Synthesis of Compositionally Homogeneous Sr(CuxZn1−x)1/2W1/2O3

A complex perovskite of Sr(Cu _x Zn_{1- x} )_1/2 W_1/2O₃ (SCZW) is synthesized by a new combination of wet and dry processess. Mixed oxides containing Cu²⁺ and Zn²⁺ (CZ) are prepared by the wet process (coprecipitate method). SCZW is obtained by the dry process (mixed-oxide method) from a mixture of CZ, SrCO₃, and WO₃. SCZW has practically no compositional, unlike solid solutions prepared by the conventional dry method. The wet–dry process method is useful because the wet process is applied to only B-site cations having the same valence.     

Microstructure and Mechanical Properties of Hot-Pressed Silicon Carbide-Aluminum Nitride Compositions

A flexural strength of up to 1 GPa was achieved in SiC-AIN materials and is attributed to a dense, equiaxial grain structure of the 2H(δ) SiC-AIN solid solution, with a relatively uniform grain size of ∼ 1 μm. The strength was found to decrease with increasing grain size. While the β→α phase transformation and the formation of various metastable polytypes make microstructural control difficult in SiC materials, excellent control is facilitated in SiC-AIN materials as a result of the stable 2H solid solution. Several mechanisms of grain refinement during the β→ 2H transition were observed, most notably the direct formation of several 2H grains from a single β grain. In addition, grain growth is limited by the diffusion-controlled nature of the transition. These mechanisms could be utilized to achieve even higher strength values, with potentially higher reliability of the materials in structural applications.     

Activity–Composition Relations in NiAl2O4─MnAl2O4 Solid Solutions and Stabilities of NiAl2O4 and MnAl2O4 at 1300° and 1400°C

Activities of NiO were measured in the oxide and spinel solutions of the system MnO–NiO–Al₂O₃ at 1300° and 1400° C with the aim of deriving information on the thermodynamic properties of the spinel phases. Synthetic samples in selected phase assemblages of the system were equilibrated with metallic nickel and a gas phase of known oxygen partial pressures at a total pressure of 1 atm. The data on NiO activities and directions of conjugation lines between coexisting oxide and spinel phases were used to establish the activity–composition relations in spinel solid solutions at 1300° and 1400°C. The MnAl₂O₄–NiAl₂O₄ solid solutions exhibit considerable negative deviations from ideality at these temperatures. The free energy of formation of MnAl₂O₄ from its oxide components (MnO + Al₂O₃) at 1300° and 1400°C is calculated to be −24.97 and −26.56 kJ. mol⁻¹, respectively. The activities determined in the stoichiometric spinel solid solutions are more negative as compared with those predicted from cation distribution models.     

Equilibrium Studies of the System'(Fe,Co)O'–(Fe,Co)3O4 by Solid-State emf Measurements in the Temperature Range 970 to 1370 K

The equilibrium reaction 3'(Fe, Co)O'( ss ) +1/2O₂ ( g ) ⇄ (Fe, Co)₃O₄( ss ) was studied in the temperature range 970 to 1370 K for seven different total compositions of molar ratios 0.5 < Fe/(Fe + Co) ≤ 1.0. The equilibrium pressures of oxygen were determined by using galvanic cells incorporating calcia stabilized zirconia as solid electrolyte and the Fe/Co ratios in the solid-solution phases by wavelength dispersive spectrometry microprobe analyses. The activities of 'FeO' in the cobaltowüstite phase were then derived from the experimental results obtained.     

Application of an Ion-Packing Model Based on Defect Clusters to Zirconia Solid Solutions: I, Modeling and Local Structure of Solid Solutions

Oxygen vacancies can be introduced into zirconia solid solution ZrO₂–MO _u ( u = 1 and 1.5) to maintain electroneutrality. Recently, the local structures around Zr⁴⁺ and M^{2 u +} ions in ZrO₂–MO _u solid solutions have been studied through EXAFS spectroscopy, diffuse scattering analysis, and single-crystal structure analysis. The present study constructs an ion-packing model for zirconia solid solutions based on some defect cluster models. The decrease of cell volume with the occurrence of vacancies is assumed to be expressed by decreasing the coordination number (CN) of cations around the vacancy. The distribution of CNs in a solid solution was calculated from a certain defect cluster model. The average interatomic distances, the average CN, and the short-range order parameters were calculated using this distribution of CNs. The local structures calculated from the model were compared with experimental data in the systems ZrO₂–MO_1.5 (M = Y, Gd, Yb, and Ca). In the ZrO₂–YO_1.5 system, the r (s–O) interatomic distance, where s represents Zr⁴⁺ or Y³⁺ and O represents O²⁻, decreased with Y content and therefore vacancy content. The probability of finding Y³⁺ around a vacancy increases with increasing yttria content from a comparison of the calculated results with the ones from recent EXAFS studies. The present model can qualitatively explain compositional and size dependences of the dopant on various local structures.     

