Crystal Structure Refinement of La0.683(Ti0.95Al0.05)O3 Perovskite by the Rietveld Method

The structural parameters of orthorhombic and tetragonal phases (space group P / mmm and P 4/ mmm ) of A-site deficient La_0.683(Ti_0.95Al_0.05)O₃ perovskite have been refined by Rietveld analysis through the X-ray powder diffraction patterns measured in the temperature range from 15° to 500°C. With an increase in temperature the unit-cell parameters a , b , and c increased, while the b / a ratio decreased and became unity between 200° and 400°C. No significant changes were observed for atomic coordinates throughout the temperature studied. These results strongly suggest that the phase transition is induced by lattice distortion.     

Electronic Structure and Bonding in Crystalline Y10[SiO4]6N2

The electronic structure and bonding of the complex ceramic crystal Y₁₀[SiO₄]₆N₂ is studied by a first-principles method. It is shown that this crystal is an insulator with a direct band gap of 1.3 eV. It has some unique properties related to the one-dimensional chain structure in the c -direction and the planar N-Y bonding in the x - y plane.     

Crystal Chemistry and Phase Transitions in Substituted Pollucites along the CsAlSi2O6-CsTiSi2O6.5 Join: A Powder Synchrotron X-ray Diffractometry Study

The crystal structures for a suite of substituted pollucites with the compositions CsTi _x Al_{1– x} Si₂O_{6+0.5 x} , 0 ≤ x ≤ 1, have been determined from Rietveld analysis of powder synchrotron XRD data. Our results indicate that the pollucite end member (CsAlSi₂O₆) has a tetragonal structure (space group I 4₁/ a ), whereas all other compositions are cubic (space group Ia 3 d ). The increased symmetry for the titanium-substituted structures is presumably due to the incorporation of additional O²⁻ anions (needed for compensating the charge imbalance between Ti⁴⁺ and Al³⁺), which effectively holds open the expanded cubic framework. In situ cooling experiments of the substituted phase CsTi_0.1Al_0.9Si₂O_6.05 reveal a displacive transformation to the tetragonal structure at ∼230 K. This transformation is tricritical in nature and is analogous to the tetragonal-to-cubic transition in pollucite on heating.     

Reaction-Formed Porous Yb4Si2N2O7 Materials with Uniform Open-Cell Network Structure

A novel porous Yb₄Si₂O₇N₂ material with uniform open-cell network structure was fabricated from the reaction between Si₃N₄, Yb₂O₃, and SiO₂. The formation of Yb₄Si₂O₇N₂ during heating was studied using X-ray diffractometry. The porous structure was characterized using scanning electron microscopy and mercury porosimeter. It is shown that the formation of Yb₄Si₂O₇N₂ phase starts at ∼1150°C and completes at 1350°C for 4 h, accompanied by the development of open-cell network structure. The necks between Yb₄Si₂O₇N₂ particles become much thicker with increasing temperature because of the coarsening of Yb₄Si₂O₇N₂ particles, thus leading to a uniform three-dimensional network structure. Furthermore, the pore size can be well controlled by adjusting reacting temperature and altering atmosphere.     

Sintering of a Crystallizable CaO-B2O3-SiO2 Glass with Silver

Effects of Ag addition on sintering of a crystallizable CaO-B₂O₃-SiO₂ glass have been investigated at 700°–900°C in different atmospheres. With Ag content increasing in the range of 1–10 vol%, the softening point, the densification, the onset crystallization temperature, and the total amount of crystalline phase formed of the crystallizable glass are reduced when fired in air. A bloating phenomenon is observed when the crystallizable CaO-B₂O₃-SiO₂ glass doped with 1–10 vol% Ag is fired at 700°–900°C for 1–4 h. Fired in N₂ or N₂+ 1% H₂, however, the above phenomena disappear completely. It is thus believed that the diffusion of Ag into the crystallizable glass, which is caused by the oxidation of Ag in air, is the root cause for the above results observed.     

Low-Temperature Chemical Synthesis of Nanocrystalline MgAl2O4 Spinel Powder

Nanocrystalline MgAl₂O₄ spinel powder was synthesized by pyrolysis of complex compounds of aluminum and magnesium with triethanolamine (TEA). The soluble metal ion–TEA complexes formed the precursor material on complete dehydration of the complexes of aluminum–TEA and magnesium–TEA. Single-phase MgAl₂O₄ spinel powder resulted after heat treatment of the precursor material at 675°C. The precursor and the heat-treated powders were characterized by X-ray diffractometry (XRD), differential thermal and thermogravimetric analysis, and transmission electron microscopy (TEM). The average crystallite size as measured from the X-ray line broadening was around 14 nm and the average particle size from TEM studies was around 20 nm.     

