Photoinduced phenomena in layer-by-layer films of poly(allylamine hydrochloride) and Brilliant Yellow azodye

The nanoscale interactions between adjacent layers of layer-by-layer (LBL) films from poly(allylamine hydrochloride) (PAH) and azodye Brilliant Yellow (BY) have been investigated, with the films employed for optical storage and the formation of surface-relief gratings. Using Fourier transform infrared spectroscopy, we identified interactions involving SO3- groups from BY and NH3+ groups from PAH. These electrostatic interactions were responsible for the slow kinetics of writing in the optical storage experiments, due to a tendency to hinder photoisomerization and the subsequent reorientation of the azochromophores. The photoinduced birefringence did not saturate after one hour of exposure to the writing laser, whereas in azopolymer films, saturation is normally reached within a few minutes. on the other hand, the presence of such interactions prevented thermal relaxation of the chromophores after the writing laser was switched off, leading to a very stable written pattern. Moreover, the nanoscale interactions promoted mass transport for photoinscription of surface-relief gratings on PAH/BY LBL films, with the azochromophores being able to drag the inert PAH chains when undergoing the trans-cis-trans photoisomerization cycles. A low level of chromophore degradation was involved in the SRG photoinscription, which was confirmed with micro-Raman and fluorescence spectroscopies.

Molecular engineering strategies to control photo-induced birefringence and surface-relief gratings on layer-by-layer films from an azopolymer

The interactions governing adsorption of layer-by-layer (LBL) films from an azopolymer, PS-119(R), and poly(allylamine hydrochloride) (PAH) have been controlled by modifying the pH of the solutions used to form the films. The thickness per bilayer was varied by one order of magnitude, from 10 to 240 A, as the pH changed from 4 to 10. Thick layers were formed at higher pHs because in this case the PAH is only partially charged adopting a loopy conformation. This change in molecular conformation caused the kinetics of isomerization and mass transport to be much slower than at lower pHs. The writing time defined as the time to achieve 50% of maximum birefringence dropped from 110 to 18 min for films prepared from solutions with pH 10 and pH 4, respectively. This decrease is probably due to the higher free volume for isomerization in the films prepared at lower pHs, in which PAH molecules are less coiled than at higher pHs. For the same reason, the rate of inscription of surface-relief gratings with an interference pattern of p-polarized light was also much slower at higher pHs. (C) 2003 Elsevier B.V. All rights reserved.

Effect of atmosphere and dopants on sintering of SnO2

Tin oxide is an n-type semiconductor material with a high covalent behavior. Mass transport in this oxide depends on the surface state promoted by atmosphere or by the solid solution of a non-isovalent oxide doping The sintering and grain growth of this type of oxide powder is then controlled by atmosphere and by extrinsic oxygen vacancy formation. For pure SnO2 powder the surface state depends only on the interaction of atmosphere molecules with the SnO2 surface. Inert atmosphere like argon or helium promotes oxygen vacancy formation at the surface due to reduction of SnO2 to SnO at the surface and liberation of oxygen molecules forming oxygen vacancies. As consequence surface diffusion is enhanced leading to grain coarsening but no densification. Oxygen atmosphere inhibits the SnO2 reduction decreasing the surface oxygen vacancy concentration. Addition of dopants with lower valence at sintering temperature creates extrinsic charged oxygen vacancies that promote mass transport at grain boundary leading to densification and grain growth of this polycrystalline oxide.

Effect of atmosphere and dopants on sintering of SnO2

Tin oxide is an n type semiconductor material with a high covalent behavior. Mass transport in this oxide depends on the surface state promoted by atmosphere or by the solid solution of aliovalent oxide doping. The sintering and grain growth of this type of oxide powder is then controlled by atmosphere and by extrinsic oxygen vacancy formation. For pure SnO2 powder the surface state depends only on the interaction of atmosphere molecules with the SnO2 surface. Inert atmosphere like argon or helium promotes oxygen vacancy formation at the surface due to reduction of SnO2 to SnO at the surface and liberation of oxygen molecules forming oxygen vacancies. As a consequence surface diffusion is enhanced leading to grain coarsening but no densification. Oxygen atmosphere inhibits SnO2 reduction by decreasing the surface oxygen vacancy concentration. Addition of dopants with lower valence at the sintering temperature creates extrinsic charged oxygen vacancies that promote mass transport at the grain boundary leading to densification and grain growth of this polycrystalline oxide.

