Vitrification and crystallization in the system of K2O-B2O3-TiO2

The vitrification and crystallization behavior of melts produced at 1400 °C in the ternary system of K₂O-B₂O₃-TiO₂ is investigated. It is shown that there are two fields of compositions (indicated in mol%) which allow obtaining the glass-ceramic materials with continuous glassy matrix after the cooling of molten compositions. In the first field [TiO₂] = 25-57, [K₂O] = 30-50 and [B₂O₃] = 0-25, the glass-ceramics consisted of the potassium-titanium-borate glassy phase and different crystalline potassium titanates (K₄Ti₃O₈, K₂Ti₂O₅, K₂Ti₄O₉, K₂Ti₆O₁₃). The ratio of TiO₂:K₂O in the obtained titanates increases with [TiO₂] and [B₂O₃]. In the second field, [TiO₂] = 7-37, [K₂O] = 0-25 and [B₂O₃] = 52-93, the obtained glass-ceramics consisted of a similar vitreous phase, as mentioned above, and TiO₂ crystals. During the cooling of the melts, short whiskers-like crystals of anatase formed in the compositions with relatively low [TiO₂] and relatively high [K₂O], whereas long fiber-shaped crystals of rutile appeared with the compositions characterized with relatively high [TiO₂] and relatively low [K₂O]. The possible application of the obtained glass-ceramic materials as a source of fibrous TiO₂, for composite reinforcement, and as solid lubricants is discussed.     

Synthesis,structural and ferroelectric properties of barium titanate based glass-ceramic nano-composites

Novel glass-ceramic nano-composites based on BaTiO₃–V₂O₅–Bi₂O₃ glasses were prepared via heat-treatment at crystallization temperature (T_cr). The nanostructural and ferroelectric properties were investigated by differential scanning calorimeter (DSC), transmission electron microscope (TEM), X-ray diffraction (XRD) and dielectric measurements, respectively. It was shown by XRD and TEM studies that appropriate heat-treatment glasses can turn into glass-ceramic nano-composites consisting of crystallites smaller than 30 nm embedded in the glassy matrix. The observed dielectric constant of heat‐treated samples, showed average broad peak around 324 K. The average Curie temperature (T_c) observed around 324 K in the present system. This observation of these glass-ceramic nano-composites can be utilized to control T_c by proper adjustment of BaTiO₃ content. This result, therefore, supports dipolar orientation and phase transition in the glass-ceramic samples dispersed with nanocrystalline BaTiO₃. Such a feature can be used for industrial applications where the shape of the application article is a necessary requirement such as integrated capacitor.     

The dielectric behavior of a thermoelectric treated B2O3-Li2O-Nb2O5 glass

A transparent glass with the composition 60B₂O₃-30Li₂O-10Nb₂O₅ (mol%) was prepared by the melt-quenching technique. Glass-ceramics, containing LiNbO₃ ferroelectric crystallites, were obtained by heat-treatment (HT) above 500 °C, with and without the presence of an external electric field. The dielectric properties of the glass and glass-ceramic were investigated, as a function of temperature (270-315 K), in the 10 mHz-32 MHz frequency range. The presence of an external electric field, during the heating process, improves the formation of LiNbO₃ crystallites. The rise of the treatment temperature and the applied field, during the heat-treatment, leads to a decrease in the dc electric conductivity (σ_dc), indicating a decrease of the charge carriers number. The dielectric permittivity (ε′) values (300 K;1 kHz) are between 16.25 and 18.83, with the exception of the 550 °C HT sample that presents a ε′ value of 11.25. An electric equivalent circuit composed by an R in parallel with a CPE element was used to adjust the dielectric data. The results reflect the important role carried out by the heat-treatment and the electric field during the HT in the electric properties of glass-ceramics.     

Dielectric properties of fine-grained PbTiO3 crystals precipitated in a glass

The spontaneous deformation of PbTiO₃ crystals precipitated in a PbOTiO₂Al₂O₃SiO₂ glass was found to decrease with decreasing grain size. This trend remains even after the glass matrix surrounding PbTiO₃ crystals is removed completely by HNO₃ acid immersion. Consequently, a linear electro-optic effect cannot be expected from transparent glass-ceramics which necessarily comprise very-fine-grained crystals. The dielectric constant of PbTiO₃ crystals surrounded by a glassy matrix shows two maxima at grain sizes 0.15 μm and 250 Å, but is still fairly high even at a grain size as small as 160 Å. This suggests that a material with a large quadratic electro-optic effect may be produced from a transparent glass-ceramic. The maxima of the dielectric constant at grain sizes 0.15 μm and 250 Å were interpreted in terms of the internal stress and internal electric field, respectively.     

