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.     

Use of industrial wastes in the formulation of olivine green pigments

This work describes the formulation and synthesis of Ni-olivine green pigments from industrial wastes, namely foundry sand and a sludge resulting from the wastewater treatment of the Ni/Cr galvanising process. This second one is considered as hazardous waste since the leached levels of nickel and chromium are above legal concentrations. Pigments were prepared by the solid state reaction method and Ni₂SiO₄ is formed at only 1050 °C. SiO₂ (in excess) and NiCr₂O₄ are present as secondary phases. By using pure reagents and following similar processing conditions, the Ni-olivine phase is only observed at 1200 °C. The green colour of the pigments is due to spin-allowed transitions of Ni²⁺ in octahedral M1 and M2 positions. The sample prepared from wastes shows a stronger and darker green hue. The colouring performance of ceramic glazes and bodies is also optimal, confirming the potential of the use of such wastes for ceramic pigments production.     

An overview of using solid wastes for pigment industry

This work reports the use of wastes (Al-rich anodizing sludge, Cr/Ni galvanizing sludge, foundry sand, tionite and marble sawing mud) to formulate distinct inorganic pigment structures that were synthesized by the solid state reaction method. One of the tested formulations is a novel pigment based on hibonite (CaO·6Al₂O₃), that was found a suitable hosting structure to accommodate cobalt or nickel chromophore ions in tetrahedral coordination, then giving strong blue or turquoise hues, respectively. The use of Cr as chromophore was tested in three distinct pigment structures: (i) red-wine Cr-CaSnSiO₅ and brown Cr-CaTiSiO₅; (ii) Cr-CaTiO₃; (iii) and Cr-TiO₂. Developed phases were determined, and the colouring mechanisms of the chromophore species were defined based on diffuse reflectance data. Then, the pigments were added to a standard transparent glaze, and the hues which developed were estimated from L*a*b* colorimetric measurements under the oxygen partial pressure in the atmosphere, to define stable workability window.     

Recycling of solid wastes in the synthesis of Co-bearing calcium hexaluminate pigment

Cobalt doped calcium hexaluminate was firstly synthesized using pure reagents; subsequently, the pure reagents were substituted with industrial wastes, the composition of which had been characterized using X-Ray diffraction and X-Ray fluorescence namely, Al-anodising sludge replaced pure aluminium whilst marble cutting rejects and foundry sand were employed as sources of calcite and silica, respectively. As expected, cobalt doped hibonite was the major phase present in calcined powders and displayed an intense blue coloration due to the incorporation of cobalt in tetrahedral positions, as confirmed by transitions from ⁴A₂(F) to the excited ⁴T₁(F) and ⁴T₁(P) states observed from UV–Vis–NIR absorption spectra. The novel waste-derived hibonite pigment showed strong and stable colouring potential when applied in different ceramic supports.     

Microhardness and wear resistance of Al2O3-TiB2-TiC ceramic coatings on carbon steel fabricated by laser cladding

Al₂O₃-TiB₂-TiC ceramic coatings with high microhardness and wear resistance were fabricated on the surfaces of carbon steel substrates by laser cladding using different coating formulations. The microstructures of these ceramic coatings with the different coating formulations were investigated using X-ray diffraction, scanning electron microscopy, and energy dispersive spectrometer. The wear resistance and wear mechanism were analyzed using Vickers microhardness and sliding wear tests. The results showed that when the amount of independent Al₂O₃ was increased to 30%, the ceramic coatings had a favorable surface formation quality and strong metallurgical bond with the steel matrix. The cladding layer was uniformly and densely organized. The black massive Al₂O₃, white granular TiB₂, and TiC distributed on the Fe substrate significantly increased the microhardness and wear resistance. The laser cladding ceramic coating had many hard strengthening phases, and thus resisted the extrusion of rigid particles in frictional contact parts. Therefore, the wear process ended with a “cutting-off” loss mechanism.     

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 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).     

