Tricalcium Silicate T1 and T2 Polymorphic Investigations: Rietveld Refinement at Various Temperatures Using Synchrotron Powder Diffraction

The lattice parameters, cell volume, and structure of a sample of phase pure triclinic tricalcium silicate were determined using in situ, high-temperature synchrotron powder diffraction and full-profile Rietveld refinement. The temperature range covered was from ambient to 740°C. Evidence of superstructure was found. The T₂ type structure with disordered SiO₄ tetrahedra was observed, and an average structure for the subcell ( P     , a = 11.7416(2) Å, b = 14.2785(2) Å, c = 13.7732(2) Å, α= 105.129(1)°, β= 94.415(1)°, and γ= 89.889(1)°) is presented. Differential thermal analysis and X-ray fluorescence was also performed.     

Tricalcium Silicate and Its Stability Within the System CaO-SiO2

A portion of the system CaO-SiO₂ has been reinvestigated by high-temperature microscopy. Direct observations at the liquidus establish a primary-phase region for tricalcium silicate, which is shown in a revised phase diagram to melt incongruently. The tricalcium silicate primary-phase field extends from the eutectic with dicalcium silicate at 2050 °C., 69.5% CaO, to the incongruent boundary with lime at 2070°C., 71.5% CaO, with a possible error in composition of ± 0.25%. The estimated accuracy of these temperatures is ±3° relative to one another, and ± 10° relative to the melting points of alumina and dicalcium silicate, for which the values 2040°C. and 2130°C. taken from the literature have been assumed.     

Effect of P2O5 on the Crystallization of Lead Silicate Glasses

The effect of P₂O_S on the devitrification of binary lead silicate glasses containing 64 and 59 mol% PbO was studied. Glasses underwent isothermal crystallization treatments at 400°, 450°, 500°, and 550°C. A polymorph of 3PbO₂SiO₂ was the major product of crystallization for all compositions of glasses. Secondary products of crystallization were found to be a polymorph of PbOSiO₂ in the 59 mol% and a low-temperature polymorph of 2PbOSiO₂ in the 64 mol% PbO glasses. Dominant mode of crystallization in both binary glasses was surface devitrification at all temperatures studied. Addition of P₂O₅ promoted internal crystallization in the form of spherulites. 400°C was found to be the most effective temperature for nucleating spherulitic growth. Crystallization at 400°C led to high concentrations of spherulites in all glasses containing at least 0.5 mol% P₂O₅. Concentrations of 0.5 mol% P₂O₅ were needed to produce detectable levels of spherulitic nucleation at r<400°C.     

Hydration of Tricalcium Silicate Followed by 29Si NMR with Cross-Polarization

The use of cross-polarization (CP) NMR in conjunction with magic angle sample spinning (MASS) to examine the hydration reaction of tricalcium silicate (C₃S) is described. In particular the very early stages of the reaction both with and without admixtures has been studied as well as the hydration in a ball mill. The combination of CP and non-CP ²⁹Si NMR permits the distinction between silicate units associated with protons, i.e., in hydrated material, and those in anhydrous material. It has been found that in paste hydration there is steady formation of a small amount of hydrated monomeric silicate units during the induction period. In ball mill hydration the formation of the crystalline calcium silicate hydrate, afwillite, which contains only hydrated monomeric silicate species, can be monitored. These results are interpreted in terms of possible mechanisms for C₃S hydration.     

Synthesis and Structural Characterization of Trimetallic Perovskite-Type Rare-Earth Orthoferrites, LaxSm1–xFeO3

Ultrafine powders of trimetallic orthoferrites containing lanthanum and samarium in various ratios were synthesized by thermal decomposition at low temperatures of the corresponding hexacyano complexes to modulate the functional properties of these perovskite-type oxides. The precursors and their decomposition products were analyzed by simultaneous thermogravimetric and differential thermal analyses, X-ray diffractometry, and Raman spectroscopy. Single-phase trimetallic precursors and oxides were obtained. The crystal structure of the perovskite-type oxides was orthorhombic, and the lattice parameters were affected by the ionic size of the rare-earth elements present in the oxides. Raman spectra showed a broadening of the vibrational bands with increased lanthanum content. This was ascribed to some disorder in the oxygen sublattice, related to distortions of the cation–oxygen coordination, and to a reduction of the orthorhombic distortion in the unit-cell basal plane. Most of the Raman modes above 200 cm⁻¹, associated with the vibration of oxygen ions, showed a frequency increase with effective cation mass, defined as m _eff= xm _La+ (1 – x ) m _Sm, i.e., with samarium content. This was explained by assuming that the force constants increased with decreased Ln–O and Fe–O interatomic distances observed for high samarium content.     

