Glass-ceramic glazes for future generation floor tiles

Glaze in the CaO–MgO–Al₂O₃–SiO₂ system was heated at 950–1190 °C for 2 h and characterized. X-ray diffraction showed that only trace amount of mullite was formed in the glass-ceramic glaze heated at 950 °C. Both mullite and α-cordierite were formed in the glass-ceramic glaze heated at 1050 °C as primary and secondary phases. Glass-ceramic glazes heated at 1120 °C and 1190 °C contained α-cordierite and mullite as major and minor phases. Rietveld analysis revealed that the amount of α-cordierite increased and mullite decreased with increasing heating temperature. Field emission scanning electron microscopy showed presence of mullite crystals dispersed within residual glassy phase in the glass-ceramic glazes heated at 950 °C and 1050 °C. In the microstructures of glass-ceramic glazes heated at 1120 °C and 1190 °C α-cordierite crystals were mainly appeared. Energy Dispersive X-ray analysis corroborated X-ray diffraction results. Vickers microhardness measurement demonstrated highest hardness (8.38 ± 0.07 GPa) of the glass-ceramic glaze heated at 1190 °C.     

Effect of boron oxide on the microstructure of mullite-based glass-ceramic glazes for floor-tiles in the CaO–MgO–Al2O3–SiO2 system

The effect of increasing replacement of Al₂O₃ by B₂O₃ in a parent glass on the sintering and further crystallization of mullite was investigated. The composition of the parent glass was chosen in the mullite primary phase field of the CaO–MgO–Al₂O₃–SiO₂ quaternary system. Glass powder pellets were heated under standard (10 °C/min and 2 h of hold time) and fast heatings (25 °C/min and 5 min of hold time) at different temperatures from 700 to 1190 °C. Sintering of B₂O₃-containing glasses took place in the range between 850 and 1050 °C. X-ray diffraction results showed that mullite formed as unique crystalline phase for glasses containing amounts of B₂O₃ larger than 6 wt%. For lower amounts of boron oxide cordierite was formed as secondary crystalline phase. Quantitative determination of mullite by Rietveld analysis indicated that the higher amount of mullite present in the glass-ceramic fast heated at 1160 °C was 19.5 wt% for the glass containing 9 wt% of B₂O₃. The final microstructure of the glass-ceramic glazes showed the presence of well shaped, long acicular mullite crystals dispersed within the residual glassy phase. Results of glass-ceramic glazes when applied as slurry and under industrial heating conditions pointed out promising mechanical properties.     

Effect of iron on the microstructure of basalt glass-ceramics obtained by the petrurgic method

Basalt glasses may form glass-ceramic materials upon a thermal treatment (TT) if the Fe₂O₃/FeO ratio is greater than 0.5. In this work, a Serra Geral Formation basalt was used to produce different glass-ceramic materials by changing its chemical composition, removing Fe₂O₃ via magnetic separation and adding 20 wt% Fe₂O₃. Glass-ceramics were prepared by melting at 1500°C, followed by a crystallization plateau at 950°C. This petrurgic TT yields dendritic structures upon surface crystallization. With the increase of the iron content, crystallization was more pronounced, as observed in thermal analysis results and optical/scanning electron microscopy. The microstructure analysis shows that these glass-ceramics exhibit at least two different types of crystallization. On the surface, the predominant crystallization was dendritic, while in bulk, crystallization occurred in the form of randomly distributed submicrometric spheroid crystals.     

Influence of phosphorus pentoxide on crystallisation,microstructure and mechanical properties of potassium fluorophlogopite glass ceramics

Abstract

Potassium fluorophlogopite glass ceramics were prepared. Differential thermal analysis showed that there were two exothermic peaks at ～750 and 950°C, corresponding to the Avrami exponent ～1·5 and 2·0. Spherical particles were found using a scanning electron microscope when the glass ceramics were heat treated at 750 and 800°C. With the increase in heat treatment temperature, a kind of lamellar crystals was gradually formed, and the shape of crystals changed from spherical to lamellar when the Avrami exponent changed from 1·5 to 2·0. Mechanical tests showed that material cutting and bending strength increased, while the Vickers hardness decreased with the increasing of P₂O₅ content and heat treatment temperature.     

