Preparation and properties of ferromagnetic glass ceramics and glass fibers based on the composition of SiO2-B2O3-Fe2O3-SrO

The ferromagnetic glass ceramics in the system SiO₂-B₂O₃-Fe₂O₃-SrO were prepared via four different fabrication methods, i.e., fiber-drawing, melt-quenching, natural-cooling, and annealing, without performing any nucleation and crystallization heat treatments. The influences of chemical composition and fabrication method on the spontaneous crystallization of magnetite were investigated by X-ray diffraction, scanning and transmission electron microscopy. The X-ray diffraction patterns show the presence of nanometric magnetite crystals in the glass matrix, and the increasing boron oxide can promote the spontaneous crystallization of magnetite. The estimated size of crystallized magnetite varies between 12 and 50 nm. The magnetic properties of the glass ceramics derived from the four fabrication methods were analyzed using a Vibrating sample magnetometer (VSM), Agilent HP8722ES vector network analyzer and Mössbauer spectra. We find that both the saturation magnetization (M_S) and coercivity (H_jc) depend on the chemical composition and fabrication method. The calorimetric measurements were carried out using Orton Standard Dilatometers.     

Synthesis and properties of ferrimagnetic glass-ceramics and glass fibers derived from pyrite slag

Ferrimagnetic nano-crystal glass-ceramics and glass fibers were prepared based on the ferrosilicate glass system of SiO₂–Fe₂O₃–B₂O₃–Al₂O₃ using large amount of pyrite slag (PS) and small quantities of pure chemicals. Two different fabrication methods were employed, eg, annealing and fiber-drawing method, without performing any nucleation and crystallization heat treatments. The influence of PS content on the magnetite spontaneous crystallization is investigated by the X-ray diffraction, FTIR, SEM, and TEM. The X-ray diffraction patterns show the presence of nanometric magnetite crystals in glass matrix. The ferrimagnetic glass fibers with a diameter of about 20 μm were one-step drawn. The magnetic hysteresis loops of the glass-ceramic and glass fiber samples were analyzed using a vibrating sample magnetometer (VSM). Electromagnetic parameters of samples were also examined.     

Apatite formation on melt-derived bioactive glass powder based on SiO2-CaO-Na2O-P2O5 system

The higher melting temperature and longer soaking time during conventional glass melting route promoted the search for alternative in developing new bioactive glass (BG) composition with improved in fabrication temperature and melting time. The current project involved fabrication of new BG compositions based on SiO₂-CaO-Na₂O-P₂O₅ system via melt derived route. It was confirmed that all bioactive glass composition can be melted at temperature lower than 1400 °C. Formation of Si-O-Si (tetrahedral) functional group highlighted that silicate based glass was established as detected by Fourier transform infrared spectroscope (FTIR). BG bioactivity was performed by incubating the BG powder in Tris-buffer solution (pH 8) for 7, 14 and 21 days. In vitro test confirmed the apatite formation on the bioactive glass surface upon soaking in Tris-buffer solution with characteristic of carbonate group (C-O) and P-O band noticed from FTIR and present of crystalline peak observed in X-ray diffraction (XRD). Morphology of apatite formation on BG surface was observed using scanning electron microscope (SEM).     

Effect of chemical composition of intergranular glass on superplastic compressive deformation of β-silicon nitride

The effect of chemical composition of Y₂O₃–Al₂O₃–SiO₂-based intergranular glass on superplastic deformation of β-Si₃N₄ was studied by compression tests at 1873 K. All hot isostatically pressed Si₃N₄ materials had essentially the same microstructure and the same amount of glass phase, which was different in composition only. The relation between flow stress and glass composition qualitatively corresponded to the effect of chemical composition on viscosity of Y₂O₃–Al₂O₃–SiO₂ glass. However, the flow stress was not proportional to the viscosity of Y₂O₃–Al₂O₃–SiO₂ glass, probably because the composition of intergranular glass phase had changed by dissolving Si₃N₄. The strain hardening (increase of flow stress with deformation) was dependent on the chemical composition of intergranular glass. Actually, the apparent strain hardening was not proportional to the strain but was proportional to time. The crystallization of Si₂N₂O was also proportional to time, and was dependent on the chemical composition of the intergranular glass in a similar way to the strain hardening. Thus, it was suggested that the crystallization of Si₂N₂O reduced the amount of the intergranular glass, thereby increasing flow stress.     