Impurity Phases in Hot-Pressed Si3N4

Impurity phases in commercial hot-pressed Si₃N₄ were investigated using transmission electron microscopy. In addition to the dominant, β-Si₃N₄ phase, small amounts of Si₂N₂O, SiC, and WC were found. Significantly, a continuous grain-boundary phase was observed in the ∼ 25 high-angle boundaries examined. This film is ∼ 10 Å thick between, β-Si₃N₄ grains and ∼ 30 Å thick between Si₂N₂O and β-Si₃N₄ grains.     

Synthesis and Characterization of Nanocrystalline SrTiO3

The synthesis and densification of fairly dense nanocrystalline SrTiO₃ and its characterization are described in this paper in detail. Significant grain growth was avoided by the application of a two-stage sintering process using hot pressing. High-resolution transmission electron microscopy and electron energy loss spectroscopy characterizations indicate pure material with no detectable chemical inhomogeneities. The electrical measurements indicate the disappearance of bulk contribution to the electrical conduction due to the overlap of depleted space charge layers if the grain size is below 100 nm. Owing to the overlap, the capacitance appears as bulk-like rather than due to space charge polarization. Non-contact sub-millimeter optical spectroscopy measurements reveal strong suppression of the dielectric constant values at low temperature.     

Synthesis and Characterization of a Remarkable Ceramic: Ti3SiC2

Polycrystalline bulk samples of Ti₃SiC₂ were fabricated by reactively hot-pressing Ti, graphite, and SiC powders at 40 MPa and 1600°C for 4 h. This compound has remarkable properties. Its compressive strength, measured at room temperature, was 600 MPa, and dropped to 260 MPa at 1300°C in air. Although the room-temperature failure was brittle, the high-temperature load-displacement curve shows significant plastic behavior. The oxidation is parabolic and at 1000° and 1400°C the parabolic rate constants were, respectively, 2 × 10⁻⁸ and 2 × 10⁻⁵ kg²-m⁻⁴.s⁻¹. The activation energy for oxidation is thus =300 kJ/mol. The room-temperature electrical conductivity is 4.5 × 10⁶Ω⁻¹.m⁻¹, roughly twice that of pure Ti. The thermal expansion coefficient in the temperature range 25° to 1000°C, the room-temperature thermal conductivity, and the heat capacity are respectively, 10 × 10⁻⁶°C⁻¹, 43 W/(m.K), and 588 J/(kgK). With a hardness of 4 GPa and a Young's modulus of 320 GPa, it is relatively soft, but reasonably stiff. Furthermore, Ti₃SiC₂ does not appear to be susceptible to thermal shock; quenching from 1400°C into water does not affect the postquench bend strength. As significantly, this compound is as readily machinable as graphite. Scanning electron microscopy of polished and fractured surfaces leaves little doubt as to its layered nature.     

Synthesis and Structural Characterization of Single-Phase BiFeO3 Powders from a Polymeric Precursor

The present investigation reports on a simple technique for the preparation of single-phase BiFeO₃ powders using the polymerized complex method, starting from iron and bismuth nitrates. A mixed aqueous solution with citric acid, ethylene glycol, Bi, and Fe ions was polymerized. The formation mechanism, the homogeneity, and the structure of the obtained powders have been investigated by thermogravimetry, X-ray diffraction (XRD), Raman spectroscopy, and scanning and transmission electron microscopy measurements. XRD results demonstrated that thermally induced crystallization of rhombohedral BiFeO₃ from the Bi–Fe polymeric precursor occurred at temperatures as low as 400°C. Pure single-phase BiFeO₃ nanocrystallites without any impurity or amorphous phases were obtained when the precursor was treated at 600°C for 3 h.     