Valorization of Al slag in the production of green ceramic tiles: Effect of experimental conditions on microstructure and crystalline phase composition

This work reports the results of an investigation aimed at the development of sintered glass-ceramic tiles by the sinter-crystallization of mixtures composed of aluminum slag and reclaimed packaging glass. The thermal behaviors of mixtures incorporating 50 and 60 wt% Al slag were established by differential thermal analysis (DTA). Green compacts were sintered in a temperature range of 800°C-1050°C and then soaked for 10-60 minutes. The mineralogical characterizations of the sintered materials were obtained by X-ray diffraction (XRD). The achieved results indicated that the sintering of aluminum slag and packaging glass reclaimed led to a glass-ceramic material composed mainly of needle-like crystals of wollastonite (CaSiO₃). The bloating of samples during firing was evaluated according to a Cougny predictive diagram. After initial observations and according to bending strength characterizations, sintered tiles prepared from aluminum slag and glassy sand are appropriate for floor pavement and wall covering.     

Devitrification behaviour of plasma-sprayed glass coatings

Glass and glass-ceramic coatings on ceramic tiles have been manufactured by plasma-spraying high-performance CAS (in wt%—SiO₂, 60%; Al₂O₃, 15%; CaO, 23%; others, traces) and CZS (in wt%—SiO₂, 50%; CaO, 31%; ZrO₂, 16.5%; Al₂O₃, 2%; others, traces) glass frits. The CZS system has a surface crystallization at about 1050 °C. Such behaviour would not easily allow to obtain a fully crystalline bulk glass-ceramic, but the defectiveness of the plasma-sprayed coating supplies many nucleation sites. Thus, it becomes completely crystalline and well sintered after a 850 °C for 30 min + 1050 °C for 15 min treatment. The CAS frit, designed not to produce significant crystallization, is well sintered after a 850 °C for 30 min + 950 °C for 30 min thermal treatment, but remains too brittle due to its glassy nature. A 1050 °C treatment allows a few pseudowollastonite crystals to form in a glassy matrix; their formation also hinders sintering. Thus, mechanical properties are inferior to heat-treated plasma-sprayed CZS.     

Crystallization behavior and mechanical properties of high strength mica-containing glass-ceramics from granite wastes

The high-strength mica-containing glass-ceramics were prepared from granite wastes by bulk crystallization. The influences of SiO₂/Al₂O₃ molar ratio (S/A = 7.72, 9.62, 12.58, 17.82 and 29.67) on the crystallization behavior, microstructure, mechanical properties and machinability of glass-ceramics were investigated. The results demonstrated that the polymerization degree of the glass network decreased with the S/A ratio increasing, which further caused the decrease in glass transition temperature and crystallization temperatures. The increase in the S/A ratio promoted the precipitation of diopside, hectorite, kalsilite and tainiolite in glass-ceramics when the samples were heated at 750 °C, while inhibiting the precipitation of forsterite. For the glass-ceramics crystallized at 800 and 900 °C, the main crystalline phases transformed from diopside, forsterite, and nepheline to diopside, kalsilite, and tainiolite, with the S/A ratio increasing. As the SiO₂ gradually replaced Al₂O₃, the morphology of crystals changed from lamellar to granular, while the mean size of crystals reduced. The Vickers-Hardness values of glass-ceramics crystallized at 800 and 900 °C ascended with S/A ratio rising, and the values were above 6.30 GPa. The bending strength of most glass-ceramics is stable between 90 and 140 MPa, among which the maximum bending strength is 133.28 ± 14.81 MPa. The fracture toughness of the glass-ceramic crystallized at 800 and 900 °C declined, while that at 700 °C increased with a larger S/A ratio. Glass-ceramics after heat-treated at 900 °C with S/A ratio of 9.62 had the largest fracture toughness of 3.28 ± 0.15 MPa m^1/2. In preliminary tests of machinability, glass-ceramic after heat-treated at 900 °C with S/A ratio of 9.62 showed better results.     

Development and characterisation of a Y2Ti2O7-based glass-ceramic as a potential oxidation protective coating for titanium suboxide (TiOx)

A silica-based glass-ceramic, with Y₂Ti₂O₇ as the major crystalline phase, is designed, characterised and tested as an oxidation-protective coating for a titanium suboxide (TiO_x) thermoelectric material at temperatures of up to 600 °C. The optimised sinter-crystallisation treatment temperatures are found to be 1300 °C and 855 °C for a duration of 30 min, and this treatment leads to a glass-ceramic with cubic Y₂Ti₂O₇ and CaAl₂Si₂O₈ as crystalline phases. An increase of ~270 °C in the dilatometric softening temperature is observed after devitrification of the parent glass, thus further extending its working temperature range.Excellent adhesion of the glass-ceramic coating to the thermoelectric material is maintained after exposure to a temperature of 600 °C for 120 h under oxidising conditions, thus confirming the effectiveness of the T1 glass-ceramic in protecting the TiO_x material.     