The role of K2O on sintering and crystallization of glass powder compacts in the Li2O–K2O–Al2O3–SiO2 system

The effects of K₂O content on sintering and crystallization of glass powder compacts in the Li₂O–K₂O–Al₂O₃–SiO₂ system were investigated. Glasses featuring SiO₂/Li₂O molar ratios of 2.69–3.13, far beyond the lithium disilicate (LD-Li₂Si₂O₅) stoichiometry, were produced by conventional melt-quenching technique. The sintering and crystallization behaviour of glass powders was explored using hot stage microscopy (HSM), scanning electron microscopy (SEM), differential thermal (DTA) and X-ray diffraction (XRD) analyses. Increasing K₂O content at the expense of SiO₂ was shown to lower the temperature of maximum shrinkage, eventually resulting in early densification of the glass-powder compacts. Lithium metasilicate was the main crystalline phase formed upon heat treating the glass powders with higher amounts of K₂O. In contrast, lithium disilicate predominantly crystallized from the compositions with lower K₂O contents resulting in strong glass–ceramics with high chemical and electrical resistance. The total content of K₂O should be kept below 4.63 mol% for obtaining LD-based glass–ceramics.     

Raman imaging as a useful tool to describe crystallization of aluminum/iron-containing polyphosphate glasses

Polyphosphate glasses are materials of a wide spectrum of applications in many fields. The subject of the work is polyphosphate glasses containing aluminum and iron. Three compositions of the glasses were obtained and the materials have been characterized in terms of their crystallization. The differences in crystallization behavior between powder and bulk materials were compared. The crystallized materials were analyzed by Raman scattering spectroscopy and X-ray diffraction method. It was evidenced that depending on the glass composition the main crystalline phases were Al(PO₃)₃, AlPO₄, FePO₄, Fe₃(P₂O₇), Fe₄(P₂O₇)₃, FePO₄. The glass crystallization leads to enrichment of the residual glassy phase in P₂O₅ and increases its polymerization. Thus, it was observed the glass inhomogeneities are being increased due to crystallization. The two dimensions spectral maps of the bulk crystallized samples were executed to describe the mechanism and type of crystallization. The depth profiling proves the differences between surface and interior phase composition.     

Magnetite-based glass-ceramics prepared by controlled crystallization of borosilicate glasses: Effect of nucleating agents on magnetic properties and relaxation

The specific magnetic structure and magnetic relaxation phenomena in magnetite nanoentities grown in a glassy matrix by controlled crystallization of Fe-containing borosilicate and boroaluminosilicate glasses in the presence of two types of nucleating agents, Cr₂O₃ and P₂O₅, were investigated. The structure, morphology and magnetic properties are strongly influenced by the nucleating agents. Cr₂O₃ generates magnetite-based glass ceramics with magnetite configurations showing an upward relaxation of magnetization at low and high temperatures but downward at intermediate temperatures. The magnetite grown with P₂O₅ displays only downward relaxation but with different signs of the temperature derivative of the relaxation rate S in different temperature ranges. The observed effects are discussed with respect to the following factors: i) the existence of a multimodal size distribution of the magnetite (nano)particles as revealed by high resolution electron microscopy; ii) the degree of occupation of different sublattices of the magnetite structure with Fe³⁺ and Fe²⁺ ions; and iii) the interplay between the relaxation mechanisms in different temperature ranges.     

