2,O4,

Crystalline solubility relations in the system MgO-Mg₂SiO₄MgAl₂O₄ (periclase-forsterite-spinel) were studied using coprecipitated gels as starting materials. The substitution 2Al = Mg + Si was investigated along the join Mg₂SiO₄-Mg-Al₂O₄,. At 1720°C the maximum crystalline solution in forsterite is about 0.5 mole % MgAI₂O₄, and in spinel it is slightly more than 5.0 mole % Mg₂SiO₄. The solubility of MgO in forsterite was 0.5 mole % at 1860°C, whereas more than 11 mole % Mg₂SiO₄ can be dissolved in the periclase structure at this temperature. Ternary crystalline solution exists in the periclase structure to a composition of Mg_0.853Al_0.063Si_0.026O at 1710°C.     

Thermochemistry of Charge-Coupled Substitutions in Silicate Glasses: The Systems Ml/nn+ AlO2-SiO2 (M = Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Pb)

Enthalpies of solution of framework aluminosilicate glasses x M_{l/ n} ^{n +} AlO₂-(1- x )SiO₂ (M = Cs, Rb, K, Na, Li, Ba, Pb, Sr, Ca, Mg) in molten 2PbO.B₂O₃ near 973 K were measured. The sequence above represents increasing ability of the nonframework cation M to bond to the bridging oxygen. In that sequence, the enthalpy of the substitution Si⁴⁺→+ Al³⁺+ 1/ n M ^{n +} in the glass becomes less exothermic, the enthalpy of vitrification increases, and the tendency toward glass-glass immiscibility becomes more pronounced. These parameters correlate smoothly with the ionic potential, z/r , of the substituting cation.     

Morphology,mechanical, and dielectric breakdown properties of PBT/PET/TPE,PBT/PET/PA66, PBT/PET/LMPE,and PBT/PET/TiO2 blends

The morphology and thermal behavior of tertiary blends of poly(butylene terephthalate) [PBT]/poly(ethylene terephthalate) [PET] alloy resin (Alloy)/thermoplastic elastomer (TPE), Alloy/nylon 66 (PA66), Alloy/low molecular weight polyester (LMPE), and Alloy/titanium dioxide (TiO₂) have been investigated by scanning electron microscopy, differential scanning calorimetry, and thermogravimetry (TG). In case of TPE and LMPE containing blends did not show any morphological change compared with Alloy whereas for PA66 containing blends, the size of the dispersed phase increased with the increase the PA66 contents. The crystallization peak of Alloy/TPE blends became undetectable with an increasing TPE content. In contrast, the crystallization temperature (T_c1) of Alloy/PA66, Alloy/LMPE, Alloy/TiO₂ blends increased significantly as the PA66, LMPE, and TiO₂ content increases. TG traces show a significant shift of the weight loss towards higher temperature for Alloy/TiO₂ blend whereas Alloy/TPE, Alloy/PA66 and Alloy/LMPE blends slightly decreases in thermal stability than Alloy. To investigate the applicability for insulation material, the prepared blend samples were extruded an electric wire and the breakdown voltage (BDV) of wires was investigated. The melt flow rate of Alloy increased as the amount of TPE increased, and a contrary trend was found when the increase of the amount of TiO₂. The dielectric breakdown test applies a voltage that is greater than the product's rated operating voltage for a specific period of time during which dielectric breakdown must not occur. The BDV of Alloy/TPE and Alloy/PA66 blends is higher than other blends before and after thermal aging 225°C for 30 min. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Phase Equilibria in the Systems NiO-Cr2,O3,-O2, MgO-Cr2O3−O2, and CdO-Cr2,O3,-O2, at High Oxygen Pressures

