(Table 3, page 8) Chemical composition and physical cahracteristics of manganese nodules from the Pacific Ocean

This paper reviews the state of the art in processing and extraction of ocean floor manganese nodules. It briefly reviews the mining sites where the abundant rich nodules occur and also discusses the metal distribution in nodules in view of economical processing and extraction of these metal values. The paper discloses in a detailed manner the physical and chemical characteristics of nodules, including porosity, surface area, water content and the effect of temperature on crystal structure of major constituents of nodules. In the extraction aspect of nodules, the paper reviews two different extraction schemes revealed in the literature, namely hydrometallurgical treatment and pyrometallurgical treatment. The hydrometallurgical treatments include acid leaching, ammonia leaching, leaching with reducing agents and leaching after high temperature pre-treatments such as in sulfating rousting, while the pyrometallurgical processes include smelting, chlorination-vaporization and segregation. The paper also covers metal recovery processes from leach liquor. An economic survey of processing nodules has been made in terms of problems associated with metal-marketing, and impact of metal production from nodules on mineral industries.

Changes in the annual harmful algal blooms of Alexandrium minutum : effects of environmental conditions and drainage basin inputs in the Rance estuary (Brittany, France)

Time series of physico-chemical data and concentrations (cell L-1) of the toxic dinoflagellate Alexandrium minutum collected in the Rance macrotidal estuary (Brittany, France) were analyzed to understand the physico-chemical processes of the estuary and their relation to changes in bloom development from 1996 to 2009. The construction of the tidal power plant in the north and the presence of a lock in the south have greatly altered hydrodynamics, blocking the zone of maximum turbidity upstream, in the narrowest part of the estuary. Alexandrium minutum occurs in the middle part of the estuary. Most physical and chemical parameters of the Rance estuary are similar to those observed elsewhere in Brittany with water temperatures between 15–18 °C, slightly lowered salinities (31.8–33.1 PSU), low river flow rates upstream and significant solar radiation (8 h day-1). A notable exception is phosphate input from the drainage basin which seems to limit bloom development: in recent years, bloom decline can be significantly correlated with the decrease in phosphate input. On the other hand, the chemical processes occurring in the freshwater-saltwater interface do not seem to have an influence on these occurrences. The other hypotheses for bloom declines are discussed, including the prevalence of parasitism, but remain to be verified in further studies.

INVESTIGATIVE COMPARISON OF TANK AND RECOVERED ASPHALT SAMPLES THROUGH PHYSICAL PERFORMANCE TESTING AND CHEMICAL ANALYSIS

Despite the development of improved performance test protocols by renowned researchers, there are still road networks which experience premature cracking and failure. One area of major concern in asphalt science and technology, especially in cold regions in Canada is thermal (low temperature) cracking. Usually right after winter periods, severe cracks are seen on poorly designed road networks. Quality assurance tests based on improved asphalt performance protocols have been implemented by government agencies to ensure that roads being constructed are at the required standard but asphalt binders that pass these quality assurance tests still crack prematurely. While it would be easy to question the competence of the quality assurance test protocols, it should be noted that performance tests which are being used and were repeated in this study, namely the extended bending beam rheometer (EBBR) test, double edge-notched tension test (DENT), dynamic shear rheometer (DSR) test and X-ray fluorescence (XRF) analysis have all been verified and proven to successfully predict asphalt pavement behaviour in the field. Hence this study looked to probe and test the quality and authenticity of the asphalt binders being used for road paving. This study covered thermal cracking and physical hardening phenomenon by comparing results from testing asphalt binder samples obtained from the storage ‘tank’ prior to paving (tank samples) and recovered samples for the same contracts with aim of explaining why asphalt binders that have passed quality assurance tests are still prone to fail prematurely. The study also attempted to find out if the short testing time and automated procedure of torsion bar experiments can replace the established but tedious procedure of the EBBR. In the end, it was discovered that significant differences in performance and composition exist between tank and recovered samples for the same contracts. Torsion bar experimental data also indicated some promise in predicting physical hardening.

Physical modeling and numerical simulations of degradation mechanisms in devices and insulators for power applications

In this thesis, a TCAD approach for the investigation of charge transport in amorphous silicon dioxide is presented for the first time. The proposed approach is used to investigate high-voltage silicon oxide thick TEOS capacitors embedded in the back-end inter-level dielectric layers for galvanic insulation applications. In the first part of this thesis, a detailed review of the main physical and chemical properties of silicon dioxide and the main physical models for the description of charge transport in insulators are presented. In the second part, the characterization of high-voltage MIM structures at different high-field stress conditions up to the breakdown is presented. The main physical mechanisms responsible of the observed results are then discussed in details. The third part is dedicated to the implementation of a TCAD approach capable of describing charge transport in silicon dioxide layers in order to gain insight into the microscopic physical mechanisms responsible of the leakage current in MIM structures. In particular, I investigated and modeled the role of charge injection at contacts and charge build-up due to trapping and de-trapping mechanisms in the oxide layer to the purpose of understanding its behavior under DC and AC stress conditions. In addition, oxide breakdown due to impact-ionization of carriers has been taken into account in order to have a complete representation of the oxide behavior at very high fields. Numerical simulations have been compared against experiments to quantitatively validate the proposed approach. In the last part of the thesis, the proposed approach has been applied to simulate the breakdown in realistic structures under different stress conditions. The TCAD tool has been used to carry out a detailed analysis of the most relevant physical quantities, in order to gain a detailed understanding on the main mechanisms responsible for breakdown and guide design optimization.

