Structure Evolution of Ge-Doped CaTiO3 (CTG) at High Pressure: Search for the First 2:4 Locked-Tilt Perovskite by Synchrotron X-ray Diffraction and DFT Calculations.

This research investigates the high-pressure behavior of the Ca(Ti0.95Ge0.05)O3 perovskite, a candidate of the locked-tilt perovskite family (orthorhombic compounds characterized by the absence of changes in the octahedral tilt and volume reduction under pressure controlled solely by isotropic compression). The study combines experimental high-pressure synchrotron diffraction data with density functional theory (DFT) calculations, complemented by the X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), to understand the structural evolution of the perovskite under pressure. The results show that CTG undergoes nearly isotropic compression with the same compressibility along all three unit-cell axes (i.e., Ka0 = Kb0 = Kc0, giving a normalized cell distortion factor with pressure dnorm(P) = 1). However, a modest increase in octahedral tilting with pressure is revealed by DFT calculations, qualifying CTG as a new type of GdFeO3-type perovskite that exhibits both isotropic compression and nonlocked tilting. This finding complements two existing types: perovskites with anisotropic compression and tilting changes and those with isotropic compression and locked tilting. The multimethod approach provides valuable insights into the structural evolution of locked-tilt perovskites under high pressure and establishes a protocol for the efficient study of complex high-pressure systems. The results have implications for the design of new functional materials with desirable properties.

Ceramisation of hazardous elements: Benefits and pitfalls of the inertisation through silicate ceramics.

The addition of wastes to silicate ceramics can considerably expand the compositional spectrum of raw materials with a possible inclusion of hazardous components. The present work quantitatively examines relevant literature to determine whether the benefits of incorporating hazardous elements (HEs) into silicate ceramics outweigh the pitfalls. The mobility of various HEs (Ba, Zn, Cu, Cr, Mo, As, Pb, Ni, and Cd) has been parameterised by three descriptors (immobilisation efficiency, mobilised fraction, and hazard quotient) using leaching data. HEs can be incorporated into both crystalline and glassy phases, depending on the ceramic body type. Moreover, silicate ceramics exhibit a remarkably high immobilisation efficiency (often exceeding 99.9%), as accomplished for Ba, Cd, Ni, and Zn elements. The pitfalls of the inertization process include an insufficient stabilisation of incorporated HEs, as indicated by the high hazard quotients (beyond the permissible limits established for inert materials) obtained in some cases for Mo, As, Cr, Pb, and Cu elements. Such behaviour is related to oxy-anionic complexes (Mo, As, Cr) that can form their own phases or are not linked to the tetrahedral framework of aluminosilicate glass. Pb and Cu elements are preferentially partitioned to glass with a low coordination number, while As and especially Mo are not always stabilised in silicate ceramics. These drawbacks necessitate conducting additional studies to develop appropriate inertisation strategies for these elements.

Porcelain versus Porcelain Stoneware: So Close, So Different. Sintering Kinetics, Phase Evolution, and Vitrification Paths.

Five porcelain and porcelain stoneware bodies were investigated to compare sintering mechanisms and kinetics, phase and microstructure evolution, and high temperature stability. All batches were designed with the same raw materials and processing conditions, and characterized by optical dilatometry, XRF, XRPD-Rietveld, FEG-SEM and technological properties. Porcelain and porcelain stoneware behave distinctly during sintering, with the convolution of completely different phase evolution and melt composition/structure. The firing behavior of porcelain is essentially controlled by microstructural features. Changes in mullitization create conditions for a relatively fast densification rate at lower temperature (depolymerized melt, lower solid load) then to contrast deformations at high temperature (enhanced effective viscosity by increasing solid load, mullite aspect ratio, and melt polymerization). In porcelain stoneware, the sintering behavior is basically governed by physical and chemical properties of the melt, which depend on the stability of quartz and mullite at high temperature. A buffering effect ensures adequate effective viscosity to counteract deformation, either by preserving a sufficient skeleton or by increasing melt viscosity if quartz is melted. When a large amount of soda-lime glass is used, no buffering effect occurs with melting of feldspars, as both solid load and melt viscosity decrease. In this batch, the persistence of a feldspathic skeleton plays a key role to control pyroplasticity.

Predicting Viscosity and Surface Tension at High Temperature of Porcelain Stoneware Bodies: A Methodological Approach.

