Crystallization Kinetics of α-Agl in Ag I-Based Silver Orthoborate Glasses

Kinetics for nucleation and growth of α-AgI crystals in AgI-based silver orthoborate glasses, in which only α-AgI crystals were found to crystallize in the heating process of the glasses, were studied by isothermal and nonisothermal measurements using differential scanning calorimetry and by observations of the microstructure of the glasses using scanning electron microscopy. The values of both n and m , dependent on the crystallization mechanism, were found to be 3, indicating that a constant number of nuclei of α-AgI precipitated in a glass matrix grew three-dimensionally. The preannealing of the glasses at temperatures between glass transition and crystallization did not affect the DSC isothermal curves in the crystal growth process, which suggested that the number of α-Agl nuclei would have been saturated in the glass when the glasses were prepared by quenching the AgI-based melts.     

Formation of Frozen α-Agl in Twin-Roller-Quenched Agl─Ag2 O─MxOy (MxOy= WO3, V2O5) Glasses at Ambient Temperature

Superionic conductor α-AgI, which is stable only above 147°C, was successfully frozen at ambient temperature in AgI─Ag₂O─M_xO_y (M_xO_y= WO₃, V₂O₅) glass matrices by a twin-roller-quenching technique. The system with WO₃, provided the larger composition regions where α-AgI was frozen at ambient temperature, compared to the system with V₂O₅. The matrix glasses with higher glass-transition temperatures had a stronger effect in depressing the α–β transformation of AgI. The α-AgI-frozen samples exhibited extremely large conductivities of 3 × 10⁻²-5 × 10⁻²S.cm⁻¹at 25°C.     

Influences of Zirconia and Silicon Nucleating Agents on the Devitrification of Li2O · Al2O3· 6SiO2 Glasses

The effects of Si and ZrO₂ dopants on the crystallization and phase transformation process in Li₂O · Al₂O₃· 6SiO₂ glasses were investigated using differential thermal analysis, X-ray powder diffractometry (XRD), and high-resolution transmission electron microscopy (TEM) interactively. Phase separation was observed in the studied glasses prior to substantial crystallization. Elemental Si (1 mol%) significantly aided in glass devitrification. Dropletlike phase-separated regions in the as-quenched or heat-treated glass devitrified at ∼760°C, which in turn provided sites for the heterogeneous nucleation and growth of β-quartz(ss) (solid solution), which transformed to β-spodumene(ss) at higher temperature. Low-temperature surface crystallization in these glasses occurred as low as 760°C. ZrO₂ has limited solubility in this glass system. Small ZrO₂ crystallites (·5 nm) in the as-quenched glass acted as sites for the heterogeneous nucleation and subsequent growth of large (<5 μm) β-quartz(ss) crystals in glasses containing 1.0 mol% or more ZrO₂. The transformation from β-quartz(ss) to β-spodumene(ss) was increasingly inhibited with ZrO₂ additions. The nucleating efficiency of Si was significantly greater than that of ZrO₂ in this glass system.     

Crystallization of MgO-Al2O3-SiO2-ZrO2 Glasses

The crystallization of MgO-Al₂O₃-SiO₂-ZrO₂ glasses at 1000°C was studied. Isothermal heat treatments of a cordierite-based glass (2MgO.2Al₂O₃.5SiO₂= Mg₂Al₄Si₅O₁₈) with 7 wt% ZrO₂ produced surface crystallization of α-cordierite and tetragonal ZrO₂ ( t -ZrO₂). These phases advanced into the glass by cocrystallization of t -ZrO₂ rods in an α-cordierite matrix with a well-defined orientation relation. The t -ZrO₂ rods were unstable with respect to diffusional breakup (a Rayleigh instability) and decomposed into rows of aligned ellipsoidal and spheroidal particles. The t -ZrO₂ was very resistant to transformation to monoclinic symmetry. With a similar glass containing 15 wt% ZrO₂, surface crystallization of α-cordierite and t -ZrO₂ was accompanied by internal crystallization of t -ZrO₂ dendrites. Transformation of the dendrites to mono-clinic symmetry was observed under some conditions.     

