Influence of Al2O3 and B2O3 on Sintering and Crystallization of Lithium Silicate Glass System

This article reports on the effect of Al₂O₃ and B₂O₃ added as dopants on the preparation of glass‐ceramics (GCs) belonging to the lithium silicate glass system. The GCs are prepared by sintering route using glass powders. The reasons for the crystallization of the metastable crystalline phase lithium metasilicate (LS) are discussed and the impact of the dopants on the thermodynamics and kinetics of crystallization is investigated. The addition of dopants modifies the thermodynamic equilibrium of the system and this change is mainly entropy driven and also slowdown the kinetics of crystallization. Differential thermal analysis and hot‐stage microscopy are employed to investigate the glass‐forming ability, sintering, and crystallization behavior of the studied glasses. The crystalline phase assemblage studied under nonisothermal heating conditions in the temperature range of 800°C–900°C in air. Well sintered and dense glass‐ceramics are obtained after sintering of glass powders at 850°C–900°C for 1 h featuring crystalline phase assemblage dominated by lithium disilicate (LS₂).     

A Comprehensive Study of the Carbon Contamination in Tellurite Glasses and Glass‐Ceramics Sintered by Spark Plasma Sintering (SPS)

Highly transparent tellurite glasses and glass‐ceramics based on the 85TeO₂–15WO₃ composition (mol%) were produced by spark plasma sintering (SPS) from powders previously prepared by the conventional melt‐quenching technique and then grinded. We report a study based on the understanding of carbon contamination that is commonly observed by this nonconventional sintering technique and which constitutes a drawback for optical applications. First, the influence of the particle size of the initial amorphous powders as well as an additional pressureless sintering step prior to SPS experiments and the use of a physical carbon diffusion barrier have been investigated to reduce the carbon contamination in glass bulks. Second, once reducing the carbon contamination, glass‐ceramics were obtained by varying the SPS conditions. The noncentrosymmetric γ‐TeO₂ phase crystallized within the bulk volume while maintaining good optical transparency and led to the generation of second harmonic. This approach paves the way to further applications in the domain of linear and nonlinear optics.     

Rapid preparation of low thermal expansion transparent LAS nanocrystalline glass by one-step thermoelectric treatment

The Li₂O–Al₂O₃–SiO₂ (LAS) glass ceramics are prepared by one-step thermoelectric treatment. The influence of thermoelectric treatments on LAS glass-ceramics were studied. The crystal phase composition and microstructure of the LAS glass-ceramics were investigated by DSC, SEM, XRD and FTIR. Moreover, the thermal expansion performance and light transmittance of LAS nanocrystalline glass were characterized. The results show that low-expansion transparent LAS nanocrystalline glass can be produced in a short time by thermoelectric treatment. The free energy of nucleation and the degree of polymerization of the glass network are reduced by the electric field. The key is that the electric field polarizes Ti and Zr ions at the crystallization temperature, so that the crystal nuclei repel the same poles. This allows uniform crystal distribution, promotes crystallization and reduces one-step crystallization of crystal agglomeration. This proves that the rapid preparation of nanocrystalline glass by the one-step method is feasible, and provides a reference for the future one-step processing of glass-ceramics.     

Densification and Phase Development of Spodumene–Cordierite Glass Powder Mixtures

The sintering and crystallization of spodumene-cordierite glass-ceramics that are made from mixtures of Li₂O-Al₂O₃-SiO₂ (LAS) and MgO-Al₂O₃-SiO₂(MAS) glass powders were investigated. Pure LAS and MAS powders have good sinterability. However, the densification of LAS was drastically reduced when small amounts of MAS were added. When larger amounts of MAS were added, the amount of densification further increased. The decrease in the Li₂O content in the LAS glass promoted the densification of the mixed glass samples. The above-mentioned results can be explained by examining the crystallization temperature, which is influenced by the interactions between the LAS and MAS glass particles. The lower the temperature of crystallization, the less sintering occurred. For the sintered samples, the phase that crystallized from the MAS glass was alpha-cordierite, and that which crystallized from the LAS glass was ß-spodumene or high-quartz solid solution, depending on the Li₂O content in the LAS glass.     

