O uso de calorimetria em ecologia

The macroscopic effects caused by sun radiation and the mankind-nature interactions in a ecosystem are firstly presented. However, the importance of calorimetric determinations to clarify some phenomena related to the living microorganism populations and their interactions with the food additive or inhibitor agents are reported. The collect values illustrate the occurence a great deal of effects in this microscopic world. For this subject, the reachest Latosol soil was selected due to the content of organic matter and consequently in microorganisms. Microbial activity was stimulated by addition of glucose, which showed to be the best nutrient source. Inhibitory effect was detected with many compounds used in the agriculture like some herbicides and fungicides. Although the assays are based on the use of the microcalorimetry, other techniques like respirometry contributes strongly to the understanding of the ecosystem. The main objective in this exposition is to stimulate by means of many interesting examples, the importance of preserving the environment in order to establish direct analogies by using the Chemistry in the daily life.

Modeling the transport phenomena within arterial wall: porous media approach

The transport of macromolecules, such as low-density lipoprotein (LDL), and their accumulation in the layers of the arterial wall play a critical role in the creation and development of atherosclerosis. Atherosclerosis is a disease of large arteries e.g., the aorta, coronary, carotid, and other proximal arteries that involves a distinctive accumulation of LDL and other lipid-bearing materials in the arterial wall. Over time, plaque hardens and narrows the arteries. The flow of oxygen-rich blood to organs and other parts of the body is reduced. This can lead to serious problems, including heart attack, stroke, or even death. It has been proven that the accumulation of macromolecules in the arterial wall depends not only on the ease with which materials enter the wall, but also on the hindrance to the passage of materials out of the wall posed by underlying layers. Therefore, attention was drawn to the fact that the wall structure of large arteries is different than other vessels which are disease-resistant. Atherosclerosis tends to be localized in regions of curvature and branching in arteries where fluid shear stress (shear rate) and other fluid mechanical characteristics deviate from their normal spatial and temporal distribution patterns in straight vessels. On the other hand, the smooth muscle cells (SMCs) residing in the media layer of the arterial wall respond to mechanical stimuli, such as shear stress. Shear stress may affect SMC proliferation and migration from the media layer to intima. This occurs in atherosclerosis and intimal hyperplasia. The study of blood flow and other body fluids and of heat transport through the arterial wall is one of the advanced applications of porous media in recent years. The arterial wall may be modeled in both macroscopic (as a continuous porous medium) and microscopic scales (as a heterogeneous porous medium). In the present study, the governing equations of mass, heat and momentum transport have been solved for different species and interstitial fluid within the arterial wall by means of computational fluid dynamics (CFD). Simulation models are based on the finite element (FE) and finite volume (FV) methods. The wall structure has been modeled by assuming the wall layers as porous media with different properties. In order to study the heat transport through human tissues, the simulations have been carried out for a non-homogeneous model of porous media. The tissue is composed of blood vessels, cells, and an interstitium. The interstitium consists of interstitial fluid and extracellular fibers. Numerical simulations are performed in a two-dimensional (2D) model to realize the effect of the shape and configuration of the discrete phase on the convective and conductive features of heat transfer, e.g. the interstitium of biological tissues. On the other hand, the governing equations of momentum and mass transport have been solved in the heterogeneous porous media model of the media layer, which has a major role in the transport and accumulation of solutes across the arterial wall. The transport of Adenosine 5´-triphosphate (ATP) is simulated across the media layer as a benchmark to observe how SMCs affect on the species mass transport. In addition, the transport of interstitial fluid has been simulated while the deformation of the media layer (due to high blood pressure) and its constituents such as SMCs are also involved in the model. In this context, the effect of pressure variation on shear stress is investigated over SMCs induced by the interstitial flow both in 2D and three-dimensional (3D) geometries for the media layer. The influence of hypertension (high pressure) on the transport of lowdensity lipoprotein (LDL) through deformable arterial wall layers is also studied. This is due to the pressure-driven convective flow across the arterial wall. The intima and media layers are assumed as homogeneous porous media. The results of the present study reveal that ATP concentration over the surface of SMCs and within the bulk of the media layer is significantly dependent on the distribution of cells. Moreover, the shear stress magnitude and distribution over the SMC surface are affected by transmural pressure and the deformation of the media layer of the aorta wall. This work reflects the fact that the second or even subsequent layers of SMCs may bear shear stresses of the same order of magnitude as the first layer does if cells are arranged in an arbitrary manner. This study has brought new insights into the simulation of the arterial wall, as the previous simplifications have been ignored. The configurations of SMCs used here with elliptic cross sections of SMCs closely resemble the physiological conditions of cells. Moreover, the deformation of SMCs with high transmural pressure which follows the media layer compaction has been studied for the first time. On the other hand, results demonstrate that LDL concentration through the intima and media layers changes significantly as wall layers compress with transmural pressure. It was also noticed that the fraction of leaky junctions across the endothelial cells and the area fraction of fenestral pores over the internal elastic lamina affect the LDL distribution dramatically through the thoracic aorta wall. The simulation techniques introduced in this work can also trigger new ideas for simulating porous media involved in any biomedical, biomechanical, chemical, and environmental engineering applications.