Fast sinter-crystallization of a glass from waste materials

A glass belonging to the CaO-Al₂O₃-SiO₂ system and corresponding to the melting of a mixture of industrial inorganic waste (feldspar mining residues, lime from fume abatement systems of the glass industry and recycled soda-lime glass) has been successfully transformed into dense and strong sintered glass-ceramics, even for very short holding times (30 min at 960 °C) and a very rapid heating, consisting of direct insertion of pressed fine glass powders in furnace (‘fast sinter-crystallization’). The addition of kaolin clay, conceived as binder for pressed glass powders, proved to positively influence the phase balance, the homogeneity and the degree of crystallization of fast sintered glass-ceramics, thus justifying the achievement of remarkable mechanical properties (bending strength exceeding 100 MPa, micro-hardness exceeding 7 GPa).     

Studies of Er doped germanate-oxyfluoride and tellurium-germanate-oxyfluoride transparent glass-ceramics

An erbium doped germanate-oxyfluoride glass 60GeO₂ · 20PbO · 10PbF₂ · 10CdF₂ (GPOF) and a tellurium-germanate-oxyfluoride glass 30TeO₂ · 30GeO₂ · 20PbO · 10PbF₂ · 10CdF₂ (TGPOF) were prepared in the bulk form. By appropriate heat treatment of the as-prepared glasses above, transparent glass-ceramics were obtained with the formation of β-PbF₂ nanocrystals in the glass matrix confirmed by X-ray diffraction. Optical absorption and photoluminescence measurements were performed on as-prepared glass and glass-ceramics. The luminescence of Er³⁺ ions in transparent glass-ceramics revealed sub-band splitting generally seen in a crystal host. The intensity of red and near infrared luminescence significantly increased in transparent glass-ceramic compared to that in as-prepared glass. Two luminescence bands at 758 nm from ⁴F_7/2 → ⁴I_13/2 and at 817 nm from ²H_11/2 → ⁴I_13/2 transitions were observed from transparent glass-ceramic but cannot be seen from the corresponding as-prepared glass. These results are attributed to the change of ligand field of Er³⁺ ions and the decrease of effective phonon energy when Er³⁺ ions were incorporated into the precipitated β-PbF₂ nanocrystals.     

Crystallization behavior of glasses in the system of Na2O-CaO-MgO-Fe2O3-Al2O3-SiO2 with high contents of nickel oxide

The structural behavior of nickel oxide in glassy and glass-ceramic materials, obtained in the system of Na₂O-CaO-MgO-Fe₂O₃-Al₂O₃-SiO₂, was investigated. The influence of the NiO content on the vitrification, crystallization, structure and exploitation properties of two model compositions, with different ratios [CaO]/[MgO] was analyzed. On the basis of DSC and XRD data, it is shown that NiO promoted the formation of bunsenite crystals, as nuclei for crystallization. On the other hand, NiO promoted formation of pyroxenes even for compositions with low MgO contents, which formed gehlenite without NiO admixtures. It is shown that in the composition with relatively high MgO contents, NiO could participate in the formation of two types of pyroxenes with the structure and chemical composition similar to (MgO_0.4NiO_0.6)(CaO_0.9NiO_0.1)Si₂O₆ and diopside-hedenbergite solid solutions. The optimal contents of NiO in both model compositions was about of 7 wt%, since higher contents reduced the exploitation properties. The glass-ceramics with optimal contents of NiO were also produced using Ni bearing galvanic slurry and coal ash; the resulting materials showed similar exploitation properties to those mentioned above.     

Effect of heat-treatment condition on crystallization behavior and thermal expansion coefficient of Li2O-ZnO-Al2O3-SiO2-P2O5 glass-ceramics

