The effect of Al2O3 on sintering and crystallization of MgSiO3-based glass-powder compacts

The influence of Al₂O₃ (8 wt.%) on sintering and crystallization features of glass powders based on magnesium silicate (MgSiO₃) was experimentally determined. The investigated compositions were Y_0.125Mg_0.875Si_0.875B_0.125O₃ and Y_0.125Mg_0.725Ba_0.15Si_0.875B_0.125O₃. For the experiments, glasses in bulk and frit forms were produced by melting in Pt-crucible at 1600 °C for 1.5 h. Glass-powder compacts were sintered at different temperatures between 900 °C and 1100 °C. The evolution of crystalline regime was determined by in situ recording of X-ray diffractograms of fine glass powders at elevated temperatures. The results and their discussion showed that addition of 8 wt.% Al₂O₃ in glass batches affected the thermal properties of the glasses and resulted in MgSiO₃-based glass ceramics well sintered between 900 °C and 1100 °C. In the BaO-free MgSiO₃ glass ceramics, clino- and orthoenstatite crystallize while the presence of BaO favours the formation of hexacelsian.     

The effect of fluoride ions on the structure and crystallization kinetics of La2O3-containing diopside based oxyfluoride glasses

Oxyfluoride glasses in the system CaO–MgO–BaO–SiO₂–Al₂O₃–La₂O₃–CaF₂ were obtained by adding CaF₂ (3–8 wt%) to a parent diopside based glass composition, Ca_0.8Ba_0.1MgAl_0.1La_0.1Si_1.9O₆. The characterization of the glasses has been made by density, dilatometry and FTIR measurements. Non-isothermal crystallization kinetic studies in conjunction with XRD and SEM have been employed in order to investigate the effects of fluoride ion additions on crystallization behaviour and mechanism of glasses.     

Effect of A2O3 (A = La,Y, Cr,Al) on thermal and crystallization kinetics of borosilicate glass sealants for solid oxide fuel cells

Influence of various intermediate oxides on thermal, structural and crystallization kinetics of 30BaO–40SiO₂–20B₂O₃–10A₂O₃ (A = Y, La, Al, Cr) glasses has been studied. The highest glass transition temperature (T_g) with high thermal stability is observed in Y₂O₃ containing glasses as compared to other glasses. The thermal expansion coefficient (TEC) increases with increasing heat treatment duration in all the glasses. The maximum increase in TEC is observed in Cr₂O₃ containing glass ceramics. FTIR study showed that transmission bands due to silicate and borate chains become sharper with splitting after heat treatment. A selected glass sample (BaCr) has been tested for interaction and adhesion with Crofer 22 APU interconnect material for its application as a sealant in solid oxide fuel cell.     

Crystallization process and some properties of novel transparent machinable calcium-mica glass-ceramics

Bulk glass having a calcium-mica composition (Ca_0.5Mg₃AlSi₃O₁₀F₂) is homogeneous glass. The crystallization mechanism of the mica is surface crystallization and transparency is lost completely when crystallization occurs on the surface. In this study, by decreasing SiO₂ and increasing CaO and Al₂O₃ from the chemical composition of Ca_0.5Mg₃AlSi₃O₁₀F₂, and moreover by replacing a small amount of K₂O instead of CaO, the phase separation appears in the glasses. Because of this phase separation, the mica begins to be crystallized not only on the surface but also in the bulk at lower temperatures. Consequently, the novel transparent machinable mica glass-ceramic can be obtained by heating the glasses having the chemical composition of Ca_0.6Mg₃Al_1.2Si_2.8O₁₀F₂ and K_0.01Ca_0.595Mg₃Al_1.2Si_2.8O₁₀F₂. As a larger amount of calcium-mica is separated, the bending strength decreases and the fracture toughness increases. Furthermore, by replacing K⁺ ion instead of Ca²⁺ ion in the interlayer of calcium-mica, the interlayer bonding strength becomes high, resulting in the increase of the bending strength.     