Surface Studies of Thiolate Adsorbates on Some Metals

The results and discussions in this thesis are based on my studies about selfassembled thiol layers on gold, platinum, silver and copper surfaces. These kinds of layers are two-dimensional, one molecule thick and covalently organized at the surface. They are an easy way to modify surface properties. Self-assembly is today an intensive research field because of the promise it holds for producing new technology at nanoscale, the scale of atoms and molecules. These kinds of films have applications for example, in the fields of physics, biology, engineering, chemistry and computer science. Compared to the extensive literature concerning self-assembled monolayers (SAMs) on gold, little is known about the structure and properties of thiolbased SAMs on other metals. In this thesis I have focused on thiol layers on gold, platinum, silver and copper substrates. These studies can be regarded as a basic study of SAMs. Nevertheless, an understanding of the physical and chemical nature of SAMs allows the correlation between atomic structure and macroscopic properties. The results can be used as a starting point for many practical applications. X-ray photoelectron spectroscopy (XPS) and synchrotron radiation excited high resolution photoelectron spectroscopy (HR-XPS) together with time-offlight secondary ion mass spectrometry (ToF-SIMS) were applied to investigate thin organic films formed by the spontaneous adsorption of molecules on metal surfaces. Photoelectron spectroscopy was the main method used in these studies. In photoelectron spectroscopy, the sample is irradiated with photons and emitted photoelectrons are energy-analyzed. The obtained spectra give information about the atomic composition of the surface and about the chemical state of the detected elements. It is widely used in the study of thin layers and is a very powerful tool for this purpose. Some XPS results were complemented with ToF-SIMS measurements. It provides information on the chemical composition and molecular structure of the samples. Thiol (1-Dodecanethiol, CH3(CH2)11SH) solution was used to create SAMs on metal substrates. Uniform layers were formed on most of the studied metal surfaces. On platinum, surface aligned molecules were also detected in investigations by XPS and ToF-SIMS. The influence of radiation on the layer structure was studied, leading to the conclusion that parts of the hydrocarbon chains break off due to radiation and the rest of the layer is deformed. The results obtained showed differences depending on the substrate material. The influence of oxygen on layer formation was also studied. Thiol molecules were found to replace some of the oxygen from the metal surfaces.

Correlação entre a estrutura atômica superficial e o processo de adsorção-dessorção reversível de hidrogênio em eletrodos monocristalinos Pt(111), Pt(100) e Pt(110)

Platinum is widely used as electrode in electrocatalytic processes, however the use of polycrystalline electrodes introduces a series of variables in the electrochemical system due to the aleatory contribution of all the crystallographic orientations with different surface packing of atoms. Single crystal platinum electrodes of low Miller index present surface structure of high regularity and serve as model to establish a correlation among the macroscopic and microscopic properties of the electrochemical interface. Therefore, the main aim of this work is the study of the voltammetric profiles of the reversible adsorption-desorption of hydrogen on Pt(100), Pt(110) and Pt(111), in order to correlate the electrochemical properties of each different orientation with the surface atomic structure.

Síntese de nanotubos de carbono de parede simples por sublimação de grafite em atmosfera de hélio

Macroscopic samples of fullerene nanostructures are obtained in a modified arc furnace using the electric arc method with a Helium atmosphere at low pressures. High purity graphite rods are used as electrodes but, when drilled and the orifices filled with powders of transition metals (Fe, Co, Ni) acting as catalysts, the resulting particles are carbon nanostructures of the fullerene family, known as Single Wall Nanotubes (SWNTs). They have typical diameters of 1.4 nm, lengths up to tenths of microns and they are arranged together in bundles containing several SWNTs. Those samples are observed and analyzed using Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) techniques.

Novos materiais à base de nanofibras de carbono como suporte de catalisador na decomposição da hidrazina

Today satellites propulsion is based on the use of monopropellant and/or bipropellant chemical systems. The maneuvering of satellite is based on the hydrazine decomposition micropropulsors catalyzed by metallic iridium supported on g-alumina. This reaction is a surface reaction and is strongly exothermic and implies that the operation of the micropropulsor is controlled by the mass and heat diffusions. For this reason and for the fact that the propulsor operation is frequently in pulsed regime, the catalyst should support high pressure and temperature variations within a short time period. The performance and the durability of the commercial catalyst are jeopardized by the low thermal conductivity of the alumina. The low thermal conductivity of the alumina support restricts the heat diffusion and leads to the formation of hot spots on the catalyst surface causing the metal sintering and/or fractures of the support, resulting in loss of the activity and catalyst destruction. This work presents the synthesis and characterization of new carbon composite support for the active element iridium, in substitution of the commercial catalysts alumina based support. These supports are constituted of carbon nanofibers (30 to 40 nm diameter) supported on a macroscopic carbon felt. These materials present high thermal conductivity and mechanical resistance, as well as the easiness to be shaped with different macroscopic shapes. The mechanical stability and the performance of the iridium supported on the carbon composite support, evaluated in a laboratory scale test in hydrazine decomposition reaction, are superior compared to the commercial catalyst.

