Reinforcement of single-firing ceramic glazes with the addition of polycrystalline tetragonal zirconia (3Y–TZP) or zircon

The addition of fine-grained polycrystalline tetragonal zirconia (3%Y₂O₃–TZP, or 3Y–TZP) to conventional, single-firing, ceramic glazes was studied with the aim to enhance their hardness, fracture toughness and wear resistance for floor tile applications. The stability of the added tetragonal zirconia towards solution in the glaze and/or zircon crystallization was found strongly dependent on glaze composition, firing treatment, and on the way of preparing the samples (uniaxially-pressed pellets or thin-layer coatings). 3Y–TZP remained stable in fast-fired pellets, but partial crystallization of prismatic zircon microcrystals (2–3 μm) occurred in samples prepared as thin-layer coatings. Addition of 10–30 wt.% of 3Y–TZP to a conventional single-firing glaze that was industrially enameled (thin films) onto low-porous floor tiles, promoted an important enhancement of Vickers microhardness (H_v from 6.0 to 8.4 GPa), fracture toughness (K_IC from 1.35 to 2.23 MPa m^1/2), and wear resistance (PEI abrasion number from 2 to 5). The achieved reinforcement was higher with 3Y–TZP than with zircon addition, and must be attributed to the stress-induced transformation-toughening mechanism promoted by the undissolved stabilized tetragonal zirconia, and also to partial zircon crystallization. The possibility of obtaining ceramic coatings mechanically reinforced with 3Y–TZP additions, while also maintaining a glossy aspect, was also confirmed.     

Zircon-free frits suitable for single fast-firing opaque wall tile glazes and their industrial productions

Wall tile glazes with a smooth surface texture, high glossiness, and whiteness are usually based on zirconium containing frits. However, these frits are quite expensive and therefore, there have recently been certain attempts to lower the production cost such as taking suitable glass–ceramic glaze systems into an account. With the present work, the frit-based glaze compositions belonging to the K₂O–MgO–CaO–ZnO–Al₂O₃–B₂O₃–SiO₂ glass–ceramic system were studied to prepare newly synthesized wall tile glazes for industrial single fast-firing. The design of a glass–ceramic glaze for this type of tiles should ensure that the selected frit precursor is technically and commercially compatible with the manufacturing conditions generally used in the production of glazed ceramic wall tiles. The aim of the study is to develop zircon-free, frit-based, glossy opaque glass–ceramic glazes for wall tiles by optimizing the CaO/MgO and adjusting the Al₂O₃/alkali ratios in the starting frit compositions. Frit production, glaze preparation, application, and single fast-firing of wall tiles were, first of all, conducted under laboratory working conditions and then, successful recipes were adapted to the relevant industry. The frit crystallization capability and crystallization temperature range were determined by differential thermal analysis (DTA). Thermal expansion coefficient values of glazes were determined by a dilatometer. Characterization of single fast-fired glass–ceramic glazes was made by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) techniques. Colour and gloss analyses of the final glazes were measured with a spectrophotometer and a gloss meter, respectively.     

Development of sapphirine opaque glazes for ceramic tiles

The purpose of this work is to produce more excellent opaque wall tile glazes by using sapphirine instead of zirconium silicate as an opacifier. In order to achieve it, the chemical compositions were precisely adjusted in the system of SiO₂-Al₂O₃-MgO-K₂O-Na₂O-B₂O₃. The morphological characteristics of the glaze were determined by differential scanning calorimetry (DSC), X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). And the optical properties of the glaze were characterized by a spectrophotometer and a gloss meter. The results reveal that well-shaped crystals of sapphirine (Mg₂Al₄SiO₁₀) with needle-like morphology were formed as only crystal phase. The glaze is provided with better opacity whiteness and gloss compared with commercial zircon-based glass-ceramic glazes, and it is mainly composed of cheap mineral raw materials. Those features make it as an alternative one for improving the properties of conventional opaque ceramic glazes.     