High temperature properties of B6O-materials

B₆O is a potential superhard material with a hardness of 45 GPa measured on single crystals. Recently it was found that different oxides can be utilized as an effective sintering additive which allows densification under low pressures. In this work the effect of addition of Y₂O₃/Al₂O₃ on high temperature properties was investigated using impulse excitation technique (IET), hardness measurements and dilatometric measurements. The IET technique reveals the softening of the residual B₂O₃ in the materials without additives at 450 °C; in the materials with Y₂O₃/Al₂O₃ the softening is observed at only about 800 °C. This data agrees with the values found for different borate glasses.The materials showed no pronounced reduction of hardness at these temperatures. This is additional evidence, supporting previous observations that the material consists of pure grain boundaries between B₆O grains. Hardness values (HV5) of up to 17 GPa at 1000 °C were observed.     

Preparation,structural and thermo-mechanical properties of lithium aluminum silicate glass–ceramics

Lithium aluminum silicate glasses of composition (wt%) 12.6Li₂O–71.7SiO₂–5.1Al₂O₃–4.9K₂O–3.2B₂O₃–2.5P₂O₅ were prepared by the melt quench technique. These glasses were converted to glass–ceramics based on DTA data. X-ray diffraction (XRD) and Fourier transform infra-red spectroscopy (FTIR) were used to discern the phases evolved in the glass–ceramics. Phase morphology was studied using scanning electron microscopy (SEM). Thermal expansion coefficient (TEC) and glass transition temperature (T_g) of all samples were measured using thermo-mechanical analyzer (TMA). It was found that 3 h dwell time at crystallization temperature yielded samples with good crystallinity with a TEC of 9.461 × 10⁻⁶ °C⁻¹. Glass–ceramic-to-metal compressive seal with SS-304 was fabricated using LAS glass–ceramic. The presence of metal housing and compressive stresses at the glass–ceramic-to-metal interface reduced average grain size and changed the overall microstructure.     

Synthesis and characterization of clinopyroxene based glasses and glass-ceramics along diopside (CaMgSi2O6)-jadeite (NaAlSi2O6) join

The crystallization behavior and mechanical characterization of glasses based upon the compositions along diopside (CaMgSi₂O₆)-jadeite (NaAlSi₂O₆) join has been investigated. Six glasses were obtained by the melt-quenching technique. Structural and thermal behaviors of these glasses were investigated by density and molar volume, infrared spectroscopy (FTIR) and dilatometry. The crystallization behavior of glasses was investigated by using differential scanning calorimetry (DSC). Sintering and crystallization behavior of the glass-ceramics were investigated under non-isothermal heating conditions up to temperatures of 850 °C. Mechanical characterization of glasses was investigated by using the measurement of Vickers indentation hardness and elastic constants such as Young's modulus (E), shear modulus (G), bulk modulus (K) and Poisson's ratio (ν). These data of the glasses were correlated with the structure of glasses, nature and role played by glass forming cations.     

Crystallization behavior and IR structure of yttrium aluminosilicate glasses

The crystallization of four Y₂O₃-Al₂O₃-SiO₂ (YAS) glasses were investigated to prepare YAS glass ceramics precipitated singly/mainly Y₂Si₂O₇ or Y_4.67(SiO₄)₃O apatite, and to explore the crystallization difference between the stoichiometric parent glass (SPG) and non-stoichiometric parent glass (NSPG). The DSC results revealed that glass locating at the higher liquidus surface temperature has lower crystallization peak temperature, which indicating that the corresponding glass has higher crystallization potential to crystallize easily. Crystallization of the NSPG samples is along surface and caused by phase separation, while SPG sample is the surface crystallization at the first exothermic peak temperature and overall crystallization at the second exothermic peak temperature. Glass ceramics only containing y-Y₂Si₂O₇ or Y_4.67(SiO₄)₃O apatite are obtained successfully, and which are illustrated by fitting FTIR spectra. These results can provide technical guide for controlling the crystallization process and the types of precipitated crystals in YAS glass for different application potentials.     

