Crystal engineering using functionalized adamantane

We performed a first-principles investigation on the structural, electronic and optical properties of crystals made of chemically functionalized adamantane molecules. Several molecular building blocks, formed by boron and nitrogen substitutional functionalizations, were considered to build zinc blende and wurtzite crystals, and the resulting structures presented large bulk moduli and cohesive energies, wide and direct bandgaps, and low dielectric constants (low-kappa materials). Those properties provide stability for such structures up to room temperature, superior to those of typical molecular crystals. This indicates a possible road map for crystal engineering using functionalized diamondoids, with potential applications ranging from space filling between conducting wires in nanodevices to nano-electromechanical systems.

Sediment deformation in Miocene and post-Miocene strata, Northeastern Brazil: Evidence for paleoseismicity in a passive margin

Stratigraphic intervals characterized by varied and complex styles of soft-sediment deformation structures are well preserved in Miocene and Late Pleistocene to Holocene deposits of a sedimentary basin located in Northeastern Brazil. The Miocene strata, represented by the Barreiras Formation, record only brittle structures, including numerous faults and fractures with straight and high angle-dipping planes that are often filled with sands derived from overlying beds. Folds consisting of broad anticlines and synclines are also present in this unit. The late Pleistocene to Holocene deposits, named Post-Barreiras Sediments, contain an indurated sandy package with a large variety of ductile and brittle deformation structures (i.e., massive sandstones with isolated sand fragments and breccias, undulatory strata, sand dykes and diapirs, sinks and bowls, pebbly pockets, plunged sediment mixtures, fitted sand masses, cone-shaped cracks, fault grading and sedimentary enclaves). These features, confined to sharp-based stratigraphic horizons that progressively grade downward into undisturbed deposits, are related to seismic shocks of high surface-wave magnitude (i.e., Ms>5 or 6). Amalgamated seismites suggest that previously formed seismites were affected by subsequent seismic-wave propagation. Seismic waves caused by activity along one, or most likely, several tectonic structures would have propagated throughout the depositional environment, producing laterally extensive seismites. The close proximity to earthquake epicenters would have promoted pervasive re-sedimentation due to pore overpressure, resulting high volumes of massive sandstones and breccia. The similarity between deposits with correlatable strata from many other areas along the Brazilian coast allows raise the hypothesis that the seismic episodes might have affected sedimentation patterns in a large (i.e., extension of several hundreds of kilometers) geographic area. Thus, the modern seismicity recorded along Northeastern Brazil was recurrent during the Quaternary and, perhaps, also in the Pliocene. The estimated high magnitude of the seismic events and the great regional extent of the affected area demonstrate that the Brazilian coast experienced tectonic stress through the last geological episodes of its evolution, which would have favored sediment accumulation and penecontemporaneous re-sedimentation. This geological context is unexpected in a passive margin, inducing to revisit the debate on how active is a passive margin. (C) 2010 Elsevier B.V. All rights reserved.

On a product formula for the Conley-Zelmder index of symplectic paths and its applications

Using invariance by fixed-endpoints homotopies and a generalized notion of symplectic Cayley transform, we prove a product formula for the Conley-Zehnder index of continuous paths with arbitrary endpoints in the symplectic group. We discuss two applications of the formula, to the metaplectic group and to periodic solutions of Hamiltonian systems.

N3-Dye-Induced Visible Laser Anatase-to-Rutile Phase Transition on Mesoporous TiO(2) Films

Titanium dioxide has been extensively used in photocatalysis and dye-sensitized solar cells, where control of the anatase-to-rutile phase transformation may allow the realization of more efficient devices exploiting the synergic effects at anatase/rutile interfaces. Thus, a systematic study showing the proof of concept of a dye-induced morphological transition and an anatase-to-rutile transition based on visible laser (532 nm) and nano/micro patterning of mesoporous anatase (Degussa P25 TiO(2)) films is described for the first time using a confocal Raman microscope. At low laser intensities, only the bleaching of the adsorbed N3 dye was observed. However, high enough temperatures to promote melting/densification processes and create a deep hole at the focus and an extensive phase transformation in the surrounding material were achieved using Is laser pulses of 25-41 mW/cm(2), in resonance with the MLCT band. The dye was shown to play a key role, being responsible for the absorption and efficient conversion of the laser light into heat. As a matter of fact, the dye is photothermally decomposed to amorphous carbon or to gaseous species (CO(x), NO(x), and H(2)O) under a N(2) or O(2) atmosphere, respectively.