Crystallization Behavior of Novel Silicon Boron Oxycarbide Glasses

Homogeneous silicon boron oxycarbide (Si-B-O-C) glasses based on SiO _x C_{4– x} and BO _y C_{3– y} mixed environments were obtained by pyrolysis under inert atmosphere of sol–gel-derived precursors. Their high-temperature structural evolution from 1000° to 1500°C was followed using XRD, ²⁹Si and ¹¹B MAS NMR, and chemical analysis and compared with the behavior of the parent boron-free Si-O-C glasses. The XRD study revealed that, for the Si-O-C and the Si-B-O-C systems, high-temperature annealing led to the crystallization of nanosized β-SiC into an amorphous SiO₂-based matrix. NMR analysis suggested that the β-SiC crystallization occurred with a consumption of the mixed silicon and boron oxycarbide units. Finally, by comparing the behavior of the Si-O-C and Si-B-O-C glasses, it was shown that the presence of boron increased the crystallization kinetics of β-SiC.     

Novel Low-Temperature Synthesis of Ferroelectric Neodymium-Doped Bismuth Titanate Nanoparticles

In this study, we report on the synthesis of nanopowders of ferroelectric Bi_3.5Nd_0.5Ti₃O₁₂ ceramic at temperatures below 500°C via a simple chemical method using citric acid as a solvent. The calcined powders were characterized using X-ray diffraction (XRD), differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). Heating the as-dried powders in air first leads to crystallization of the Bi₂Ti₂O₇ phase at ∼310°C, followed by crystallization of the perovskite Nd-doped Bi₄Ti₃O₁₂ phase at ∼490°C as suggested by the peaks in the DSC analysis and confirmed by the evolution of phases in XRD patterns of the powders calcined at various temperatures. TEM of particles calcined at 550°C for 1 h in air showed an average particle size of 50–60 nm. The temperature dependence of capacitance of nanopowders calcined at 700°C for 1 h in air showed a Curie temperature of ∼615°C evincing a ferroelectric transition.     

High-Temperature Transmission Electron Microscopy and X-Ray Powder Diffraction Studies of Polymorphic Phase Transitions in Ba4Nb2O9

Polymorphic phase transitions in Ba₄Nb₂O₉ were studied by thermal analyses, high-temperature transmission electron microscopy and X-ray powder diffractometry. Two stable polymorphs were isolated, low-temperature α-modification and high-temperature γ-modification, with the endothermic phase transition at 1176°C. The α→γ transformation is accompanied by the formation of a 120° domain structure, which is a consequence of hexagonal→orthorhombic unit cell reconstruction. Reheating the presintered γ-Ba₄Nb₂O₉ results in the formation of a metastable γ'-modification (formerly known as β-polymorph) in the temperature range between 360° and 585°C, before the γ→α transformation at 800°C. Above ∼490°C Ba₄Nb₂O₉ becomes moderately sensitive to a loss of BaO. In air the surface of Ba₄Nb₂O₉ grains decomposes to nanocrystalline Ba₅Nb₄O₁₅ and BaO, which instantly reacts with atmospheric CO₂ to form BaCO₃. Surface reaction delays γ→α transformation up to 866°C in air. In vacuum the loss of BaO is even more enhanced and consequently the formation of minor Ba₃Nb₂O₈ phase is observed above 1150°C.     

Effect of heat treatment on AgI-rich chalcogenide glasses with enhanced ionic conductivity

The glass-ceramics of AgI-based electroconductive chalcogenide system was realized using an appropriate heat treatment at a fairly high temperature (T_g + 40°C) and different times ranging from 4 to 20 hours. The crystallization behavior and electroconductive properties of the heat-treated samples were studied in detail. Transmission study was performed, and the results show that the cut-off edge of the short wavelength is red-shifted at prolonged annealing time but remains an excellent transmittance in the mid-infrared (IR) region. XRD and scanning electron microscopy results indicated that the precipitated crystalline phases are mainly β-/γ-AgI. Moreover, a small amount of α-AgI, which rarely existed at room temperature, is precipitated in the AgI-rich chalcogenide glass-ceramics. The ionic conductivity of all glass-ceramics was enhanced by heat treatment in contrast to that of base glass. Raman analysis exhibited the structure variation in the glass sample after heat treatments. This study provided an observation of crystallization in chalcogenide glass containing large amounts of AgI and be of good guidance to fabricate novel AgI-based chalcogenide glass-ceramics that can be candidates in infrared optics and solid electrolyte applications.     