Compositional modifications to floor tile glazes opacified with zircon

Abstract

In the ceramic tile industry opaque glazes with considerable zircon content are widely used. However, the high cost of zircon limits its wide use in relevant glaze compositions. In the present study, a model opaque glaze was modified by changing the alumina/silica ratio, adding potassium oxide, or using a higher content of opaque frit while gradually eliminating the zircon content in the glaze batch. After glaze preparation, application, and single firing of glazed floor tiles under industrial conditions glazes were characterised by XRD, SEM, and EDX. The optimum alumina/silica ratio was found to be 0·26. Colour parameters L, a, and b of starting and final glazes showed that an increase in opaque frit content gives more positive improvement in opacity and in dry abrasion resistance than potassium oxide addition. Removal of zircon from the glazes resulted in a decrease of ～13–18% in glaze cost without detrimental effect on opacity.     

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.     

Effect of iron oxide content on the crystallisation of a diopside glass–ceramic glaze

The effect of iron oxide content on the crystallisation of a diopside glass–ceramic glaze was investigated using a glass–ceramic frit in the K₂O–ZnO–MgO–CaO–Al₂O₃–SiO₂ system and a granite waste glass. Measurements by X-ray diffraction (XRD) combined with scanning electron microscopy (SEM) and EDX microanalysis showed that the distribution of Fe³⁺ ions among different crystalline phases such as franklinite (ZnFe₂O₄) and hematite Fe₂O₃ depends on the iron content in the original diopside mixture. Thus, the original glaze crystallises to franklinite or hematatite when iron content is greater than 2 and 15%, respectively.     

Influence of firing temperature on the color developed by a (Zr,V)SiO4 pigmented opaque ceramic glaze

The analysis of the physical interactions between pigments, opacifiers and glazes is fundamental to understand the optical behavior of ceramic glazes. Furthermore is important to verify if the glaze devitrifies because the crystallized phases can contribute to the optical properties of the system. The size and the quantity of the formed crystals can change significantly the glaze color. The mean goal of this study was to evaluate the influence of firing temperature on the color stability of an opaque ceramic glaze colored by a blue vanadium–zircon pigment taking into account all the optical components. Quantitative X-ray diffraction analysis was conducted in order to evaluate the pigment dissolution at the three studied temperature and the quantity of the in situ formed zircon crystals from the used frit. The reported study demonstrated the importance to consider all the components in a multicomponent optical system as a ceramic glaze.     

Injection‐molded high‐density polyethylene–hydroxyapatite–aluminum oxide hybrid composites for hard‐tissue replacement: Mechanical,biological, and protein adsorption behavior

In this article, we report the mechanical and biocompatibility properties of injection‐molded high‐density polyethylene (HDPE) composites reinforced with 40 wt % ceramic filler [hydroxyapatite (HA) and/or Al₂O₃] and 2 wt % titanate as a coupling agent. The mechanical property measurements revealed that a combination of a maximum tensile strength of 18.7 MPa and a maximum tensile modulus of about 855 MPa could be achieved with the injection‐molded HDPE–20 wt % HA–20 wt % Al₂O₃ composites. For the same composite composition, the maximum compression strength was determined to be 71.6 MPa and the compression modulus was about 660 MPa. The fractrography study revealed the uniform distribution of ceramic fillers in the semicrystalline HDPE matrix. The cytocompatibility study with osteoblast‐like SaOS2 cells confirmed extensive cell adhesion and proliferation on the injection‐molded HDPE–20 wt % HA–20 wt % Al₂O₃ composites. The cell viability analysis with the 3(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay revealed a statistically significant difference between the injection‐molded HDPE–20 wt % HA–20 wt % Al₂O₃ composites and sintered HA for various culture durations of upto 7 days. The difference in cytocompatibility properties among the biocomposites is explained in terms of the difference in the protein absorption behavior. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The controllable microstructure of porous Al2O3 ceramics prepared via a novel freeze casting route

In traditional aqueous slurry freezing casting processing, the growth method of ice crystals is hard to control, resulting in the uncontrollable pore's morphologies of the porous ceramics. In the experimental, the pure Al₂O₃ sol was used to substitute water as a medium for preparing ceramic slurry. With Al₂O₃ sol addition, it becomes easy to control the microstructure and pore's morphologies of the porous Al₂O₃ ceramics via adjusting of the solid loading, composition of the ceramic slurries, as well as the cooling methods. The SEM micrographs showed that the sol-contained ceramic slurry combined with freeze casting processing can easily prepare the porous Al₂O₃ ceramics with different pore sizes and different morphologies. The porous Al₂O₃ ceramics prepared from 70 wt.% to 90 wt.% solid loading sol-contained Al₂O₃ slurries and sintered at 1500 °C for 2 h have open porosities from 81.7% to 64.6%.     