Extrusion of alumina and cordierite-based tubes containing Al-rich anodising sludge

An Al-rich anodising sludge has been used as the feedstock to produce alumina and cordierite-based tubes produced by extrusion. The extrudability is strongly dependent on the materials composition and on the resultant plasticity of the pastes. For the process to be successful, the design and operating conditions need to be considered in detail.In this work, the effect of die design, ram speed and pressure was evaluated using the Benbow–Bridgwater model of paste extrusion. In general, predicted and measured values were in good agreement. This approach revealed differences in the flow between the two ceramic formulations and it was possible to relate the rheological observations during extrusion to the quality of the final product.     

Use of ceramic industry milling and glazing waste as an active addition in cement

The beneficial effects of pozzolans on cement manufacture have encouraged their use in that industry. Traditional natural pozzolan have become less available of late, however, due to a decline in quarrying intensity aimed at minimizing the impact on the landscape. At the same time, environmental policies pursue the reduction or elimination of spoil heaps by valorizing industrial waste and by‐products as raw materials, in keeping with the principles of the circular economy. The quest for new types of waste and by‐products with pozzolanic properties has consequently become a priority line of research. This study explored the valorization of one such by‐product, the ceramic sludge resulting from fired clay industry milling and glazing, as a component in new, more eco‐sustainable cements. The sludge was characterized physically, chemically, morphologically, and mineralogically to determine its suitability as a pozzolanic addition in cement. The findings showed that ceramic sludge consists in clustered particles ranging in size from 100 μm to 1 μm. SiO₂, Al₂O₃, and Fe₂O₃ together comprise over 70% of the total composition, while the reactive silica content is greater than the 25% required by the existing legislation. The predominant minerals are quartz, kaolinite, and muscovite, with some zircon. A study of pozzolanic reaction kinetics in the ceramic sludge/lime system revealed that over time this waste can fix lime, generating products such as calcium aluminate hydrates and C–S–H gels. The cements made with ceramic sludge proved to be standard‐compliant in terms of water demand, setting, drying shrinkage and mechanical strength.     

Effect of nano-TiO2 on properties of 3 mol% yttria-stabilized zirconia ceramic via layered extrusion forming

Layered extrusion forming (LEF), as an additive manufacturing technology, can freely form ceramic components. In this paper, 3 mol% yttria-stabilized zirconia (3YSZ) ceramic powder, nano-TiO₂ dispersion solution and methylcellulose were used as raw materials to prepare water-based ceramic slurry with 84 wt.% solid content. The ceramic green body was then prepared by the LEF technology, following by drying, degreasing and sintering to obtain ceramic components. The effects of addition amount of nano-TiO₂ dispersion solution and sintering temperature on properties of the 3YSZ ceramic were investigated. The optimal comprehensive performance of the 3YSZ ceramic was obtained when the content of nano-TiO₂ dispersion solution was 4.35 wt.% and sintering temperature was 1550 ℃, and the bending strength, linear shrinkage, apparent density were 328 ± 5 MPa, 18.31 %, 5.9 g/cm³, respectively. Moreover, the mechanisms of performance improvement were investigated. Finally, 3YSZ ceramic components with complex structure were fabricated by using the optimal process scheme.     

Synthesis of black pigments containing chromium from leather sludge

The black ceramic pigments with spinel structure have been prepared by using Cr-rich leather sludge in this paper. The washed Cr-rich leather sludge calcined at 1100 °C for 1 h as chromium oxide precursor (named as CA) was mixed with an appropriate proportion of other industrial metallic oxides, followed synthesizing black ceramic pigment by sintering. Both non-washed and washed sludge fired at 1100 °C were characterized by X-ray fluorescence (XRF) in order to determine their chemical compositions and X-ray diffraction (XRD) analysis to confirm that CA mainly contains Cr₂O₃ crystal phase. The results show that CA could be used as a source of chromium to prepare black pigment. The crystalline phases of obtained pigments were characterized by XRD. Furthermore, the morphology as well as the composition of pigments was investigated by scanning electron microscopy (SEM) and energy dispersion spectroscopy (EDS). The color coordinates of pigments were examined and compared with the commercial pigments based on CIE-L* a* b* values measured using UV–vis spectroscopy. The obtained pigments sintered at 1200 °C with 35–55 wt% content of CA possess the excellent black spinel structure and color effect. Under optimized conditions, the pigment has low average spectral reflectance (7%).     