Crystallization of Li2O · Al2O3· 6SiO2 Glasses Containing Niobium Pentoxide as Nucleating Dopant

Niobium pentoxide (T form, orthorhombic system) was utilized to promote devitrification in Li₂O · Al₂O₃· 6SiO₂ glasses. Two or more mole percentage of this nucleating dopant enhanced crystallization in these glasses. Glasses containing 4.0 and 8.0 mol% T-Nb₂O₅ exhibited a high tendency to form dispersed TT-Nb₂O₅ (monoclinic system) precipitates during the glass quenching process. The crystallization process in glasses containing 2.0 or 4.0 mol% T-Nb₂O₅ occurred as microphase separation, followed by the formation of dispersed TT-Nb₂O₅ crystalline precipitates (760°C), followed by β-quartz solid-solution ( ss ) formation (850° to 900°C) heterogeneously nucleated from the precipitates. β-quartz( ss ) transformed to β-spodumene( ss ), along with a polymorphic transition from the TT-Nb₂O₅ to M-Nb₂O₅ (tetragonal system) crystalline phase.     

Nucleation and Crystallization of NaNbO3 from Glasses in the Na2O-Nb2O5-SiO2 System

Transparent glass-ceramics, in which the major phase was NaNbO₃, were obtained by heat treatment of glasses in the Na₂O-Nb₂O₅-SiO₂ system. The structure of the glass and the changes occurring during crystallization as a function of temperature and heating rate were examined by X-ray diffraction, transmission and replication electron microscopy, density, and other measurements. On heating, a rather abrupt formation of uniformly dispersed particles was observed. In the early stages of crystallization, these particles contained NaNbO₃ as loose, radially grown dendrites of identical crystal orientation which became dense during later stages of crystallization. The particle sizes ranged from 200 to 10,000 A, depending on the SiO₂ content of the glass. Transparency of the crystallized material was dependent on the particle size rather than on the amount of NaNbO₃ formed. The temperature at which crystallization occurred increased with the heating rate whereas the viscosity at crystallization decreased. For a given value of the rate of crystal formation per °C of temperature increase, the product (viscosity)ⁿ× (heating rate) was constant. The nucleation and growth phenomena which occurred in these glasses was attributed to microheterogeneities of higher Nb₂O₅ content which formed part of the glass structure.     

Crystallization Kinetics of Lithium Orthosilicate Glasses

The formation of crystalline Li₄SiO₄ and Li₂SiO₃ from lithium orthosilicate glasses has been studied by means of in situ high-temperature X-ray diffraction. The first phase that crystallizes from the glass could not be identified, but was followed by the transformation to crystalline orthosilicate and metasilicate. Orthosilicate formation was tracked at temperatures between 600° and 650°C, whereas at higher temperatures, the formation of a small amount of crystalline metasilicate occurs. The kinetics of the initial phase of both crystallization processes are described by the Avrami–Erofeev equation, resulting in activation energies of 90 kJ/mol for the formation of the unidentified phase, and 68 kJ/mol for the formation of Li₄SiO₄. The rate constant for the crystallization of the unidentified phase is 0.014 s⁻¹ at 510°C, equaling that of the orthosilicate formation at 630°C. After isothermal heat treatment for 100–800 s, depending on temperature, 80%–95% of the sample is crystallized and further crystallization is controlled by diffusion in both cases.     

Microstructural Characterization and Fracture Toughness of Cordierite-ZrO2 Glass-Ceramics

Crystallization of an MgO-Al₂O₃-SiO₂-ZrO₂ sintered glass frit was studied. Heat treatment at 850° or 900°C caused initial crystallization of μ-cordierite and tetragonal ( t ) ZrO₂. The t -ZrO₂ crystallized with an irregular dendritic morphology and could be transformed to monoclinic ( m ) symmetry under certain conditions; the cordierite underwent the μ→α a transformation with extended annealing. Heat treatments at 1000°C caused crystallization of t -ZrO₂ rods and spheroids in an α-cordierite matrix; these ZrO₂ crystals, however, are resistant to transformation to m -ZrO₂. The beneficial effects of ZrO₂ on the fracture toughness of cordierite-based glass-ceramics are described.     