Effect of TiO2 on the crystallization,thermal expansion and wetting behavior of Nd2O3-Al2O3-SiO2 glass ceramic filler

The crystallization behavior, microstructure, crystalline phases, microhardness, coefficient of thermal expansion (CTE), and wetting behavior of Nd₂O₃-Al₂O₃-SiO₂ (NAS) glass ceramics with different TiO₂ content were investigated. The results show that the content of crystals increases and the size of crystals decreases with the increase of TiO₂ content. Moreover, the formation of Nd₂SiO₅ leads to the increase and the precipitation of Al₆Si₂O₁₃ results in the decrease in the CTE value of NAS glass ceramics. As a result, the CTE of NAS glass ceramics can be controlled in the range of 4.2–9.2 × 10⁻⁶/℃. These values are suitable for matching bonding to most ceramics with different CTE. Indeed, contact angle measurement demonstrates that the NAS glasses with 3 %, 6 % and 9 % TiO₂ possess excellent wettability on the Al₂O₃, ZrO₂ and zirconia toughened alumina (ZTA) ceramic, respectively.     

High wear resistance white ceramic glaze containing needle like zircon single crystals by the addition of sepiolite n-ZrO2

Sepiolite with homogeneous zirconia nanoparticles distribution has been added to a transparent ceramic glaze to study opacification, mechanical and wear resistance properties. It has been observed that monodispersed zircon single crystals with needle-like shape have been formed in the ceramic glaze. These in situ zircon single crystals give white color and increase opacification (L = 94 vs L = 90), mechanical properties (hardness and toughness) and wear resistance by a factor of 4 compared to the commercial crystalline glaze containing a similar fraction of micrometer commercial zircon.     

Al2O3–Y3Al5O12(YAG)–ZrO2 ternary composite rapidly solidified from the eutectic melt

In situ fabrication of new ceramic eutectic composites by rapid solidification of eutectic drops is a cheap and quick method compared to fabrication of directional solidification or multi-step fabrication methods of fiber reinforced/layered composites for high temperature use. This study reports the fabrication of ceramic composites during rapid solification of eutectics melts in the ternary oxide alumina–yttria–zirconia system. Layered ternary eutectics are obtained in the alumina–YAG–zirconia subsystem. The microstructure of Al₂O₃–Y₃Al₅O₁₂–ZrO₂ composites rapidly solidified from melts is presented.     

Effect of ZnO on Crystallization of Zircon from Zirconium‐Based Glaze

The promotion of zircon (ZrSiO₄) crystallization by ZnO from a zirconium‐based frit glaze was studied and the possible mechanism was discussed. X‐ray diffraction was used to analyze the relative quantities of zircon and other transitional crystals in the samples. The results show that ZnO can significantly decrease the crystallization temperature of zirconium‐based glaze, depress the formation of Ca₂ZrSi₄O₁₂, and promote the devitrification of transitional crystals t‐ZrO₂ and Ca₂ZnSi₂O₇, as well as lead to the formation of more zircon than the ZnO‐free glaze. It was also found that zircon not only can form from the interaction between t‐ZrO₂ and SiO₂ but also can devitrify directly from the glass phase of zirconium‐based glaze.     

Crystallization of Zircon in Stoneware Glazes

High levels of zircon are required to impart opacity in glazes. Zircon additions of <3 wt% dissolve into the glassy phase; additions of >12% cause all the zircon to crystallize from the glaze. Dynamic high-temperature X-ray diffraction has shown that, during heating, a portion of the zircon dissolves and subsequently recrystallizes, using undissolved zircon crystals as seeds. This recrystallization does not occur at lesser zircon levels, because of a lack of seed crystals. When zirconia is added to the glaze, zircon is formed as elongated crystals at the glaze surface. Lesser zircon levels have been observed in the glazes that have zirconia additions.     