Integrated utilization of high alumina fly ash for synthesis of foam glass ceramic

Due to the numerous increase of the building energy consumption and huge volume of industrial wastes produced in China, the development of thermal insulation materials is quite needed. Herein, foam glass ceramic, a kind of thermal insulation materials, was fabricated by using solid wastes high alumina fly ash and waste glass as the main raw materials. First, in this study the proportion scheme of this research was designed by using Factsage 7.1 and the foaming agent was CaSO₄. Secondly, the decomposition of calcium sulfate and the influence of process parameters, namely the sintering temperature and the foaming agent additive amount, on the microstructure and mechanical properties of foam glass ceramic were investigated. The experimental results showed that when the proposed foam glass ceramic was sintered at between 1180 and 1220?°C, it exerted excellent macro and micro properties. The optimum parameters were 2% CaSO₄ addition and sintering temperature of 1200?°C, and the corresponding bulk density and compress strength values were 0.98?g/cm³ and 9.84?MPa, respectively. Overall these results indicated that the preparation of foam glass ceramic made up a promising strategy for recycling industrial waste into new kind of building insulation materials.     

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.     

3D CaP porous scaffolds with grooved surface topography obtained by the sol-gel method

The influence of surface topography on cellular behaviour and its importance for the development of three-dimensional scaffolds for bone tissue engineering are a topic of growing interest. To date, the introduction of topographical patterns into the surface of 3D porous ceramic scaffolds has proven difficult, due partly to the brittle nature of ceramic materials as well as the currently available fabrication technologies. In this study, a grooved pattern was introduced into the surface of 3D multilayer porous ceramic scaffolds by the chemical etching technique. The patterned scaffolds were characterised by X-Ray Diffraction (XRD), Scanning Electron Microscopy with Energy Dispersive X-Ray Spectroscopy (SEM-EDX) and Digital Holographic Microscopy (DHM). Their bioactivity was also evaluated in vitro by immersion in simulated body fluid (SBF) for 12 h, 1, 7, 14 and 21 days. Scaffolds were constituted mainly with a mixture of the calcium pyrophosphate (Ca₂O₇P₂) and β-tricalcium phosphate (Ca?(PO?)?) phases. The pyrophosphate on the external layer was dissolved as a result of the etching process, leaving grooves on the surface. Ridges and grooves were nano-/micrometric, with dimensions of around 900 nm–1.5 μm in width and 200 nm–300 nm in depth. Moreover, the mechanical properties and bioactive capacity of the patterned scaffolds were not affected by chemical etching, making them suitable to be used in bone tissue engineering.     

Synthesis and characterization of calcium silicate insulating material using avian eggshell waste

This work focuses on the synthesis of calcium silicate insulating material via solid state reaction using avian eggshell waste as alternative calcium source. The calcium silicate formulations were mixed in a molar ratio SiO₂:CaO (1:1) and fired at 1100 °C for 24 h. The calcium silicate formulations were characterized by XRD, TG-DTA, dilatometry, SEM/EDS, and thermophysical properties (thermal diffusivity, heat capacity per unit volume, and thermal conductivity). The synthesized calcium silicate materials are composed mainly of wollastonite with minor amounts of larnite and rankinite. It was found that a processing of the avian eggshell waste (raw eggshell waste and calcined eggshell waste) had an influence on the thermophysical properties. Calcium silicate pieces were prepared by uniaxial pressing at 82 MPa, curing, and then testing to determine their use as thermal insulating material. The microstructure was evaluated by SEM. The results showed that both raw and calcined avian eggshell wastes could be used as an alternative calcium source in the calcium silicate formulation. It was found that the calcium silicate pieces reached low thermal conductivity values (0.252–0.293 W/mK). Thus, the developed calcium silicate materials using avian eggshell waste act as a good thermal insulation ceramic material.     