Prominent Nanocrystallization of 25K2O·25Nb2O5·50GeO2 Glass

Some K₂O-Nb₂O₅-GeO₂ glasses are prepared, and their crystallization behaviors are examined. 25K₂O·25Nb₂O₅·50GeO₂ glass with the glass transition temperature T _g= 622°3C and crystallization onset temperature T _x= 668°3C shows a prominent nanocrystallization. The crystalline phase is K_3,8Nb₅Ge₃O_20,4 with an orthorhombic structure. The sizes of crystals in the crystallized glasses heat-treated at 630° and 720°3C for 1 h are °10 and 20–30 nm, respectively, and the crystallized glasses obtained by heat treatments at 620°-850°3C for 1 h maintain good transparency. The density of crystallized glasses increases gradually with increasing heat-treatment temperature, and the volume fraction of crystals in the sample heat-treated at 630°3C for 1 h is estimated to be ∼35%. The usual Vickers hardness and Martens hardness (estimated by nanoindentation) of 25K₂O·25Nb₂O₅·50GeO₂ glass change steeply by heat treatment at T _g, i.e., at around 35% volume fraction of nanocrystals. The present study demonstrates that the composite of nanocrystals and the glassy phase has a strong resistance against deformation during Vickers indenter loading in crystallized glasses.     

Behavior of Silver and Palladium Mixtures during Heating

The behavior of mixtures of silver and palladium during heating in both air and an inert atmosphere was studied using X-ray diffractometry (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dilatometry, and scanning electron microscopy (SEM). In situ high-temperature XRD studies on a commercial 20% palladium material with submicrometer-sized particles indicated that an intermetallic phase, most likely Ag₃Pd, formed in air between 300° and 400°C, the same temperature range where a 13% linear expansion was measured by dilatometry. The DSC data indicated an exothermic peak at 340°C, a temperature where the TGA results indicated that the material had picked up only 0.2% oxygen, compared with the maximum of 1.4% at 525°C. No PdO was detected by XRD at 400°C, which suggests that oxygen was being incorporated in the intermetallic. Microstructural examination using SEM indicated that larger particles, with internal pores, had formed after heating in air to 375°C. When the material was heated in argon for 1 h at 400°C, no intermetallic phase or alloy formed, and minimal expansion occurred. When mixtures of larger silver particles (5–30 μm) with palladium particles (1–3 μm) were heated in air, the maximum amount of expansion that occurred increased from 0% for pure palladium up to a maximum of 18% at 75% silver. This result supports the conclusion that expansion is a result of formation of this new phase, in the presence of oxygen, not of the oxidation of the palladium.     

Nano α-Al2O3 Powder Preparation by Calcining an Emulsion Precursor

An experimental study has been conducted to evaluate the formation of nano α-Al₂O₃ under various conditions, such as different calcining temperatures and emulsion ratios of aqueous aluminum nitrate solutions and oleic acid with a high-speed stirring mixer. Four batches of the precursor powders were calcined at three different temperatures of 1000°, 1050°, and 1100°C for 2 h and a terminal product of nano α-Al₂O₃ powders was obtained. The products have been identified by X-ray diffraction (XRD), specific surface area measurement scanning electron microscope, and transmission electron microscope (TEM). The XRD results show that the phase of powders is determined to be α-Al₂O₃, indicating that the overall process has been effective. The optimum calcination temperature of the precursor powder for crystallization of nano α-Al₂O₃ was found to be 1000°C for 2 h. The TEM image indicates that the particle grains have a sub-spherical shape with a mean size of 50–100 nm.     

A Chemical Route to BiNbO4 Ceramics

The liquid phase sintering of fine BiNbO₄ powders allows to obtain dense ceramics with excellent microwave dielectric properties (ɛ=44–46; Q × f =16,500–21,600 GHz) at T ≥700°C. The thermal decomposition of freeze-dried precursors results in the crystallization of a metastable β'-BiNbO₄ polymorph that transforms into a stable orthorhombic α-modification at T ≥700°C. The dependence of sinterability on the powder synthesis temperature shows the maximum at 600°C, corresponding to the formation of crystalline BiNbO₄ powders with a grain size 80–100 nm. Sintering temperature reduction to 700°C prevents the deterioration of silver contacts during co-firing with BiNbO₄ ceramics. In situ scanning electron microscopy observation of the morphological evolution during sintering shows that the intense shrinkage soon after the appearance of a CuO–V₂O₅ eutectics-based liquid phase is accompanied by complete transformation of the ensemble of primary BiNbO₄ particles.     

