The intercalation of H2O, CO2, and other fluid species in expandable clay minerals (smectites) may play a significant role in controlling the behavior of these species in geological C-sequestration and enhanced petroleum production and has been the subject of intensive study in recent years. This paper reports the results of a computational study of the effects of the properties of the charge balancing, exchangeable cations on H2O and CO2 intercalation in the smectite mineral, hectorite, in equilibrium with an H2O-saturated supercritical CO2 fluid under reservoir conditions using Grand Canonical Molecular Dynamics (GCMD) methods. The results show that the intercalation behavior is greatly different with cations with relatively low hydration energies and high affinities for CO2 (here Cs+) than with cations with higher hydration energies (here Ca2+). With Cs+, CO2 intercalation occurs in a 1-layer structure and does not require H2O intercalation, whereas with Ca2+ the presence of a sub-monolayer of H2O is required for CO2 intercalation. The computational results provide detailed structural, dynamical and energetic insight into the differences in intercalation behavior and are in excellent agreement with in situ experimental XRD, IR, quartz crystal microbalance, and NMR results for smectite materials obtained under reservoir conditions.
The structural and spectroscopic features of the EuAl3(BO3)4 individual skeletal microcrystals synthesized by a melt solution method have been studied. Their infrared spectra taken from the as-grown microcrystal surfaces mainly contain the lines of the rhombohedral modification of EuAl3(BO3)4 and additional peaks of its monoclinic modification. TEM and X-ray diffraction studies confirm that these additional peaks in the IR spectra belong to the monoclinic C2/c polytype of the EuAl3(BO3)4 compound. We are the first to demonstrate the presence of coherent monoclinic domains in rhombohedral EuAl3(BO3)4 crystals by TEM. Cathodoluminance spectroscopy shows that the microcrystals generate strong emission lines in the range 580–630 nm, and their intensities are strongly influenced by the crystal orientation.
Mechanical performances of titanium biomedical implants manufactured by superplastic forming are strongly related to the process parameters: the thickness distribution along the formed sheet has a key role in the evaluation of post-forming characteristics of the prosthesis. In this work, a finite element model able to reliably predict the thickness distribution after the superplastic forming operation was developed and validated in a case study. The material model was built for the investigated titanium alloy (Ti6Al4V-ELI) upon results achieved through free inflation tests in different pressure regimes. Thus, a strain and strain rate dependent material behaviour was implemented in the numerical model. It was found that, especially for relatively low strain rates, the strain rate sensitivity index of the investigated titanium alloy significantly decreases during the deformation process. Results on the case study highlighted that the strain rate has a strong influence on the thickness profile, both on its minimum value and on the position in which such a minimum is found.