Incorporation of wastes from granite rock cutting and polishing industries to produce roof tiles

The present work aimed at studying the incorporation of wastes from natural rock cutting and polishing to produce roof tiles. The sintered products incorporating the sludge were targeted to have similar or even enhanced properties in comparison to those made of a standard reference paste industrially used to fabricate concurrent products available in the market. Firstly, the raw materials, including the sludge, were characterised by particle size distribution, density, X-ray diffraction (XRD), thermal properties and loss on ignition. Different formulations were prepared to evaluate the effects of each component on plasticity of pastes, drying and firing processes, and on the final properties of the tiles. Finally, the most promising formulations were selected and characterised for sintered density, water absorption, and flexural bending strength. The results obtained made it possible to conclude about the possibility of producing roof tiles incorporating 10% of granite wastes having excellent properties (water absorption <6%, lower pyroplastic deformation index, and bending strength values of about 14 MPa and 38 MPa for the green and sintered products, respectively). Therefore, the sludge derived from the granite cutting and polishing industries can be classified as a by-product suitable to replace natural non-plastic raw material in traditional ceramic formulations. This will contribute to preserve non-renewable natural resources, while it allows minimization of the negative environmental impact due to its disposal.     

The effects of fine fire clay sanitaryware wastes on ceramic wall tiles

In the last decade, environmental preservation has become an important issue. Specifically, recycling of sanitaryware fine fire clay (FFC) waste is important for reducing costs. In this study, the use of FFC waste as an alternative raw material in the production of ceramic wall tiles was investigated. Five ceramic wall tile bodies were prepared by substituting kaolin (max. 15 wt%) with FFC wastes. All formulations were mixed, pressed into pellets and sintered at 1145 °C. The sintering behaviour was evaluated using an optical dilatometer. Water absorption, linear shrinkage and bending strength were also measured. This study revealed that FFC wastes are good alternative raw materials, and the corresponding formulations were shown to be viable in the manufacturing of ceramic tiles. The most remarkable conclusion from this study was that the addition of FFC waste decreased moisture expansion.     

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.     

Obtainment of porcelain floor tiles added with petroleum oily sludge

This study focuses on the processing of vitrified floor tiles incorporated with a petroleum oily sludge. Floor tile formulations containing up to 5 wt% of the petroleum oily sludge in replacement of kaolin were prepared. The tile formulations were granulated by the dry process, pressed, and fired at temperatures between 1200 and 1250 °C using a fast-firing cycle. The specimens were characterized before and after firing. XRD was used to identify the crystalline phases present during sintering and SEM was used to show how the structure changes during densification. Three parameters were used to describe densification: linear shrinkage, water absorption, and flexural strength. The results showed that the petroleum oily sludge could be used as an alternative raw material in the floor tile formulations. The densification behavior of the floor tile pieces is influenced by the petroleum oily sludge addition and firing temperature. The vitrified floor tiles produced reached the technical characteristics of porcelain floor tiles, depending on petroleum oily sludge content and firing temperature.     

陶瓷废料的组成与火山灰活性研究

摘要：通过X射线衍射分析、玻璃相含量测定、28d抗压强度比及火山灰活性等试验,研究了陶瓷玻化砖废料、瓷质废料、炻质废料和陶质花盆四种类型陶瓷废料的组成与火山灰活性,为开拓陶瓷废料的应用提供依据。研究结果表明：陶瓷抛光砖粉与废陶瓷玻化砖尽管主要成分相近,但前者氯含量较高,用于水泥混合材受到限制;几种类型的陶瓷废料均具有火山灰活性,其水泥胶砂28d抗压强度比均高于62％,废陶瓷玻化砖为82．1％,瓷质废料为80．8％,炻质废料为78．3％,陶质废料为77．3％。陶瓷玻化砖废料的玻璃相含量较高,瓷质废料其次,炻质和陶质废料的玻璃相含量较低。玻璃相含量较高的陶瓷废料其水泥胶砂28d抗压强度比．较高。     