Por que todos os nitratos são solúveis?

The solubility rules presented in the majority of introductory texts of chemistry usually do not comprise a systematic analysis of the dissolution processes, neither from a microscopic nor from a macroscopic point of view. The solubility of nitrates in aqueous solution is discussed in this article, focusing on the thermodynamic data and the properties of the nitrate ion.

Decomposição catalítica da hidrazina sobre irídio suportado em compósitos à base de nanofibras de carbono para propulsão espacial: testes em condições reais

The aim of this work is to present the catalytic performance of iridium supported on carbon nanofibers with macroscopic shaping in a 2 N hydrazine microthruster placed inside a vacuum chamber in order to reproduce real-life conditions. The performances obtained are compared to those of the commercial catalyst Shell 405. The carbon-nanofiber based catalyst showed better performance than the commercial catalyst from the standpoint of activity due to its texture and its thermal conductivity.

Anatomia macroscòpica i microscòpica de l'aparell genital femení d'Ophidion barbatum (L.) (Pisces, Ophididae)

S'ha realitzat un estudi de l'anatomia macroscòpica i microscòpica de I'ovari d'Ophidion barbatum (L.) (Pisces, Ophidiidae), utilitzant material recollit per pescadors del port de Blanes (mar català) durant el mes d'octubre de 1985. L'absència d'òrgan copulador en els mascles d'aquesta espècie i la posició de l'orifici nasal anterior, a una certa alçada respecte al llavi superior, ens permet identificar-la com una espècie ovípara, del subordre Ophidioidei, dins de l'ordre Ophidiiformes. L'ovari és únic i continuat caudalment per l'oviducte. Els nombrosos cordons intraovarics que tapien la cavitat augmenten considerablement la superfície germinal. El desenvolupament de l'ovari es correspon amb el tipus asincrònic (Marza, 1938) i la fresa repetida al llarg d'una estació reproductiva més o menys llarga és una estrategia que augmenta la fecunditat, normalment limitada pel volum corporal de la femella. Dins de l'ordre Ophidiiformes, el tipus d'ovari únic sense restes de paret mitjana sembla ser la norma entre les espècies de reproducció ovípara. Aquest fet esta en contradicció amb la teoria de Mendoza (1943) que, fora d'algunes excepcions, l'ovari únic es troba principalment en els teleostis vivípars

A Practical Micro Mechanical Model Based Local Approach Methodology for the Analysis of Ductile Fracture of Welded T-Joints

This thesis concentrates on developing a practical local approach methodology based on micro mechanical models for the analysis of ductile fracture of welded joints. Two major problems involved in the local approach, namely the dilational constitutive relation reflecting the softening behaviour of material, and the failure criterion associated with the constitutive equation, have been studied in detail. Firstly, considerable efforts were made on the numerical integration and computer implementation for the non trivial dilational Gurson Tvergaard model. Considering the weaknesses of the widely used Euler forward integration algorithms, a family of generalized mid point algorithms is proposed for the Gurson Tvergaard model. Correspondingly, based on the decomposition of stresses into hydrostatic and deviatoric parts, an explicit seven parameter expression for the consistent tangent moduli of the algorithms is presented. This explicit formula avoids any matrix inversion during numerical iteration and thus greatly facilitates the computer implementation of the algorithms and increase the efficiency of the code. The accuracy of the proposed algorithms and other conventional algorithms has been assessed in a systematic manner in order to highlight the best algorithm for this study. The accurate and efficient performance of present finite element implementation of the proposed algorithms has been demonstrated by various numerical examples. It has been found that the true mid point algorithm (a = 0.5) is the most accurate one when the deviatoric strain increment is radial to the yield surface and it is very important to use the consistent tangent moduli in the Newton iteration procedure. Secondly, an assessment of the consistency of current local failure criteria for ductile fracture, the critical void growth criterion, the constant critical void volume fraction criterion and Thomason's plastic limit load failure criterion, has been made. Significant differences in the predictions of ductility by the three criteria were found. By assuming the void grows spherically and using the void volume fraction from the Gurson Tvergaard model to calculate the current void matrix geometry, Thomason's failure criterion has been modified and a new failure criterion for the Gurson Tvergaard model is presented. Comparison with Koplik and Needleman's finite element results shows that the new failure criterion is fairly accurate indeed. A novel feature of the new failure criterion is that a mechanism for void coalescence is incorporated into the constitutive model. Hence the material failure is a natural result of the development of macroscopic plastic flow and the microscopic internal necking mechanism. By the new failure criterion, the critical void volume fraction is not a material constant and the initial void volume fraction and/or void nucleation parameters essentially control the material failure. This feature is very desirable and makes the numerical calibration of void nucleation parameters(s) possible and physically sound. Thirdly, a local approach methodology based on the above two major contributions has been built up in ABAQUS via the user material subroutine UMAT and applied to welded T joints. By using the void nucleation parameters calibrated from simple smooth and notched specimens, it was found that the fracture behaviour of the welded T joints can be well predicted using present methodology. This application has shown how the damage parameters of both base material and heat affected zone (HAZ) material can be obtained in a step by step manner and how useful and capable the local approach methodology is in the analysis of fracture behaviour and crack development as well as structural integrity assessment of practical problems where non homogeneous materials are involved. Finally, a procedure for the possible engineering application of the present methodology is suggested and discussed.