Sealing Glass‐Ceramics with Near‐Linear Thermal Strain,Part II: Sequence of Crystallization and Phase Stability

The sequence of crystallization in a recrystallizable lithium silicate sealing glass‐ceramic Li₂O–SiO₂–Al₂O₃–K₂O–B₂O₃–P₂O₅–ZnO was analyzed by in situ high‐temperature X‐ray diffraction (HTXRD). Glass‐ceramic specimens have been subjected to a two‐stage heat‐treatment schedule, including rapid cooling from sealing temperature to a first hold temperature 650°C, followed by heating to a second hold temperature of 810°C. Notable growth and saturation of Quartz was observed at 650°C (first hold). Cristobalite crystallized at the second hold temperature of 810°C, growing from the residual glass rather than converting from the Quartz. The coexistence of quartz and cristobalite resulted in a glass‐ceramic having a near‐linear thermal strain, as opposed to the highly nonlinear glass‐ceramic where the cristobalite is the dominant silica crystalline phase. HTXRD was also performed to analyze the inversion and phase stability of the two types of fully crystallized glass‐ceramics. While the inversion in cristobalite resembles the character of a first‐order displacive phase transformation, i.e., step changes in lattice parameters and thermal hysteresis in the transition temperature, the inversion in quartz appears more diffuse and occurs over a much broader temperature range. Localized tensile stresses on quartz and possible solid‐solution effects have been attributed to the transition behavior of quartz crystals embedded in the glass‐ceramics.     

Modification of glass network and crystallization of CaO–Al2O3–MgO–SiO2 based glass ceramics with addition of iron oxide

Modification of glass network and crystallization process of a CaO–Al₂O₃–MgO–SiO₂ (CAMS) based glass ceramic to form diopside through addition of iron oxide were investigated using differential thermal analysis (DTA), Raman spectrum, X-ray diffraction, SEM and EBSD techniques. The experimental results showed that addition of Fe₂O₃ led to remarkable reductions in both the glass transition temperature (Tg) and crystallization temperature (Tp) of the CAMS glass ceramic. At addition level below 5 wt%, the Tg and Tp temperatures were 651°C and 903°C, respectively, and the crystallization only occurred on the surface of the glass ceramic samples. Increasing the addition level to 10 wt% and 15 wt%, not only led to reduction in the Tg and Tp temperatures to 643-641°C and 892-876°C, respectively, but also promoted the formation of crystalline diopside throughout the CAMS samples. Based on the results of Raman spectrums, it was confirmed that Fe₂O₃ addition reduced the strength of glass connection as a result of chemical reactions between the isolated Si–O tetrahedron and Fe³⁺ ion, forming Fe³⁺O₄–SiO₄, which can be regarded as Q₂ unit. And this is the first experimental evidence that proving the approach of Fe³⁺ mending glass network. Microstructural examination also identified the formation of large numbers of spherical Fe-enriched regions within the CAMS glass matrix as a result of the amorphous phase separation due to the Fe₂O₃ addition. The interfaces between the Fe-enriched regions and the glass matrix acted as preferred nucleation sites for the diopside, facilitating the crystallization. Crystallographic analysis using EBSD technique determined the <001> as the most favorite growth direction for the diopside crystals in the CAMS based glass ceramic.     

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.     

Crystallization,structure and properties of MgO-Al2O3-SiO2 highly crystalline transparent glass-ceramics nucleated by multiple nucleating agents

Generally, highly crystalline transparent glass-ceramics possess excellent physical and chemical properties compared to organic and other inorganic optical materials. We have successfully prepared highly crystalline transparent glass-ceramics in the MgO-Al₂O₃-SiO₂ system by "extreme-time" nucleation & "finite-time" crystallization processes using P₂O₅, ZrO₂ and TiO₂ as multiple nucleating agents. The results revealed that the crystallization of glass is controlled by a three-dimensional interfacial crystal growth process. These glass-ceramics mainly consisted of cordierite crystals with a residual glassy phase, and crystallinity increased with crystallization time, but light transmittance decreased with crystallization time due to enlarged grain sizes. EDS mapping revealed a uniform distribution of elements within the glass-ceramic. In the optimal preparation condition (825?°C/96?h?+?990?°C/3?h), these glass-ceramics exhibited a high crystallinity (87.3?vol. %), high transmittance (78%), and excellent mechanical properties. This work provides a roadmap for preparing highly crystalline transparent glass-ceramics for applications in optical engineering.     