The shear viscosity and the glass-vapor surface tension at high temperature are crucial to understand the viscous flow sintering kinetics of porcelain stoneware. Moreover, the pyroplastic deformation depends on the viscosity of the whole body, which is made up of a suspension of crystals dispersed in the melt. The existing fundamental theoretical background, along with semi-empirical constitutive laws for viscous flow sintering and glass densification, can be exploited through different approaches to estimate the physical properties at high temperatures starting from amount and chemical composition of the melt. In this work, a comprehensive attempt to predict the properties of the liquid phase is proposed by means of a detailed overview of existing models for viscosity and surface tension of glasses and melts at high temperature. The chemical composition of the vitreous phase and its physical properties at high temperature are estimated through an experimental approach based on the qualitative and quantitative chemical and phase analyses (by Rietveld refinement of X-ray powder diffraction patterns) of different porcelain-like materials. Repercussions on the firing behavior of ceramic bodies, are discussed. Comparative examples are provided for porcelain stoneware tiles, vitreous china and porcelain bodies, disclosing differences in composition and properties but a common sintering mechanism.

Bimetallic Nanoparticles as Efficient Catalysts: Facile and Green Microwave Synthesis.

This work deals with the development of a green and versatile synthesis of stable mono- and bi-metallic colloids by means of microwave heating and exploiting ecofriendly reagents: water as the solvent, glucose as a mild and non-toxic reducer and polyvinylpirrolidone (PVP) as the chelating agent. Particle size-control, total reaction yield and long-term stability of colloids were achieved with this method of preparation. All of the materials were tested as effective catalysts in the reduction of p-nitrophenol in the presence of NaBH4 as the probe reaction. A synergistic positive effect of the bimetallic phase was assessed for Au/Cu and Pd/Au alloy nanoparticles, the latter showing the highest catalytic performance. Moreover, monoand bi-metallic colloids were used to prepare TiO2- and CeO2-supported catalysts for the liquid phase oxidation of 5-hydroxymethylfufural (HMF) to 2,5-furandicarboxylic acid (FDCA). The use of Au/Cu and Au/Pd bimetallic catalysts led to an increase in FDCA selectivity. Finally, preformed Pd/Cu nanoparticles were incorporated into the structure of MCM-41-silica. The resulting Pd/Cu MCM-41 catalysts were tested in the hydrodechlorination of CF3OCFClCF2Cl to CF3OCF=CF2. The effect of Cu on the hydrogenating properties of Pd was demonstrated.

Ceramic Ink-Jet Printing for Digital Decoration: Physical Constraints for Ink Design.

In the last decade, the drop-on-demand (DOD) ink-jet printing has become the leading technology for the decoration of ceramic tiles. The inks employed for such application are colloidal suspensions of oxide particles (0.3 µm) whose stability (against agglomeration and over time) is fundamental to get successfully the tile decoration. Jettability from the DOD print heads is a key requirement along with proper colour after sintering. This means that a careful set up of inks properties (viscosity, density, surface tension) is required. The phenomena involved in the different stages of the ink-jet printing process (drop ejection from the nozzles, impact and spreading on the substrates) are described through dimensionless numbers as Reynolds, Weber, and Bond numbers, or their combinations. In literature physical constraints, obtained with a semi-theoretical approach on the basis of experimental evidences on other systems, allow to define a reference region in the space of the dimensionless numbers (here called "printable fluid region," PFR) where the inks should be suitable for the application. In this paper, 26 inks currently used for ceramic tile decoration were characterized and mapped in the space of dimensionless numbers for several printing conditions. For typical nozzle diameters (20-50 gm) and drop velocities (6-8 m/s), it has been found that they fall in the region identified by 3 < Re < 30, 27 < We < 160, and 0.6 < 1/Oh < 2.5, where Re, We, and Oh, are the Reynolds, Weber and Ohnesorge numbers, respectively. Such experimental region can be taken as reference to tune the colloidal interactions in proper way, though the thresholds delimiting the PFR should be better defined.

TiO2 Nanosols Applied Directly on Textiles Using Different Purification Treatments.

Self-cleaning applications using TiO2 coatings on various supporting media have been attracting increasing interest in recent years. This work discusses the issue of self-cleaning textile production on an industrial scale. A method for producing self-cleaning textiles starting from a commercial colloidal nanosuspension (nanosol) of TiO2 is described. Three different treatments were developed for purifying and neutralizing the commercial TiO2 nanosol: washing by ultrafiltration; purifying with an anion exchange resin; and neutralizing in an aqueous solution of ammonium bicarbonate. The different purified TiO2 nanosols were characterized in terms of particle size distribution (using dynamic light scattering), electrical conductivity, and ζ potential (using electrophoretic light scattering). The TiO2-coated textiles' functional properties were judged on their photodegradation of rhodamine B (RhB), used as a stain model. The photocatalytic performance of the differently treated TiO2-coated textiles was compared, revealing the advantages of purification with an anion exchange resin. The study demonstrated the feasibility of applying commercial TiO2 nanosol directly on textile surfaces, overcoming problems of existing methods that limit the industrial scalability of the process.

Structural relaxation around Cr3+ in YAlO3-YCrO3 perovskites from electron absorption spectra.