Chalcogenide glass for AgI-based nanolayered films

Glass in the system GeSe₂–Sb₂Se₃–AgI in monolith and film states has been investigated. Special attention has been paid to the crystallization stability and ionic conductivity of glass and films. The films were fabricated by the laser ablation of glass in a vacuum. The fabricated glass has been studied by the methods of X-ray diffraction and differential thermal analyses and impedance measurement. The sputtered films have been studied by X-ray diffraction and Raman spectroscopy in order to control their stability to crystallization and to compare their structure with that of monolith glass. It has been demonstrated that glass containing 40 mol % AgI is characterized with the softening point that is substantial for chalcogenide glass (190°C) and high crystallization stability, whereas the logarithm of their specific conductivity at 100°C is a value of the order of–3.5 at the activation energy of around 0.5 eV.     

Effect of ZrO2 crystallization on ion exchange properties in aluminosilicate glass

Ion exchange has the potential to improve the mechanical properties of glass ceramics. In this work, ZrO₂ nanocrystals embedded transparent glass ceramics were prepared and effect of the crystallization on ion-exchange properties was investigated. The crystallization of ZrO₂ did not affect the transmittance and Vickers hardness due to the small nanocrystal size and the low crystallinity, but significantly enhanced the ion exchange depth of layer (DOL). X-ray diffraction, high resolution transmission electron microscope, Raman spectra and nuclear magnetic resonance analysis demonstrated that with the crystallization of ZrO₂, the charge compensator (Na⁺) was released, which promoted the transformation of highly coordinated Al into [AlO₄]⁻ tetrahedral units and the formation of Na⁺ balanced non-bridging oxygens. These changes in structure of glass made the Na⁺ more mobile and increased the DOL upon the crystallization. Results reported here may be useful for the development of glass-ceramic materials suitable for chemical strengthening.     

A modified B2O3 containing Li2O-Al2O3-SiO2 glass with ZrO2 as nucleating agent - Crystallization and microstructure studied by XRD and (S)TEM-EDX

Glass-ceramics based on lithium-alumo-silicate glasses are commercially important for a wide range of applications, due to their special properties, like a vanishing thermal expansion. In order to tailor these properties, the composition of the glass and the temperature/time schedule are crucial factors. For the industrial production of most lithium-alumo-silicate glasses, high melting temperatures are required due to the high viscosities of the respective melt compositions. In this study, a simplified lithium-alumo-silicate glass composition with ZrO₂ as nucleating agent, on the basis of the commercially available Robax^® composition, is studied. Adding boron oxide leads to lower viscosities of the glass melt and notably lower melting temperatures may be supplied. The resulting glass is investigated using X-ray diffraction and transmission electron microscopy. During the crystallization process, phases such as ZrO₂ and β-quartz types are formed. The microstructure of the glass ceramics is notably coarser than that of glass-ceramics which are obtained from lithium-alumo-silicate glasses of standard compositions. EDX-analyses indicate a considerable enrichment of chemical elements in comparatively small areas of the microstructure. Especially boron oxide is found to be enriched in the residual glass of the investigated glass-ceramics.     

Synthesis, characterization and in vitro bioactivity of magnesium-doped sol-gel glass and glass-ceramics

Bioactive glass and glass-ceramics in the system CaO-MgO-SiO₂-P₂O₅ have been prepared by the sol-gel and high temperature sintering techniques. The obtained samples were characterized by thermogravimetric and differential thermal analysis (TG/DTA), N₂-adsorption measurement, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). In vitro bioactivity tests were also conducted in simulated body fluid (SBF). The studies of crystallization kinetics under non-isothermal conditions showed the activation energy for crystallization to be 381 kJ/mol and the crystallization mechanism gradually changed from three-dimension growth to two-dimension crystallization with the increase of heating rate. Sintering temperature had great influence on the samples texture and structure. In addition, the apatite-formation on glass and glass-ceramics was confirmed by in vitro tests, and crystallization decreased the samples bioactivity.     

