Avaliação do uso de poli(tereftalato de etileno) (PET) como matriz de imobilização de cinzas de incineradores

Industrial hazardous wastes must receive appropriate treatment to ensure a safe disposal to humans and environment. One of the techniques adopted for this purpose is the stabilization/solidification in polymer matrices. This paper evaluated the use of recycled polyethylene terephthalate as an incorporation matrix of incinerator ash. The polymer and the ash were submitted to an extrusion process in different percentages. The final product was evaluated through thermal and leaching tests and the leachate extracts constituents were determinated by atomic absorption spectrophotometry. The results showed a reduction in the release of substances up to 99% by mass for the conditions used.

Membrane emulsification in preparation of single site catalyst

In the theory part the membrane emulsification was studied. Emulsions are used in many industrial areas. Traditionally emulsions are prepared by using high shear in rotor-stator systems or in high pressure homogenizer systems. In membrane emulsification two immiscible liquids are mixed by pressuring one liquid through the membrane into the other liquid. With this technique energy could be saved, more homogeneous droplets could be formed and the amount of surfactant could be decreased. Ziegler-Natta and single-site catalysts are used in olefin polymerization processes. Nowadays, these catalysts are prepared according to traditional mixing emulsification. More homogeneous catalyst particles that have narrower particle size distribution might be prepared with membrane emulsification. The aim of the experimental part was to examine the possibility to prepare single site polypropylene catalyst using membrane emulsification technique. Different membrane materials and solidification techniques of the emulsion were examined. Also the toluene-PFC phase diagram was successfully measured during this thesis work. This phase diagram was used for process optimization. The polytetrafluoroethylene membranes had the largest contact angles with toluene and also the biggest difference between the contact angles measured with PFC and toluene. Despite of the contact angle measurement results no significant difference was noticed between particles prepared using PTFE membrane or metal sinter. The particle size distributions of catalyst prepared in these tests were quite wide. This would probably be fixed by using a membrane with a more homogeneous pore size distribution. It is also possible that the solidification rate has an effect on the particle sizes and particle morphology. When polymeric membranes are compared PTFE is probably still the best material for the process as it had the best chemical durability.

Feasibility studies of the weldability of structural steels used in the offshore environment

The rising demand for oil and gas has made it very necessary for the oil and gas industries to explore the offshore. There is a huge resources which is available in the offshore. The search for oil and gas is faced with greater challenges because of the nature of the marine environment as it poses difficult and harsh conditions for the construction of offshore structures. The major problem of the construction of offshore structure is the ability to produce a sound weld that gives the whole structure the structural integrity needed to withstand the harsh environmental conditions. This research work presents the performance of typical offshore steels with improved weldability. The ability of reducing the carbon content of thermo-mechanically rolled steels down to 0.08% makes it possible to achieve good weldability, toughness and strength for high strength steels used in offshore applications. Importantly, the ideal welding procedure should be strictly followed as recommended. The fabrication process is as important as the welding procedure in achieving a sound weld which is free of weld defects such as hydrogen induced cracking, lamellar tearing and solidification cracking. This research work also considers the corrosion as it affects offshore structure and necessary measures to mitigate the problem caused by corrosion.

Sinkin stabiloiminen pilaantuneesta maa-aineksesta: 28 vuorokauden stabilointiajan riittävyys liukoisuustesteissä eri sinkkiyhdisteillä