In situ synthesis of orange rutile ceramic pigments by non-conventional methods

Different precursor-mixtures of orange Cr,Sb-TiO₂ ceramic pigment have been obtained by non-conventional methods (heterogeneous ammonia coprecipitation, urea homogeneous coprecipitation, PECHINI polyester method and an original aqueous–organic coprecipitation method in water–diethylenglycol medium) in order to produce in situ the pigment through the ceramic body firing. The pigmenting performances of powders were appraised in two cases: (a) as ceramic pigment for glazed porcelain stoneware and (b) as ceramic inks for screen printing of porcelain stoneware. Samples were characterised by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), UV–vis-NIR spectroscopy by diffuse reflectance method, CIE-L*a*b* colour parameters, BET specific surface area and crystallite size measured by the Scherrer method. The colouring performance of raw powders obtained by non-conventional methods in glazed porcelain stoneware improves that of the ceramic samples fired at 1100 °C used as reference. TEM observations indicate nanostructured powders with pigmenting performance depending on factors such as their specific surface area (BET), the crystalline phases detected by XRD (e.g. anatase–rutile presence) and their crystallite size (Scherrer measurements). Ammonia coprecipitated samples, both in water and in water–diethylenglycol medium without surfactant addition, or modified by the addition of sodium dodecyl sulphate as surfactant, stand out by their colouring performance.     

Crystalline phases and physical properties of modified stoneware body with glaze sludge

Ceramic stoneware body has been modified with ceramic and glass industrial wastes by replacing 25–100% as flux in the formula. The effects of solid wastes added to the bodies were studied after firing in the temperature range 950–1280 °C. The physical properties of linear shrinkage, bulk density, apparent porosity, water absorption and 3-point bending strength were determined. A composition which related to the general stoneware properties was found when using soda-lime cullet and glaze sludge. It had a firing range lowered to 1050–1100 °C. SEM results demonstrated the sintered microstructure increased in density with increase in solid waste in the modified body. XRD results after firing showed the crystalline phases comprised of mullite, albite calcian and quartz. Thermal expansion was measured in the range 6.53–6.67 × 10^?6 K^?1 at 30–500 °C. The modified bodies were capable of forming prototype products by slip casting and jiggering.     

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.     

Adhesion of extrusion‐coated polymer sealing layers to a fiber‐based packaging material with an atomic layer deposited aluminum oxide surface coating

Adhesion of extrusion‐coated polymer sealing layers on an atomic layer deposited (ALD) aluminum oxide (Al₂O₃) surface coating was investigated with a view to gain information on the applicability of ALD deposited barrier layers in fiber‐based packaging materials. The polymers used for the sealing layer were low density polyethylene (LDPE), polyethylene terephthalate (PET), and polylactide (PLA). They were extrusion‐coated onto the ceramic side of paper/PET/Al₂O₃ substrates, where the Al₂O₃ layer was a few tens of nanometers thick. According to the results, good adhesion was obtained for LDPE coating, whereas the other coatings showed a considerable lack of adhesion. Presumably, the oxidation faced by LDPE in the air gap of the extrusion‐coating process was able to create an extensive number of reactive sites that strongly bonded with the hydroxyl groups on the oxide surface of the substrate. With the PET and PLA coatings, such oxidation did not occur and the adhesion obtained remained at a relatively poor level. With all of the coatings, the adhesion levels were improved using corona discharge equipment as a pretreatment prior to the extrusion‐coating process. POLYM. ENG. SCI., 52:1985–1990, 2012. © 2012 Society of Plastics Engineers     

Evaluation of solid wastes in the manufacture of ceramic tableware glazes

The recovery and reuse of industrial wastes are of great importance to the environment. Today, a large amount of waste is produced due to marble production, and it is extremely important to bring such wastes to the ceramic industry, to solve the pollution problem and to provide cost-efficient ceramic production. In this study, marble waste was used for ceramic earthenware glaze and body formulations. Marble waste was used in two different formulations as glaze and body. Chemical analysis, morphological features, crystallographic information of different formulations were made with XRF, SEM and XRD, respectively. When the hardness test results of the ceramic body and glazed samples were examined, the hardness values of the marble waste added samples increased by 1.9% compared to the standard samples. According to the results obtained, it has been seen that using marble waste in the ceramic industry is very important for both economic and environmental reasons.