Simulação computacional de materiais bidimensionais: funcionalização de defeitos extensos no grafeno e retenção de contaminantes por argilominerais

In this work are considered two bidimensional systems, with distints chacacteristcs and applicabilitys. Is studied the adsorption of transition metals (MT) Fe, Co, Mn and Ru in extended defects, formed by graphene grain boundaries. First in pristine graphene The hollow site of carbon hexagon, in pristine graphene, are the most stable for MT adsorption. The Dirac cone in eletronic structure of graphene was manteined with the presence of MT. For the considered grain boundaries the MT has a greater stability for absorption in the grain boundaries sites in comparison with pristine graphene. Through the energy barrier values, are observed diffusion chanels for MT localized on the grain boundaries. This diffusion chanels indicate a possible formation of nanolines of MT in graphene. For the first stage of the nanolines, ate observed a better stability for the system with greater MT concentration, due to MT-MT interactions. Also, due to the magnetic moment of the MT, the nanolines show a magnetization. For the most stable configurations the system are metallics, particularly for Fe the band structure indicates an anisotropic spin current. In a second study, are considereted the retention capacity for metallic contaminants Cd and Hg in clayminerals, kaolinite (KAO) and montmorillonite (MMT). Through the adsorption energies of contaminantes in the clayminerals, was observed a increase in stability with the increase of contaminants concentration, due to the interaction Cd-Cd and Hg-Hg. Also, was observed that KAO has a strong interaction beteween monolayers than MMT. In this sence, for the adsoption process of contaminantes in the natural form of KAO and MMT, the latter has a better retention capacity, due to the small net work for contaminant intercalation. However, when the modification of clayminerals, with molecules that increase the spacing between monolayers, exist a optimal condition, which the contaminant absorption are more stable in KAO system than in MMT. In the Langmuir adsorption model for the clayminerals in the optimal monolayer spacing, the retention capacity for Cd and Hg in KAO system are 21% greater than in MMT system. Also, for the X-ray Absorption Near Edge Spectroscopy (XANES) for the K edge of Cd and Hg, are found a positive shift of absorption edge with the decreasing of monolayer spacing. This result indicates a possible way to determine the concentration of adsorbed contaminats in relation to unabsorbed ones, from the decomposition of experimental XANES in the obteined spectras.

Efeitos da internacionalização no desvio da estrutura de capital alvo e na velocidade de ajuste

This dissertation investigates the effects of internationalization in two gaps related to the capital structure that have not been discussed by the Brazilian literature yet. To this, were developed two independent sections. The first examined what the effects of internationalization on the deviation from the target capital structure. The second examined what the effects of internationalization on speed of adjustment (SOA) of the capital structure. It used data from Brazil, multinational and domestic companies, from 2006 to 2014. The results of the first analysis indicate that internationalization helps reduce the difference between the target and the current debt. That is, to the extent that the level of internationalization increases; whether only export or a combination of export, assets and employees abroad, the gap between the current structure and the target structure decreases. This reduction is given as a function of internationalization as a consequence of the upstream effect of the upstream-downstream hypothesis. Thus, as the Market Timing theory, it can be seen as an opportunity for adjustment of the capital structure, and with the reduction of deviation, there is also a reduction in the cost of capital of the firm. The result of the second analysis indicates that internationalization is able to significantly increase the speed adjustment, ensuring for the multinational a faster adjustment of its capital structure. Exports increase the SOA in 9 to 23%. And when also kept active assets and employees abroad the increase is 8 to 20%. In terms of time, while domestic company takes more than three years to reduce half of the deviation that has, while multinacional companies take on average one and a half year to reduce the same proportion of the deviation. The validity of the upstream-downstream hypothesis for the effect of internationalization in SOA was confirmed by comparing the results for US companies. Thus, the phenomenon of internationalization increases SOA when companies are from less stable markets, such as Brazil; and it has a less significcative effect when companies are derived from more stable markets, because they already have a high speed of adjustmennt. In addition, the adequacy analysis of the estimators also showed the model pooled OLS (Ordinary Least Squares) presents the highest quality in predicting the SOA than the system GMM (Generalized Method of Moments). For future studies it is suggested to analyze the effect of international event, by itself, and to validate the hypothesis using samples of different markets and the use of other estimators.