Sintered glass-ceramics from Municipal Solid Waste-incinerator fly ashes—part I: the influence of the heating rate on the sinter-crystallisation

A glass composition, made by mixing 70% of MSW ashes and 30% of waste from feldspar production, was studied. The batch was melted at 1350 °C and the melt was quenched in water. The chemical stability of the glass was investigated by TCLP leaching test. DTA experiment, at 10 °C/min heating rate in the 20–1200 °C range, showed that the glass has a high crystallisation trend with a gehlenite (2CaO.Al₂O₃.SiO₂) formation at 935 °C. The percentage of crystal phase formed as a function of the heat treatment was measured by density variation and XRD. In order to obtain sintered glass ceramics, the frit was heat treated in Al₂O₃ moulds at 950, 1000 and 1050 °C by 2 and 20 °C/min heating rates. At high heating rate predominantly surface crystallisation occurred with fibre-like crystals growing perpendicularly from the surface; at low heating rate bulk crystallisation took place. At low rate, the sintering was inhibited by the crystallisation process. Non porous sintered samples were obtained by a 30 °C/min heating rate and a 40 min isothermal step at 1120 °C, near the liquidus temperature.     

Microstructure and properties of SiCf/SiC composite joints with CaO–Y2O3–Al2O3–SiO2 interlayer

Using CaO, Y₂O₃, Al₂O₃, and SiO₂ micron-powders as raw materials, CaO–Y₂O₃–Al₂O₃–SiO₂ (CYAS) glass was prepared using water cooling method. The coefficient of thermal expansion (CTE) of CYAS glass was found to be 4.3 × 10^?6/K, which was similar to that of SiC_f/SiC composites. The glass transition temperature of CYAS glass was determined to be 723.1 °C. With the increase of temperature, CYAS glass powder exhibited crystallization and sintering behaviors. Below 1300 °C, yttrium disilicate, mullite and cristobalite crystals gradually precipitated out. However, above 1300 °C, the crystals started diminishing, eventually disappearing after heat treatment at 1400 °C. CYAS glass powder was used to join SiC_f/SiC composites. The results showed that the joint gradually densified as brazing temperature increased, while the phase in the interlayer was consistent with that of glass powder heated at the same temperature. The holding time had little effect on phase composition of the joint, while longer holding time was more beneficial to the elimination of residual bubbles in the interlayer and promoted the infiltration of glass solder into SiC_f/SiC composites. The joint brazed at 1400 °C/30 min was dense and defect-free with the highest shear strength of about 57.1 MPa.     

Development of a new glass–ceramic by means of controlled vitrification and crystallisation of inorganic wastes from urban incineration

This paper reports the results of a study of the feasibility of recycling the solid residues from domiciliary waste incineration by producing a glass-ceramic. The major components of the raw material (TIRME F+L), which was from a Spanish domiciliary incinerator, were CaO, SiO₂ and Al₂O₃ but nucleating agents, such as TiO₂, P₂O₅, and Fe₂O₃ were also present in reasonable amounts. It was found that a relatively stable glass with suitable viscosity could be obtained by mixing 65 wt% TIRME F+L with 35 wt% glass cullet. The heat treatment required to crystallise the glass produced from this mixture, designated TIR65, was nucleation at 560°C for 35 min followed by crystal growth at 100°C for 120 min. The resulting glass-ceramic contained a number of crystalline phases, the most stable being clinoenstatite (MgSiO₃), or perhaps a pyroxenic phase which incorporates Ca, Mg and Al in its composition, and åkermanite (Ca₂MgSi₂O₇). The microstructure contained both fibre-like and dendritic crystals. The mechanical properties were acceptable for applications such as tiles for the building industry. ©     

Preparation and sealing effects of Mg–Al–Si–Ba–O-based glass-ceramic coatings on NTC thermistors

Herein, Mg–Al–Si–Ba–O-based glass ceramics were studied as potential candidates to protect Mn–Co–Ni–O-based negative temperature coefficient (NTC) thermistors at high temperatures such as 900 °C. The ceramics were prepared in three glass formulations (1#: 15MgO–15Al₂O₃-44.7SiO₂–25BaO, 2#: 17MgO–17Al₂O₃–41SiO₂–25BaO and 3#: 17MgO–17Al₂O₃–41SiO₂–20BaO–5Y₂O₃ (in mol%)) and their glass-transition temperatures (T_g) were determined using the differential scanning calorimetry (DSC) method. Scanning electronic microscopy (SEM) and X-ray diffraction (XRD) were used to characterize the parent glasses and glass-ceramic coatings. The sealing effects of the glass ceramics were examined by conducting an insulation test. The glass-ceramic sealing structures were subjected to 1000 thermal shock cycles at temperatures varying from room temperature to 900 °C. Notably, the sealing structure of glass-ceramic coating 1# was compact at a T_g of 760.9 °C. The glass-ceramic coatings effectively maintained the NTC properties of the sensitive ceramics in all three formulations. Interestingly, the glass-ceramic coating 3# containing Y₂O₃ demonstrated an increase in electrical resistance. Both the NTC thermistors coated with 1# and 2# glass formulations successfully passed 1000 thermal shock cycles without visible failures, and their resistance change ratios were well below the requisite 20%.     