Rotifer abundance, biomass, and secondary production after the recovery of hydrologic connectivity between a river and two marginal lakes (Sao Paulo, Brazil)

Rotifera density, biomass, and secondary production on two marginal lakes of Paranapanema River were compared after the recovery of hydrologic connectivity with the river (Sao Paulo State, Brazil). Daily samplings were performed in limnetic zone of both lakes during the rainy season immediately after lateral inflow of water and, in the dry period, six months after hydrologic connectivity recovery. In order to identify the factors that affect rotifer population dynamics, lake water level, volume, depth, temperature, transparency, dissolved oxygen, pH, alkalinity, conductivity, suspended solids, nutrients, and chlorophyll-a were determined. Variations of water physical and chemical factors that affect rotifer population were related to the lake-river degree of connection and to water level rising after drought. The water lateral inflow from the river resulted in an increase in lake water volume, depth, and transparency and a decrease in water pH, alkalinity, and suspended solids. The lake with the wider river connection, more frequent biota exchange, and larger amount of particulate and dissolved materials was richer and more diverse, while rotifer density, biomass, and productivity were lower in both periods studied. Density, biomass, and secondary production were higher in the lake with the smaller river connection and the higher physical and chemical stability. Our results show that the connectivity affects the limnological stability, associated to seasonality. Stable conditions, caused by low connectivity in dry periods, were related with high density, biomass and secondary production. Conversely, instability conditions in rainy periods were associated to elevated richness and diversity values, caused by exchange biota due to higher connectivity. (C) 2008 Elsevier GmbH. All rights reserved.

Chemical interaction between EVA and Portland cement hydration at early-age

Ethylene/vinyl acetate (EVA) copolymer. as latex or redispersable powder, is added to mortars and concrete to improve the fracture toughness, impermeability and bond strength to various substrates. The physical and chemical interactions were already proved after one day of hydration but during the first hour just the physical interaction was identified and some evidences of a chemical interaction. The aim of this paper was to evaluate the chemical interaction between EVA and Portland cement during the first hours of hydration in the thermogravimetric analysis. The results confirmed that the EVA hydrolyses in pH alkaline and consumes calcium ions from the solution, forming an organic salt (calcium acetate). reducing the calcium hydroxide content. And, its interaction occurred in the first 15 min of hydration. (C) 2009 Elsevier Ltd. All rights reserved.

Radial variation of the wood anatomical structure of Gmelina arborea trees from different climatic and management conditions in Costa Rica

The evaluations of the effect of the climatic conditions and of the intensity of forest management in the trunk of the Gmelina arborea Linn. Roxb. trees are restricted to its physical-mechanical properties and use. The present work has as objective to study the radial variations of the wood anatomy of the gmelina trees sampled in plantations of 30 sites in Costa Rica, characterized by two climatic conditions (tropical dry and humid) and three intensities of forest management (intensive, moderate and without management). The results of the analyses demonstrated the existence of radial variation of the different anatomical parameters, except for the fiber lumen diameter and multiple vessels in the wood of the gmelina trees. For the wood anatomical elements, fibers (width, lumen diameter, and length), vessels (multiple vessels, diameter and frequency) and radial parenchyma (height) relationships were observed with the climate (tropical humid and dry). The radial variations of the wood anatomical elements were, also, influenced by the management regimes of the gmelina trees.

Effects of chemical interesterification on physicochemical properties of blends of palm stearin and palm olein

Chemical interesterification is an important technological option for the production of fats targeting commercial applications. Fat blends, formulated by binary blends of palm stearin and palm olein in different ratios, were subjected to chemical interesterification. The following determinations, before and after the interesterification reactions, were done: fatty acid composition, softening point, melting point, solid fat content and consistency. For the analytical responses a multiple regression statistical model was applied. This study has shown that blending and chemical interesterifications are an effective way to modify the physical and chemical properties of palm stearin, palm olein and their blends. The mixture and chemical interesterification allowed obtaining fats with various degrees of plasticity, increasing the possibilities for the commercial use of palm stearin and palm olein. (C) 2009 Elsevier Ltd. All rights reserved.