Preparation of Orthorhombic Ba2YCu3O7 Powder by Single-Step Calcining

A single calcination step, solid-state process that provides orthohombic Ba₂YCu₃O₇ powder is described. BaCO₃, Y₂O₃, and CuO are used as precursor materials. The only phase identifiable by X-ray diffraction is the orthorhombic Ba₂YCu₃O₇. The use of a vacuum during the inital stages of the calcining process promotes complete decomposition of the carbonate, and no residual carbonate is observed. An oxygen atmosphere during the later stages of calcining ensures proper oxidation to Ba₂YCu₃O₇. The use of a similar combination vacuum-oxygen calcining schedule should also be beneficial in the preparation of chemically derived powders.     

Effect of Neodymium:Yttrium Aluminum Garnet Laser Irradiation on Crystallization in Li2O–Al2O3–SiO2 Glass

A 355-nm neodymium:yttrium aluminum garnet laser, produced by a harmonic generator, was used for the nucleation process in photosensitive glass containing Ag⁺ and Ce³⁺ ions. The pulse width and frequency of the laser were 8 ns and 10 Hz, respectively. Heat treatment was conducted at 570°C for 1 h, following laser irradiation, to produce crystalline growth, after which a LiAlSi₃O₈ crystal phase appeared in the laser-irradiated Li₂O–Al₂O₃–SiO₂ glass. The present study compares the effect of laser-induced nucleation on glass crystallization with that of spontaneous nucleation by heat treatment.     

Compressive Creep and Oxidation Resistance of an Si3N4 Material Fabricated in the System Si3N4-Si2N2O-Y2Si2O7

The compressive creep behavior and oxidation resistance of an Si₃N₄/Y₂Si₂O₇ material (0.85Si₃N₄+0.10SiO₂+0.05Y₂O₃) were determined at 1400°C. Creep re sistance was superior to that of other Si₃N₄ materials and was significantly in creased by a preoxidation treatment (1600°C /120 h). An apparent parabolic rate constant of 4.2 × 10⁻¹¹ kg²·m-⁴·s⁻¹ indicates excellent oxidation resistance.     

Neutron Powder Diffraction Study of Y-Sialon with La2O3 or Nd2O3 Addition

Neutron diffraction data of α-sialon and complementary phases were collected on the neutron powder diffraction (NPD) diffractometer installed in the NFL Studsvik, at a wavelength of 1.470 Å. Calculations were carried out by using the FullProf 2000 utilizing the crystal structure of the yttrium α-sialon phase. Selected profile and structure parameters were refined in the calculations. The calculated data showed that either La or Nd were also present in the α-sialon crystal structure in the presence of Y. The comparison of the present phases' weight contents, which were determined by the qualitative phase analysis between NPD and X-ray diffraction data, was carried out.     

Metastable Crystal Structure of Strontium- and Magnesium-Substituted LaGaO3

The metastable crystal structure of strontium- and magnesium-substituted LaGaO₃ (LSGM) was studied at room and intermediate temperatures using powder X-ray diffractometry and Rietveld refinement analysis. With increased strontium and magnesium content, phase transitions were found to occur from orthorhombic (space group Pbnm ) to rhombohedral (space group R [Threemacr] c ) at the composition La_0.825Sr_0.175Ga_0.825Mg_0.175O_2.825 and, eventually, to cubic (space group Pm [Threemacr] m ) at the composition La_0.8Sr_0.2Ga_0.8Mg_0.2O_2.8. At 500°C in air and at constant strontium and magnesium content, a phase transformation from orthorhombic (space group Pbnm ) to cubic (space group Pm [Threemacr] m ) was observed. For the orthorhombic modification, thermal expansion coefficients were determined to be α _a ,ortho = 10.81 × 10⁻⁶ K⁻¹, α _b ,ortho = 9.77 × 10⁻⁶ K⁻¹, and α _c ,ortho = 9.83 × 10⁻⁶ K⁻¹ (25°–400°C), and for the cubic modification to be α_cubic= 13.67 × 10⁻⁶ K⁻¹ (500°–1000°C).     

Sc2O3 Nanopowders via Hydroxyl Precipitation: Effects of Sulfate Ions on Powder Properties

Hydroxyl-type Sc₂O₃ precursors have been synthesized via precipitation at 80°C with hexamethylenetetramine as the precipitant. The effects of starting salts (scandium nitrate and sulfate) on powder properties are investigated. Characterizations of the powders are achieved by elemental analysis, X-ray diffractometry (XRD), differential thermal analysis/thermogravimetry (DTA/TG), high-resolution scanning electron microscopy (HRSEM), and Brunauer-Emmett-Teller (BET) analysis. Hard-aggregated precursors (γ-ScOOH·0.6H₂O) are formed with scandium nitrate, which convert to Sc₂O₃ at temperatures ≥400°C, yielding nanocrystalline oxides of low surface area. The use of sulfate leads to a loosely agglomerated basic sulfate powder having an approximate composition of Sc(OH)_2.6(SO₄)_0.2·H₂O. The powder transforms to Sc₂O₃ via dehydroxylization and desulfurization at temperatures up to 1000°C. Well-dispersed Sc₂O₃ nanopowders (∼64.3 nm) of high purity have been obtained by calcining the basic sulfate at 1000°C for 4 h. The effects of SO₄²⁻ on powder properties are discussed.     

