Hidróxidos duplos lamelares: síntese, estrutura, propriedades e aplicações

The layered double hydroxides, known as anionic clays and represented by the general formula [M2+1-x M3+x (OH) 2]x+ Am-x/m·nH 2O, are a group of materials which are of much interest currently. They present a variety of potential applications as adsorbents, catalysts and catalyst support, ion-exchangers, antacids and as a polymer stabilizer. It is possible to obtain a broad variety of layered double hydroxides (LDHs), depending on the identity and ratio of the cations M2+ and M3+, as well as the interlamelar anion. The aim of this review is to give out some information about this class of materials, concerning to the synthesis, characterization, properties and applications.

O relevante papel do agente sililante na modificação de superfícies de polímeros

The applicability of the silylant agents of the general formula Y3Si-R-X, depends on the reactivity of Y group (halide or alcoxide) attached to silicon and the organic function X (halide, amine, thiol, cyanide, etc) in the extreme position of the chain. Both groups are linked together by an organic chain R, containing usually three methylene groups. A series of these agents can be covalently bonded to an inorganic matrix, since the available OH groups are distributed on the surface, making silica gel the most common support. However, other inorganic oxides, zeolites, lamellar inorganic phosphates and chrysotile can also have these agents anchored. Some illustration are presented for immobilized surface in the use as extractors of cations from dilute aqueous or non-aqueous solutions, catalysts agents, ionic exchanged materials, support for enzyme immobilization, chromatographic applications, use in some industrial features and in many other areas. The evolution of this exciting research field to produce new materials, for many tecnological applications, is strongly dependent on the development of a sensible systematic process for the synthesis of a series of new specific silylant agents.

Statistical Inversion Theory in X-ray Tomography

In this thesis the X-ray tomography is discussed from the Bayesian statistical viewpoint. The unknown parameters are assumed random variables and as opposite to traditional methods the solution is obtained as a large sample of the distribution of all possible solutions. As an introduction to tomography an inversion formula for Radon transform is presented on a plane. The vastly used filtered backprojection algorithm is derived. The traditional regularization methods are presented sufficiently to ground the Bayesian approach. The measurements are foton counts at the detector pixels. Thus the assumption of a Poisson distributed measurement error is justified. Often the error is assumed Gaussian, altough the electronic noise caused by the measurement device can change the error structure. The assumption of Gaussian measurement error is discussed. In the thesis the use of different prior distributions in X-ray tomography is discussed. Especially in severely ill-posed problems the use of a suitable prior is the main part of the whole solution process. In the empirical part the presented prior distributions are tested using simulated measurements. The effect of different prior distributions produce are shown in the empirical part of the thesis. The use of prior is shown obligatory in case of severely ill-posed problem.

Determinacion de la configuracion E-Z de los acidos Fumarico y Maleico. Un experimento orientado a incentivar el desarrollo de la investigacion cientifica en alumnos de Pregrado

In this work we intend to eliminate the idea that laboratory exercises seem like cookbooks. That is, exercises shall be presented as a problematic situation. Based on observation and experimentation, the students should determine the E-Z configuration of maleic and fumaric acids. The basis of this laboratory exercise is the acid-catalyzed isomerization of maleic acid to fumaric acid. Students are given the starting material, reagents and the experimental procedure. They are told that the starting material is a dicarboxylic acid containing a C=C double bond of formula C4H4O4. Students determine melting points, solubilities, acidity and chromatographic patterns for both the starting material and the product, so that a configuration of each acid can be proposed. This type of experiment yields excellent results, because the students are left to deduce that maleic acid is less stable than fumaric acid. Additionally, they conclude that maleic acid is the "Z" isomer and fumaric acid is the "E" isomer. Finally, this laboratory exercise allows the students to develop simultaneously their critical-thinking skills with the respective laboratory techniques and not to see chemistry as recipes to be followed.

Una nova xarxa social: RFV (Reusencs de fora vila) : Aprofitar el potencial del segle XXI

A partir de l'anàlisi d'un fet local, proposo la creació d'una nova xarxa social que permeti connectar els reusencs que viuen i treballen fora de Reus, i que estan escampats pel món. De Reus al món s'oferirà informació d'allò que passa a la ciutat i del món a Reus es retornarà talent, idees i connexions. Analitzarem les xarxes socials, el seu origen, la web 2.0, quines són les xarxes socials amb més presència arreu del planeta. Situarem en context les relacions que la ciutat de Reus manté amb els seus fills il·lustres, i amb aquells que han decidit progressar lluny de la ciutat. Avaluarem quina és la millor fórmula per crear una nova xarxa social i amb quines eines s'haurà de construir. L'objectiu de tot plegat és una nova xarxa social: RFV.

