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The growing demand for fluxes, dictated by the shift toward porcelain stoneware, is urging the ceramic tile industry to find a viable alternative to feldspathic materials. Sericite, a microcrystalline form of muscovite, is present in many ceramic raw materials. It melts during firing and can be a suitable substitute for potassic feldspar. The aim of this study is to understand in depth the effects of replacing feldspar with sericite in porcelain stoneware batches with nearly the same chemical composition. Characterization includes phase composition (X-ray powder diffraction, XRPD Rietveld), melt chemical composition (calculated), sintering behavior (optical thermo-dilatometry), and microstructure (scanning electron microscope (SEM). The results indicate a different vitrification path, mostly in the early stage of sintering, related to the different mineralogical composition and particle size distribution of sericite for K-feldspar. Nevertheless, at temperatures higher than 1150°C, the bodies have similar phase composition, microstructure, melt chemical composition, and physical properties. Densification kinetics is faster in the batch with sericite, while the body with feldspar is able to reach a higher bulk density. [ABSTRACT FROM AUTHOR]

Abstract: A reappraisal of crystal structure, optical properties and technological behaviour of black spinels in the Co—Cr—Fe—Mn system was carried out to define the best compositions and disclose the role of crystal chemistry in colouring performance and pigment-glaze interactions. Twenty ternary and quaternary spinel formulations were designed using crystallochemical criteria and prepared by simulating the industrial synthesis. Powder samples were characterized through X-ray diffraction (Rietveld), optical, Raman and Mössbauer spectroscopies, and technological testing in several glazes and glassy coatings. Black spinels fall in a relatively narrow field of unit cell and inversion parameters in between “chromites” and “magnetites”. Their cation distribution is governed by Co2+ occupancy of tetrahedrally-coordinated site T and Cr3+ occupancy of octahedrally-coordinated site M, with Mn3+ hosted at M, while Mn2+ and Fe3+ are distributed over both sites. Nevertheless, Raman and Mössbauer spectra indicate a growing disorder in cation partitioning going towards the iron-rich terms. The pigment technological behaviour depends to a large extent on crystal chemistry of spinels, with no effect by grain or crystallite size. The best colouring performance corresponds to recommended compositions able to withstand corrosion and change in crystal chemistry in contact with melted glaze. Three different pathways can give rise to excellent black pigments: (a) strongly disordered spinels having an inversion parameter i∼0.2; (b) moderately disordered spinels, free of Mn3+, with i<0.1; (c) apparently ordered and normal spinels halfway from cobalt chromite and cobalt ferrite. Poor technological performances are due to different conditions leaving room to colour bleaching (low Cr amount), glaze bloating (excess of Mn3+) and limited resistance to corrosion (oversaturation of site M by Cr+Fe with formation of kenotetrahedral spinels or eskolaite—hematite solid solutions). [Copyright &y& Elsevier]

The advent of inkjet printing as digital decoration of ceramic materials has irreversibly modified the industrial decoration technology, imposing companies to change the colorant production process. The inkjet application requires micronized particles in the ultrafine particle size range (smaller than 1 μm). Particles size reduction of ceramic colorants is performed by a high-energy comminution process in wet-operated bead mills, affecting colorants properties. Since a deep knowledge of milling-induced microstructural changes is still lacking, the micronization effects on a set of five industrial ceramic colorants are thoughtfully investigated in this work by simulating the industrial process at a pilot plant. Particle size distribution and energy consumption are monitored during the comminution process. The compositional (including crystallite size and microstrain analysis of the main phases) and morphological variation of four ceramic pigments (yellow zircon, brown spinel, pink malayaite, and green eskolaite) and one dye (blue olivine) is investigated by XRPD (Rietveld method) and SEM analyses. The analytical approach combined with a physical/semiempirical modelling of the colorants elastic features versus the energy demand for particle reduction has yielded details on the nature of the micronization-induced microstructural changes in ceramic colorants. Specifically, the comminution efficiency as well as the crystalline phase stability are related to the intrinsic properties of each colorant. Brittle breakage rather than plastic deformation on comminution are also system dependent. When an euhedral to subhedral crystal habit is maintained a brittle fracture is preserved throughout the comminution progress, while the formation of flake-like particles and particle agglomeration are strong evidences of plastic deformation. The last evidence deals with the material elastic features. Materials with high bulk modulus convert the grinding energy to lattice defects that lead to particle breakage by brittle fractures, while materials with lower bulk modulus convert/dissipate part of the supplied energy in plastic deformations, drastically decreasing the comminution process efficiency. [ABSTRACT FROM AUTHOR]

Ce-doped garnets find their use as scintillators as well as phosphors. Among synthetic garnets, gallium gadolinium aluminium garnet (GGAG) is a relatively new and interesting material, a mixed garnet that has displayed very good scintillation and luminescence properties. In the presented work Ce-doped GGAG ceramic samples were produced by reaction sintering from commercial oxide powders. The mixed powders were pressed into pellets and sintered. In order to achieve transparency of a ceramic material, it is crucial to eliminate porosity. Therefore, a number of process parameters and their influence on the microstructure and optical quality of the ceramics were studied: starting powders, sintering additives and sintering conditions. The sintering process consisted of two steps, viz. pressureless sintering in air followed by hot isostatic pressing. Luminescence properties of the sintered ceramics were studied by means of photo-luminescence and correlated to the fabrication process parameters. [ABSTRACT FROM AUTHOR]

In recent times, there has been an increasing demand for white-firing clay materials in ceramic tile production, due to a progressive shift towards porcelain stoneware bodies. Furthermore, the recent geopolitics events have challenging the industries possibilities to satisfy their clay demand for porcelain stoneware production by well-established commercial channels. In this framework, there is a need to expand the reserves of ball clays, especially in Mediterranean countries, which have a low frequency of clay deposits suitable for the production of porcelain stoneware. For this purpose, the Tabarka clays in Northern-West of Tunisia have been studied. They have already been investigated in the literature for the production of various types of ceramic tiles (but not porcelain stoneware). The technological behaviour of bodies, containing 40% clay, was assessed by simulating the industrial tile manufacturing process on a laboratory scale. Tabarka clays (TC) were compared with high and low plasticity ball clays (which define a reference range for the raw materials currently used). TC exhibit a fine grain size distribution and plasticity approaching the most plastic ball clays currently used. The behaviour of the bodies containing TC during grinding, pressing, and drying is fully suitable, with values of the technological parameters that lie within the reference range. Using TC, a slightly higher temperature was necessary during firing to get the desired water absorption (<0.5%). This was due to the kaolinite-rich composition of TC that is more refractory than ball clays taken as reference, which contain illite and illite-smectite interstratified terms, along with kaolinite. The properties of fired bodies based on TC fulfil the technical requirements for porcelain stoneware tiles. • Two clays from the north of Tunisia were tested for porcelain stoneware tiles production. • The batches were designed and samples were prepared simulating the industrial process. • The properties of semi-finished products were comparable to the benchmark. • The higher amount of kaolinite led to limited refractoriness increase. • The new clays are suitable for porcelain stoneware tiles and slabs manufacturing. [ABSTRACT FROM AUTHOR]