Structure–function relationship during the early and long-term hydration of one-part alkali-activated slag

Understanding the mechanisms controlling the early (fresh) and long-term (hardened) hydration of one-part alkali-activated slags (AAS) is key to extend their use as low CO2 substitutes for ordinary Portland cement (OPC). Their “just add water” use makes them easier and less hazardous to manipulate than the more studied two-part ones. This is due to the absence of liquid alkaline activators, which are environmentally and energy demanding. In this work, numerous experimental techniques have been linked to obtain a comprehensive physico-chemical characterization of a one-part AAS activated with Na2CO3 and Ca(OH)2 powders at several water to solid ratios (w/s). Calorimetry and pH/conductivity measurements describe the functioning of the activators immediately after contact with water. Early reactivity is characterized through in situ X-ray powder diffraction (XRPD) and small amplitude oscillatory shear (SAOS) rheology, which reveal a rapid precipitation of nanometric hydration products (nano-C-A-S-H), which results in a continuous increase in the paste cohesivity until setting. Moreover, SAOS shows that rejuvenating the paste by means of shearing (performed externally to the rheometer in this study) is enough to restore the initial cohesion (i.e., workability) for long time spans until setting occurs. The long-term hydration is characterized by ex situ XRPD on aged AAS pastes, in parallel with mechanical testing on AAS mortar. A correlation can be observed between the amount of nano-C-A-S-H and the increase in compressive strength. Overall, this formulation shows satisfactory fresh and solid properties, demonstrating suitability for low- and normal-strength applications

Water Availability and Deformation Processes in Smectite-Rich Gouges During Seismic Slip

Smectite clays occur in subduction zone fault cores at shallow depth (approximately 1 km; e.g., Japan Trench) and landslide d\ue9collements (e.g., Vajont, Italy, 1963). The availability of pore fluids affects the likelihood that seismic slip propagates from deeper to shallow fault depths or that a landslide accelerates to its final collapse. To investigate the deformation processes active during seismic faulting we performed friction experiments with a rotary machine on 2-mm-thick smectite-rich gouge layers (70/30 wt % Ca-montmorillonite/opal) sheared at 5-MPa normal stress, at slip rates of 0.001, 0.01, 0.1, and 1.3 m/s, and total displacement of 3 m. Experiments were performed on predried gouges under vacuum, under room humidity and under partly saturated conditions. The fault shear strength measured in the experiments was included in a one-dimensional numerical model incorporating frictional heating, thermal, and thermochemical pressurization. Quantitative X-ray powder diffraction and scanning electron microscopy investigations were performed on pristine and deformed smectite-rich gouges. Under dry conditions, cataclasis and amorphization dominated at slip rates of 0.001\u20130.1 m/s, whereas grain size sensitive flow and, under vacuum, frictional melting occurred at fast slip rates (1.3 m/s). Under partly saturated conditions, frictional slip in a smectite foliation occurred in combination with pressurization of water by shear-enhanced compaction and, for V = 0.01\u20131.3 m/s, with thermal pressurization. Pseudotachylytes, the only reliable microstructural markers for seismic slip, formed only with large frictional power (>2 MW/m2), which could be achieved at shallow depth with high slip rates, or, at depth, with high shear stress in dehydrated smectites

In situ time resolved synchrotron powder diffraction study of mordenite

The step by step thermal dehydration process of the zeolites mordenite from Pashan (Poona, India) (Na3.51K0.14Ca1.89Mg0.09Sr0.01)[Fe0.033+Al7.40Si40.53O96].27.26H(2)O, has been studied in situ by synchrotron powder diffraction. The time-resolved experiment was performed using a translating imaging plate system. The structure refinements by full profile Rietveld analysis were performed in the Cmcm space group in the temperature range from 25 to 830degreesC. The results of structure refinements indicate that the slight cell-volume contraction (similar to1.9%) is related to the release of water molecules from the channels: above 375degreesC, the water loss lead to an enlargement of the 8-membered ring parallel to [010], which occurred by a flattening of T3-O9-T3 and T4-O4-T3 bridges. The dehydration process is reflected not only in the content of water molecules in the zeolite channel, but also in the temperature behaviour of the unit cell parameters. The cell parameters b and c decreased regularly as the temperature rose, whereas a decreased up to 400degreesC then increased up to 630degreesC, and finally decreased until the end of experiment. The removal of water molecules was accompanied by a spreading of the initial Ca sites into many positions bonded to the framework oxygens. The increased interaction with the framework oxygens of Ca sites was intimately related to the distortion of the 12-ring which is in turn related to the lengthening of the a cell parameter