Effects of nucleation agents on the preparation of transparent glass–ceramics

Formation of transparent glass–ceramic in the system MgO–SiO₂–Al₂O₃–K₂O–B₂O₃–F with and without addition of LiF and NaF has been investigated. Crystallization of glass-sample was conducted by controlled thermal heat-treatment, at determined nucleation and crystallization temperatures. In this regard, the effects of addition of LiF and NaF were investigated on the crystallization behavior and transparency of the samples.Low transmission (less than 80% at 600 nm) was observed in the basic composition (K).The addition of NaF and LiF caused more intense phase separation in the system.The results indicated that the glass–ceramic can remain transparent if fine grains with nano size are precipitated but will turn into opaque when large grains appear, because of the difference in the refractive index between glass and precipitated crystals.     

3D printing ceramic cores for investment casting of turbine blades,using LCD screen printers: The mixture design and characterisation

The primary objective of this study is to demonstrate the possibility of developing silica, alumina, and zircon-based photocurable ceramic suspensions that can be used for visible light photopolymerization (> 450 nm) and to optimise the binder formulations for the purpose of LCD-based ceramic 3D printing applications. Reference ceramic components for this work are ceramic cores employed in the investment casting of high-pressure turbine blades and vanes. Arguably, one of the most critical steps in photoinduced ceramic 3D printing is developing suitable ceramic suspensions, having high ceramic loading, low viscosity, and short curing times. Ceramic suspensions with four different novel binder formulations and commercial ceramic powders used in core manufacturing (SiO₂, Al₂O₃ and ZrSiO₄) were investigated to achieve the best trade-off between: (1) their curing performance (cure depth and curing speed), (2) rheological properties of the binder mixtures at the solid loadings of 60 vol.% for SiO₂, 55 vol.% for ZrSiO₄, and 45 vol.% for Al₂O₃; and (3) the green body mechanical properties of the mixtures after printing. The effect of ceramic particles on the selected binders was examined individually, and the correlation between cure depth (C_d), volumetric loading, and curing speed are evaluated. The results show all binders designed in this study provide an adequate cure depth, even at high ceramic loadings. When the curing behaviour of all unloaded binder mixtures from the previous study [1] compared with the 10 vol.% SiO₂ loaded mixtures, the cure depth of all formulated binder mixtures increased 50–55 % and the curing thickness of 60 vol.% SiO₂ loaded suspensions were still slightly higher than their unloaded counterparts. The rheology outcomes indicate that lower viscosity binders always result in lower viscosity of the ceramic loaded inks, even without taking the effect of dispersants into account. Besides, the addition of N-Vinyl-2-Pyrrolidone (NVP) monofunctional monomer to the binder mixtures significantly reduces the viscosity and changes the normally linear relationship of the mix viscosity and its silica loading content. Among the binder formulations loaded with 60 vol.% of SiO₂, the formulation providing the lowest viscosity and highest mechanical property consists of 5 wt.% of NVP, 45 wt.% of HDDA and 50 wt.% of Photocentric 34 resin. Although this binder mixture showed the highest green flexural strength when loaded by 55 vol.% ZrSiO₄, all other mixtures loaded with zircon flour also demonstrated a near-fluid behaviour, below 200 s^?1. In Al₂O₃ loaded mixtures, the HDDA di-functional binder formulations present lowest viscosity and the di- and multifunctional monomer blends (HDDA-Photocentric27) showed the highest mechanical properties when used in a 50/50 ratio. This work summarises the best binder choices for silica, alumina and zircon based ceramic suspensions used in core printing for investment casting applications through LCD screen printing.     