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.     

Effect of substitution of ZrO2 by SnO2 on crystallization and properties of environment-friendly Li2O–Al2O3–SiO2 system (LAS) glass-ceramics

In this study, a transparent and environmentally friendly Li₂O–Al₂O₃–SiO₂ (LAS) glass-ceramic was prepared by melt-quenching and two-step heat treatment. The influence of the substitution amount of ZrO₂ by SnO₂ on the crystallization, microstructure, transparency, and mechanical properties of LAS glass and glass-ceramics was investigated by means of differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Ultraviolet–visible Spectrophotometer, three-point bending strength test, and microhardness test. The results indicate that the main crystalline phase of LAS glass ceramics was a β-quartz solid solution when heat treated at 780 °C for 2 h and 870 °C for 1.5 h. When the substitution amount of ZrO₂–SnO₂ increased from 0.4 mol% to 2.5 mol%, the grain size and thermal expansion coefficient of LAS glass-ceramics first decreased and then increased, and the crystallinity first increased and then decreased. When the substitution amount of ZrO₂–SnO₂ was 0.8 mol%, the transparency of the LAS glass-ceramics was maximum, the bending strength was 96 MPa, and the Vickers hardness was 10.9 GPa.     

Phase Evolution of SiO2–Al2O3–ZnO–CaO–ZrO2–TiO2‐Based Glass with Added Y‐PSZ Particles

Yttria partially stabilized zirconia Y‐PSZ/glass‐ceramic composites were prepared by reaction sintering using powder mixtures of a SiO₂–Al₂O₃–ZnO–CaO–ZrO₂–TiO₂‐based glass and yttria partially stabilized zirconia (Y‐PSZ). The glass crystallized during sintering at temperatures of 1173, 1273, and 1373 K to give a glass‐ceramic matrix for high‐temperature protecting coatings. With the increasing firing time, the added zirconia reacted with the base glass and a glass‐ceramic material with dispersed zircon particles was prepared in situ. Furthermore, the added zirconia changed the crystallization behavior of the base glass, affecting the shape, amount, and distribution of zircon in the microstructure. The bipyramid‐like zircon grains with imbedded residual zirconia particles turned out to have two growth mechanisms: the inward growth and the outward growth, and its rapid growth was mainly dominated by the later one. For comparison, the referenced glass‐ceramic was prepared by sintering using exclusive glass granules and its crystallization behavior at 1173–1373 K was examined as well. Scanning electron microscopy (SEM), energy dispersive X‐ray spectroscopy (EDS), transmission electron microscopy (TEM), and X‐ray diffraction (XRD) were used to characterize the crystallization behavior of the base glass and the phase evolution of the Y‐PSZ/glass‐ceramic composites.     

Fast sinter crystallisation of waste glasses

Abstract

Two glasses, belonging to the CaO–Al₂O₃–SiO₂ system and corresponding to the melting of mixtures of industrial wastes (recycled glasses, mining residues, ashes, asbestos containing cements, etc.), have been successfully converted into dense glass ceramics by sintering with concurrent crystallisation. The usage of fine glass powders (<37 μm) allowed very short sintering treatments, due to the enhanced nucleating activity of glass surfaces. In particular, dense glass ceramics could be produced by direct insertion of pressed glass powders in the furnace at the sintering temperature, followed by rapid cooling at room temperature after a 30 min holding time. The proposed approach evidences the feasibility of sintered glass ceramics by the fast and economic processes employed for traditional ceramics, with the advantage of superior mechanical properties (bending strength exceeding 100 MPa, Vickers' microhardness exceeding 6 GPa). Like in traditional ceramics, clay and water could be used for the shaping of pressed tiles, thus posing the conditions for massive industrial production.     

