Co- and Ni-exchanged ferrierite: The contribution of synchrotron X-ray diffraction data to siting of TMIs

High-silica zeolites exchanged with transition metal ions (TMIs) are the subject of great interest for their unusual catalytic activity and selectivity. Structural information like coordination and accessibility of TMIs in zeolites are important factors for understanding their catalytic activity. Siting of TMIs in zeolites is typically obtained by spectroscopic (EXAFS, EPR, UV-vis and IR) and computational methods, as in the case of Co-ferrierite. However, some controversy exists in the literature concerning the model for incorporation of bare Co ions in ferrierite. We show here that the results of our synchrotron X-ray powder diffraction studies on Co- and Ni-exchanged ferrierite (Si/Al = 8.5) are in a good agreement with the model of Co siting based on an indirect spectroscopic approach and help to validate this model. By direct structural evidences, a possible explanation for the larger catalytic activity of Co sites in the main channels of ferrierite can be inferred. A combination of data from in situ XRD continuous monitoring of the Co ion migration during calcination and crystal-chemical considerations allows to device a strategy for the design of optimised co-cations containing Co-ferrierite catalysts

Mineralogical study of historical bricks from the Great Palace of the Byzantine Emperors in Istanbul based on powder X-ray diffraction data

This study concerns the Quantitative Phase Analysis (QPA) of historical bricks coming from the complex of the Great Palace of the Byzantine Emperors in Istanbul. The studied samples are characterised by different chemical compositions (low and high calcium content), variable firing temperatures and different amounts of soluble salts as damage products. In the low-Ca samples, the decrease of the phyllosilicate content (from 23.4 to 6.9 wt%) is associated to the increase of the amorphous fraction (from 24 to 48%). This clear negative correlation between the phyllosilicate content and the amorphous fraction indicates that in low-Ca systems vitrification processes are overwhelming with respect to nucleation and recrystallisation processes. By contrast, high-Ca samples present newly formed Ca(Mg) silicates (diopside from 5.7 to 27.2%; anorthite from 1.4 to 8.7%) and aluminium silicates (gehlenite only in two samples, 6.2 and 7.7%) associated to the decrease of quartz (from 27.7 to 11.5%), phyllosilicate (from 6.5% until complete break down) and amorphous (from 30 to 14%) phase fractions. These findings support the role played by the CaO(MgO) content deriving from carbonates decomposition which reacts with Al2O3 and SiO2 oxides from dehydroxylated clay minerals and quartz grains. The above results have been obtained by X-ray powder diffraction data using the combined Rietveld refinement – internal standard method in order to estimate both the crystalline and the amorphous phase fractions. In addition, the coexistence of two distinct plagioclases in high-Ca samples was modelled as follows: a primary albite, which tends to incorporate Ca during the firing process as demonstrated by the increasing of gamma crystallographic angle, and a newly formed anorthite. Finally, by difference between the X-ray fluorescence data and the chemical compositions inferred by QPA, it proved possible to roughly estimate the residual chemical composition attributable to the amorphous fraction. On the basis of our data,we believe that Rietveld refinement combined with the internal standard method represent a powerful tool to better characterise complex polycrystalline and amorphous mixture as in the case of historical bricks

Dissolution-precipitation kinetics during C3S hydration: A holographic interferometry study

Tricalcium silicate C3S has been widely employed in model systems to interpret the complex mechanisms of cement hydration. The present study aims at providing an accurate description of the dissolution rate of C3S by implementing a new approach based on holographic interferometry. We propose a protocol that allows the measurement of the pure dissolution rate constant of the C3S phase by experiments performed in supersaturated conditions with respect to C-S-H. In these experiments, a flat polycrystalline surface of C3S was monitored in a quiescent solution. The amount of calcium released within the holographic cell was measured and the aqueous solution composition was constrained to the C-S-H stoichiometry at the interface. An equilibrium approach was applied to assess interfacial pH, saturation indexes, and C-S-H precipitation at the experimental conditions. The rate law of the pure dissolution of C3S was assessed in conditions ranging from far to close-to-equilibrium

Development of a sustainable binder made of recycled high-performance concrete (HPC)

The high consumption of ordinary Portland cement (OPC) in high-performance concrete (HPC), combined with the growing accumulation of construction and demolition wastes (CDW), raises severe environmental and economic concerns. This study addresses both issues by proposing a novel sustainable binder made of milled recycled HPC (mRHPC). A series of HPC mix designs (R-HPC) was developed replacing OPC by mRHPC (0-100%), and characterized in fresh and hard-ened states. The residual reactivity of mRHPC was detected using X-ray diffraction, calorimetry, and rheological oscillatory measurements (SAOS). Replacement up to 30% resulted in comparable 28-day compressive and flexural strengths to that of the OPC reference specimen while slightly improving fresh properties. Furthermore, the performance of steel fiber reinforced R-HPC over-lays was investigated in repair application, and 30% replacement ratio enhanced the tensile bond strength by a factor of 2.4. The measured improved flow properties and reduced drying shrinkage can explain this remarkable result

Magnesium K-edge EXAFS study of bond-length behavior in synthetic pyrope-grossular garnet solid solutions

Direct structural characterization of the changes in the local environment of Mg occurring in the garnet structure as a function of the Ca content are determined by Mg K-edge X-ray absorption fine structure on synthetic samples along the pyrope-grossular join. With increasing Ca content, the short Mg-O2 distance of the dodecahedron slightly decreases, while the long Mg-O4 distance tends to increase, so that the dodecahedron is more distorted in grossular-rich garnets than in end-member pyrope. This quantitative direct description of the changes in the local environment of Mg in the pyrope-grossular solid solution confirms and better defines previous experimental and recent computational results

XAS investigation of tantalum and niobium in nanostructured TiO2 anatase

Sol–gel routes were used to prepare Ta 10 at% and Nb 5 at% and 10 at% doped titania nanosized powders. When fired between 410°C and 850°C the doped titania powders are in the anatase phase; further heating up to 1050°C is required to obtain the rutile phase. The presence of dopant atoms delays the rate of transformation as compared with pure titania powders. Doping also affects the rate of grain growth and increases the conductance response to gas. To better understand the role played by dopant atoms in inhibiting both phase transformation to rutile and grain growth, X-ray Absorption Spectroscopy measurements were performed at the LIII–LI absorption edges of Ta and Nb K absorption edge. Analysis was restricted to the anatase phase because the transformation to rutile phase, obtained by firing at 1050°C, is accompanied by the formation of undesired Ta and Nb oxides (Ta2O5 and Nb2TiO7, respectively). Extended X-ray Absorption Fine Structure and X-ray Absorption Near-Edge Spectroscopy analysis results indicate that in nanostructured anatase both tantalum and niobium atoms substitute Ti cations with +5 valence state