Aplicação catalítica de peneiras moleculares básicas micro e mesoporosas

Catalysis by solid acids has received much attention due to its importance in petroleum refining and petrochemical processes. Relatively few studies have focused on catalysis by bases and even les on using basic molecular sieves. This paper deals with the potential application of micro and mesoporous molecular sieves in base catalysis reactions. The paper is divided in two parts, the first one dedicated to the design of the catalysts and the second to some relevant examples of catalytic reactions, which find a huge field of applications essentially in the synthesis of fine chemicals. Here, recent developments in catalysis by basic molecular sieves and the perspectives of applications in correlated catalytic processes are described.

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.

Private micro-irrigation costs using reclaimed water

The cost of reusing water in micro-irrigation at the field level has not been studied in depth although the use of effluents in agriculture is a viable alternative in areas where water is scarce or there is intense competition for its use. The aim of the present study is to analyse the private costs of water reuse in micro-irrigation in an experimental plot. This analysis is intended to provide information about the decision a farmer would make when the choice to use conventional or reclaimed water is guided by cost criteria. The components of the total costs of different combinations of four types of filters and five emitters that can be installed in micro-irrigation systems using reclaimed water have been studied with the data obtained from an experimental plot in conditions similar to those of fruit orchards. Different scenarios that compared the costs of using conventional or reclaimed water in terms of water price and nutrient content were also studied. The results show that a proper combination of filters and emitters can save up to 33% in irrigation costs. Capital costs and maintenance costs were the most variable among the different combinations. Scenario analysis showed that the greater price of reclaimed water could be compensated by high nutrient contents, which would reduce fertilizer costs

Aspectos físico-químicos e biológicos relacionados à ocorrência de Biomphalaria glabrata em focos litorâneos da esquistossomose em Pernambuco

This study analyzes the physico-chemical and biological parameters of freshwater aquatic environments in coastal areas of the State of Pernambuco, Brazil, where snail vector foci and cases of schistosomiasis have been recorded. The tests were carried out using standard methods and sediments were analyzed using the X-ray fluorescence technique. The micro-algae were analyzed using conventional microscopy. The most abundant chemical elements in the sediments were Fe, Ca, Si and Al and there were high concentrations of electrolytes in comparison with data published in the literature. The mean values for salinity (7.7 g/L) and sulfate (489 mg/L) were much higher than normal for freshwater environments. The micro-algae identified are those that inhabit environments with higher levels of salinity. The snail Biomphalaria glabrata seems, therefore, to be more tolerant to salty environments and this constitutes a risk of spread of schistosomiasis.

Cohesive Elements for Shells

A cohesive element for shell analysis is presented. The element can be used to simulate the initiation and growth of delaminations between stacked, non-coincident layers of shell elements. The procedure to construct the element accounts for the thickness offset by applying the kinematic relations of shell deformation to transform the stiffness and internal force of a zero-thickness cohesive element such that interfacial continuity between the layers is enforced. The procedure is demonstrated by simulating the response and failure of the Mixed Mode Bending test and a skin-stiffener debond specimen. In addition, it is shown that stacks of shell elements can be used to create effective models to predict the inplane and delamination failure modes of thick components. The results indicate that simple shell models can retain many of the necessary predictive attributes of much more complex 3D models while providing the computational efficiency that is necessary for design

Determination of chemical elements in africanized Apis mellifera (Hymenoptera: Apidae) honey samples from the State of Piauí, Brazil

Honey is a food used since the most remote times, appreciated for its characteristic flavor, considerable nutritional value and medicinal properties; however, little information exists about the presence of chemical elements in it. The objectives of this work were to determine the chemical elements present in 38 honey samples, collected directly from beekeepers from the State of Piauí, Brazil and to verify whether they presented any contamination. The chemical elements were determined by means of Total Reflection X-ray Fluorescence. The means of three replicates were: K (109.671 ± 17.487), Ca (14.471 ± 3.8797), Ti (0.112 ± 0.07), Cr (0.196 ± 0.11), Mn (0.493 ± 0.103), Fe (1.722 ± 0.446), Co (0.038), Ni (0.728 ± 0.706), Cu (0.179 ± 0.0471), Zn (0.967 ± 0.653), Se (not detected), Br (not detected), Rb (0.371 ± 0.097), Sr (0.145 ± 0.45), Ba (11.681), Hg (not detected), and Pb (0.863) µg g-1.