Phase equilibria were determined for the systems NiO-Cr₂O₃−O₂, MgO-Cr₂O₃,-O₂, and CdO-Cr₂O₃−O₂ from 450° to above 850° C and at oxygen pressures of from 2 to 3500 atm. Only two intermediate phases were found in the nickel system: NiCrO., (CrVO₄ structure) and the spinel NiCr₂O₄. The magnesium and cadmium systems are similar in that they have three analogous phases: the low-temperature α-MgCrO₄ and α-CdCrO₄ (both with the CrVO₄ structure), the high-temperature β-MgCrO₄ and β-CdCrO₄ (both with the α-MnMoO₄ structure), and the spinels MgCr₂O₄ and CdCr₂O₄. The cadmium system contains an additional phase, Cd₂CrO₅, which is primitive monoclinic.     

Acoustic Emission and Microcracking in Sapphire, Sintered Al2O3, Al/Al2O3 Composite, and Aluminum

A range of materials with brittle to ductile behavior (single-crystal and polycrystalline alumina, aluminum/alumina composite, and metallic aluminum) were investigated by acoustic emission (AE) methods for microcracking during hardness indentations or cooling from elevated temperatures (800°C). During indentation, the extent of crack formation (and the AE counts) decreased in the following order: sapphire, sintered alumina, aluminum/alumina composite with no microcracking in metallic aluminum. During cooling from 800°C, polycrystalline alumina exhibited more extensive microcracking than the aluminum/alumina composite, suggesting that the metallic phase in the aluminum/alumina composite absorbs stresses more than the glassy boundary phase in sintered alumina.     

Microwave Dielectric Properties of Sr(B'1/2Nb1/2)O3 [B'=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Er, Yb, and In] Ceramics

Sr(B'_1/2Nb_1/2)O₃ [B'=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Er, Yb, and In] ceramics were prepared by the conventional solid-state ceramic route. The crystal structure and microstructure of the ceramics were characterized by X-ray diffraction and scanning electron microscopic methods, and the dielectric properties were measured in the microwave range. Addition of a small amount of CeO₂ as a sintering aid improved the densification and dielectric properties of the ceramics. The effects of cation substitution and glass addition on the microwave dielectric properties of the ceramics were also investigated. Glass addition resulted in the lowering of the processing temperature of the materials without much affecting the dielectric properties, whereas cation substitution resulted in the variation of the temperature coefficient of resonant frequencies. A correlation of dielectric properties with the tolerance factor and ionic radii of B'-site elements of the ceramics has been observed.     

Ferroelectric Phase Transitions in the System PbTiO3,-KNbO3,

The formation of a complete series of solid solutions in the system PbTiO₃-KNbO₃ was established by X-ray and dielectric studies. The room-temperature symmetry of the entire system was tetragonal except for compositions containing more than 96 mole % KNbO₃, which had orthorhombic symmetry. The axial ratio, c/a , and the ferroelectric Curie temperature decreased from both the end-members. The lowest Curie temperature observed in the system was 175°C for the composition with 80 mole % KNbO₃. A generalization has been made on the variation of ferroelectric Curie temperatures with compositions in binary systems of perovskitetype solid solutions with and without a common cation.     

Retention of Cobalt, Cesium, and Strontium in the Hydrates of C3S, C3A, and Gypsum

The retention of cobalt, cesium, and strontium as trace elements in the hydrates of simple ordinary portland cement components has been investigated. The combined characterization of the solid by SEM, electron microprobe, XRD, and SIMS, as well as the chemical analysis of the solutions, allowed us to identify the likely localization of these trace elements in the solid. In particular, cobalt is dramatically incorporated into the solid during the hydration of C₃S; we show that this is due to the formation of a cobalt oxychloride, a compound which is unstable at temperatures ≥60°C. Cesium is retained in small amounts in the C-S-H and CH mixture. The formation of hydrated aluminates notably increases its retention. Finally, small quantities of strontium are also retained in silicates and, in the presence of gypsum, its retention is markedly higher. This is likely due to the formation of sulfoaluminates.     

