Tailored waste based glasses as secondary raw materials for porcelain stoneware

Abstract

The high temperature processing of porcelain stoneware products is attractive for the possibility to incorporate several inorganic wastes. However, even if recycling is an environmental benefit, it can be disadvantageous for the overall properties of the ceramic product, if wastes are not selected in terms of their chemical and physical characteristics. In the present work several kind of industrial and urban wastes, such as mining residues, lime, glass from dismantled cathode ray tubes and soda lime glass were used, after their vitrification. These newly formed glasses were used as partial substitution for natural feldspar sands (the glass content being from 5 to 7 wt-% of the total mix). Owing to the specific ('tailored') chemical formulation of the newly formed glasses, the modified products exhibited higher crystallisation, with a more homogeneous microstructure, leading to significant improvements in reliability and indentation fracture toughness.     

Effect of soda-lime glass on sintering and technological properties of porcelain stoneware tiles

The feasibility of waste glass recycling in ceramic tile production was assessed with special reference to fully vitrified products (porcelain stoneware). Soda-lime float or container glass was introduced, in replacement of sodic feldspar, in typical porcelain stoneware bodies (up to 10 wt.%) that underwent a laboratory simulation of tilemaking process, with a technological and compositional characterization of both fired and unfired tiles. Soda-lime glass had no significant effect on semi-finished products, but it influenced remarkably the firing behaviour, increasing shrinkage and closed porosity, decreasing open porosity and bulk density, and lowering mechanical and tribological performances. Waste glass promotes a more effective melting of quartz and a partial dissolution of mullite, leading to a more abundant and less viscous liquid phase, which accelerates the sintering kinetics. In conclusion, soda-lime glass can be used in small amounts (5% or less) with tolerable modifications of technological behaviour and performances of porcelain stoneware tiles.     

Influence of Test Methods on Fracture Toughness of a Dental Porcelain and a Soda Lime Glass

The aim of this study was to investigate the influence of the test method on fracture toughness of a dental porcelain and a soda lime glass. Three methods were used to determine fracture toughness: the indentation strength (IS) by bending, chevron-notched beam (CNB), and the single-edge-notched beam (SENB). In the IS method, the ratio of elastic modulus to hardness ( E / H ) in the formula was determined by two methods: individual measurement for E and H (IS_M) as well as direct estimation from Knoop's indentation method (IS_K). The tested materials were a dentin porcelain, a traditional feldspar-based leucite-reinforced glass ceramic (Carrara Vincent), and a soda lime glass. Carrara Vincent showed a higher toughness ( P <0.01) than glass with all three test methods. The toughness values manifested significant differences between the methods used ( P <0.01). The two-way analysis of variance suggested that the materials tested and the test methods used had interaction effects, which statistically means that differences in materials and methods influenced the comparability of the toughness result. In this study, a first step was made to compare different toughness test methods by testing the toughness of a traditional feldspar-based leucite-reinforced glass ceramic and a soda lime glass that has a homogeneous microstructure. An interaction effect of the method and the material used was shown. As a consequence, none of the methods tested is suitable as a universal fracture toughness test method. Further research is needed to investigate more extensively the influence of material composition on the fracture toughness test methods' comparability.     

Sintered Glass–Ceramics and Glass–Ceramic Matrix Composites from CRT Panel Glass

Sintering with simultaneous crystallization of powdered glass represents an interesting processing route for glass–ceramics, especially originating from wastes. Highly dense glass–ceramic samples may be obtained from a simple and short treatment at a relatively low temperature. In addition, glass–ceramic matrix composites may be obtained by mixing glass with suitable reinforcements. In this work sintered nepheline glass–ceramics, based on panel glass from cathode ray tubes, are illustrated. A limited addition of Al₂O₃ platelets caused a significant improvement in the mechanical properties (elastic modulus, bending strength, microhardness, fracture toughness), already remarkable for the un-reinforced glass–ceramic, compared with traditional nepheline glass–ceramics.     

A Glass–Ceramic Derived from High TiO2-Containing Slag: Microstructural Development and Mechanical Behavior

A novel glass–ceramic material was developed from the melt of a TiO₂-containing iron-making slag with additional waste glass. The high percentage (∼20 wt% TiO₂) of this network-modifying oxide has promoted a crystallization of the parent glass, resulting in a fine-grained, homogeneous polycrystalline material with high mechanical properties ( E =120 GPa, flexural strength=∼180 MPa, and Vickers hardness=7 GPa) after a heat treatment at 1100°C for 2 h. The room temperature and elevated temperature fracture toughness were also studied. The main crystalline phases of the glass–ceramic material were of the pyroxene series until heat-treatment temperature reached 1000°C, at which titanium-rich perovskite and armalcolite crystals became the dominant phases. The end material is high-strength, aesthetically acceptable (metallic gray or opaque brown colored), and suitable for structural and architectural applications.     