Structural, optical and bioactive properties of calcium borosilicate glasses

Glass of composition 40SiO₂–20B₂O₃–30CaO–10M₂O₃ (M = Al, Cr, Y and La) were prepared by the splat quenching technique to investigate the effect of M₂O₃ on their bioactivity, structural and optical properties. Y₂O₃ and Cr₂O₃ containing glasses formed a crystalline hydroxyapatite (HA) layer after dipping in simulating body fluid (SBF) for 25 days. On the other hand, HA layer could not form in Al₂O₃ and La₂O₃ glasses. However, during soaking in SBF solution, these glasses exhibit higher dissolution rate, lower density and increased optical band gap as compared to unsoaked glasses. Their oxygen molar volume was also higher than for Y₂O₃ and Cr₂O₃ glasses. The change in composition affects the cross-link formation in the glass matrix and finally its durability and bioactivity in SBF. The results show that M₂O₃ plays an important role in controlling chemical durability and bioactivity of the glasses.     

Influence of barium oxide on the crystallization, microstructure and mechanical properties of potassium fluorophlogopite glass-ceramics

The influence of barium oxide, heat treatment time and temperature on the crystallization, microstructure and mechanical behavior of the system Ba_x·K_1−2x·Mg₃·Al·Si₃O₁₀·F₂ (where x = 0.0, 0.3 and 0.5) was investigated in order to develop novel, high strength and machinable glass-ceramics. Three glasses were prepared and characterized by differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microscope (SEM) techniques and some mechanical testing methods.The crystallization kinetics of glass-ceramics was also studied. Activation energy and Avrami exponent calculated for the crystallization peak temperature (T_p) of three different glass batches. The Vickers hardness decreased slightly on formation of the potassium fluorophlogopite and barium fluorophlogopite phases, but decreased significantly on formation of an interconnected ‘house of cards’ microstructure.     

Wetting and penetration of cordierite and mullite materials by non-stoichiometric cordierite liquids

The wetting and penetration of two non-stoichiometric cordierite liquids (labelled G1 = 25 wt.% Al₂O₃, 63 wt.% SiO₂ and 12 wt.% MgO, and G2 = 20 wt.% Al₂O₃, 64 wt.% SiO₂ and 16 wt.% MgO) on sintered cordierite and mullite substrates were investigated. Their chemical compositions (G1 and G2) correspond to those glasses present in materials sintered from a commercial powder of non-stoichiometric cordierite powder at 1450 or 1400 °C, respectively.     

Joining of mullite ceramics with yttrium aluminosilicate glass interlayers

Pellets of yttrium aluminosilicate glass (Y₂O₃:Al₂O₃:SiO₂ = 30:20:50 mol%) powder were used as the filler interlayers (0.4 mm thick) to join two mullite substrates. The glass interlayer partially melted at joining temperature to bond the substrates and then crystallized during cooling to have better bonding strength. The results showed that joining could be performed at 1390–1420 °C for 1–5 h with applied pressure of 0.02 MPa. After joining, the thickness of glass layers varied between 250 μm and 80 μm, depending upon the temperatures. The glass interlayer crystallized into cristobalite, mullite and Y₂Si₂O₇. When joining mullite/3 mol%yttria–zirconia substrates using the same glass pellet, a layer of zircon/mullite was formed at the interface, indicating that reaction occurred between glass and substrates. The formation of zircon usually accompanied with cracks in the substrates. These cracks deteriorated the strength. The achievable three-point bending strengths were 139 MPa for joined mullite and 76 MPa for joined mullite/3 mol%yttria–zirconia.     