Stable Wollastonite-Cuspidine Glass-Ceramic Using Inexpensive Raw Materials

Transparent glasses within the K₂O-CaO-SiO₂-F composition were prepared. The influence of CaF₂, TiO_2, Li₂O, Li₂O-TiO₂ and CeO₂ additions on the crystallization of the parent glass has been investigated. Crystallization process gave wollastonite and cuspidine as the major phases whereas; xontolite and traces of miserite were developed as subordinate ones. Wollastonite was developed alone in the temperature range of 800 °C-1100 °C in Li₂O-containing the base glass. Wollastonite and cuspidine were stable in the 800-1100 °C range in Li₂O+TiO₂-containing samples and within the 900 °C-1100 °C range in CaF₂ and CeO₂ containing samples. The microstructure of the Li₂O-containing glass-ceramic showed an interlocked needle in nano-scale wollastonite crystals, while fibrous textures were developed in all other crystallized samples at 1000 °C. The thermal expansion coefficient value of the crystallized samples was between 7.596 to 8.708 X10 ^?6 °C^?1 (20-500 °C) and the higher values reflect the increase of crystallization content of cuspidine and even the traces of miserite. This glass-ceramic is thought to be important in dental laboratories.     

Preparation and mechanical properties of machinable alumina/mica composites

Using a mica-crystallizing glass powder in which a large amount of mica crystal was precipitated and a larger amount of MgF₂ component was contained as the raw materials of mica, machinable alumina/mica composites were obtained at 1400 °C. In the firing process, magnesia component in the mica crystals reacted with alumina to form spinel at 1150–1200 °C. The reaction made the mica crystals melt. However, the mica crystals were precipitated again during the cooling. Because a larger amount of MgF₂ component was contained in the mica-crystallizing glass powder, the nucleation of the mica crystals was caused during the cooling by the residual magnesium and fluorine in the liquid phase and succeedingly the mica crystals were precipitated. The precipitated mica crystals grew to anisotropicaly larger size than alumina grains, which lowered the bending strength and Vickers hardness and little heightened the fracture toughness.     

Fabrication and properties of dense α-cordierite glass-ceramic coating on porous BN/Si2N2O ceramic

α-Cordierite glass-ceramic coating was fabricated on the porous BN/Si₂N₂O ceramic by glass-ceramic method. The effect of the heating temperature on the phase composition, microstructure, mechanical properties, water resistance and dielectric properties of the coatings was investigated. A large amount of α-cordierite precipitated from the glass phase when the heating temperature was 1050?°C and the content of α-cordierite in the coating increased with increasing the heating temperature. The resulting α-cordierite glass-ceramic coatings had a good wettability and adhesion with the porous ceramic substrate. The coating/substrate interface was continuous without defects. When the heating temperature was 1050–1200?°C, the resulting coatings possessed positive mechanical properties and good water resistance due to the high densification. And the dielectric constant and loss tangent of the coated samples prepared at 1050–1200?°C were 4.1–4.3 and 0.005–0.01 respectively in the frequency of 21–36?GHz.     

Effect of the Quenching Temperature on the Fields of Thermal Stresses and on the Mechanical and Thermal Properties of PMMA

This study explores the photoelasticimetry as a means to investigate factors affecting the residual stresses, particularly the thermal stresses, in polymethyl methacrylate (PMMA). The aim was to study the effect of quenching temperature in three different media: air, water, and ethylene glycol, on the impact strength and thermal properties of PMMA. These temperatures varied from a fixed value of 120°C to various values below Tg and the fields of distribution of cooling stresses have been obtained using a charge-coupled device (CCD) camera. It was observed that the quenching in water at 20°C gives rise to an important density of tensile stresses. However, in the ethylene glycol at 110°C this density has a tendency to disappear. An approximate evaluation of these stresses in a point near the specimen center has been assessed, and it was found that the distribution profile of the fields of tensile stresses was much closer to a parabolic form. Notched Izod impact strength and heat deflection temperature (HDT) were measured, and were found to be particularly sensitive to thermal stresses.