Coupled Thermo-Hydro-Mechanical and Chemical Analysis of Expansive Clay Subjected to Heating and Hydration

A fully coupled formulation combining reactive transport and an existing thermo-hydro-mechanical (THM) code is presented. Special attention has been given to phenomena likely to be encountered in clay barriers used as part of containment systems of nuclear waste. The types of processes considered include hydrolysis, complex formation, oxidation/reduction reactions, acid/base reactions, precipitation/dissolution of minerals and cation exchange. Both kinetically-controlled and equilibrium-controlled reactions have been incorporated. The total analytical concentrations (including precipitated minerals) are adopted as basic transport variables and chemical equilibrium is achieved by minimizing Gibbs Free Energy. The formulation has been incorporated in a general purpose computer code capable of performing numerical analysis of engineering problems. A validation exercise concerning a laboratory experiment involving the heating and hydration of an expansive compacted clay is described.     

Direction of magnetization and domain wall mobility in (Dy,Y)Fe2

Magnetization measurements in the (Dy _x Y_1−x )Fe₂ intermetallic compounds show evidence of blocking of domain wall motion. This effect is a function of concentrationx. The direction of magnetization is also dependent on the Dy concentration. We have used the Mossbauer spectroscopy of⁵⁷Fe to verify the direction of magnetization in the series as a function ofx and temperature. The results show that this change in easy direction occurs at higher temperatures than those where the blocking is detected through DC magnetization measurements. supported by RHAE/SCT.     

Should Epstein strip arrangement be changed?

The paper describes effect of texture on the anisotropy of magnetic properties and shows that an Epstein strip arrangement including strips cut in a direction 45° to the rolling direction gives property values that are closer to the average values than the traditional RD+TD arrangement.     

Potentiometric studies on the complexation of copper(II) by phenolic acids as discrete ligand models of humic substances

Studies on the complexation of copper(II) by phenolic acids, as ligand models of humic substances were done by potentiometry. The acids under study were: 3,4-dihydroxyhydrocinnamic acid or hydrocaffeic acid (1), 3,4-dihydroxyphenylacetic acid (2) and 3,4-dihydroxybenzoic acid or protocatechuic acid (3). Acidity constants of the ligands and the formation constants of metal-ligand complexes were evaluated by computer programs. The carboxylic group of the phenolic acids has different pK_a1 values, being the dissociation constants intrinsically related with the distance between the function and the aromatic nucleus. The results obtained allow concluding that acidity constants of the catechol moiety of the compounds are similar with pK_a2 and pK_a3 values between 9.47-9.41 and 11.55-11.70. The complexation properties of the three ligands towards copper(II) ion are quite similar, being the species found not different either in nature or stability. Although the model ligands have some structural differences no significant differences were found in their complexation properties towards copper(II). So, it can be postulated that complexation process is intrinsically related with the presence of a catechol group.     

A new method for obtaining adsorption isotherms on colloidal suspensions via electrokinetic sonic amplitude measurement

The standard methods for obtaining adsorption isotherms on colloidal suspensions are usually very time consuming and involve a large number of steps and assumptions that increase the experimental errors. In this work, an alternative method is proposed to evaluate the adsorption behavior of electrosteric-stabilized systems based on electrokinetic sonic amplitude signal measurements. The new method, entitled "zeta-sorption", is noticeably less time-consuming when compared to conventional procedures but showed great precision and reliability confirmed by comparison with data obtained from conventional routes on alumina-polyacrylate and alumina-citric acid aqueous suspensions. The experimental conditions that restrict the applicability of the new method were identified and justified by discussing the possible ion exchanges.     

Molecular-level control of the photoluminescence from PPV nanostructured films

The fabrication of varied molecular architectures in layer-by-layer (LbL) films is exploited to control the photoluminescence (PL) of poly(p-phenylene vinylene) (PPV) in an unprecedented way. This was achieved by controlling the F?rster energy transfer between PPV layers (donors) and layers of a commercial azodye, Brilliant Yellow (BY) (acceptors). Energy transfer was controlled by inserting spacer layers of inert polymers between PPV and BY layers and by photoaligning the BY molecules via trans-cis-trans isomerization. The PPV/BY LbL films displayed polarized PL whose intensity could be varied almost continuously by changing the time of photoalignment, which was carried out by impinging a linearly polarized laser light simultaneously to the PL experiments. For PPV/BY films with no spacer layers, PL was completely quenched, but its intensity increased with the number of spacing layers. Further increase in PL was obtained by photoaligning the BY molecules perpendicularly to the PPV molecules. This minimizes energy transfer, since F?rster processes are directional, dipole-dependent resonant transfers. Energy transfer is also controlled by imparting a preferential orientation of the PPV chains on PPV/BY LbL films deposited onto flexible Teflon substrates that may be stretched.     

Kinetic study of template removal of Al-MCM-41 synthesized at room temperature

The Al-MCM-41 molecular sieve with Si/Al = 20 molar ratio was synthesized at room temperature and characterized by X-ray diffractometry, surface area, thermogravimetry, and infrared spectroscopy. The kinetic study was conducted by Vyazovkin and Ozawa method, in order to verify the activation energy during the Hofmann degradation between 130 and 370 °C, in which most of surfactant removal occurs. The results suggest that the activation energy for template removal is close to 80 kJ mol^?1 lower in Al-MCM-41 synthesized at room temperature, when compared to results obtained for mesopores Al-MCM-41 and MCM-41 synthesized by hydrothermal method. This lower activation energy may be understood as consequence of textural properties, such as higher pore size.