Microwave sintering of IR-transparent Y2O3–MgO composite ceramics

A method for preparation of dense Y₂O₃–MgO composite ceramics by the microwave sintering was developed. The initial powders were obtained by glycine-nitrate self-propagating high-temperature synthesis (SHS) with different oxidant-to-fuel ratio. Density and IR-transmission of microwave sintered Y₂O₃–MgO ceramics increase with respect to dispersity of the SHS-powders and reach its maximum values for the powder prepared in a 20% fuel excess. The sintering behavior of Y₂O₃–MgO compacts was investigated by optical dilatometry and measuring an electric conductivity upon heating. Significant microwave radiation power surges at temperatures of 900–1000 °C, caused by the decomposition of magnesium carbonate, have been found. As a result of matching the conditions for the synthesis of powders and sintering modes, a transmission of composite ceramics of 78% at a wavelength of 6 μm was achieved at a maximum processing temperature of 1500 °C.     

Lowering of sintering temperature and microwave dielectric properties of BaTi4O9 ceramics prepared by the polymeric precursor method

Low temperature sintering and microwave dielectric properties of barium polytitanate (BaO–4TiO₂) ceramics prepared by means of polymeric precursor route based on the Pechini process were investigated. Pure and fine BaTi₄O₉ powders with particle sizes of 100–200 nm were derived by thermal decomposition of amorphous gel precursor (above 750 °C). They formed single orthorhombic BaTi₄O₉ phase and showed fine and well-dispersed by XRD and SEM observation. The high sintering ability of the prepared powders enabled the fabrication of dielectric ceramics at low sintering temperatures (1200–1300 °C). The well-sintered BaTi₄O₉ ceramics with high relative densities (95%) were found to show excellent microwave dielectric properties compared to those prepared by conventional method at the same sintering temperature.     

Mechanical Properties of a Lithium Disilicate Strengthened Lithium Aluminosilicate Glass‐Ceramic

A glass composition in the Li₂O–Al₂O₃–SiO₂ (LAS)‐ternary phase diagram is presented, which enables the crystallization of Li₂Si₂O₅ as well as LiAlSi₂O₆ upon a well‐defined heat treatment. Li₂Si₂O₅ is the minor crystalline phase in the glass‐ceramic and generates through the bulk strengthening of the LAS glass‐ceramic. A flexural strength as higher as 400 MPa is measured in the proposed glass‐ceramic formulation, thus outperforming conventional LAS‐glass‐ceramics. A combination of the presence of those two crystalline phases of very different mechanical properties and coefficient of thermal expansion as well as the microstructure are believed to contribute largely to the enhancement of the measured properties.     

Inversion of quartz solid solutions at cryogenic temperatures

Quartz solid solution crystals of six different compositions were obtained from crystallization of glass powders belonging to the Li₂O–Al₂O₃-SiO₂ (LAS) system. They were analyzed in situ by laboratory-based X-ray diffraction down to cryogenic temperatures (−190°C). Temperature-resolved analysis of their lattice parameters allowed determination of the critical inversion temperature T_c in these materials, marking the displacive phase transition from a high-quartz- to a low-quartz-like lattice. Integrating available data from other literature sources, an updated phase diagram for the occurrence of high and low quartz solid solution phases is provided for the LAS system; these data are expected to support future development of functional materials relying on these crystalline phases.     

Double-layer waste-derived glass-ceramics prepared by low temperature sintering/sinter-crystallisation

Lightweight glass-ceramics with a dense surface layer were produced by a novel sintering approach. The surface porosity of a glass-ceramic body from the direct sintering of an engineered mixture of fly ash from thermal power plants, recycled soda-lime glass and boron waste (residues of the mining and purification of valuable boron containing minerals) was sealed by a glaze, deriving from the sinter-crystallisation of glass powders produced from the same mixture. The use of boron waste, providing B₂O₃, allowed a substantial viscous flow, for the substrate, even at the relatively low temperature (850–950°C) adopted for a single firing treatment (simultaneous sintering of substrate and sinter-crystallisation of glaze). The dense sinter-crystallised layer, besides imparting improvements in the mechanical properties, was found to feature an enhanced chemical stability.     