O legado das bifenilas policloradas (PCBs)

Polychlorinated biphenyls (PCBs) are a class of 209 chemical compounds with the molecular formula C12H10-nCl n, where 1 <= n <= 10. They were commercially produced as complex mixtures for various uses, being employed principally as dielectric fluids in capacitors and transformers. They are not easily degraded due their chemical and physical stability and tend to bioaccumulate in the organisms. After the discovery of their xenobiotic activity, restrictions were imposed for their use, as well as for their discards. Nowadays the development of recovery processes for contaminated environment urges to be done due to the extension of reached areas.

Synthesis and characterization of manganese-glycine and copper-glycine adducts

This work reports the synthesis and characterization of adducts of general formula MCl2.ngly, where M= Mn and Cu; n= 2 and 4, and gly= glycine. The manganese adducts were synthesized by dissolution of both, manganese chloride and glycine in water, whereas the copper adducts were obtained by using an alternative solid state synthesis approach. For all adducts, the obtained infrared data shows that the coordination involves the amine nitrogen atom, as well as an oxygen atom of the COO- group. The TG curves for the synthesized adducts exhibit only one mass loss step associated with the release of glycine molecules.

Myynti ja takaisinvuokraussopimukset rahoituslähteenä ja sopimusten käsittely konsernin IFRS-tilinpäätöksessä

Myynti ja takaisinvuokraussopimukset ovat yleistyneet viime vuosina. Myynti ja takaisinvuokraussopimuksessa yritys myy omistamansa hyödykkeen, yleensä kiinteistön, rahoitusyhtiölle ja liisaa sen saman tien takaisin. Menettelyssä yritys säilyttää hyödykkeen käyttöoikeuden, mutta saa samalla vapautettua hyödykkeeseen sitoutuneen varallisuuden. Myynti ja takaisinvuokraussopimukset luokitellaan tavallisten leasingsopimusten tavoin IFRS-lainsäädännössä rahoitusleasingsopimuksiin ja muihin vuokrasopimuksiin. Lisäksi myynti ja takaisinvuokraussopimuksia koskien on annettu joitakin erityissäännöksiä. Työssä tarkastellaan Case-yrityksen X Oyj:n omistaman hyödykkeen uudelleenrahoitusta myynti ja takaisinvuokraussopimuksella. Tutkimuksessa selvitetään miten hyödykkeen uudelleenrahoitus vaikuttaisi konsernin IFRS-muotoiseen tilinpäätökseen. Työssä tutkitaan uudelleenrahoituksen rahoituksellisia motiiveja ja pyritään määrittämään leasingsopimuksen kilpailukykyä verrattuna velkarahoitukseen. Rahoitusteoriassa leasingsopimuksen arvo määritetään yleensä käytäen NAL-kaavaa eli niin kutsuttua Net Advantage of Leasing-kaavaa. Sitä sovelletaan myös tässä työssä. Leasingrahoitusta vertailtaessa velkaan on huomioitava myös, että rahoitusmuodoilla on hyvin erilaiset vaikutukset yrityksen verotukseen, kassavirtoihin ja nettotulokseen.

Microemulsões: estrutura e aplicações como sistema de liberação de fármacos

Depending on formula composition, microemulsions may be used as a vehicle for drug administration. In this work the main applicable parameters used in the development of pharmaceutical microemulsions (ME) are analyzed. The conceptual description of the system, theoretical parameters related to formation of internal phases and some aspects of ME stability are described. The pseudo ternary phase diagram is used to characterize ME boundaries and to describe different structures in several regions of the diagram. Some applications of ME as drug delivery systems for different administration routes are also analyzed. ME offer advantages as drug delivery systems, because they favor drug absorption, being in most cases faster and more efficient than other methods in delivering the same amount of drug.