Utilizing P₂O₅ as nucleation agent, a Li₂O-ZnO-Al₂O₃-SiO₂ glass was prepared by conventional melt quenching technique and subsequently converted to glass-ceramics with different crystal phases. During the processing, two-step heat-treatments including nucleation and crystallization were adopted. The effects of heat-treatment on the crystal type, the microstructure and the thermal expansion behavior of the glass-ceramics were studied by means of differential scanning calorimetry, X-ray powder diffraction analysis, scanning electron microscopy and thermal expansion coefficient tests. It was shown that the crystallization of occurred after the glass was treated at 580 °C. As the temperature increased from 580 °C to 630 °C, cristobalite and were identified as main and second crystal phases, respectively, in the glass-ceramic. An increase in the temperature to 700 °C, the β-quartz solid solution in the glass-ceramic accompanied by a decrease in cristobalite content. The transformation from to γ₀-Li₂ZnSiO₄ took place from 700 °C to 750 °C. The resulting crystallization phases in the glass-ceramics obtained at the temperature higher than 750 °C were β-quartz solid solution and γ₀-Li₂ZnSiO₄. The glass-ceramics containing or β-quartz solid solution crystal phase possessed a microstructure formed by the development of dendritic crystals. The thermal expansion coefficient of the glass-ceramics varied from 36.7 to 123.8 × 10⁻⁷ °C⁻¹ in the temperature range of 20-400 °C, this precise value is dependent on the type and the proportion of the crystalline phases presented.     

Structural, optical and dielectric properties of glass-nanocomposite

Transparent glass-nanocomposite sample [50Li₂B₄O₇-50(SrO-Bi₂O₃-Nb₂O₅)] (mol %) was prepared by a conventional melt-quenching technique. Fluorite (Bi₃NbO₇) and SrBi₂Nb₂O₉ (SBN) was produced by heat-treating the as-prepared sample at 773 K for 6 h (HT773). The nanocrystallites of fluorite and SBN phases in the Li₂B₄O₇ glass matrix were established by differential thermal analysis (DTA) which is confirmed by X-ray powder diffraction (XRD), infrared spectroscopy and transmission electron microscopic (TEM) studies. The influence of heat-treating the as-prepared sample on the optical properties (transmission, optical band gap and Urbach energy) has been investigated. Properties such as dielectric constant and dielectric loss as a function of frequency (120 Hz -100 k Hz) and temperature (300-829 K) are reported.     

A low silica, barium borate glass-ceramic for use as seals in planar SOFCs

A low silica, barium borate glass-ceramic for use as seals in planar SOFCs containing 64 mol%BaO, 3 mol%Al₂O₃ and 3 mol%SiO₂ was studied. Coefficient of thermal expansion (CTE) between 275-550 °C, glass transition temperature (T_g), and dilatometric softening point (T_s) of the parent glass were 11.9 × 10⁻⁶ °C⁻¹, 552 °C, and 558 °C, respectively. Glass-ceramic was produced by devitrification heat treatment at 800 °C for 100 h. It was found that nucleation heat treatment, seeding by 3 wt%ZrO₂ as glass-composite and pulverization affected the amount, size and distribution of crystalline phases. SEM-EDS and XRD results revealed that crystalline phases presented in the devitrified glass-ceramic were barium aluminate (BaAl₂O₄), barium aluminosilicate (BaAl₂Si₂O₈) possibly with boron associated in its crystal structure, and barium zirconate (BaZrO₃). CTE of the devitrified glass-ceramic was in the range of (10.1-13.0) × 10⁻⁶ °C⁻¹. Good adhesion was obtained both in the cases of glass and devitrified glass-ceramic with YSZ and AISI430 stainless steel. Interfacial phenomena between these components were discussed.     

Effect of P2O5 on the early stage crystallization of K-fluorrichterite glass-ceramics

The addition of 2 mol% P₂O₅ to stoichiometric K-fluorrichterite (KNaCaMg₅Si₈O₂₂F₂, KFR) has been reported to enhance the mechanical properties and improve the in vitro biocompatibility of this glass-ceramic by promoting the formation of enstatite and fluorapatite (FA). Here, the effect of further increasing the P₂O₅ concentration on phase evolution of KFR has been investigated. XRD data showed that mica crystallized in samples with 4 and 5 mol% P₂O₅ (GP4 and GP5, respectively) at 650 °C, but no diopside was detected at higher temperatures, in contrast with the general phase evolution in KFR based glass-ceramics. More importantly, however, the addition of ?4 mol% P₂O₅ induced phase separation of the glass into a silica glass matrix and phosphate rich droplets prior to crystallization. EDS traces taken from samples heat-treated at 600 °C, revealed that the silica glass matrix was deficient in Mg and unlikely to be the host for crystallization of mica. Conversely, the P₂O₅ rich regions contained excess Mg and were considered to be the host for the formation of mica and FA.     