Phase Equilibrium in a Portion of the Ternary System Ba OA-I2,O3,-SiO2,

Phase-equilibrium relations on the liquidus surface in the system Ba0-A1₂O₃-SiO₂ have been investigated by the quenching method. The compositions investigated within the ternary area were those containing less than 30%, A1₂O₃ and more than 20% SiO₂ by weight. Petrographic and X-ray techniques were employed in the determination of the crystalline phases.
The crystal phases that separate from melts within the area investigated are barium orthosilicate (2BaO. SiO₂,), barium metasilicate (BaO 2SO₂,), solid solutions, sanbornite (BaO 2SiO₂), tridymite and cristobalite (SO₂), mullite (3A1₂O₃ 2SiO₂), and celsian (BaO A1₂O3_.2SiO₂). Diagrams show the isotherms and indices of refraction of the glasses.
Five quintuple points and eleven boundary curves have been determined within = .5yo compositional variations. The liquidus-surface temperatures have been obtained within limits of ± 125°C.     

Dense Perovskite, La1-xA'xFe1-yCoyO3-δ (A'= Ba, Sr, Ca), Membrane Synthesis, Applications, and Characterization

La_{1- x} A' _x Fe_0.8Co_0.2O_3-δ (A'= Ca, Sr, Ba) perovskite powders were synthesized to attain the desired properties of high O₂ flux and stability under reducing conditions. Steady-state oxygen permeation rates for La_{1- x} A' _x Fe_0.8-Co_0.2O_3-δ perovskite membranes in nonreacting experiments with air on one side and helium on the other side of the membrane were in the order A' _x = Ba_0.8 > Ba_0.6 > Ca_0.6 > Sr_0.6. Partial oxidation of methane to syngas (CO + H₂) was performed in a dense La_0.2Ba_0.8Fe_0.8Co_0.2O_3-δ membrane reactor at 850°C in which oxygen was separated from air and simultaneously fed into the methane stream. The reducing atmosphere affected the membrane reaction-side surface while barium enrichment occurred on the air-side surface. Oxygen continuously transported from the air side appeared to stabilize the membrane interior, and the reactor was operated for up to 850 h.     

Activities in Li2O-, Na2O, and K2O-SiO2 Solutions

Activities of alkali metal oxides and silica are calculated for regions of the Li₂O-SiO₂, Na₂O-SiO₂, and K₂O-SiO₂ phase diagrams where volatility, cell potential, and thermodynamic data are available. For the high-silica composition regions, activities are calculated from the stable phase diagrams and assumptions based on sub-regular solution behavior. These data permit estimates of the phase boundaries for the metastable two-liquid regions in the Li₂O and Na₂O systems which may be compared with experiment. An estimate is also made of the critical point for K₂O-SiO₂ to determine whether metastable phase separation in this system will be experimentally obtainable.     

Lattice Parameters, Ionic Conductivities, and Solubility Limits in Fluorite-Structure MO2 Oxide [M = Hf4+, Zr4+, Ce4+, Th4+, U4+] Solid Solutions

Changes in the lattice parameters of fluorite type MO₂ oxides (M = Hf⁴⁺, Zr⁴⁺, Ce⁴⁺, Th⁴⁺, U⁴⁺) due to the formation of solid solutions can be predicted by proposed empirical equations. The equations show the generalized relationship between dopant size and ionic conductivity in the binary systems of these oxides, illustrating that the smaller the difference between the dopant ionic radius and the critical dopant radius, the higher the conductivity. The solubility limit of the same periodic group elements in fluorite-structure MO₂ oxides decreaes linearly with the square of Vegard's slope for each solute as determined from the proposed equations.     