Investigation of transport phenomena in a hybrid ion exchange-electrodialysis system for the removal of copper ions

Hybrid ion exchange electrodialysis processes allow the removal of metal ions from dilute waste liquids and the recovery of more concentrated solutions. The work reported here was aimed at investigating the two steps in the treatment process, namely, adsorption of metal ions onto the packed bed of resin and electromigration (i.e., the transport of these ions in the complex system under the applied electrical field). The case of copper sulfate was investigated. Dowex resins with a cross-linking degree of 2 and 8% were used. The flux of copper through the resin bed and the current efficiency for ion transfer to the cathode compartment were determined as a function of potential gradient and copper ionic fraction in the bed. Apparent diffusion coefficients of Cu²⁺ in the overall system were deduced from the experimental data.     

Free energy and confinement force of macromolecules in a slit at full equilibrium with a bulk solution

Nondilute athermal and theta solutions of nonadsorbing flexible macromolecules in equilibrium with repulsive slit-like pores were examined by the lattice Monte Carlo simulations. The free energy of confinement ΔA/kT and the force f/kT exerted by polymers on the slit were computed as a function of the slit width D in a wide range of bulk concentrations φ. The free energy and force profiles in nondilute solutions were found to deviate considerably from the ideal chain theory; the perturbation of chains by a presence of the slit walls were substantially reduced in nondilute solutions. The free energy and force functions appropriate for nondilute solutions were derived by fitting the simulation data. Further, the relative pressure p_I/p_E exerted by the nonadsorbing confined molecules on the slit walls was calculated. The depletion effect relevant to colloid stabilization was found in dilute solutions to be slightly weaker for excluded-volume chains than for ideal chains. The relative pressure equation was modified to cover semidilute solutions, by using the mean-field and scaling expressions of the osmotic pressure. Both the relative pressure p_I/p_E and the intra-slit concentration profiles φ_I(x) in tandem display a suppression of the depletion effect with increasing φ in simidilute solutions.     

Pressure-volume-temperature properties for binary and ternary polymer solutions of poly(ethylene glycol), poly(propylene glycol), and poly(ethylene glycol methyl ether) with anisole

Pressure-volume-temperature properties were measured for polymer solutions of poly(propylene glycol) (PPG)+anisole, polymer blends of PPG+poly(ethylene glycol methyl ether) (PEGME), and the blends of PPG+PEGME and poly(ethylene glycol) (PEG)+PPG with anisole at temperatures from 298.15 to 348.15 K and pressures up to 50 MPa. The Tait equation represents accurately the pressure effect on the liquid densities over the entire pressure range. The excess volumes change from positive to negative as increasing the mole fraction of PPG in the binary systems of PPG+anisole and PPG+PEGME. The volumetric data of the related binary systems were correlated with the Flory-Orwoll-Vrij and the Schotte equations of state to determine the binary parameters. By using these determined binary parameters, both equations predicted the specific volumes of the polymer blends with anisole to average absolute deviations of better than 0.13%.     

Green and blue materials for the ceramic industry from pink MgCoxNi1-xSiO4 (0 ≤ x ≤ 1) solid solutions

In this study, MgCo_xNi_1-xSiO₄ (0.0 ≤ x ≤ 1.0) solid solutions with an olivine structure were synthetized via the chemical coprecipitation method and materials with a smaller M(II) (M = Co, Ni) amount than Co₂SiO₄ and Ni₂SiO₄ compounds were obtained. At 1200 °C, the Co(II) and Ni(II) were randomly distributed in the MgCo_xNi_1-xSiO₄ (0.0 ≤ x ≤ 1.0) solid solutions with the olivine structure, but the occupation of Co(II) and Ni(II) ions in M1 (4a) octahedral sites was obtained at a higher level than in M2 (4c) octahedral sites. The Mg(II) ions prefer the M2 sites. This preference explains the main contribution of the M1 sites in spectra of octahedral Co(II) ions and the M1-O and M2-O distances jointly explain the pink colour of the MgCo_xNi_1-xSiO₄ (0.0 ≤ x ≤ 1.0) solid solutions, while the colour of Co₂SiO₄ is blue. Spectra can be interpreted as the sum of Ni(II) and Co(II) ions in octahedral sites. When these solid solutions are enamelled, the pink colouring changes to green or blue because of the presence of tetrahedral Co(II).     

Towards new zero-thermal-expansion materials: Li-free quartz solid solutions stuffed with transition metal cations

Stuffed aluminosilicate quartz solid solutions (Qss) represent the main functional component of state-of-the-art zero-thermal-expansion glass-ceramics. For the first time, we present the synthesis of Li-, Mg- and Zn-free Qss solely stuffed with transition metal cations (Fe²⁺, Ni²⁺, Co²⁺); partial Li⁺ co-doping enables also significant Mn²⁺ incorporation. They were obtained by glass powder crystallization; Qss crystals exhibit compositionally tunable coefficients of thermal expansion (CTEs), from ? 2 × 10^?6 K^?1 to ～10 × 10^?6 K^?1 in the range 30–300 °C. Co²⁺-bearing crystals exhibit the closest-to-zero CTE value (0.2 ×10^?6 K^?1) and the most isotropic behavior in the whole Qss family, opening up new perspectives for the development of Li-free low-expansion materials. From a structural point of view, we identified the unit cell volume (and not the pseudo-hexagonality of the aluminosilicate framework) as the key structural parameter leading to low or negative CTEs in Qss, with a linear correlation extending to non-stuffed non-silicate quartz-like phases.