CaO–SiO2–Al2O3–Y2O3 glasses as model grain boundary phases for Si3N4 ceramics

The glasses with compositions derived from the eutectic composition [37.78 (Y₃Al₅O₁₂)·62.22 (SiO₂)] of the quasi-binary glass system (Y₃Al₅O₁₂)-(SiO₂) with addition of up to 20 mol.% CaO were investigated as model grain boundary phases for Si₃N₄ ceramics. The influence of CaO as model impurity on the physical properties of the glass (density, thermal expansion) and on the crystallisation behaviour was studied. Although the initial composition of the basic glass was that of yttrium-aluminium garnet (Y₃Al₅O₁₂–YAG), no crystalline YAG was detected. Apart from yttrium disilicate (Y₂Si₂O₇), anorthite (CaAl₂Si₂O₈), tricalcium aluminate (Ca₃Al₂O₆), and calcium yttrium oxide silicate (Ca₄Y₆O(SiO₄)₆), a new phase was detected, not found in the powder diffraction file (PDF) database. Cavities were formed within the devitrified glass due to the volume contraction after crystallisation. Possible implications for the mechanical properties of Si₃N₄ ceramics sintered with addition of Y₂O₃–Al₂O₃ are discussed in terms of the observed compositional dependences of the physical properties of CaO–Y₂O₃–Al₂O₃–SiO₂ glasses.     

The effect of precursor composition and sintering additives on the formation of β-sialon from Al, Si and Al2O3 powders

A study was performed to investigate the effect of increasing the Al or Al₂O₃ precursor content, above the stoichiometric amount, on the formation of β-sialon by pressureless sintering of Al, Si and Al₂O₃ powders in flowing nitrogen gas. The effect of adding Y₂O₃ or Fe to the precursor mixture, on the β-sialon formation, was also studied. The phase morphology and yield produced by the various compositions were examined using X-ray diffraction (XRD). Additional Al₂O₃ decreases the β-sialon phase yield and results in a greater amount of Al₂O₃ in the final sintered material. Additional Al improved the conversion to β-sialon up to a maximum of 4 wt% Al beyond which the β-sialon:15R sialon ratio in the sintered material decreases. 1 wt% Y₂O₃ was determined to be the optimum sintering additive content, as yttrium aluminium garnet (YAG) was found to be present in materials formed from higher Y₂O₃ containing precursors. The presence of Fe in the precursor powder retards the formation of β-sialon by preferentially forming Fe silicides at low temperatures, thus depleting the reaction system of elemental Si, favouring the formation of 15R sialon.     

Effect of MgO/Al2O3 ratio on the crystallization behaviour of Li2O–MgO–Al2O3–SiO2 glass-ceramic and its wettability on Si3N4 ceramic

The composition governs the crystallization ability, the type and content of crystal phases of glass-ceramics. Glass-ceramic joining materials have generated more research interest in recent years. Here, we prepared a novel Li₂O–MgO–Al₂O₃–SiO₂ glass-ceramic for the application of joining Si₃N₄ ceramics. We investigated the influence of the MgO/Al₂O₃ composition ratio on microstructure and crystallization behaviour. The crystallization kinetics demonstrated that the glasses had excellent crystallization ability and high crystallinity. β-LiAlSi₂O₆ and Mg₂SiO₄ were precipitated from the glass-ceramics, and the increase of MgO concentration was conducive to the precipitation of Mg₂SiO₄. Among the glass-ceramic samples, the thermal expansion coefficient of LMAS2 glass-ceramic was 3.1 × 10^?6/°C, which was very close to that of Si₃N₄ ceramics. The wetting test showed that the final contact angle of the glass droplet on the Si₃N₄ ceramic surface was 32° and the interface was well bonded.     

Synthesis of Glass-Ceramic Materials in the BaO–PbO–B2O3–Al2O3–TiO2 System

The influence of PbO, B₂O₃, and Al₂O₃ additives on the glass formation and crystallization of glasses with a high total content of BaO and TiO₂ (65–75 wt % or 76–86 mol %) is investigated. It is shown that glasses of the compositions (wt %) 31–35 BaO, 12–17 PbO, 34–42 TiO₂, 10–13 Al₂O₃, and 2–3 B₂O₃ are promising materials for use in preparing glass-ceramic ferroelectrics based on the melting–molding–crystallization technology. These compounds are characterized by a relatively low melting temperature (1450°C), the absence of spontaneous crystallization during molding, and the possibility of controlling the phase composition of the material through the appropriate choice of the crystallization temperature.     