Tässä kandidaatintyössä selvitettiin, onko 28 vuorokautta riittävä aika sinkillä pilaantuneen maaperän massastabilointiin, ja kuinka sinkin esiintymismuoto vaikuttaa sen stabilointiaikaan. Kokeellisessa osassa jäljiteltiin malmijätteessä, orgaanisessa aineksessa sekä liuenneena maaperässä esiintyvän sinkin stabiloitumista lisäämällä maanäytteeseen sinkkiä eri yhdisteinä; sinkkirakeina, -kloridina ja -asetaattina. Näytteet stabiloitiin sementti-lentotuhkaseoksella 1–28 vuorokauden pituisia ajanjaksoja, minkä jälkeen ne kuvattiin pyyhkäisyelektronimikroskoopilla (SEM) ja niille tehtiin liukoisuustestit. Liukoisuustestien tuloksista voidaan huomata sinkkikloridin stabiloituvan jo ensimmäisen vuorokauden aikana ja pysyvän samalla tasolla koko tarkasteluajan. Sinkkirakeiden ja -asetaatin stabiloituminen ei ole yhtä tasaista; alun sitoutumisen jälkeen niiden liukoisuuksissa on havaittavissa selkeät piikit 21 vuorokauden kohdalla. Tämän jälkeen ne alkavat sitoutua uudelleen. Tulosten perusteella sinkin esiintymismuoto vaikuttaa sen stabilointiaikaan, eikä 28:aa vuorokautta voida pitää riittävänä aikana sinkillä pilaantuneen maa-aineksen stabilointiin. Vaikka liukoinen sinkki stabiloituu jo yhdessä vuorokaudessa, ei malmijätteessä tai orgaanisessa aineksessa esiintyvä sinkki ehdi stabiloitua vakaalle tasolle vielä 28 vuorokaudenkaan aikana. Tämä tulisi ottaa huomioon suunniteltaessa ja toteutettaessa sinkkiä sisältävien maiden kunnostushankkeita.

Chocolate rheology

Rheology is the science that studies the deformation and flow of solids and fluids under the influence of mechanical forces. The rheological measures of a product in the stage of manufacture can be useful in quality control. The microstructure of a product can also be correlated with its rheological behavior allowing for the development of new materials. Rheometry permits attainment of rheological equations applied in process engineering, particularly unit operations that involve heat and mass transfer. Consumer demands make it possible to obtain a product that complies with these requirements. Chocolate industries work with products in a liquid phase in conching, tempering, and also during pumping operations. A good design of each type of equipment is essential for optimum processing. In the design of every process, it is necessary to know the physical characteristics of the product. The rheological behavior of chocolate can help to know the characteristics of application of the product and its consumers. Foods are generally in a metastable state. Their texture depends on the structural changes that occur during processing. Molten chocolate is a suspension with properties that are strongly affected by particle characteristics including not only the dispersed particles but also the fat crystals formed during chocolate cooling and solidification. Chocolate rheology is extensively studied, and it is known that chocolate texture and stability is strongly affected by the presence of specific crystals

Influvence of Alloying Additions on the Structure and Properties of Ai-7Si-0.3Mg Alloy

Cast Ai-Si alloys are widely used in the automotive, aerospace and general engineering industries due to their excellent combination of properties such as good castability, low coefficient of thermal expansion, high strength-to-weight ratio and good corrosion resistance. The present investigation is on the influence of alloying additions on the structure and properties of Ai-7Si-0.3Mg alloy. The primary objective of this present investigation is to study these beneficial effects of calcium on the structure and properties of Ai-7Si-0.3Mg-xFe alloys. The second objective of this work is to study the effects of Mn,Be and Sr addition as Fe neutralizers and also to study the interaction of Mn,Be,Sr and Ca in Ai-7Si-0.3Mg-xFe alloys. In this study the duel beneficial effects of Ca viz;modification and Fe-neutralization, comparison of the effects of Ca and Sr with common Fe neutralizers. The casting have been characterized with respect to their microstructure, %porosity and electrical conductivity, solidification behaviour and mechanical properties. One of the interesting observations in the present work is that a low level of calcium reduces the porosity compared to the untreated alloy. However higher level of calcium addition lead to higher porosity in the casting. An empirical analysis carried out for comparing the results of the present work with those of the other researchers on the effect of increasing iron content on UTS and % elongation of Ai-Si-Mg and Ai-Si-Cu alloys has shown a linear and an inverse first order polynomial relationships respectively.