The effects of SiO2 and K2O on glass forming ability and structure of CaOTiO2P2O5 glass system

The effects of SiO₂ and K₂O were investigated on the glass forming ability (GFA) and structural characteristics of CaOTiO₂P₂O₅ system. Differential thermal analyzer (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), FT-IR and ³¹P magic angle spinning NMR methods were applied for characterizations of the system.Unwanted crystallization in the initial three components base glass composition was observed by adding SiO₂ and crystalline phases such as TiP₂O₇, rutile (TiO₂) and cristobalite (SiO₂) were formed in it.The results showed that K₂O prevents crystallization of glasses and promotes the formation of glass. FT-IR and X-ray diffraction showed that the addition of K₂O caused the formation of phosphate–silicate network as POSi, and formation of isolated droplet phases (rich of Si and P) separated from the phosphate matrix.The optimum amounts of SiO₂ and K₂O in phosphate structure were respectively 6 and 2 wt.%, 0 in accordance with glass forming ability (GFA) parameters. Despite addition of SiO₂ along with K₂O; the ³¹P MAS NMR and infrared spectrums of glasses show that no Q² sites were in the phosphate network. The Q¹ and the pyrophosphate groups was the predominant structural unit in these glasses.     

Effect of soluble Cr2O3 on the silicate network,crystallization kinetics,mineral phase,microstructure of CaO-MgO-SiO2-(Na2O) glass ceramics with different CaO/MgO ratio

Cr₂O₃ is often used as a glass additive to prepare glass ceramics. Chromium element exists mainly in two parts in the glass ceramics: chromium-containing spinel and soluble chromium in glass matrix. Herein, effect of soluble chromium on the CaO-MgO-SiO₂-(Na₂O) glass system is researched. Glass and glass ceramics were characterized by Raman spectrum, X-ray diffraction, scanning electron microscopy, energy dispersive spectrometry. It is found that the addition of Cr₂O₃ increased the Q²si structure unit in glass networks, especially in glass systems with high MgO content. The crystallization temperatures of the systems were increased with the addition of Cr₂O₃. Soluble chromium reduced the crystallization activation energy of the glass system slightly, but did not alter its crystallization behavior (surface crystallization). With the increase of MgO content, the mineral phases of the glass ceramics gradually changed from wollastonite to diopside. Cr₂O₃ reduced the lattice parameters of the mineral phases. The addition of Cr₂O₃ has a significant effect on grain refinement and structural compactness of the glass ceramics system with high MgO content.     

Effect of Al2O3 and K2O content on structure,properties and devitrification of glasses in the Li2O–SiO2 system

The effect of Al₂O₃ and K₂O content on structure, sintering and devitrification behaviour of glasses in the Li₂O–SiO₂ system along with the properties of the resultant glass–ceramics (GCs) was investigated. Glasses containing Al₂O₃ and K₂O and featuring SiO₂/Li₂O molar ratios (3.13–4.88) far beyond that of lithium disilicate (Li₂Si₂O₅) stoichiometry were produced by conventional melt-quenching technique along with a bicomponent glass with a composition 23Li₂O–77SiO₂ (mol.%) (L₂₃S₇₇). The GCs were produced through two different methods: (a) nucleation and crystallization of monolithic bulk glass, (b) sintering and crystallization of glass powder compacts.Scanning electron microscopy (SEM) examination of as cast non-annealed monolithic glasses revealed precipitation of nanosize droplet phase in glassy matrices suggesting the occurrence of phase separation in all investigated compositions. The extent of segregation, as judged from the mean droplet diameter and the packing density of droplet phase, decreased with increasing Al₂O₃ and K₂O content in the glasses. The crystallization of glasses richer in Al₂O₃ and K₂O was dominated by surface nucleation leading to crystallization of lithium metasilicate (Li₂SiO₃) within the temperature range of 550–900 °C. On the other hand, the glass with lowest amount of Al₂O₃ and K₂O and glass L₂₃S₇₇ were prone to volume nucleation and crystallization, resulting in formation of Li₂Si₂O₅ within the temperature interval of 650–800 °C.Sintering and crystallization behaviour of glass powders was followed by hot stage microscopy (HSM) and differential thermal analysis (DTA), respectively. GCs from composition L₂₃S₇₇ demonstrated high fragility along with low flexural strength and density. The addition of Al₂O₃ and K₂O to Li₂O–SiO₂ system resulted in improved densification and mechanical strength.     