Effect of some rare-earth oxides on structure, devitrification and properties of diopside based glasses

Four diopside based glasses containing an equimolar concentration of different rare-earth oxides (La₂O₃, Nd₂O₃, Gd₂O₃ and Yb₂O₃) respectively, were obtained by melt-quenching technique. Structural and thermal behaviour of the glasses was investigated by density and molar volume, infrared spectroscopy (FTIR), dilatometry, and scanning electron microscopy (SEM). All the glasses exhibited amorphous phase separation. The crystallization behaviour of the glasses was investigated by using differential thermal analysis (DTA). Sintering, crystallization, microstructure, and properties of the glass-ceramics were investigated under non-isothermal heating conditions in the temperature range of 800–900 °C.     

Effects of nitrogen and fluorine on crystallisation of Ca-Si-Al-O-N-F glasses

The effect of nitrogen and fluorine substitution on the crystallisation of a new generation of oxyfluoronitride glasses in the Ca-Si-Al-O-N-F system has been studied. Glasses were nucleated for 5 h at the nucleation temperature of Tg + 50 °C and crystallised for 10 h at the maximum crystallisation temperature (900-1050 °C depending on the glass composition) determined from differential thermal analysis. For the oxide glass, crystallisation results in formation of wollastonite (CaSiO₃), gehlenite (Ca₂Al₂SiO₇) and anorthite (CaAl₂Si₂O₈) along with a small amount of residual glass. For crystallisation of oxyfluoride glasses (0 equiv.% N), when fluorine content increases, cuspidine (Ca₄Si₂O₇F₂) is the major crystalline phase at the expense of gehlenite while in oxyfluoronitride glasses containing 20 equiv.% N, gehlenite is always the dominant crystalline phase at different fluorine contents. At constant fluorine content (5 equiv.%), an increase in nitrogen content favours the formation of gehlenite rather than anorthite or wollastonite suggesting that this phase may be able to accommodate N into its crystal structure. While a small amount of nitrogen substitution for oxygen can be assumed in the gehlenite structure, the residual glass in the glass-ceramic is expected to be very N-rich. In terms of properties, hardness is shown to be more sensitive to changes in microstructure, phase morphology and crystal size compared with elastic modulus which is related to the amounts of constituent phases present.     

Synthesis and electrical conductivity of La-Sr-X-Mg-O (X = Ti, Zr, Al) perovskite solid solution

Perovskite solid solutions of (La_0.6Sr_0.4)(X_1−yMg_y)O_3−δ (X = Ti, Zr, Al) were prepared by a coprecipitation method using corresponding aqueous solutions and ammonium carbonate solution. The freeze-dried powders were sintered in air at 1000-1500 °C for 1-36 h. Single phase solid solutions were produced in the compositions of (La_0.6Sr_0.4)(Zr_0.6Mg_0.4)O_3−δ and (La_0.6Sr_0.4)(Al_0.9Mg_0.1)O_3−δ where (3 − δ) < 3. For the compositions of X = Ti and Zr for y = 0.1 where (3 − δ) > 3, two phases including perovskite solid solution were produced at 1400-1500 °C. The stability of perovskite solid solution was closely related to the fraction of lattice oxygen atom (3 − δ). A relatively high conductivity was measured for (La_0.6Sr_0.4)(Al_0.9Mg_0.1)O_3−δ (σ = 4.15 × 10⁻⁴ S/cm at 600 °C, activation energy 113.4 kJ/mol). The influence of fraction of oxide ion vacancy on the activation energy was small for δ = 0.1-0.3 of perovskite solid solution.