Formation and Structural Characterization of 1:1 Ordered Perovskites in the Ba(Zn1/3Ta2/3)O3–BaZrO3 System

The phase stabilities in the(1−x)Ba(Zn_1/3Ta_2/3)O₃ (BZT)-xBaZrO₃(BZ)system have been investigated using samples prepared by the mixed oxide method. The substitution of Zr⁴⁺destabilizes the 1:2 cation ordering in BZT and pro-motes the formation of a cubic, 1:1 ordered structure with a doubled perovskite repeat. The homogeneity range of the 1:1 phase extends from x = 0.04 to approximately x = 0.25; substitutions beyond this range stabilize a disordered perovskite. The limits of stability of the 1:1 ordering coin-cide with compositions previously found to exhibit anoma-lies in their dielectric loss. The range of homogeneity is consistent with a "random layer" model for the 1:1 ordered "Ba{β';_1/2β^1/2}O₃" structure. In this model the B× positions are assumed to be occupied exclusively by Ta⁵⁺, and the b× sites by a random distribution of Zn₂₊, Zr₄₊, and the remaining Ta 5+ cations. The validity of the model, where the ordered solid solutions can be represented by Ba{[Zn_{2− y /3}Ta_{(1−2 y )/3}Zr y ]_1/2[Ta]_1/2}O₃(y =2x)was con-firmed by Rietveld refinements conducted using data col-lected with a synchrotron X-ray source.     

Structural and Thermophysical Properties of (PbO)0.5(SiO2)0.5 Glasses: Effect of SnO2 Incorporation

¹¹⁹Sn and ²⁹Si solid-state nuclear magnetic resonance studies on lead silicate glasses containing different amounts of SnO₂ confirmed that tin exists in the glass as distorted SnO₆ polyhedra and there is no direct interaction between tin and silicon structural units. Transmission electron microscopic studies have established that tin structural units are uniformly distributed in the glass. Significant changes in the values of glass transition temperature, microhardness, and thermal expansion coefficient with SnO₂ incorporation into the glass have been attributed to the increased rigidity of the glass network brought about by the replacement of weaker Pb–O linkages with stronger Sn–O linkages.     

Effect of Bi2O3 on Impurity Ion Distribution and Electrical Resistivity of Li-Zn Ferrites

Preventing the incorporation of impurities in Li-Zn ferrite grains during sintering is essential for production of ceramics with reproducible magnetic and electrical properties. Li-Zn ferrites of composition Li_0.3Zn_0.4Mn_0.05Fe_2.25O₄ were prepared with Bi₂O₃ and borosilicate sintering additives. The distribution of impurity ions in the sintered ferrites was investigated using transmission electron microscopy (TEM) coupled with energy dispersive spectroscopy (EDS). Ceramics prepared with Bi₂O₃ contained Si, Ca, and S impurities, located at grain boundaries and triple point regions. The low viscosity and good wetting properties of the Bi₂O₃ and to a lesser extent the borosilicate liquid phase allowed impurities to be selectively removed from the growing ferrite phase during sintering, thus improving sample resistivities.     

Synthesis and Characterization of Bulk Zr2Al3C4 Ceramic

Polycrystalline Zr₂Al₃C₄ was fabricated by an in situ reactive hot-pressing process using zirconium (zirconium hydrides), aluminum, and graphite as starting materials. The investigation on reaction path revealed that the liquid Al played an important role in triggering the formation of ternary zirconium aluminum carbides. The mechanical properties of Zr₂Al₃C₄ at room temperature were measured (Vickers hardness of 10.1 GPa, Young's modulus of 362 GPa, flexural strength of 405 MPa, and fracture toughness of 4.2 MPa·m^1/2). The electrical resistivity and thermal expansion coefficient were determined as 1.10 μΩ·m and 8.1 × 10⁻⁶ K⁻¹, respectively.     

Chemical Durability of Sodium Silicate Glasses Containing AI2O3 and ZrO2

A sodium silicate glass and ternary glasses derived from it by substituting AI₂O₃ and ZrO₂ for SiO₂ were exposed to water and aqueous solutions of pH 1.4 to 12.7; the kinetics of the reactions were studied. Diffusion of alkali ions and leaching of alkali and SiO₂ from the glasses were influenced by the occupancy of surface sites by alkali ions above a critical pH; however, the activation energies of the processes varied linearly with the logarithm of mole fraction of surface sites occupied by H^plus;. Identical slopes were obtained for all glasses for a given process. The results are explained on the basis that transport of alkali ions is retarded as a result of increased boundary concentration and that suitable sites for reaction are lacking.     