Nucleation and Crystal Growth of a MgO–CaO–Al2O3–SiO2Glass with Added Steel Fly Ash

The nucleation and growth of diopside Ca(Mg,Al)(Si,Al)₂O₆crystals on the free surface of a 24 wt% MgO, 14 wt% CaO, 9 wt% Al₂O₃, and 53 wt% SiO₂glass, with a 2 wt% addition of steel fly ash, were investigated through DTA, XRD, SEM, and optical microscopy. Crystallization was complete at ∼920°C with an activation energy of 589 kJ/mol. Samples with polished free surfaces were nucleated at selected temperatures in the range of 730° to 820°C, and then heat-treated at 870°C for 15 min for crystal growth. Nucleation was predominantly observed at the surface, and the number of diopside crystals per unit of area and the mechanism of crystallization were determined. It was concluded that nucleation reaches a maximum at 750°C, corresponding to an average density of diopside crystals of 8.4 × 10⁶ nuclei/cm², and that between 900° and 1100°C, a uniformly crystallized layer is formed at an exponential rate. The crystallized volume fraction increased significantly in the 880°–890°C growth range, and remained almost constant at higher temperatures. In the 860°–910°C range, the size of the diopside crystals formed in the samples nucleated at the temperature of the maximum nucleation rate, and linearly increased, reaching values between 1.0 and 3.0 μm at 870° and at 910°C, respectively.     

Growth of Pb((Zn1/3Nb2/3)0.91Ti0.09)O3 Single Crystals Using an Allomeric Seed Crystal and Their Electrical Properties

Single crystals of Pb((Zn_1/3Nb_2/3)_0.91Ti_0.09)O₃ (PZNT 91/9), 28 mm in diameter and 30 mm in length, have been successfully grown using a modified Bridgman technique with an allomeric seed crystal. X-ray fluorescence analysis (XRFA) measurement confirms that the effect of segregation is not serious. The segregation coefficient k for PbTiO₃ content during crystal growth is 0.99, which causes some fluctuation in the composition along the growth direction. The fluctuation of composition and the complicated domain structure cause a variation of electric properties. Dielectric measurement indicates that PZNT 91/9 crystals exhibit an almost normal ferroelectric phase transition at ∼183°C from the tetragonal phase to the cubic phase. In addition, a weak frequency-dependent ferroelectric-ferroelectric phase transition is observed at ∼85°C, which is attributed to partial conversion of the rhombohedral phase to a tetragonal phase. The dielectric thermal hysteresis behavior and the existence of polarization above the Curie temperature verify that the phase transitions at ∼85° and 183°C are first order with a slight diffuse character and first order, respectively. It is demonstrated that the effects of segregation can be decreased and the homogeneity of the obtained PZNT 91/9 single crystals can be improved by optimizing growth parameters.     

Phase Relationships in the Si3N4–SiO2–Lu2O3 System

Phase relationships in the Si₃N₄–SiO₂–Lu₂O₃ system were investigated at 1850°C in 1 MPa N₂. Only J-phase, Lu₄Si₂O₇N₂ (monoclinic, space group P 2₁/ c , a = 0.74235(8) nm, b = 1.02649(10) nm, c = 1.06595(12) nm, and β= 109.793(6)°) exists as a lutetium silicon oxynitride phase in the Si₃N₄–SiO₂–Lu₂O₃ system. The Si₃N₄/Lu₂O₃ ratio is 1, corresponding to the M-phase composition, resulted in a mixture of Lu–J-phase, β-Si₃N₄, and a new phase of Lu₃Si₅ON₉, having orthorhombic symmetry, space group Pbcm (No. 57), with a = 0.49361(5) nm, b = 1.60622(16) nm, and c = 1.05143(11) nm. The new phase is best represented in the new Si₃N₄–LuN–Lu₂O₃ system. The phase diagram suggests that Lu₄Si₂O₇N₂ is an excellent grain-boundary phase of silicon nitride ceramics for high-temperature applications.     

Habit Modifications of SnO2 Crystals in SnO2–Cu2O Flux System in the Presence of Trivalent Impurity Cations

SnO₂ single crystals have short prismatic habits bounded by well-developed {110} and {111} faces in a pure SnO₂–Cu₂O flux system. When trivalent cations are added to the system, the habits drastically change to needle, acicular, or whisker forms with large aspect ratios. The addition of trivalent cations also greatly increases the nucleation rate and drastically decreases the crystal size. SEM observations and EPMA investigations reveal that the flat {111} faces transform to rounded or rough { hkl } faces by the addition of trivalent cations. This roughening transition of {111} faces, keeping {110} faces unchanged, is the cause of drastic habit modification that is attributed to the breaking of the periodic bond chain in {111} faces by impurity cations.