Stability of clavulanic acid under variable pH, ionic strength and temperature conditions. A new kinetic approach

Clavulanic acid (CA) is a beta-lactam antibiotic that alone exhibits only weak antibacterial activity, but is a potent inhibitor of beta-lactamases enzymes. For this reason it is used as a therapeutic in conjunction with penicillins and cephalosporins. However, it is a well-known fact that it is unstable not only during its production phase, but also during downstream processing. Therefore, the main objective of this study was the evaluation of CA long-term stability under different conditions of pH and temperature, in the presence of variable levels of different salts, so as to suggest the best conditions to perform its simultaneous production and recovery by two-phase polymer/salt liquid-liquid extractive fermentation. To this purpose, the CA stability was investigated at different values of pH (4.0-8.0) and temperature (20-45 degrees C), and the best conditions were met at a pH 6.0-7.2 and 20 degrees C. Its stability was also investigated at 30 degrees C in the presence of NaCl, Na(2)SO(4), CaCl(2) and MgSO(4) at concentrations of 0.1 and 0.5 M in Mcllvaine buffer (pH 6.5). All salts led to increased CA instability with respect to the buffer alone, and this effect decreased in following sequence: Na(2)SO(4) > MgSO(4) > CaCl(2) > NaCl. Kinetic and thermodynamic parameters of CA degradation were calculated adopting a new model that took into consideration the equilibrium between the active and a reversibly inactivated form of CA after long-time degradation. (C) 2009 Elsevier B.V. All rights reserved.

Aluminium alloys - their physical and mechanical properties: Grain formation in AlSi7Mg0.35 foundry alloy at low superheat

Hypoeutectic AI-Si alloys represent the most widely used alloy system for cast aluminium applications. This system has a unique behaviour with respect to grain formation where an increase in silicon content results in a transition to larger grain sizes after a minimum at an intermediate concentration. As a result of the already large solute content, grain refinement by solute additions is inefficient and nucleant particles from the common aluminium grain refiners are not as effective as in wrought alloys. However, casting conditions, such as a low pouring temperature, that promote the formation of wall crystals tie. crystals nucleated in the thermally undercooled layer at or next to mould walls) are very effective in yielding a small grain size. This paper presents results of an investigation of the effect of low superheat and mould preheat temperature on grain size. It was found that pouring temperature controls the effectiveness of the wall mechanism while mould preheat has little effect until high preheat temperatures at which a large increase in grain size occurs. The observed changes in grain size are explained in terms of the balance between nucleation rate and survival rate of crystal nuclei resulting from changes in superheat and mould temperature.

The relationship between radiation-induced chemical processes and transverse relaxation times in polymer gel dosimeters

The effects of ionizing radiation in different compositions of polymer gel dosimeters are investigated using FT-Raman spectroscopy and NMR T-2 relaxation times. The dosimeters are manufactured from different concentrations of comonomers (acrylamide and N,N'-methylene-bis-acrylamide) dispersed in different concentrations of an aqueous gelatin matrix. Results are analysed using a model of fast exchange of magnetization between three proton pools. The fraction of protons in each pool is determined using the known chemical composition of the dosimeter and FT-Raman spectroscopy. Based on these results, the physical and chemical processes in interplay in the dosimeters are examined in view of their effect on the changes in T-2 The precipitation of growing macroradicals and the scavenging of free radicals by gelatin are used to explain the rate of polymerization. The model describes the changes in T-2 as a function of the absorbed dose up to 50 Gy for the different compositions. This is expected to aid the theoretical design of new, more efficient dosimeters, since it was demonstrated that the optimum dosimeter (i.e, with the lowest dose resolution) must have a range of relaxation times which match the range of T-2 values which can be determined with the lowest uncertainty using an MRI scanner.

Development of biocompatible and “smart” porous structures using CO2-assisted processes

Dissertação apresentada para a obtenção do grau de Doutor em Engenharia Química, especialidade Engenharia da Reacção Química, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Influence of commercially available polyimide and formation conditions on the performance and structure of asymmetric polyimide organic solvent nanofiltration membranes

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para a obtenção do grau de Mestre em Engenharia Química e Bioquímica

Racial inequalities in the socioeconomic, demographic and health conditions of elderly from Maranhão State, Legal Amazon, Brazil: a population-based study

Aging with quality of life does not occur equally among the racial groups of Brazilian elderly, and few studies have analyzed this issue in the states of the Brazilian Legal Amazon. The objective of this study was to investigate racial inequalities in the socioeconomic, demographic and health conditions of elderly residents of Maranhão state, Brazil. The present work is a cross-sectional study of 450 elders aged 60 years or older included in the 2008 National Household Sample Survey. The prevalence of socioeconomic, demographic, health and habit indicators and of risk factors were estimated in white, brown and black racial categories that were self-reported by the survey participants. The chi-square test was used for comparisons (a=5%). The majority of the elderly respondents identified themselves as brown (66.4%) or white (23.3%). There were significant socioeconomic, demographic, habit and lifestyle differences among the racial groups. Most of the black and brown elderly lived alone, reported lower educational levels and were in the lowest quintile for income. These respondents were also highly dependent on the Unified Health System (Sistema Único de Saúde - SUS), exhibited low rates of screening mammograms and lower physical activity levels and had a greater proportion of smokers. However, there was no difference in the prevalence of health indicators or in the proportion of elderly by gender, age, social role in the family or the urban-rural location of the household. These results indicate the presence of racial inequalities in the socioeconomic and demographic status and in the practice of healthy habits and lifestyles among elderly from Maranhão, but suggest equity in health status. The results also suggest the complexity and challenges of interlinking race with socioeconomic aspects, and the findings reinforce the need for the implementation of public policies for these population groups.