Novel Synthesis of SrBi2Nb2O9 Powders From Hydroxide Precursors

Simple hydroxide precursors were used for the first time for the synthesis of a typical Aurivillius compound (SrBi₂Nb₂O₉ (SBN)) at a low temperature. This method is very advantageous because it circumvents the use of SrCO₃ in the case of conventional ceramics as well in the coprecipitation methods, thereby lowering the formation of the product phase. Commercially purchased strontium hydroxide is mixed thoroughly with freshly precipitated bismuth and niobium hydroxides in a stoichiometric ratio and heated at different temperatures ranging from 100°C to 750°C for 12 h. The sequence of the reaction and evolution of the product phase was monitored by X-ray diffraction (XRD) studies by recording the XRD for samples calcined at different temperatures. The incipient SBN phase begins to form at temperatures as low as 400°C, and phase formation was complete only at 650°C as revealed by the XRD observations. The differential thermal/thermogravimetric analyses) also corroborate this result. The morphology and average particle size of these powders were investigated by transmission electron microscopy studies.     

Coarsening Behavior of Tricalcium Silicate (C3S) and Dicalcium Silicate (C2S) Grains Dispersed in a Clinker Melt

Microstructural evolution during the heat treatment of cement clinker was investigated. Two model specimens, which consisted of faceted tricalcium silicate (C₃S) and spherical dicalcium silicate (C₂S) grains dispersed in a liquid matrix, were prepared with 5 wt% of large seed particles. The seed particles of faceted C₃S grains grew extensively, whereas those of the spherical C₂S grains grew rather slowly, relative to the matrix grains. As a consequence, C₃S grains exhibited a bimodal size distribution that was typical of exaggerated grain growth, whereas C₂S grains retained a uniform and normal size distribution. These results suggest that the growth of faceted C₃S grains was controlled by the interface atomic attachment, such as two-dimensional nucleation, and that of spherical C₂S grains was controlled by diffusion through the liquid matrix. The dependence of growth mechanisms on grain morphology has been explained in terms of the atomistic structure of the solid/liquid interface.     

Synthesis and Characterization of Thin Ferroelectric PbZr0.52Ti0.48O3 Fibrils

Thin fibrils (usually 20–100 nm in diameter) of ferroelectric PbZr_0.52Ti_0.48O₃ have a preferred nucleation and growth in the [001] direction in small particles. X-ray diffraction with the X-ray beam facing the fibril surfaces, which lie along the [001] direction, thus involves reflections of manifested intensity from (100) and (010) planes. No reflection occurs from the perpendicular planes to the [001] fibrils. A transmission electron micrograph with the corresponding electron diffraction from fibrils confers the results of the preferred growth. The fibrils have a modified orthorhombic crystal structure of lattice parameters a =0.4038 nm, b =0.4017 nm, and c =04148 nm, with an enhanced 8.033 g/cm³ density over 8.006 g/cm³ in the usual tetragonal structure of a =0.4036 nm and c =04146 nm. Surface anisotropy in a fibril that imposes (and drives) a shear stress over growing crystallites (within the fibril) along the [001] surface favors this specific crystal structure in them according to the precursor structure. A single-phase sample is obtained in 2 h by heating of an amorphous template of precursor (of the metal cations with a polymer of polyvinyl alcohol and sucrose) at 500°–800°C in air.     

Synthesis and Characterization of a New Sillenite Compound—Bi12(B0.5P0.5)O20

A new sillenite compound, Bi₁₂(B_0.5P_0.5)O₂₀, was synthesized using a solid-state reaction method. The stoichiometry was confirmed by XRD analyses, microstructural investigations, and quantitative elemental analysis. An investigation of the dielectric properties at frequencies from 100 Hz to 1 MHz revealed a broad, highly frequency-dispersive, relaxor-like dielectric anomaly, which appeared in the temperature range of −80°–100°C. The permittivity, Q × f value, and temperature coefficient of the resonant frequency, measured at ∼5.5 GHz, were determined to be 37.4, 850 GHz, and −19 ppm/K, respectively.     

Hydrothermal Synthesis and Characterization of CdWO4 Nanorods

Cadmium tungstate (CdWO₄) nanorods were successfully synthesized by a hydrothermal process at as low a temperature as 70°C. The products were characterized by X-ray powder diffraction, transmission electron microscopy, and photoluminescent spectra techniques. The results showed that the morphology of nanocrystallites significantly varied with the reaction temperature, and CdWO₄ nanorods exhibited a better luminescent property than nanofibers.