Process of pyroplastic shaping for special-purpose porcelain stoneware tiles

A novel technique to manufacture special-purpose tiles (i.e. trim pieces, steps, skirting boards, etc.) has been recently developed on the basis of a pyroplastic shaping of porcelain stoneware tiles. This innovative process involves a second firing, peaking at temperatures close to those of sintering, whose effect was investigated by comparing industrially manufactured tiles before and after pyroplastic shaping. Characterization by XRF, XRPD, SEM and standard testing (ISO 10545) put in evidence that pyroplastic bending induced little changes in the water absorption and bulk density values, as in phase composition. Limited variations occurring to closed porosity, mechanical strength and microstructure do not significantly affect the overall technological performance of the special-purpose tiles, which is substantially the same of the original porcelain stoneware tiles. A detailed microstructural characterization was performed for the first time on porcelain stoneware tiles: coarse grains (>10 μm) represent 10–15% of total volume, while fine-grained crystals, dispersed in the glassy phase, amount from 30% to 65% of the viscous matrix. The pyroplastic behaviour was found to depend in a complex way on such microstructural and compositional features, which deeply affect the effective viscosity of the matrix.     

Steel particles–porcelain stoneware composite tiles: An advanced experimental–computational approach

Innovative porcelain stoneware tiles with a surface layer containing 2.4 wt% of stainless-steel particles were produced by the Double Charge Technology. Considering this layer as a composite material, the effects of the metal particles on the mechanical behaviour of the ceramic matrix were extensively investigated in terms of Young's modulus, fracture toughness and flexural strength. With this aim, composite materials were prepared by using the same silicate-based ceramic matrix with increasing weight percentages of the same stainless-steel powder. The composites were accurately characterised. In particular, due to the high sintering temperature, possible changes at the interface between metal particles and ceramic matrix were thoroughly analysed by means of SEM and EDS microanalysis. To clarify the role of the observed chromium-rich interphase on the mechanical behaviour of the steel particles–stoneware composites, analytical equations were used and simulations were performed by using the Object Oriented Finite (OOF) element method.     

Boron mining and enrichment waste: A promising raw material for porcelain tile production

Boron mining and enrichment waste (BW) from boric acid (H₃BO₃) production is a by-product of the boron industry. BW exhibits B₂O₃ contents of 16-31 wt%, and therefore, could be used to effectively lower the sintering temperature of ceramics without increasing their thermal expansion coefficient. Herein, we introduced 3-10 wt% of BW to a formulation used for commercial porcelain tile production, and achieved a sintering temperature decrease of 38°C (to 1195°C). The resulting porcelain tiles exhibited a strength of 44.80 MPa and water absorption percentage of 0.01%, and therefore, met TS ISO EN 10545 requirements. Thus, this study paves the way for the use and valorization of BW in the production of porcelain tiles and could inspire the search for other opportunities to utilize BW in ceramic production.     

Development of ceramic floor tile compositions based on quartzite and granite sludges

In the present work, industrial sludges derived from cutting and polishing natural stones (granite and quartzite) were characterised in terms of particles size distribution, chemical and mineralogical composition, and thermal behaviour and their potential to be incorporated as main components in red-clay-based stoneware tiles was evaluated. High levels (60–70 wt.%) of incorporation were attempted aiming at designing new formulations intended to be less expensive and possess better final properties (lower water absorption and higher flexural strength) in comparison to an industrial reference body used in the production of rustic tiles by extrusion, characterised 8–9% water absorption and a flexural strength of 17–18 MPa. Extruded rods of different formulations were produced and fired at 1100 °C, 1125 °C, 1150 °C and 1200 °C. The experimental results showed that all the new formulations performed better with the most significant improvements being obtained with incorporation of granite sludge. Flexural strength values more than triplicate and water absorption decreased by more than one order of magnitude in comparison to the reference paste. The new products fulfil the requirements of the ISO 13006 standard, group BIa (porcelain tiles).     