Enhanced ionic conductivity of Sm,Gd-doped ceria induced by modification of powder synthesis procedure

Nanostructured Ce_0.85Gd_0.05Sm_0.10O_2?δ powders have been obtained by a classical and a modified Pechini method. The textural parameters of the synthesized powders were evaluated using N₂ adsorption–desorption. X-ray diffraction (XRD) showed that the powders were single phase with fluorite-type structure. The dilatometry measurements evidenced a strong influence of the synthesis procedure of Gd, Sm-co-doped ceria on its sintering behavior. A decrease in powder sintering temperature down to 1200 °C was obtained when Triton X-100 was added into the synthesis reaction mixture. The AC impedance spectroscopy of the sintered pellets was also performed in the 200–800 °C temperature range, in air. The sample prepared using the non-ionic surfactant exhibited higher ionic conductivities and lower activation energies than the sample synthesized by classical Pechini method over the entire investigated temperature range.     

Chemical Synthesis,Sintering and Piezoelectric Properties of Ba0.85Ca0.15 Zr0.1Ti0.9O3 Lead‐Free Ceramics

The preparation of Ba_0.85Ca_0.15 Zr_0.1Ti_0.9O₃ (BCZT) powders by wet chemical methods has been investigated, and the powders used to explore relationships between the microstructure and piezoelectric properties (d₃₃ coefficient) of sintered BCZT ceramics. Sol–gel synthesis has been shown to be a successful method for the preparation of BCZT nanopowders with a pure tetragonal perovskite phase structure, specific surface area up to 21.8 m²/g and a mean particle size of 48 nm. These powders were suitable for the fabrication of dense BCZT ceramics with fine‐grain microstructures. The ceramics with the highest density of 95% theoretical density (TD) and grain size of 1.3 μm were prepared by uniaxial pressing followed by a two‐step sintering approach which contributed to the refinement of the BCTZ microstructure. A decrease in the grain size to 0.8–0.9 μm was achieved when samples were prepared using cold isostatic pressing. Using various sintering schedules, BCZT ceramics with broad range of grain sizes (0.8–60.5 μm) were prepared. The highest d₃₃ = 410.8 ± 13.2 pC/N was exhibited by ceramics prepared from sol–gel powder sintered at 1425°C, with the relative density of 89.6%TD and grain size of 36 μm.     

Microwave dielectric properties of glass-ceramic composites for low temperature co-firable ceramics

Ba–B–Si glass was added to Ba–Nd–Sm–Bi–Ti–O (BRT₁₁₄) microwave dielectric material for LTCC applications. Conventional one-step processing method for preparing glass-BRT₁₁₄ composite materials yields low dielectric constant, since the glass was easy to react with BRT₁₁₄ and forms a low dielectric constant phase, Ba₃B₆Si₂O₁₆. A large proportion of pores appeared. The nature of glass, whether it is sol-gel derived or fused, shows marked influence on the microstructure and microwave dielectric properties of the composites. A two-step process containing precoating the BRT₁₁₄ powders with a thin layer of glass, followed by conventional samples preparation process, tremendously improved the densification behaviour of the material. The formation of pores and interactions between glass and BRT₁₁₄ was greatly suppressed such that materials with high dielectric constant (ε_r=40) were achieved by sintering 9 wt.% glass-containing composite at 950 °C for 2.5 h.     