The structural relaxation around Cr(3+) in YAl(1-x)Cr(x)O(3) perovskites was investigated and compared with analogous Cr-Al joins (corundum, spinel, garnet). Eight compositions (x(Cr)((3+)) from 0 to 1) were prepared by sol-gel combustion and were analyzed by a combined X-ray diffraction (XRD) and electron absorption spectroscopy (EAS) approach. The unit cell parameters and the XRD averaged octahedral (Cr,Al)-O and ([VIII])Y-O bond distances scale linearly with the chromium fraction. The optical parameters show an expected decrease of crystal field strength (10Dq) and an increase of covalency (B(35)) and polarizability (B(55)) toward YCrO(3), but a nonlinear trend outlines some excess 10Dq below x(Cr)((3+)) approximately 0.4. The local Cr-O bond lengths, as calculated from EAS, indicate a compression from 1.98 A (x(Cr)((3+)) = 1.0) down to 1.95 A (x(Cr)((3+)) = 0.035) so that the relaxation coefficient of perovskite (epsilon = 0.54) is the lowest in comparison with garnet (epsilon = 0.74), spinel (epsilon = 0.68), and corundum (epsilon = 0.58) in contrast with its structural features. The enhanced covalent character of the Cr(3+)-O-Cr(3+) bond in the one-dimensional arrangement of corner-sharing octahedra can be invoked as a factor limiting the perovskite polyhedral network flexibility. The increased probability of Cr-O-Cr clusters for x(Cr)((3+)) greater than approximately 0.4 is associated to diverging trends of nonequivalent interoctahedral angles. The relatively low relaxation degree of Y(Al,Cr)O(3) can be also understood by considering an additional contribution to 10Dq because of the electrostatic potential of the rest of the lattice ions upon the localized electrons of the CrO(6) octahedron. Such an "excess" of 10Dq increases when the point symmetry of the Cr site is low, as in perovskite, and would be affected by the change of yttrium effective coordination number observed by XRD for x(Cr)((3+)) greater than approximately 0.4. This would justify the systematic underestimation of local Cr-O bond distances, as inferred from EAS, compared to what is derived from X-ray absorption (XAS) studies implying a stronger degree of relaxation around Cr(3+) of all the structures considered and supporting the hypothesis that 10Dq from EAS contains more information than previously retained particularly an additional contribution from the next nearest neighboring ions.

Structural concretes with waste-based lightweight aggregates: from landfill to engineered materials.

This research provides possible opportunities in the reuse of waste and particularly muds, coming from both ornamental stone (granite sludges from sawing and polishing operations) and ceramic production (porcelain stoneware tile polishing sludge), for the manufacture of lightweight aggregates. Lab simulation of the manufacturing cycle was performed by pelletizing and firing the waste mixes in a rotative furnace up to 1300 degrees C, and determining composition and physicomechanical properties of lightweight aggregates. The best formulation was used to produce and test lightweight structural concretes according to standard procedures. Both granite and porcelain stoneware polishing sludges exhibit a suitable firing behavior due to the occurrence of SiC (an abrasive component) which, by decomposing at high temperature with gas release, acts as a bloating promoter, resulting in aggregates with particle density < 1 Mg/m3. However, slight variations of mixture composition produce aggregates with rather different properties, going from values close to those of typical commercial expanded clays (particle density 0.68 Mg/m3; strength of particle 1.2 MPa) to products with high mechanical features (particle density 1.25 Mg/m3; strength of particle 6.9 MPa). The best formulation (50 wt.% porcelain stoneware polishing sludge +50 wt.% granite sawing sludge) was used to successfully manufacture lightweight structural concretes with suitable properties (compressive strength 28 days > 20 MPa, bulk density 1.4-2.0 Mg/m3).

Nano-sized ceramic inks for drop-on-demand ink-jet printing in quadrichromy.

Nano-sized ceramic inks suitable for ink-jet printing have been developed for the four-colours CMYK (cyan, magenta, yellow, black) process. Nano-inks of different pigment composition (Co(1-x)O, Au(0), Ti(1-x-y)Sb(x)Cr(y)O2, CoFe2O4) have been prepared with various solid loadings and their chemicophysical properties (particle size, viscosity, surface tension, zeta-potential) were tailored for the ink-jet application. The pigment particle size is in the 20-80 nm range. All these nano-suspensions are stable for long time (i.e., several months) due to either electrostatic (high zeta-potential values) or steric stabilization mechanisms. Both nanometric size and high stability avoid problems of nozzle clogging from particles agglomeration and settling. Nano-inks have a Newtonian behaviour with relatively low viscosities at room temperature. More concentrated inks fulfil the viscosity requirement of ink-jet applications (i.e., < 35 mPa x s) for printing temperatures in between 30 and 70 degrees C. Surface tension constraints for ink-jet printing are fulfilled by nano-inks, being in the 35-45 mN x m(-1) range. The nano-sized inks investigated behave satisfactorily in preliminary printing tests on several unfired industrial ceramic tiles, developing saturated colours in a wide range of firing temperatures (1000-1200 degrees C).