Physical Stabilization of the β→γ Transformation in Dicalcium Silicate

It has been shown that the monoclinic β -phase of dicalcium silicate (Ca₂SiO₄) can be stabilized against transformation to the orthorhombic γ -phase by physical rather than chemical factors. Stabilization was studied in different types of microstructures fabricated under various processing conditions such as different powder or grain sizes, chemical additives, cooling kinetics, or high-temperature annealing treatments. The observations can be explained in terms of a critical particle size effect controlling nucleation of the transformation. Rapid quenching through the high-temperature hexagonal ( α ) to orthorhombic ( a' _H) transformation at 1425°C, which is accompanied by a −4.7% volume decrease, causes periodic fracture of β -twins due to accumulated strains. Chemical doping with K₂O or Al₂O₃ promotes the formation of amorphous phases which mold themselves around β -Ca₂SiO₄ grains. Annealing treatments cause crystallization of the glass and subsequent transformation to the γ -phase.     

Sintering in Nitrogen Atmosphere of Iron-Rich Glass-Ceramics

The sintering and the crystallization of two iron-rich glass compositions (45–75-μm powder fractions) were studied in air and nitrogen atmospheres. The phase formation was evaluated by differential thermal analysis, while the densification, by dilatometry; the crystalline phases were identified by X-ray diffraction and the structure observed by scanning electron microscopy. It was highlighted that, due to the absence of Fe²⁺ oxidation and lower viscosity of the parent and residual glasses, the sintering in nitrogen atmospheres occurs at 100°–200°C lower temperature. In the same time the higher amount of crystal phase, formed during sinter–crystallization in inert atmosphere, improves the mechanical properties. A value of 120 MPa for the bending strength was obtained after 1-h sintering at 960°C in N₂.     

Microstructural Evolution in Fast-Heated Cordierite-Based Glass-Ceramic Glazes for Ceramic Tile

The crystallization mechanism of α-cordierite from a B₂O₃- and TiO₂-containing glass submitted to fast heating in the cordierite primary phase field of the CaO–MgO–Al₂O₃–SiO₂ quaternary system was investigated. Addition of B₂O₃ to a SiO₂-rich glass suppressed the formation of μ-cordierite. This suppression facilitated densification by viscous flow before crystallization. Powder X-ray diffractometry, field-emission electron scanning microscopy, and energy-dispersive X-ray analysis revealed that α-cordierite nucleated directly from glass on the boundaries of original particles and was probably favored by TiO₂, which acted as a nucleant. The growth kinetics of α-cordierite crystals was fast, and the crystals seemed to grow by consuming glass directly from the growing interphase. The estimated amount of α-cordierite in the glass heated at 1160°C was 69.5 wt%, as determined using the Alegre method. The final microstructure consisted of an arrangement of well-shaped hexagonal prisms, with sizes <3 μm, immersed in a residual glassy phase. The feasibility to develop new glass-ceramic glazes using the present and previous works is considered.     

Electrical Conductivity of PbO-P2O5-V2O5Glasses

The dc conductivities (α) of PbO-P₂O₅-V₂O₅ glasses containing up to 80 mol% V₂O₅ were measured at T = 100°C to T = 10°C below the glass transition temperature. Dielectric constants at 1 MHz, densities, and the fraction of reduced V ion were measured at room temperature. The conduction mechanism of glasses containing >10 mol% V₂O₅ was considered to be small-polaron hopping, as previously reported for other vanadate glasses. The temperature dependence of α was exponential, with α= (αo/ T ) exp(− W/kT ). When the V₂O₅ content was ≥50 mol%, W decreased and α increased with increasing V₂O₅ content, and the adiabatic approximation could be applied. In the composition range between 10 and 50 mol% V₂O₅, α increased with increasing V₂O₅ content, but W varied little. In this region, the hopping conduction was characterized as nonadiabatic. The effect of dielectric constants and V ion spacing on W is discussed.