Mechanical performance and microstructure of 3Y-TZP/Al2O3/GNPs medical ceramic surgical scalpel material prepared through SPS–HF dual sintering method

In this study, 3 mol% yttria-stabilized tetragonal zirconia polycrystal (3Y-TZP)/Al₂O₃/graphene nanoplatelets (GNPs) medical ceramic materials for manufacturing surgical scalpels were sintered in vacuum in an SPS–625HF furnace. The mechanical performances and microstructures of the composites were investigated, and the influence mechanisms of the sintering temperature and amount of added GNPs were studied. During the sintering process at 1400°C and 30 MPa for 5 min, the added GNPs enhanced the mechanical properties of the 3Y-TZP/Al₂O₃ composites. The results showed that the composite with .1 wt.% GNPs had 6.4% (910 ± 11 MPa) higher flexural strength than 3Y-TZP/Al₂O₃. The composite with .4 wt.% GNPs had 38.7% (12.95 ± .22 MPa m^1/2) greater fracture toughness than 3Y-TZP/Al₂O₃. The main toughening mechanisms of 3Y-TZP/Al₂O₃/GNPs were crack bridging, crack deflection, crack branching, GNPs bridging, transgranular fracture structures, and phase transformation of t-ZrO_1.95. The two-stage densification displacement curve appeared at the optimal sintering temperature of the materials, and the 3Y-TZP/Al₂O₃/GNPs composites with a two-stage densification displacement curve had excellent mechanical properties. The added GNPs can inhibit the grain growth during the sintering process, thereby refining the zirconia grains. With the increase in GNPs content, the grain size and flexural strength of the composites decreased gradually. However, higher content of GNPs was beneficial to improve the relative density and thermal diffusivity of 3Y-TZP/Al₂O₃/GNPs composite material.     

Behaviour of Cr3+ and Fe3+ ions in the gahnite crystallized from zinc opaque glazes

The amount of gahnite spinel crystallized in a glaze containing a large amount of ZnO and Al₂O₃ as well as the behaviour of Cr³⁺ ions in the glaze were studied. Crystallization of gahnite containing a small amount of Cr₂O₃ gave a pink opaque glaze. Almost all the Cr³⁺ ions migrated into the gahnite phase. The measurement of the lattice constant by X-ray diffraction analysis, as well as chemical analysis of the crystallized gahnite separated from the glaze, were used to determine the amount of Cr³⁺ ions in the gahnite phase. A similar phenomenon occurred when Fe₂O₃ was added to the base glaze composition.     

Effects of additives on combustion synthesis of Al2O3–TiB2 ceramic composite

Al₂O₃, SiC and kaolin were employed as additives in combustion synthesizing Al₂O₃–TiB₂ ceramic composite. Effects of the additives on adiabatic temperature, combustion wave velocity, volume change and composite density were studied, and bending strength of the synthesized ceramics was evaluated. By theoretical calculation, the adiabatic temperature of Al–TiO₂–H₃BO₃ system is 2314.85 °C and decreases with increasing the additive addition. With Al₂O₃ addition, the phases presented in the ceramic composite are unchanged, and the phases of SiC and 3Al₂O₃·2SiO₂ emerges when SiC and kaolin are added. The addition of the additives results in a refined TiB₂ particulate size and reduces combustion wave velocity. The highest density is achieved with the addition of kaolin from 10 to 30 wt.% making the volume change from ?4.6 to ?1.2%. The bending strength of the TiB₂–Al₂O₃ composite is improved eight times with the addition of 30 wt.% kaolin.     

Development of spinel opaque glazes for ceramic tiles

The feasibility of developing fast-firing opaque wall tile glazes obtained from zircon-free frits was studied. The structural and morphological characteristics of the glazes were determined by differential scanning calorimetry, an optical dilatometer, X-ray diffraction and scanning electron microscopy. The studied glaze was characterized by a high whiteness value L* greater than 94, very low values of a* and b* which is about ?0.65 and 0.01, respectively, and a high gloss value above 98%. The opaque effect is due to the presence of spinel crystals with a size range of 0.2–1.0 μm, which is formed by devitrification during fast-firing. The Vickers micro-hardness of the studied glaze is higher than the one of the commercial zircon based glass-ceramic glazes. This type of frit can be an alternative one for fabricating opaque ceramic glazes.