Solvatochromic and lonochromic Effects of Iron(II)bis-(1,10-phenanthroline)dicyano: a Theoretical Study

Solvatochromic and ionochromic effects of the iron(II)bis(1,10-phenanthroline)dicyano (Fe(phen)(2)(CN)(2)) complex were investigated by means of combined DFT/TDDFT calculations using the PBE and B3LYP functionals. Extended solvation models of Fe(phen)(2)(CN)(2) in acetonitrile and aqueous solution, as well as including interaction with Mg(2+), were constructed. The calculated vertical excitation energies reproduce well the observed solvatochromism in acetonitrile and aqueous solutions, the ionochromism in acetonitrile in the presence of Mg(2+), and the absence of ionochromic effect in aqueous solution. The vertical excitation energies and the nature of the transitions were reliably predicted after inclusion of geometry relaxation upon aqueous micro- and global solvation and solvent polarization effect in the TDDFT calculations. The two intense UV-vis absorption bands occurring for all systems studied are interpreted as transitions from a hybrid Fe(II)(d)/cyano N(p) orbital to a phenanthroline pi* orbital rather than a pure metal-to-ligand-charge transfer (MLCT). The solvatochromic and ionochromic blue band shifts of Fe(phen)(2)(CN)(2) were explained with preferential stabilization of the highest occupied Fe(II)(d)/cyano N(p) orbitals as a result of specific interactions with water solvent molecules or Mg(2+) ions in solution. Such interactions occur through the CN(-) groups in the complex, and they have a decisive role for the observed blue shifts of UV-vis absorption bands.

Microstructural, Mechanical and Tribological Characterisation of CVD and PVD Coatings for Metal Cutting Applications

The present thesis focuses on characterisation of microstructure and the resulting mechanical and tribological properties of CVD and PVD coatings used in metal cutting applications. These thin and hard coatings are designed to improve the tribological performance of cutting tools which in metal cutting operations may result in improved cutting performance, lower energy consumption, lower production costs and lower impact on the environment.  In order to increase the understanding of the tribological behaviour of the coating systems a number of friction and wear tests have been performed and evaluated by post-test microscopy and surface analysis. Much of the work has focused on coating cohesive and adhesive strength, surface fatigue resistance, abrasive wear resistance and friction and wear behaviour under sliding contact and metal cutting conditions. The results show that the CVD deposition of accurate crystallographic phases, e.g. α-Al2O3 rather than κ-Al2O3, textures and multilayer structures can increase the wear resistance of Al2O3. However, the characteristics of the interfaces, e.g. topography as well as interfacial porosity, have a strong impact on coating adhesion and consequently on the resulting properties.  Through the deposition of well designed bonding and template layer structures the above problems may be eliminated. Also, the presence of macro-particles in PVD coatings may have a significant impact on the interfacial adhesive strength, increasing the tendency to coating spalling and lowering the surface fatigue resistance, as well as increasing the friction in sliding contacts. Finally, the CVD-Al2O3 coating topography influences the contact conditions in sliding as well as in metal cutting. In summary, the work illuminates the importance of understanding the relationships between deposition process parameters, composition and microstructure, resulting properties and tribological performance of CVD and PVD coatings and how this knowledge can be used to develop the coating materials of tomorrow.

University System Governance and Organization

University systems rely on organizational and governance structures to balance the interest, missions, and needs of constituent campuses. This report examines organizational and governance structures of four public university systems. It explores the organizational structures of governing boards and administrative offices, as well as the role of system offices in coordinating across constituent campuses and protecting mission differentiation.