Determinação do coeficiente de atividade na diluição infinita (g¥) através da micro-extração em fase sólida (SPME)

In this study a new approach, solid phase micro extraction (SPME), is used in the evaluation of the infinite dilution activity coefficient of the solute in a given solvent. It is the purpose of the current work to demonstrate a different approach to obtain the data needed for studying the solution thermodynamics of binary liquid mixtures as well as for designing multi-component separations. The solutes investigated at the temperature 298.15 K were toluene, ethyl benzene and xylene in the solvent methanol.

Laserhitsausparametrien vaikutus ruostumattomien terästen hitsin mikrorakenteeseen

Työn teoriaosassa käsitellään ruostumattomia teräksiä ja terästen metallurgiaan vaikuttavia tekijöitä yleisesti, sekä terästen hitsattavuutta. Hitsauksesta teoriassa käydään läpi laser- ja kaasukaarihitsausta ja hitsin metallurgiaan vaikuttavia tekijöitä. Kokeellisessa osassa paneudutaan kahdeksan eri ruostumattoman teräksen hitsien metallurgiaan ja metallurgiassa tapahtuviin muutoksiin hitsausparametrien mukaan. Koemateriaaleina on neljä austeniittista ruostumatonta terästä, 201, 301LN, 316L ja 254 SMO, kaksi austeniittis-ferriittistä ruostumatonta terästä, 2101 LDX ja 2205, sekä kaksi ferriittistä ruostumatonta terästä, 430 ja 1.4003. Hitsien mikrorakenteen tutkimisessa käytettiin sekä valomikroskooppia sekä joissain tapauksissa pyyhkäisyelektronimikroskooppia. Lisäksi työn kokeellisessa osassa paneuduttiin hitsien metallografisiin syövytystekniikoihin. Kokeiden perusteella voidaan sanoa, että hitsin metallurgia riippuu hitsauksen aikaisesta lämpösyklistä ja hitsausparametreilla voidaan vaikuttaa tämän lämpösyklin muotoon. Austeniittis-ferriittisillä teräksillä hitsauksen aikaisesta lämpösyklistä riippuu pitkälti hitsin austeniitti-ferriitti-suhde. Ferriittisillä teräksillä lämpösyklin muoto vaikuttaa hitsiin muodostuvan martensiitin kovuuteen ja määrään sekä rakenteen hienojakoisuuteen. Austeniittisilla teräksillä lämpösyklinmuodon vaikutus riippuu pitkälti teräksen seostusasteesta ja seosaineista. Austeniittisilla teräksillä kokeissa havaittuja muutoksia, parametrien muutosten mukaan oli muun muassa suotautumisen voimakkuuden

Games in Education and Process Development

The aim of the thesis is to devise a framework for analyzing simulation games, in particular introductory supply chain simulation games which are used in education and process development. The framework is then applied to three case examples which are introductory supply chain simulation games used at Lappeenranta University of Technology. The theoretical part of the thesis studies simulation games in the context of education and training as well as of process management. Simulation games can be seen as learning processes which comprise of briefing, micro cycle, and debriefing which includes observation and reflection as well as conceptualization. The micro cycle, i.e. the game itself, is defined through elements and characteristics. Both briefing and debriefing ought to support the micro cycle. The whole learning process needs to support learning objectives of the simulation game. Based on the analysis of the case simulation games, suggestions on how to boost the debriefing and promote long term effects of the games are made. In addition, a framework is suggested to be used in designing simulation games and characteristics of introductory supply chain simulation games are defined. They are designed for general purposes, are simple and operated manually, are multifunctional interplays, and last about 2.5 4 hours. Participants co operate during a game run and competition arises between different runs or game sessions.

Development of beam and plate finite elements based on the absolute nodal coordinate formulation

The focus of this dissertation is to develop finite elements based on the absolute nodal coordinate formulation. The absolute nodal coordinate formulation is a nonlinear finite element formulation, which is introduced for special requirements in the field of flexible multibody dynamics. In this formulation, a special definition for the rotation of elements is employed to ensure the formulation will not suffer from singularities due to large rotations. The absolute nodal coordinate formulation can be used for analyzing the dynamics of beam, plate and shell type structures. The improvements of the formulation are mainly concentrated towards the description of transverse shear deformation. Additionally, the formulation is verified by using conventional iso-parametric solid finite element and geometrically exact beam theory. Previous claims about especially high eigenfrequencies are studied by introducing beam elements based on the absolute nodal coordinate formulation in the framework of the large rotation vector approach. Additionally, the same high eigenfrequency problem is studied by using constraints for transverse deformation. It was determined that the improvements for shear deformation in the transverse direction lead to clear improvements in computational efficiency. This was especially true when comparative stress must be defined, for example when using elasto-plastic material. Furthermore, the developed plate element can be used to avoid certain numerical problems, such as shear and curvature lockings. In addition, it was shown that when compared to conventional solid elements, or elements based on nonlinear beam theory, elements based on the absolute nodal coordinate formulation do not lead to an especially stiff system for the equations of motion.