Grain refinement studies on Mg and Mg-Al based alloys

Demand on magnesium and its alloys is increased significantly in the automotive industry because of their great potential in reducing the weight of components, thus resulting in improvement in fuel efficiency of the vehicle. To date, most of Mg products have been fabricated by casting, especially, by die-casting because of its high productivity, suitable strength, acceptable quality & dimensional accuracy and the components produced through sand, gravity and low pressure die casting are small extent. In fact, higher solidification rate is possible only in high pressure die casting, which results in finer grain size. However, achieving high cooling rate in gravity casting using sand and permanent moulds is a difficult task, which ends with a coarser grain nature and exhibit poor mechanical properties, which is an important aspect of the performance in industrial applications. Grain refinement is technologically attractive because it generally does not adversely affect ductility and toughness, contrary to most other strengthening methods. Therefore formation of fine grain structure in these castings is crucial, in order to improve the mechanical properties of these cast components. Therefore, the present investigation is “GRAIN REFINEMENT STUDIES ON Mg AND Mg-Al BASED ALLOYS”. The primary objective of this present investigation is to study the effect of various grain refining inoculants (Al-4B, Al- 5TiB2 master alloys, Al4C3, Charcoal particles) on Pure Mg and Mg-Al alloys such as AZ31, AZ91 and study their grain refining mechanisms. The second objective of this work is to study the effect of superheating process on the grain size of AZ31, AZ91 Mg alloys with and without inoculants addition. In addition, to study the effect of grain refinement on the mechanical properties of Mg and Mg-Al alloys. The thesis is well organized with seven chapters and the details of the studies are given below in detail.

Micro-layered-photolithography for Micro-Fabrication and Micro-Molding

A novel process based on the principle of layered photolithography has been proposed and tested for making real three-dimensional micro-structures. An experimental setup was designed and built for doing experiments on this micro-fabrication process. An ultraviolet (UV) excimer laser at the wavelength of 248 nm was used as the light source and a single piece of photo-mask carrying a series of two dimensional (2D) patterns sliced from a three dimensional (3D) micro-part was employed for the photolithography process. The experiments were conducted on the solidification of liquid photopolymer from single layer to multiple layers. The single-layer photolithography experiments showed that certain photopolymers could be applied for the 3D micro-fabrication, and solid layers with sharp shapes could be formed from the liquid polymer identified. By using a unique alignment technique, multiple layers of photolithography was successfully realized for a micro-gear with features at 60 microns. Electroforming was also conducted for converting the photopolymer master to a metal cavity of the micro-gear, which proved that the process is feasible for micro-molding.

Efectos de la jurisprudencia de la Corte Interamericana de Derechos Humanos en los países miembros de la OEA

Uno de los eventos jurídicos más importantes del siglo XX, sin duda, ha sido la consolidación del derecho internacional de los derechos humanos. Instrumentos internacionales y mecanismos de protección se han puesto en funcionamiento y afianzado, tanto a nivel global como regional. No obstante, en muchos casos, este desarrollo de principios, normas y órganos de protección a nivel internacional no se ha reflejado en iguales progresos en ámbito nacional. Lo cual permite todavía afirmar que si bien la universalización de los derechos ha sido una etapa sustancial para la consolidación de la protección de los derechos humanos el desafío sigue siendo el hacerlos efectivos. El artículo lleva a cabo un examen de la jurisprudencia de los países de la región que permite llegar a la consideración que se están produciendo importantes avances en este terreno y cada vez más los altos tribunales de varios países de la región utilizan como parámetro de interpretación la jurisprudencia de la Corte Interamericana para resolver cuestiones internas y concluir que en Latinoamérica, gracias a la influencia integradora de la Convención Americana y de la jurisprudencia de la Corte Interamericana con la jurisprudencia nacional, se está lentamente consolidado lo que podría ser definido como un estándar mínimo común en materia de protección de los derechos humanos. Un núcleo fundamental o esencial de derechos que poco a poco se va imponiendo en los países miembros dando origen a un nuevo ius commune para Latinoamérica.

Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles representative of atmospheric cooking aerosols. We apply and extend the recently developed KM-SUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant time scales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semisolid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols.

Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles approximating atmospheric cooking aerosols. We apply and extend the recently developed KMSUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant timescales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semi-solid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols.