Recycling of polishing porcelain stoneware residues in ceramic tiles

The possibility of recycling residues, coming from the industrial polishing process of porcelain stoneware tiles, by their incorporation in a porcelain stoneware body mix, was studied. Starting from a standard body mix, several modified body mixes were prepared by replacing different amounts of the fluxing component, a sodium feldspar sand, with these wastes. The densification behaviour of the different body mixes was investigated by determining water absorption, linear shrinkage and bulk density of the as fired specimens. Phase and microstructural examination, by quantitative X-ray diffractometry and scanning electron microscopy-energy dispersive spectroscopy, made it possible to explain the mechanical behaviour, i.e. flexural strength, Young's modulus and Weibull's modulus. The presence of polishing porcelain stoneware residues, PPR, in particular in a 10 wt% of replacement, made possible a consistent decrease in the maximum temperature of the thermal cycle. That did not cause significant variations in the mechanical strength of the materials, while a slight decrease of the elastic modulus and a remarkable increase of the reliability were registered.     

Reusing sanitaryware waste products in glazed porcelain tile production

Reusing the waste products generated in ceramic manufacturing is an environmentally responsible and sustainable approach. This study aims to protect natural resources, minimise raw material costs and manage waste-generated pollution by reusing the vitrified sanitaryware waste (VSW) products from Canakkale Kalebodur Seramik San. A. S. Six sample formulations were prepared under industrial conditions and compared with a standard tile body. The results indicated that using VSW in place of feldspar results in an increased firing shrinkage and decreased bending strength, whereas using VSW in place of pegmatite results in an increased bending strength and reduced thermal expansion coefficients. The reduction in the thermal expansion coefficients is an important finding that aids in meeting the dimensional and deformation requirements of porcelain tiles and also results in a slight lightening of the tile colour. This study shows that the fired VSW products can be used in glazed porcelain tile production as a sustainable and technologically, economically and environmentally suitable approach.     

高强度镁质日用瓷的性能研究

以MgO-A12O3-SiO2三元系统相图为理论依据确定镁质瓷配方范围。通过考察滑石用量、长石用量、高岭土用量、烧成温度对镁质瓷抗折强度的影响,对镁质瓷配方进行优化,得到抗折强度较高(160.5MPa)、白度高的镁质日用瓷配方。     

排蜡制度对热压铸滑石瓷性能的影响

通过改变热压铸滑石瓷的排蜡制度．对同一配方的滑石瓷进行了吸水率、抗弯强度、抗拉强度和断面扫描等试验．探讨了排蜡制度对热压铸滑石瓷相关性能的影响．确定了一种通用于热压铸滑石瓷的排蜡烧成制度。     

Influence of mineralogical composition of applied ball clays on properties of porcelain tiles

Relations between quality of ball clays applied in raw materials batches for manufacture of porcelain tiles, and physical properties and microstructure of obtained tiles, were investigated. Studied clays constituted 35% of the batch, while the other components were unchangeable. Stoch index, new IR 3620/3700 index and XRIR index (Stoch index multiplied by IR 3620/3700 index), were proposed to take into account crystallinity of kaolinite and contents of illite and smectites in studied clays. Relationship between XRIR index value of clay, and water absorption and abrasion resistance of the obtained ceramic material, was found. Water absorption of the tile is also correlated with grain size distribution and bending strength of used clay. Optimal ball clay for porcelain tile production should exhibit: Stoch index - min. 4.3; IR 3620/3700 index - min. 1.2; XRIR index - min. 4.8; grain size median - max. 0.27 μm; bending strength after drying - min. 8.0 MPa.     

Blue cobalt doped-hibonite pigments prepared from industrial sludges: Formulation and characterization

The structural stability of the pigment was investigated using X-ray diffraction coupled with SEM and UV–vis–IR analysis, as a function of the relative Co content and calcination temperature. A standard formulation prepared from commercial reagents was also prepared and characterized for the sake of comparison. The pigment was added to a transparent glaze and to a porcelain stoneware body. Since the relative amount of cobalt was low and the sintering temperature of the pigment was not too high (1350–1400 °C), the new pigment system offers an interesting alternative to spinel, olivine and willemite commercial blue pigments. Moreover, the use of several wastes in the pigment formulation does not diminish its colouring performance.     