Optical properties of zinc borate glasses dispersed with Eu-doped SiAlON for white LED applications

Ca-α-SiAlON:Eu²⁺ oxynitride phosphors are typical luminescent materials with high thermal tolerances. A series of zinc borate glass samples (xZnO-(100-x)B₂O₃; mol%) were prepared for investigating their ability to disperse Ca-α-SiAlON:Eu²⁺ phosphor powders. Phosphor in glass (PiG) was prepared with SiAlON and zinc borate glass through a melting process. In the x = 45–60 range, PiGs could be obtained without the degradation of the SiAlON phosphors. The PiG composed of x = 50 glass exhibited the highest quantum efficiency. The glass structures of the mother glasses were investigated by Raman spectra; there was a decrease in the boroxol ring, and pyroborate and orthoborate were formed, on increasing x. From the XRD and SEM images, it was established that ZnAl₂O₄ was formed around the SiAlON powders in PiGs with x = 50, 55, and 60, respectively. This suggests that the partial crystallizations in the PiGs are effective in enhancing the photoluminescence of the SiAlON phosphors.     

New Sintered Li2O–Al2O3–SiO2 Ultra‐Low Expansion Glass‐Ceramic

We developed a new Li₂O–Al₂O₃–SiO₂ (LAS) ultra‐low expansion glass‐ceramic by nonisothermal sintering with concurrent crystallization. The optimum sintering conditions were 30°C/min with a maximum temperature of 1000°C. The best sintered material reached 98% of the theoretical density of the parent glass and has an extremely low linear thermal expansion coefficient (0.02 × 10^?6/°C) in the temperature range of 40°C–500°C, which is even lower than that of the commercial glass‐ceramic Ceran^® that is produced by the traditional ceramization method. The sintered glass‐ceramic presents a four‐point bending strength of 92 ± 15 MPa, which is similar to that of Ceran^® (98 ± 6 MPa), in spite of the 2% porosity. It is white opaque and does not have significant infrared transmission. The maximum use temperature is 600°C. It could thus be used on modern inductively heated cooktops.     

Sintering and densification behavior of pure and alkaline earth (Ba2+, Sr2+ and Ca2+) substituted La2Mo2O9

The present work studies densification and grain growth of fast oxide ion conductor, lanthanum molybdenum oxide (La₂Mo₂O₉). Sintering variables are experimentally analyzed using sintering laws. This paper investigates sintering of pure as well as Ca²⁺, Sr²⁺ and Ba²⁺ doped compositions by linear shrinkage measurement using dilatometer, relative theoretical density calculation and microstructural analysis using scanning electron microscope. In this work fine powder prepared by citrate–nitrate auto-combustion synthesis is used as source of powders for different compositions. The investigations indicate that sintering is enhanced in compare to the powders prepared by the other synthesis routes reported earlier. The evaluation of activation enthalpy of pure La₂Mo₂O₉ and its dependence with dopant addition are also studied with the help of sintering models and equations. The sintering mechanism is found to be dominated by grain boundary diffusion. The sintering inhibition is observed for the substituted compositions.     

Stability properties and microstructure properties of microwave-sintered CeO2 doped zirconia ceramics

Nanosized CeO₂–ZrO₂ powders prepared by atmospheric pressure pyrolysis were used as raw materials to prepare CeO₂–ZrO₂ ceramics using microwave sintering. The samples were characterised using bulk density measurements, X-ray diffraction (XRD), Fourier Transform Infrared Spectrometer (FT-IR), Raman, and scanning electron microscopy (SEM). The purpose was to determine the optimised microwave sintering process for CeO₂–ZrO₂ ceramics and reveal the corresponding mechanism. The results show that with a CeO₂ addition content above 5 mol%, the tetragonal phase peak appeared obviously in the sample. The results show that the tetragonal phase peak appears when the CeO₂ content is more than 5 mol%. The dopants, namely CeO₂, have reduced the solid solution's phase transformation temperature with the assistance of microwave heating. Additionally, the grain size of the CeO₂–ZrO₂ ceramics has shown a negative relationship with Ce content at a temperature of 900 °C. The reason is that the rapid sintering due to microwave sintering and the oxygen vacancies generated by CeO₂ can effectively inhibit grain growth. The regulation mechanism on microwave sintering of CeO₂–ZrO₂ ceramic was clarified, and the technical prototype of controlled prepared CeO₂–ZrO₂ ceramics by microwave sintering was constructed.