Electrospun supramolecular polymer fibres

The electrospinning of urethane based low molecular weight polymers differing only in the nature of the hydrogen bonding end-groups has been investigated. For the end-groups with the lowest binding constants at maximum solubility only droplets, are produced at the electrode; in contrast, increasing the binding constant of the end-group results in electrospun fibres being produced. The properties of the fibres produced are subject to changes in solvent, concentration and temperature. Typical diameters for these fibres were found to be some 10 s of μm, rather than the sub-micron dimensions often produced in electrospinning systems. Such diameters are related to the high initial concentrations required; this also may influence the rate of solvent removal and preferential surface solidification which feature in these examples. A simple theoretical model is used to relate the association constant to the molecular weight required for fibre formation; significantly lower levels of association are required for higher molecular weight macromonomers compared to smaller molecular systems.

Flow-induced morphological instability of a mushy layer

A morphological instability of a mushy layer due to a forced flow in the melt is analysed. The instability is caused by flow induced in the mushy layer by Bernoulli suction at the crests of a sinusoidally perturbed mush–melt interface. The flow in the mushy layer advects heat away from crests which promotes solidification. Two linear stability analyses are presented: the fundamental mechanism for instability is elucidated by considering the case of uniform flow of an inviscid melt; a more complete analysis is then presented for the case of a parallel shear flow of a viscous melt. The novel instability mechanism we analyse here is contrasted with that investigated by Gilpin et al. (1980) and is found to be more potent for the case of newly forming sea ice.

Frazil dynamics and precipitation in a water column with depth-dependent supercooling

A morphological instability of a mushy layer due to a forced flow in the melt is analysed. The instability is caused by flow induced in the mushy layer by Bernoulli suction at the crests of a sinusoidally perturbed mush–melt interface. The flow in the mushy layer advects heat away from crests which promotes solidification. Two linear stability analyses are presented: the fundamental mechanism for instability is elucidated by considering the case of uniform flow of an inviscid melt; a more complete analysis is then presented for the case of a parallel shear flow of a viscous melt. The novel instability mechanism we analyse here is contrasted with that investigated by Gilpin et al. (1980) and is found to be more potent for the case of newly forming sea ice.

Conflicting structural and geochronological data from the Ibituruna quartz-syenite (SE Brazil): Effect of protracted ""hot"" orogeny and slow cooling rate?

The Ibituruna quartz-syenite was emplaced as a sill in the Ribeira-Aracuai Neoproterozoic belt (Southeastern Brazil) during the last stages of the Gondwana supercontinent amalgamation. We have measured the Anisotropy of Magnetic Susceptibility (AMS) in samples from the Ibituruna sill to unravel its magnetic fabric that is regarded as a proxy for its magmatic fabric. A large magnetic anisotropy, dominantly due to magnetite, and a consistent magnetic fabric have been determined over the entire Ibituruna massif. The magmatic foliation and lineation are strikingly parallel to the solid-state mylonitic foliation and lineation measured in the country-rock. Altogether, these observations suggest that the Ibituruna sill was emplaced during the high temperature (similar to 750 degrees C) regional deformation and was deformed before full solidification coherently with its country-rock. Unexpectedly, geochronological data suggest a rather different conclusion. LA-ICP-MS and SHRIMP ages of zircons from the Ibituruna quartz-syenite are in the range 530-535 Ma and LA-ICP-MS ages of zircons and monazites from synkinematic leucocratic veins in the country-rocks suggest a crystallization at similar to 570-580 Ma, i.e., an HT deformation >35My older than the emplacement of the Ibituruna quartz-syenite. Conclusions from the structural and the geochronological studies are therefore conflicting. A possible explanation arises from (40)Ar-(39)Ar thermochronology. We have dated amphiboles from the quartz-syenite, and amphiboles and biotites from the country-rock. Together with the ages of monazites and zircons in the country-rock, (40)Ar-(39)Ar mineral ages suggest a very low cooling rate: <3 degrees C/My between 570 and similar to 500 Ma and similar to 5 degrees C/My between 500 and 460 Ma. Assuming a protracted regional deformation consistent over tens of My, under such stable thermal conditions the fabric and microstructure of deformed rocks may remain almost unchanged even if they underwent and recorded strain pulses separated by long periods of time. This may be a characteristic of slow cooling ""hot orogens"" that rocks deformed at significantly different periods during the orogeny, but under roughly unchanged temperature conditions, may display almost indiscernible microstructure and fabric. (C) 2009 Elsevier B.V. All rights reserved.