Structure and crystallization specifics of alumina-bearing lanthanide borogermanate glass

The paper investigates the structure and crystallization specifics of glass behaving as a precursor of a pyroelectric material with a unique combination of properties of the composition 25La₂O₃ · 25B₂O₃ · 50GeO₂ depending on the quantity of Al₂O₃ additive. It is established that as the alumina content grows, the crystallization of glass essentially changes: the propensity of glass to oriented surface crystallization of ferroelectric LaBGeO₅ is suppressed and the share of lanthanum borate and germanate grows. The type of crystallization of glass correlates with IR spectroscopy data, indicating that modifications of the glass structure caused by increasing Al₂O₃ content lead to substantial changes in the BO₃: BO₄ ratio. __________ Translated from Steklo i Keramika, No. 6, pp. 10–14, June, 2006.     

Effect of Cr2O3 on the magnetic properties of magnetite-based glass-ceramics obtained by controlled crystallization of Fe-containing aluminoborosilicate glass

The phase structure and magnetic properties of magnetite-based glass-ceramics obtained by crystallization of Fe-containing boroaluminosilicate glass melts are presented. The use of Cr₂O₃ as nucleating agent generated magnetite configurations showing a complex temperature dependence of the relaxation of the remanent magnetization. Specifically, the expected decrease in time of the remanent magnetization occurs only in a limited temperature range, whereas it increases at low and high temperatures (upward relaxation). We tentatively attribute these effects to the complex spin structure of the tiny magnetite nanoparticles, their complex size distribution and the interplay between the relaxation mechanisms in different temperature ranges.     

Structure,crystallization, and performances of alkaline-earth boroaluminosilicate sealing glasses for SOFCs

We study the structure, crystallization, and performances of the sealing glasses with the composition (mol.%) of 12Al₂O₃·8B₂O₃·40SiO₂·40RO (R = Mg, Ca, Sr) for solid oxide fuel cells (SOFCs) before and after isothermal treatment at 700°C, which is within the operation temperature range (600-800°C) of SOFCs. The crystallization behavior has been investigated by differential scanning calorimetry and X-ray diffraction under both dynamic and isothermal conditions. The structural evolution is probed using the Raman and nuclear magnetic resonance spectroscopies. The performances of the sealing glasses are characterized in terms of the coefficient of thermal expansion, the crystallization-induced stress at glass–steel interface. We find that strong crystallization occurs at the operation temperature (700°C) far below the crystallization onset temperature measured by DSC. The structure origin of this anomalous crystallization is discussed in terms of structural heterogeneity of the three studied glasses. We determine the residual stress at the interface between the Ca-containing glass and the steel after isothermal treatment at 700°C for 48 h, but this stress does not lead to falling off the glass layer from the steel. This indicates that this glass is a good candidate to be applied in SOFCs.     