Over-loaded Cu-ZSM-5 upon heating treatment: A time resolved X-ray diffraction study

he over-loaded Cu-ZSM-5 under heating treatment (50-910 degrees C) in oxidative conditions exhibits the formation of copper aggregates, which show different oxidation states as a function of temperature (Cu-0, Cu2O and CuO). At room temperature the excess of copper is not detectable by X-ray diffraction (XRD). It is likely present as divalent copper species (Cu-x(OH)(y)) dispersed on the zeolite surface that appear amorphous at XRD. This is confirmed by the UV-Vis diffuse reflectance spectroscopy data. From Rietveld refinement of room temperature and high temperature diffraction data, there are no indications of the presence of copper clusters inside the zeolite cavities. As the heating treatment proceeds, the dispersed copper species transform to metallic copper particles with increasing diffracting domains as a function of temperature. Above 510 degrees C the metallic copper starts to progressively oxidise to Cu2O and finally CuO

Over-loaded Cu-ZSM-5 upon heating treatment: A time resolved X-ray diffraction study

he over-loaded Cu-ZSM-5 under heating treatment (50-910 degrees C) in oxidative conditions exhibits the formation of copper aggregates, which show different oxidation states as a function of temperature (Cu-0, Cu2O and CuO). At room temperature the excess of copper is not detectable by X-ray diffraction (XRD). It is likely present as divalent copper species (Cu-x(OH)(y)) dispersed on the zeolite surface that appear amorphous at XRD. This is confirmed by the UV-Vis diffuse reflectance spectroscopy data. From Rietveld refinement of room temperature and high temperature diffraction data, there are no indications of the presence of copper clusters inside the zeolite cavities. As the heating treatment proceeds, the dispersed copper species transform to metallic copper particles with increasing diffracting domains as a function of temperature. Above 510 degrees C the metallic copper starts to progressively oxidise to Cu2O and finally CuO

Application of the Rietveld method for the investigation of mortars: a case study on the archaeological site of Thamusida (Morocco)

This study presents a multi-technique approach to the investigations of mortars, involving the application of the Rietveld method. The quantitative mineralogical analysis of samples was aimed at (1) verifying its significance in relation to results obtained through other techniques and (2) evaluating its potential in mortars characterisation. Six type of mortars used in the Roman settlement of Thamusida (50 km north of Rabat, Morocco) were investigated through X-ray powder-diffraction and Rietveld refinement, optical microscopy, image analysis, scanning electron microscopy, electron microprobe analysis, X-ray fluorescence (XRF) and combined differential thermal, and thermo-gravimetric analysis (DT-TGA). All the adopted techniques yielded unique results and complementary data; however, the Rietveld method can actually Substitute thermal analysis accurately. CaO oxide contents obtained by DT/TGA and Rietveld are in good agreement, but both were only partly comparable to XRF results. In our case, XRF and Rietveld results diverge when binders contain more than 67 wt.% CaO. The discrepancies can mainly be ascribed to the presence of amorphous material and to the obtainable accuracy by QPA-Rietveld method; conversely, the nonstoichiometry of phases does not affect our results, because phases with variable compositions are present in small amounts. Results further showed that the adopted methods were suitable for mortar characterisation. All studied mortars (1) have weak hydraulic properties; (2) employed binders characterised by highly variable CaO contents and by significant amounts of SiO2; (3) used coarse to fine quartz-carbonate-rich sands as the aggregate; and (4) selectively mixed 2 or 3 parts of aggregate with I part of binder, depending on the destination of the mortar

Application of the Rietveld method for the investigation of mortars: a case study on the archaeological site of Thamusida (Morocco)

This study presents a multi-technique approach to the investigations of mortars, involving the application of the Rietveld method. The quantitative mineralogical analysis of samples was aimed at (1) verifying its significance in relation to results obtained through other techniques and (2) evaluating its potential in mortars characterisation. Six type of mortars used in the Roman settlement of Thamusida (50 km north of Rabat, Morocco) were investigated through X-ray powder-diffraction and Rietveld refinement, optical microscopy, image analysis, scanning electron microscopy, electron microprobe analysis, X-ray fluorescence (XRF) and combined differential thermal, and thermo-gravimetric analysis (DT-TGA). All the adopted techniques yielded unique results and complementary data; however, the Rietveld method can actually Substitute thermal analysis accurately. CaO oxide contents obtained by DT/TGA and Rietveld are in good agreement, but both were only partly comparable to XRF results. In our case, XRF and Rietveld results diverge when binders contain more than 67 wt.% CaO. The discrepancies can mainly be ascribed to the presence of amorphous material and to the obtainable accuracy by QPA-Rietveld method; conversely, the nonstoichiometry of phases does not affect our results, because phases with variable compositions are present in small amounts. Results further showed that the adopted methods were suitable for mortar characterisation. All studied mortars (1) have weak hydraulic properties; (2) employed binders characterised by highly variable CaO contents and by significant amounts of SiO(2); (3) used coarse to fine quartz-carbonate-rich sands as the aggregate; and (4) selectively mixed 2 or 3 parts of aggregate with I part of binder, depending on the destination of the mortar