Crystallization of 2(Ca,Sr,Ba)O-TiO2-2SiO2 composition glasses

Crystallization was examined for glasses having chemical composition of 2(Ca,Sr,Ba)O-TiO₂-2SiO₂ in which the CaO/SrO/BaO molar ratio varied. Powdered glass samples were pelleted into disks and sintered at 950 °C for 2 h. The major phase precipitated in the sintered samples was (Ca,Sr,Ba)₂TiSi₂O₈ and minor phase of perovskite such as CaTiO₃ or SrTiO₃ increased with CaO content in the samples containing more than 40 mol% of CaO in total CaO+SrO+BaO. Three regions having different slopes were found in linear relationships between SrO mol% and exothermal peak temperature on DSC curves or d[0 0 2] values determined by powder XRD method. These facts suggested that the major phase precipitated in each region was a solid solution containing a different amount of CaO, SrO, BaO and that these compositions varied depending on SrO content in the sample. The micro-crystalline structure, which could be useful in fabricating a dielectric dense body, was observed for samples containing 30-70 mol% of SrO.     

Thermo-optic properties of B2O3 doped Li2O-Al2O3-SiO2 glass-ceramics

Reduction in the temperature coefficient of the optical path length, dS/dT of Li₂O-Al₂O₃-SiO₂ glass-ceramics with near-zero thermal expansion coefficient was attempted using control of the temperature coefficient of electronic polarizability, ?, and the thermal expansion coefficient, α. The dS/dT value of 2.6 mol% B₂O₃-doped glass-ceramic was 12.5  × 10⁻⁶/°C, which was 0.9 ×  10⁻⁶/°C smaller than that of B₂O₃-free glass-ceramic. On the other hand, reduction in dS/dT through B₂O₃ doping was not confirmed in precursor glasses. Results showed that reduction in dS/dT of the glass-ceramic through B₂O₃ doping is caused by the reduction in ?. The reduction in ? from B₂O₃ doping was probably attributable to numerical reduction in non-bridging oxide ions with larger ? value by the concentration of boron ions in the residual glass phase. In addition, application of hydrostatic pressure during crystallization was effective to inhibit precipitation of β-spodumene solid solution, which thereby decreases dS/dT. The dS/dT value of B₂O₃-doped glass-ceramic crystallized under 196 MPa was 11.7 ×  10⁻⁶/°C. That value was slightly larger than that of silica glass. The α value of this glass-ceramic was smaller than that of silica glass.     

Thermal Properties and Phase Transformation of 2 mol% Y2O3-PSZ Nanopowders Prepared by a Co-precipitation Process

Two mol% Y₂O₃-PSZ precursor powders for dental applications were synthesized using ZrOCl₂·8H₂O and Y(NO₃)₃·6H₂O by a co-precipitation process at pH 7 and 348 K for 2 h. The thermal properties and phase transformation of 2Y-PSZ nanocrystallite powder have been investigated using a thermogravimetric and difference scanning calorimeter (TG/DSC), Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy (TEM), selected area electron diffraction and dilatometric analysis. Two weaker broad exothermic peaks appear at around 618 and 718 K were explored in DSC results. The TG analysis shows that minor weight loss occurs from 298 to 348 K, followed by three major weight losses at 610, 630 and 773 K. Calcinated at 773 and 1273 K, the crystallized phases are composed of the major phase of tetragonal ZrO₂ and minor phase of monoclinic ZrO₂. TEM reveals that the tetragonal ZrO₂ with an average size of less than 20.0 nm is mainly aggregated into the secondary aggregates with a size of small than 30.0 nm. The sintering curve of the compact pellet has a significant shrinkage with a linear rate of 18.5% at about 1341 K. Maximum densification rate happened at 1473 K, demonstrating the good low temperature sinterability for dental applications.     

Consolidation and mechanical properties of Cu46Zr42Al7Y5 metallic glass by spark plasma sintering

Cu₄₆Zr₄₂Al₇Y₅ metallic glass with nearly 100% relative density was obtained by spark plasma sintering (SPS) with a diameter of 15 mm, which was larger than the largest size of 10 mm for the as-cast specimen. The fracture strength of the sintered specimen reached 2044 MPa, which was 15% higher than that of the as-cast Cu₄₆Zr₄₂Al₇Y₅ glassy specimen. The densification and compressive properties of the sintered specimens were related to sintering temperature. Structural changes of the specimens sintered at various sintering temperatures resulted in the difference of macro-mechanical properties.     

Variation of luminescence properties of Na2O-CaO-SiO2: Nd glass with crystallinity

The optical absorption and emission intensities of Nd³⁺-doped transparent glass-ceramics with high crystallinity in Na₂O-CaO-SiO₂ (NSC) system were studied. The transmittance of NCS decreases with increasing degree of crystallinity, however it still remains 65.5% at λ = 710 nm when the crystallization is almost completed. Judd-Ofelt theory is performed to evaluate the radiative transition probability as well as quality factor, branching ratio and emission cross section. The maximum values of Ω₂ and emission cross section (⁴F_3/2 → ⁴I_11/2) of NCS are obtained after nucleating at 630 °C for 10 h. The quality factor increases with increasing crystallinity, while branching ratio for ⁴F_3/2 → ⁴I_11/2 is opposite. The results show that transparent glass-ceramic with high crystallinity is a potential laser host for 1.06 μm emission.     