Glass transition and crystallization of ZnO-B2O3-SiO2 glass doped with Y2O3

The effect of Y₂O₃ on the glass transition kinetics, crystallization kinetics, phase separation and crystallization behavior of 60ZnO–30B₂O₃–10SiO₂ glass has been investigated by non-isothermal differential thermal analysis, scanning electron microscopy (SEM) and X-ray powder diffraction (XRD). The glass transition activation energies E_g calculated by using both Kissinger and Moynihan model decrease from 668?kJ/mol to 573?kJ/mol for Kissinger model, and 682?kJ/mol to 587?kJ/mol for Moynihan model with the increase of yttrium oxide doping content from 0 to 6?mol%. And the glass crystallization kinetics parameters, crystallization activation energy E_c and Avrami exponent n stands for crystal growth, are also obtained on the basis of several well developed equations. Increase of about 58?kJ/mol in Ec values obtained by different theoretical equations is caused by addition of 6?mol% yttrium oxide into 60ZnO–30B₂O₃–10SiO₂ glass, and the Avrami exponent (n close to 2) suggests that crystal growth in 60ZnO–30B₂O₃–10SiO₂ glass doped with or without yttrium is mainly one-dimensional growth of crystals. The results on the phase separation and crystallization behavior occurred at 893?K and 993?K respectively for base and doped glass, are well consistent with the glass transition and crystallization kinetics results. Hence, addition of yttrium oxide into 60ZnO–30B₂O₃–10SiO₂ glass decrease the glass transition activation energy while increase the crystallization activation energy of glass, thereby the stability of glass structure is improved. Phase separation phenomenon and crystallization behavior occurred at glass surface provide some useful information for preparing glass ceramics with micro- or nano-crystals in surface.     

Reduction of crystallization ability of sodium zinc phosphate glass under X-ray radiation

The effect of X-ray radiation on the crystallization ability of maximally homogenized sodium zinc phosphate glass with a minimal light scattering value of V _v = 4 × 10^?6 cm^?1 has been investigated. The crystallization kinetics of the sodium zinc phosphate glass of the 33.9P₂O₅ · 56.6ZnO · 9.5Na₂O (mol % from analysis) composition under the conditions of homogeneous nucleation and X-ray radiation have been studied. It has been demonstrated that the crystallization properties of phosphate glasses are more sensitive to the synthesis method than those of silicate glasses. It has been established that sodium zinc phosphate glass crystals represent the main crystalline phase precipitated in the glass of the above composition. The main parameters of nucleation have been determined in glass without preliminary radiation, including stationary nucleation rate I _st, nonstationary nucleation time ??, and nucleation activation energy E _??. It have been found that the effect of the CuK _?? X-ray radiation leads to the slowing down or even cessation of the nucleation of crystals in glass (the result depends on the change in the radiation intensity along the sample depth) in the case when radiation takes place immediately during the nucleation thermal treatment of the sample in a high-temperature chamber of the X-ray device. The kinetics of sodium zinc phosphate crystallization in the samples upon their pretreatment by CuK _?? X-ray irradiation has been investigated. It has been shown that the rate of crystal nucleation in glasses exposed to X-ray radiation is lower than that in glasses without preliminary irradiation.     

The influence of TiO2 content on the properties of glass ceramics: Crystallization,microstructure and hardness

The effects of compositional variation, crystallization behavior, crystalline phases and microstructure formed in the SiO₂3Al₂O₃3CaO (SAC) glass system using various amounts of TiO₂ as nucleating agent were investigated by Differential Thermal Analysis (DTA), X-ray powder diffraction (XRD), Scanning Electron Microscope (SEM), Energy-dispersive X-ray spectroscopy (EDAX) and Fourier transform infrared spectroscopy (FTIR) techniques. The crystallization kinetics and mechanical properties of SAC glass ceramics were studied using crystallization peak temperature (T_p) of three different glasses as obtained from DTA, the activation energy (E) and Avrami exponent (n) were also determined. The crystallization peak temperature (T_p) and activation energy (E) were found to increase with the increase in TiO₂ content. The major crystalline phases were anorthite and wollastonite along with gehlenite and titanite as the minor crystalline phases present in the glass ceramic system. The studies showed that the three dimensional crystalline structure and the microhardness increased with the increase of TiO₂ content in the glass ceramics system.