Optimization of wastes content in ceramic tiles using statistical design of mixture experiments

Mineral extraction and processing industries have been cited as sources of environmental contamination and pollution. The inclusion of wastes into productive cycles represents an alternative form of restoration, which is interesting from both environmental and economic standpoints. In this work, the development of ceramic tile formulations containing kaolin processing and granite sawing wastes was investigated using the statistical design of mixture experiments methodology. Ten formulations using the raw materials, red clay, kaolin processing and granite sawing wastes, were selected and used in the mixture design. Test specimens were fired and characterized to determine their water absorption, linear firing shrinkage and modulus of rupture. Regression models were calculated, correlating the properties with the composition. The significance and validity of the models were confirmed by statistical analysis and verification experiments. The regression models were used to optimize the waste content in ceramic compositions. The results showed that formulations containing up to 62% of waste could be used in the production of ceramic tiles.     

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.     

Effect of moulding pressure on microstructure and technological properties of porcelain stoneware

The properties of green and fired porcelain stoneware bodies have been studied in samples moulded at different pressures (10, 20, 30 and 40 MPa). In green tiles, higher differences in properties have been found at lower moulding pressure. After the fast-firing process, the tiles have been tested to obtain the technological properties such us lineal shrinkage, water absorption, porosity and bending strength. Results show that higher moulding pressures (30 and 40 MPa) give rise to tiles with similar technological properties. The amount of mullite and quartz remains constant in all pieces after firing process. SEM observations show that mullite crystals are longer as moulding pressure increases, that means that initial moulding pressure has a marked effect on mullite development, which is the main responsible of final properties.     

An eco-friendly permeable brick with excellent permeability and high strength derived from steel slag wastes

Utilisation of industrial solid wastes to prepare products with high added value is an effective way that could relieve environmental pollution and create huge economic benefits. In this work, steel slag based permeable brick (SSPB) was successfully prepared by liquid phase sintering. The BSE-EDS results indicate that the microstructure of the SSPB becomes dense because of the formation of a small amount of glass-liquid phase (Na-K-Ca-Fe-Si-O glass system). The effect of sintering temperature on various properties of the SSPB was systematically studied. It is found that as the sintering temperature increases from 1210 to 1300°C, the permeability deceases gradually, as well as the apparent porosity, water retention and water absorption. In contrast, the bulk density and mechanical strengths show gradually increasing trends. Most important of all, the SSPB sintered at 1270°C for 1 hour shows an excellent permeability (5.70 × 10⁻² cm/s) and high mechanical strengths (compressive strength, 36.6 MPa; bending strength, 6.8 MPa). The prepared SSPB is not only likely to be a new type of permeable brick for sidewalk construction, but also relieve greatly environmental pollution from steel slag because of the high utilisation rate of steel slag (as high as 90%).     

Evolution with Temperature of Crystalline and Amorphous Phases in Porcelain Stoneware

Porcelain stoneware tile is a ceramic building material characterized by high technological properties, especially regarding water absorption, chemical and frost resistance, bending strength and abrasion resistance. Because mineralogy is one of the main factors affecting the mechanical properties of porcelain stoneware, a complete determination and quantification of the mineral and amorphous phases is of special importance in the study of porcelain stoneware tiles. In the present work, a reference industrial composition (50% kaolinitic clay, 40% feldspar, and 10% quartz) of porcelain stoneware tiles fired at different temperatures (400°–1400°C) was characterized by X-ray powder diffraction combined with quantitative full-phase analysis using the Rietveld method, including amorphous content. The green composition contained albite, microcline, and muscovite as fluxing agents, which start to decompose at low temperatures (400°–800°C range) and are completely dissolved above 1200°C. The mullite phase is formed from 1100° to 1230°C and at the latter temperature, quartz particles start to dissolve. Studies of mineralogical evolution have revealed that the high heating rate (45°–50°C/min) required in ceramic tile manufacture leads to significant differences in comparisons with whiteware ceramics fired at a lower heating rate (10°C/min). Thus, the formation of mullite in porcelain stoneware occurs at higher temperatures (1100°C) whereas the transformation of β-quartz to β-cristobalite does not take place. The experimental results of this study show that qualitative mineralogical analysis, based on the intensity of a particular diffraction peak for each crystalline phase, is a suitable methodology to obtain preliminary knowledge of mineralogical changes with temperature.