Ferrimagnetic wollastonite ceramics based on waste valorization

Industrial residues may be considered as an economic and environmentally friendly option for the manufacture of ceramic materials for civil and energy engineering. In this work, granite sludge, mussel shells and glass cullet were used to produce a ceramic material that presents high hardness (H_V = 5.57 GPa) and fracture toughness values (K_IC = 1.78 MPa·m^1/2) as well as soft ferrimagnetic behavior. The presence of wollastonite confers characteristics typical of porcelain stoneware (σ = 64 N/mm², WA = 0.361%) to the final products.     

FLASH sintering of porcelain stoneware: Effect of composition modifications

In this work, we have exploited FLASH sintering as an alternative sintering process in the production of porcelain stoneware. FLASH sintering of porcelain stoneware occurred at temperatures ∼ 1020 °C, for 500 V cm^-1, 2 mA mm^-2 in 30 s. These conditions are significantly less severe than those typically applied in its conventional sintering, 1150–1250 °C for 1 h. Despite the reduction of time and sintering temperature, FLASH sintered samples exhibit heterogeneous microstructure and elemental distribution, with localized glassy phase formed on the positive pole. By decreasing the feldspar content, less localized glassy phase and more uniform microstructures were obtained, being of relevance the highest density and microstructure uniformity attained in the composition without feldspar. These results extend the FLASH sintering applicability and illustrate its importance for the development of alternative sintering technologies in traditional ceramic industry, that in addition may benefit from the reduction of feldspar in the porcelain stoneware production.     

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.     

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.     

Microstructural Variation in Porcelain Stoneware as a Function of Flux System

Fired microstructures of standard porcelain stoneware tile and tile made from mixes containing waste glass as part of the flux system were studied by XRD, SEM, and TEM. The standard porcelain stoneware microstructure consists of 100–1000 μm long mullite needles, feldspar relics, and partially dissolved α-quartz embedded in a glassy matrix. The use of soda–lime–silica (SLS) glass in the flux system led to crystallization of plagioclase, wollastonite, and sodium silicates. CaO-rich areas adjacent to quartz particles, as a result of interactions between SLS glass and silica from the quartz, and eutectic morphologies, revealed that SLS glass accelerated liquid formation and thus sintering and densification. Formation of these additional phases led to lower levels of quartz, mullite, and Na-feldspar in the microstructure although lower firing temperatures could be used to achieve full density due to generation of more fluid liquid. Use of PbO-containing waste glasses had little effect on the microstructure compared with standard composition while use of mixed PbO-containing and SLS glasses led to microstructures containing plagioclase but to lower extent than in tile with higher levels of SLS.     

Recycling of CRT panel glass as fluxing agent in the porcelain stoneware tile production

In the present work, the feasibility to substitute feldspar raw material in a porcelain stoneware body with Panel Cathode Ray Tube (CRT) glass was investigated. A standard batch and a composition, where 35 wt.% Na-feldspar was substituted by CRT glass, were sintered at different temperatures in the range of 1000–1250 °C. The degree of the densification was studied by evaluation of the closed and total porosity, while the sintering rate was estimated by non-isothermal dilatometric measures. The variation of the crystalline phase composition was evaluated by XRD analysis. From the preliminary study other ceramic samples with different percentages of CRT glass (i.e. 2.5, 5 and 10 wt.%) were prepared and fired in industrial kiln. The sintering parameters, the microstructure and the mechanical properties were measured and compared with the standard composition.     

Bone china formulated with waste glass

Abstract

Abstract

Bone china is known for its technical and aesthetical quality with distinguishable whiteness, brightness and high mechanical strength. In this work, the use of waste glass was investigated in a bone china composition. This makes the production of this porcelain even more interesting from the environmental point of view, since most of its raw materials are from recyclable sources. Potash feldspar was partially replaced by waste glass, and the technical and slip rheological properties, phase development and microstructure after firing of the ceramic bodies were evaluated. The results revealed that waste glass provides a reduction in firing temperature and large plateau for firing while maintaining the quality of the final porcelain, including thermal expansion and mechanical strength.     

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.     

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。     

Temperature–Time–Mechanical Properties of Glass–Ceramics Produced from Coal Fly Ash

Physical and mechanical properties of glass–ceramics fabricated from thermal power plant fly ash were analyzed and compared with suggest a temperature–time–mechanical (T–T–M) diagram. Coal fly ash with SiO₂–Al₂O₃–MgO–CaO as major components and TiO₂ as a nuclear agent were used to develop glass–ceramic materials which were heat treated at 900°–1050°C for 0.5–4 h for crystallization. It was verified that the high aspect ratio of unknown crystallines in the microstructure contributed high hardness, strength, fracture toughness, and wear resistance. These results are correlated with heat treatment conditions and microstructure and a T–T–M properties (hardness, strength, elastic constant, toughness, and wear rate) diagram on glass–ceramics produced from coal fly ash is proposed.     