Caracterización de las amterias primas líticas del yacimiento paleolítico de la Dolina de l'Esquerda de ls Alzines (macizo del Garraf, Barcelona)

[spa] El presente estudio se centra en la caracterización macroscópica y microscópica de las materias primas silíceas del yacimiento de la Dolina de l'Esquerda de les Alzines, un yacimiento del Pleistoceno superior ubicado en el macizo del Garraf. El objetivo ha sido establecer distintas variedades de sílex, mediante la descripción macroscópica y microscópica de los elementos del conjunto lítico, para disponer, por vez primera, de unas categorías definidas de los recursos abióticos silíceos disponibles y explotados durante la prehistoria en este macizo. Además, mediante el presente estudio se ha evaluado también la posible procedencia y el área captación de dichas materias. [eng]The present study focuses on the macroscopic and microscopic characterization of siliceous raw materials from the archeological site of Dolina de l'Esquerda de les Alzines, an Upper Pleistocene deposit located in the Garraf Massif. The aim of this study has been to establish different varieties of chert, by a precise description of the elements of the lithic assemblage, to provide for the first time a few categories defined from the siliceous abiotic resources available and exploited during Prehistory in the massif. Furthermore, through the present study we also assessed the possible origin and procurement area of such materials.

Cristais líquidos colestéricos: a quiralidade revela as suas cores

Chirality deeply impacts the macroscopic properties on all scales of the universe from elemental particles through biological structures up to astronomic systems. Specifically, chiral liquid crystals give rise to self-organized macrostructures with unparalleled properties. Here we present easy experiments with a special class of chiral liquid crystals that show temperature-induced selective reflection of light (thermochromic effect). Understanding this thermochromic effect allows undergraduate students better realize important properties of super and supramolecular systems.

An experimental and theoretical study of multiphase flow in a circulating fluidized bed

A systematic averaging procedure has been derived in order to obtain an integral form of conservation equations for dispersed multiphase flow, especially applicable to fluidized beds. A similar averaging method is applied further to formulate macroscopic integral equations, which can be used in one-dimensional and macroscopic multi dimensional models. Circulating fluid bed hydrodynamics has been studied experimentally and both macroscopic and microscopic flow profiles have been measured in a cold model. As an application of the theory, the one dimensional model has been used to study mass and momentum conservation of gas and solid in a circulating fluid bed. Axial solid mixing has also been modelled by the one dimensional model and mixing parameters have been evaluated.

A quantidade de matéria nas ciências clássicas

The chemical amount values vary in a discrete or continuous form, depending on the approach used to describe the system. In classical sciences, the chemical amount is a property of the macroscopic system and, like any other property of the system, it varies continuously. This is neither inconsistent with the concept of indivisible particles forming the system, nor a mere approximation, but it is a sound concept which enables the use of differential calculus, for instance, in chemical thermodynamics. It is shown that the fundamental laws of chemistry are absolutely compatible to the continuous concept of the chemical amount.

O efeito de Coriolis: de pêndulos a moléculas

Coriolis force is an effect which arises in rotating reference frames such as the Earth. This force influences large oceanic motions, atmospheric inertial circles, horizontal and vertical deviations in moving bodies. The Foucault's pendulum is another special case about the Coriolis force influence on macroscopic processes. This pendulum is an example of how experimental sciences can be essential for philosophical and social changes, since it was crucial to prove the Earth's rotation. The Coriolis force has an important role also at microscopic level; it couples vibrational and rotational molecular motions and this fact has consequences in spectroscopic and energetic molecular processes. These points are discussed in this paper.