Electrical properties of Bi3.15Nd0.85Ti2.8-xZr0.2MnxO12 thin films with different Mn content synthesized by chemical solution deposition (CSD)

Bi_3.15Nd_0.85Ti_2.8-xZr_0.2Mn_xO₁₂ (BNTZM) thin films with various Mn content (x = 0, 0.005, 0.01, 0.03, and 0.05) have been prepared on Pt/Ti/SiO₂/Si (100) substrates by a chemical solution deposition (CSD) technique. The crystal structures of BNTZM thin film have been analyzed by X-ray diffraction (XRD). The dependence of Mn contents on the ferroelectric, dielectric properties, and leakage current of these BNTZM films have been thoroughly investigated. The XRD analysis demonstrated that all the BNTZM thin films were of typical bismuth-layer-structured ferroelectrics (BLSF) polycrystalline structure and exhibited a highly preferred (117) orientation. Among these BNTZM films, the BNTZM thin film with Mn content equal to 0.01 exhibits the maximum remnant polarization (2P_r) of 48μC/cm² and a low coercive field (2E_c) of 177 kV/cm. In addition, the BNTZM thin film with x = 0.01 (Mn) showed a fatigue-free behavior up to 1 × 10¹⁰ read/write cycles.     

Nano- and micro-indentation studies on lithium borate-barium bismuth niobate glasses

The structure and mechanical properties of multifunctional lithium tetra-borate based glasses and glass-ceramics of the system (100 − x) Li₂B₄O₇₋x(BaO-Bi₂O₃-Nb₂O₅) with x = 10, 20 and 30 in molar ratio, have been characterized. Nano- and micro-indentation techniques were employed to evaluate the elastic modulus, hardness and toughness of the as-cast and annealed glasses. These were complemented with detailed structural investigations using X-ray diffraction, microscopy (optical, scanning electron and high resolution transmission electron microscopies) and nuclear magnetic resonance spectroscopy. These investigations reveal a smooth variation of the mechanical properties with composition except for the composition corresponding to x = 20. This deviation has been attributed to subtle changes in the glass-structure due to amorphous phase-separation and heat-treatment-assisted nano-crystallization.     

Lithium aluminosilicate glass-ceramic containing Na2O for low-temperature anodic bonding in microelectronic mechanical systems

In this study, one kind of lithium aluminosilicate-β-quartz glass-ceramic containing Na₂O has been chosen, which can be used for low-temperature bonding with a higher bonding rate for the manufacture of microelectronic mechanical systems. The microstructure of the glass-ceramic is analyzed by transmission electron microscopy, high resolution transmission electron microscopy, selected-area diffraction, energy dispersive spectrometry and X-ray diffraction. The influence of the heat treatment process of the glass on the properties and the microstructure of the glass-ceramics is discussed. The microstructure of the glass-ceramic has the continuous glassy region with higher alkali metal ion content, which benefits the low-temperature anodic bonding.     

Spectroscopic and dielectric properties of a lithia-containing glass

Glass of the composition 65SiO₂-20CaO-15Li₂O (mol %) was prepared and subjected to heat treatment. The obtained samples were characterized before and after heat treatment by DTA, TG, XRD, SEM, IR and dielectric spectroscopy. DTA showed an endothermic peak at 954 °C, accompanied by a pronounced change in the microstructure, as revealed by SEM. XRD showed that metasilicate predominates on heat treatment at 726 °C, while on heat treatment at 726 °C, then at 954 °C, disilicate crystallizes as the main phase. The IR spectra of the heat-treated glasses revealed that the vibrations of O-H groups are drastically decreased, while those due to non-bridging oxygens Si-O⁻ are increased. The dielectric constant (ε′), the loss tangent (tan δ) and the ac conductivity (σ_ac) for the prepared glasses were investigated before and after heat treatment over a moderately wide range of frequency and temperature. The activation energy of the dielectric relaxation process was found to depend on the techniques of sample preparation. A drop of dielectric constant values was observed for the heat-treated sample, which can be attributed to the ordering of the induced crystalline phases. The conductivity behavior suggests a hopping mechanism responsible for conduction.