High chemical stability of stoneware tiles containing waste metals

Stoneware tiles were produced by the incorporation of galvanic waste to industrial compositions that were processed from kaolinitic clay, feldspar, quartz and recycled domestic glass. The galvanic waste required a calcination step to eliminate the gas forming species prior to its incorporation into industrial processes and crystalline phases were formed. After that, the effective incorporation of metals from the galvanic waste was attained through the formation and the refinement of crystalline phases that acted as pigments. During the fast firing the calcined galvanic waste only got partially dissolved in the liquid phase that developed in spinel phase nanocrystals. The followed procedure allowed to effective immobilization of up to 10 wt% of waste with heavy metals in a porcelain stoneware that satisfy both the mechanical and the chemical standards required to massively commercialize such a product.     

Composition and ceramic properties of ball clays for porcelain stoneware tiles manufacture in Poland

The paper presents the results of investigations of mineralogical, grain and chemical composition, and ceramic properties of 18 white-firing ball clays from five producing regions in eastern and central Europe. Relationships between the bending strength of the clay after drying and its grain size and mineralogical composition were studied. High contents of illite and illite/smectite minerals in the clay, and low crystallinity of kaolinite and illite, strongly influenced plasticity but also improved sinterability, as appropriate phase transitions of clay minerals began at lower temperatures. The clays were also highly reactive towards other components of the ceramic batches for porcelain stoneware tile production. The ball clays from the Donetsk region in Eastern Ukraine are recommended for the porcelain stoneware tile production in Poland, while the Polish, German and Czech clays may be used only as supplementary components.     

Fast-Sintered Gehlenite Glass–Ceramics from Plasma-Vitrified Municipal Solid Waste Incinerator Fly Ashes

Plasma heating is a highly efficient industrial treatment for municipal solid waste incinerator fly ashes, converted into leach-resistant glass. The viscous flow sintering of glass powders appears a very promising way for the subsequent conversion of the vitrified waste, not refined and available as glass flakes, into valuable glass–ceramics. Because of the particular glass composition, the densification of glass–ceramics was much hindered by the strong tendency of glass toward surface crystallization. The crystallization of glass was successfully coupled to a low porosity, thus yielding strong gehlenite-based glass–ceramics (with a bending strength exceeding 100 MPa), by adopting a fast sintering treatment (direct insertion of glass compacts at 1050°C, with an holding time of 1 h).     

硅灰石在日用陶瓷坯体中的应用研究

为了研制出在1100℃~1150℃烧成的致密日用陶瓷,在坯料配方中加入较多的硅灰石,利用硅灰石本身的针状形貌以及与粘土生成的钙长石可提高坯体的烧结强度;同时加入钾长石、锂瓷石、黑滑石、玻璃粉、硼钙石作为坯料中的助熔剂,通过多种成分的低共熔作用,大幅度降低了坯体的烧成温度,缩短了烧成时间,实现了低温快速一次烧成。通过采用正交试验法多批次试验,优选出了较好的坯料配方,其中硅灰石的含量达到13%左右;烧成时从室温升温至1120℃为150m in,保温40m in,得到的坯体平整、致密,白度达到64,抗折强度达到160M Pa。     

Technological behavior of porcelain stoneware bodies with Egyptian syenites

The progressive depletion of the main feldspathic flux deposits in the World is forcing the ceramic industry to search for suitable substitutes. The aim of this study is to assess the potential of some feldspar sources in the Egyptian Eastern Desert, particularly syenites from Abu Khruq, in the manufacture of ceramic tiles. Beneficiated samples obtained by laboratory-scale mineral processing were tested into porcelain stoneware batches (from 10% to 30% wt in replacement of feldspars) and compared with a reference body through a laboratory reproduction of the industrial processing. The technological behavior of unfired tiles does not suffer any significant alteration due to the use of syenites. On the other hand, syenite-bearing bodies exhibit some changes in the phase composition and the chemistry of the melt, that turns richer in alkali, especially K₂O. The consequently increased sintering rate depends mainly on the viscosity of the liquid phase formed during firing. In conclusion, syenites can be used without technological hindrances to manufacture porcelain stoneware tiles. The firing behavior of syenite-bearing batches can be reasonably adjusted by setting key parameters (eg, the feldspar amount and the Na/K ratio), but the darker color of fired bodies requires to further lower the iron oxide.