Biased managers, organizational design, and incentive provision

We model the tradeoff between the balance and the strength of incentives implicit in the choice between hierarchical and matrix organizational structures. We show that managerial biases determine which structure is optimal: hierarchical forms are preferred when biases are low, while matrix structures are preferred when biases are high.

A abertura comercial brasileira e o impacto no processo gerencial das micro e pequenas empresas do setor de confecção do Espírito Santo

ESTA MONOGRAFIA OBJETIVOU IDENTIFICAR ATÉ QUE PONTO A ABERTURA DO MERCADO BRASILEIRO AFETOU O PROCESSO GERENCIAL DAS MICRO E PEQUENAS EMPRESAS DO SETOR DE CONFECÇÃO DO ESPÍRITO SANTO. UTILIZOU-SE METODOLOGIA DIVERSIFICADA CONSISTENTE DE REVISÃO BIBLIOGRÁFICA SOBRE O TEMA, ANÁLISE E INTERPRETAÇÃO DE DADOS FORNECIDOS PELO SEBRAE-ES, IBGE E UNIVERSIDADE FEDERAL DO ESPÍRITO SANTO (UFES) E PESQUISA DE CAMPO EM QUE FORAM ENTREVISTADOS EMPRESÁRIOS DO SETOR DE CONFECÇÃO EM MUNICÍPIOS DO ESTADO. PELO ESTUDO, CONCLUI-SE QUE: O PROCESSO DE GLOBALIZAÇÃO TEM AFETADO A ECONOMIA BRASILEIRA E, PARTICULARMENTE, A CAPIXABA; EM RELAÇÃO AO SETOR DE CONFECÇÃO, O IMPACTO DA GLOBALIZAÇÃO NÃO TEM SIDO ACENTUADO; E O PROCESSO GERENCIAL DAS MICRO E PEQUENAS EMPRESAS DO RAMO DE CONFECÇÃO NO ESTADO, SURGIU COMO UMA DAS PRINCIPAIS CAUSAS DA FRAGILIDADE E INEFICÁCIA DO SETOR, TORNANDO-SE INADIÁVEIS E IMPERATIVAS AÇÕES QUE PROPICIEM O DESENVOLVIMENTO GERENCIAL, A FIM DE PERMITIR-LHE CONTRIBUIR PARA A DISTRIBUIÇÃO SOCIAL DOS MEIOS DE PRODUÇÃO.

Diagnóstico das micro e pequenas empresas da cadeia produtiva moveleira da serra gaúcha : importância para o desenvolvimento setorial

The increasing of afluence demands the companies to be competitive and have a deep knowledge about the area wich they are participating. Through the search of management and produtive information, and the analisys of internal and external information, the company could identify strong and weak points , threats and oportunities, alowing the obtaince of competitive advantages. This research shows the result of a close search study about the usage of strategic planning and management technics, setting in evidence the necessity of micro and small furniture companies and furniture supply chain, represented in this case by sub-contract companies. Still looking to accentuate the importance that this study will represent to the setorial development, specially to the furniture companies wich have a big importance due to the report of small utilization of management technics in the sub-contract companies. Through analisys, it was possible to find out some common caracteristics in all 171 conmpanies evaluated, wich are showing likely 'sinalization', such as: - lower level os scholarship (96,5% elementary school, 3% until high school, 0,5% university/college graduration); - external market from Brazilian MPE¿s (5% export products to Mercosul and just 1% export products to Latin America, absenting exportations to other markets); - carefree with modern technics of management, certificates ISO 9000, 14000, MRP, CQT, among others; - carefree with strategic planning; - lower utilization of operacionl procedures, rules and function description; - ignoring the participating of market; - lower utilization of human resources index as a management form; - Small utilization of costs tabs (31%), with a small informatization level (8%) and apllying with non-management form; - low utilization of quality statistics (4%), re-working index (9%), among others. In syntesis, the basis expose that the great marjority of companies don¿t have knowledge about planning and the modern technics of management.