The Effect of Dopants on the Dielectric Properties of Ba(B'1/2Ta1/2)O3 (B'=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Yb, and In) Microwave Ceramics

Low-loss dielectric ceramics based on Ba(B'_1/2Ta_1/2)O₃ (B'=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Yb, and In) complex perovskites have been prepared by the solid-state ceramic route. The dielectric properties (ɛ_r, Q _u, and τ_f) of the ceramics have been measured in the frequency range 4–6 GHz by the resonance method. The resonators have a relatively high dielectric constant and high quality factor. Most of the compounds have a low coefficient of temperature variation of the resonant frequencies. The microwave dielectric properties have been improved by the addition of dopants and by solid solution formation. The solid solution Ba[(Y_{1− x} Pr _x )_1/2Ta_1/2]O₃ has x =0.15, with ɛ_r=33.2, Q _u× f =51,500 GHz, and τ_f≈0. The microwave dielectric properties of Ba(B'_1/2Ta_1/2)O₃ ceramics are found to depend on the tolerance factor ( t ), ionic radius, and ionization energy.     

Anodic chlorination of aniline in N,N-dimethyl-formamide and N,N-dimethylacetamide

A pertinent electrochemical synthesis of 2,4,6-trichloroaniline (TCA) in anhydrous media was studied. The influence of the solvent, the chlorinating reagent, the electricity passed and the nature of the anode material, were investigated. TCA was produced in electrolytic solutions whose solvents were amides with strong nucleophilicity as N,N-dimethylformamide (DMF) and N,N-dimethylacetoamide (DMAc), and was obtained selectively by the controlled potential electrolysis of aniline in the solution containing LiCl. The definition of the experimental conditions corresponding to an optimum and selective electrolysis of TCA was described.     

Wilson parameters for the system H2, N2, CO,CO2, CH4, H2S,CH3OH,and H2O

Parameters for the Wilson equation have been determined for 24 of the 28 binary pairs in the system: H₂, N₂, CO, CO₂, CH₄, H₂S, CH₃OH, and H₂O. The data for eleven pairs were fit using the symmetric convention, with the remaining pairs satisfying the unsymmetric convention. Coefficients for the missing pairs could be estimated from Henry's Law constants. References have been included for the heat capacities of liquid methanol and carbon dioxide. Heats of mixing were also found in the literature. This information, plus readily available gas heat capacities, provides sufficient information to calculate multicomponent material and energy balances for the columns used in the separation of H₂S and CO₂ by cold methanol absorption.     

Interactions of CO, HCl, and SOx in pulverised coal flames

The effect of HCl and SO₂ on CO oxidation in pulverised coal flames was investigated experimentally and kinetically in an entrained flow combustion reactor. Two bituminous coals (German ‘Goettelborn’ and a Polish coal) were used as fuels with a feeding rate of 1 or 1.5 kg/h. HCl or SO₂ is introduced into the reactor premixed with the primary air. Experimental results indicate that HCl addition may inhibit CO oxidation in coal flames and increases CO emission. Reducing temperature in the reactor will enhance the inhibitory effect of HCl on CO oxidation. The measured CO profiles along the reactor height clearly show that the addition of HCl may inhibit CO oxidation. In the experimental range of SO₂ addition, the inhibiting effect of SO₂ on CO oxidation is less significant than HCl. A detailed kinetic mechanism is used to model the reactions, and the controlling reactions are analysed.     

Tape Casting, Pressureless Sintering, and Grain Growth in Ti3SiC2 Compacts

In this work we demonstrate that fine Ti₃SiC₂ powders can be tape-cast and/or cold-pressed and pressureless-sintered in Ar- or Si-rich atmospheres to produce fully dense, oriented microstructures in which the basal planes are parallel to the surfaces. Carbon- and/or Si-rich environments suppress grain growth. In the case of the tape casting, the C-residue from binder burnout results in small core grains relative to the surface grains that can grow significantly. When sintering in high Si activities, titanium silicide phases form at the grain boundaries that slow grain growth. Annealing the latter in Ar at 1600°C, for extended periods (30 h), rids the samples of these grain-boundary phases, which in turn results in grain growth. The advantage of the latter process is that the final grain size distribution is more uniform from surface to bulk.