The role of fast atom bombardment mass spectroscopy (FABMS) in cluster characterization

Fast atom bombardment mass spectroscopy has been used to study a large number of cationic phosphine-containing transition-metal-gold clusters, which ranged in mass from 1000 to 4000. Many of these clusters have been previously characterized and were examined in order to test the usefulness of the FABMS technique. Results showed that FABMS is excellent in giving the correct molecular formula and when combined with NMR, IR, and microanalysis gave a reliable characterization for cationic clusters¹. Recently FABMS has become one of the techniques employed as routine in cluster characterization2,3 and also is an effective tool for the structure analysis of large biomolecules4. Some results in the present work reinforce the importance of these data in the characterization of clusters in the absence of crystals with quality for X-ray analysis.

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.

Building complexity in O2-binding copper complexes : site-selective metalation and intermolecular O2-binding at dicopper and heterometallic complexes derived from an unsymmetric ligand

A novel unsymmetric dinucleating ligand (LN3N4) combining a tridentate and a tetradentate binding sites linked through a m-xylyl spacer was synthesized as ligand scaffold for preparing homo- and dimetallic complexes, where the two metal ions are bound in two different coordination environments. Site-selective binding of different metal ions is demonstrated. LN3N4 is able to discriminate between CuI and a complementary metal (M′ = CuI, ZnII, FeII, CuII, or GaIII) so that pure heterodimetallic complexes with a general formula [CuIM′(LN3N4)]n+ are synthesized. Reaction of the dicopper(I) complex [CuI 2(LN3N4)]2+ with O2 leads to the formation of two different copper-dioxygen (Cu2O2) intermolecular species (O and TP) between two copper atoms located in the same site from different complex molecules. Taking advantage of this feature, reaction of the heterodimetallic complexes [CuM′(LN3N4)]n+ with O2 at low temperature is used as a tool to determine the final position of the CuI center in the system because only one of the two Cu2O2 species is formed

Aspectos estruturais relacionados ao processo de troca iônica no niobato lamelar K4Nb6O17

The niobate with formula K4Nb6O17 has a layered structure formed by stacked negative sheets and exchangeable cations in the interlayer region. In this study we discuss some structural aspects related to the ion exchange in layered hexaniobate based on X-ray diffractometry and vibrational Raman spectroscopy data. Hexaniobate has two distinct interlayer regions and the potassium ions of one interlayer in particular are preferably exchanged by other cations, leading to an interstratified material.

Emprego do sal di-sódico de edta como padrão no preparo de soluções

The hydrated sodium salt of EDTA, Na2H2Y·2H2O, cannot be used as a primary standard for titrations due to uncertainties in the water content. An alkalimetric titration of the homogenized solid in the presence of a small excess of BaCl2·2H2O allows one to titrate quantitatively the released two hydrogen cations with end-point indication by phenolphthalein or potentiometry. This leads one to calculate the average molar mass of the reagent and its water content, allowing to use it to prepare EDTA standard solutions. One titrated sample led to the formula Na2H2Y·1.876 H2O, and 370.01 g.mol-1 for the average molar mass.

Grado de impacto en el suelo y la vegetación en áreas de uso público del Parque Nacional de Tierra del Fuego (Argentina)

En los últimos años, el uso turístico de las áreas protegidas ha aumentado considerablemente, y con él, el grado de impacto. Es por este motivo que se requieren medidas de gestión adecuadas para identificar, conocer y evaluar estos impactos potenciales y así poder actuar ofreciendo un uso recreativo de estas áreas a la vez que se asegura su conservación. El objetivo del presente trabajo fue establecer el grado de impacto que sufre la vegetaciòn y el suelo del Parque Nacional de Tierra del Fuego en las zonas de acampada y compararlas con las áreas adyacentes, como controles. Asimismo, se buscó establecer cuales son los indicadores de impacto de mayor relevancia para poder ser usados como herramientas de gestión. La evaluación se efectuó mediante el muestreo de 40 parcelas, transectas y intertransectas en donde se analizaron variables vegetacionales (cobertura arbórea, arbustiva y herbácea, porcentaje de suelo desnudo, daño en árboles y arbustos, y presencia de raíces expuestas) y del suelo (pH, materia orgánica, densidad aparente y humedad). El grado de impacto se estableció numéricamente con una fórmula matemática en donde se seleccionaron los parámetros evaluados y se corrigieron con factores de correción, dando un impacto clasificado como “compatible” en el área de Río Pipo y “moderado” en el área de Laguna Verde. También se formularon propuestas de manejo para prevenir y/o minimizar los impactos producidos en las zonas de camping.