Bioprocessos para remoção de dióxido de carbono e óxido de nitrogênio por micro-algas visando a utilização de gases gerados durante a combustão do carvão

The aim of this work was to study the removal of CO2 and NO by microalgae and to evaluate the kinetic characteristics of the cultures. Spirulina sp. showed µmax and Xmax (0.11 d-1, 1.11 g L-1 d-1) when treated with CO2 and NaNO3. The maximum CO2 removal was 22.97% for S. obliquus treated with KNO3 and atmospheric CO2. The S. obliquus showed maximum NO removal (21.30%) when treated with NO and CO2. Coupling the cultivation of these microalgae with the removal of CO2 and NO has the potential not only to reduce the costs of culture media but also to offset carbon and nitrogen emissions.

Micro- and nanostructuring of poly(ethylene-2,6-naphthalate) surfaces, for biomedical applications, using polymer replication techniques

Here we investigate the formation of superficial micro- and nanostructures in poly(ethylene-2,6-naphthalate) (PEN), with a view to their use in biomedical device applications, and compare its performance with a polymer commonly used for the fabrication of these devices, poly(methyl methacrylate) (PMMA). The PEN is found to replicate both micro- and nanostructures in its surface, albeit requiring more forceful replication conditions than PMMA, producing a slight increase in surface hydrophilicity. This ability to form micro/nanostructures, allied to biocompatibility and good optical transparency, suggests that PEN could be a useful material for production of, or for incorporation into, transparent devices for biomedical applications. Such devices will be able to be autoclaved, due to the polymer's high temperature stability, and will be useful for applications where forceful experimental conditions are required, due to a superior chemical resistance over PMMA.

Determinação de metil-etil-cetona em amostras de urina com amostragem por micro extração em fase sólida (MEFS) em headspace associada à cromatografia gasosa com detector de ionização de chama (CG-DIC)

Methyl ethyl ketone (MEK) is a solvent commonly used in chemical, paint and shoe industry. The aim of this study was to develop and validate a method for urinary quantification of MEK, employing headspace solid phase micro extraction sampling (SPME) coupled to gas chromatography with flame ionization detection (GC-FID). The calibration curve (y=4.6851x-0.0011) presented good linearity with r²=0.9993. Accuracy (94-109%), intra-assay precision (4.07-5.91%) and inter-assay precision (3.03-5.62%) were acceptable. The quantification limit was 0.19 mg/L. This low cost method can be used routinely in the biological monitoring of occupational exposure to MEK, according to the requirements of the Brazilian legislation.

Estudo por espectroscopia micro-Raman dos mecanismos de separação de fase em vidros fosfatos de metais de transição

Glass-ceramics are prepared by controlled separation of crystal phases in glasses, leading to uniform and dense grain structures. On the other hand, chemical leaching of soluble crystal phases yields porous glass-ceramics with important applications. Here, glass/ceramic interfaces of niobo-, vanado- and titano-phosphate glasses were studied by micro-Raman spectroscopy, whose spatial resolution revealed the multiphase structures. Phase-separation mechanisms were also determined by this technique, revealing that interface composition remained unchanged as the crystallization front advanced for niobo- and vanadophosphate glasses (interface-controlled crystallization). For titanophosphate glasses, phase composition changed continuously with time up to the equilibrium composition, indicating a spinodal-type phase separation.

Determinação espectrofotométrica de hexametilenotetramina (HMT) em medicamentos, utilizando ácido cromotrópico e forno de micro-ondas

This paper proposes a methodology for spectrophotometric determination of hexamethylenetetramine (HMT) by using chromotropic acid in a phosphoric acid media employing a domestic microwave oven as a source of heating. The reddish-purple soluble product is quantitatively formed after 30 s of irradiation and obeys the Beer´s law in the range between 0.1-1.2 mg L-1 HMT (r = 0.99925). The method was applied successfully in commercial pharmaceutical preparations containing dyes in their composition. The results showed that the method proposed is feasible for simplicity, speed, low cost, precision and accuracy when compared with United States Pharmacopeia official method.