Mechanisms of surface-relief gratings formation in layer-by-layer films from azodyes

Surface-relief gratings are photoinscribed on ionically adsorbed layer-by-layer (LBL) films of an azodye, Brilliant Yellow (BY), which was layered alternately with a polyelectrolyte. Photoinscription is performed by impinging an interference pattern of p- or s-polarized laser light with moderate intensity onto the LBL film, which is unlikely to cause thermal effects. Large-scale mass transport occurs due to the force associated with the field gradient of the light pattern. The ionic interactions between adjacent layers appear to provide the means for the chromophores to drag the polymer chains upon photoizomerization. LBL films were produced from two different polyelectrolytes and under two distinct pH values leading to markedly different film properties especially concerning photodegradation. Exposure to the laser light, for instance, leads to higher photodegradation in the poly(dimethyl diallylammonium chloride)/BY system, in comparison to the poly(allylamine hydrochloride)/BY films. Mass transport in the latter case is predominantly light-driven, which is consistent with the higher amplitude of modulation for p-polarized light (70 nm) compared to that caused by s-polarized light (18 nm). © 2003 Elsevier Ltd. All rights reserved.

The electro-oxidation of carbon monoxide and ethanol on supported Pt nanoparticles: The influence of the support and catalyst microstructure

The sluggish kinetics of ethanol oxidation on Pt-based electrodes is one of the major drawbacks to its use as a liquid fuel in direct ethanol fuel cells, and considerable efforts have been made to improve the reaction kinetics. Herein, we report an investigation on the effect of the Pt microstructure (well-dispersed versus agglomerated nanoparticles) and the catalyst support (carbon Vulcan, SnO2, and RuO2) on the rate of the electrochemical oxidation of ethanol and its major adsorbed intermediate, namely, carbon monoxide. By using several structural characterization techniques such as X-ray diffraction, X-ray absorption spectroscopy, and transmission electron microscopy, along with potentiodynamic and potentiostatic electrochemical experiments, we show that by altering both the Pt microstructure and the support, the rate of the electrochemical oxidation of ethanol can be improved up to a factor of 12 times compared to well-dispersed carbon-supported Pt nanoparticles. As a result of a combined effect, the interaction of Pt agglomerates with SnO2 yielded the highest current densities among all materials studied. The differences in the activity are discussed in terms of structural and electronic properties as well as by mass transport effects, providing valuable insights to the development of more active materials. © 2013 Springer-Verlag Berlin Heidelberg.

A influência do Arco do Desmatamento sobre o ciclo hidrológico da Amazônia

Este trabalho buscou quantificar algumas alterações no ciclo hidrológico da Amazônia propiciadas pelo desmatamento da região, principalmente devido à faixa conhecida como "Arco do Desmatamento". Neste sentido, foram realizados experimentos numéricos utilizando o modelo BRAMS (Brazilian Regional Atmospheric Modeling System) tendo o submodelo de vegetação dinâmica GEMTM (General Energy and Mass Transport Model) a ele acoplado. Foram investigados os impactos causados pelo Arco do Desmatamento atual em relação à floresta intacta, bem como as futuras modificações, causados pelo avanço do desmatamento até o ano de 2050. Como condições de contorno na superfície para o modelo BRAMS, foram usados cenários oriundos de modelos empíricos de desmatamento para os anos de 2002 e 2050. Os resultados mostraram que o avanço do Arco do Desmatamento até 2050 tem uma complexa relação com as variáveis analisadas. Por exemplo, a precipitação apresentou distribuição espacial heterogênea, com áreas de anomalias positivas e negativas que se mostraram coerentes com as anomalias de outras variáveis, como a evapotranspiração e a divergência de umidade. Também foram encontradas algumas áreas que evidenciaram as possíveis influências dos grandes rios e topografia da região sobre essa precipitação. Os balanços de radiação e energia também foram afetados pelo desmatamento, sendo que grande parte das alterações é devido à mudança do albedo da superfície, a qual ocorre com a substituição da floresta pela pastagem. Quanto às alterações propiciadas pelo Arco do Desmatamento atual em relação à floresta intacta, foi observado que todas as variáveis foram afetadas, entretanto a maioria dos impactos ainda é localizada sobre a área mais afetada pelo desmatamento, diferentemente dos resultados encontrados para o cenário de 2050, onde as modificações já se dão a nível regional.

Evolução geológica das sequências do embasamento do Cinturão Araguaia na região de Paraíso do Tocantins (TO), Brasil

Estudos isotópicos baseados nas metodologias Pb-Pb em zircão e Sm/Nd (rocha total), permitiram avanços no entendimento do quadro geológico evolutivo e litoestratigráfico do embasamento do segmento sul do Cinturão Araguaia. Os processos geológicos identificados aconteceram a partir do Arqueano (2,6 Ga e T_DM 2,78 – 3,25 Ga) e se estenderam até o Neoproterozoico. Os ortognaisses do Complexo Rio_dos Mangues posicionam-se no Paleoproterozoico (2,05 – 2,08 Ga) e T_DM 2,35 – 2,21 Ga. Um forte encurtamento crustal e fusão parcial de compartimentos isolados e espessados, gerou corpos ígneos de 1,85 e 1,82 Ga e o Granito Serrote (1,86 Ga), que provêm de fontes entre 2,50 e 2,43 Ga. No final do Mesoproterozoico a região foi marcada por processos tafrogenéticos, evidenciados por magmatismo máfico e alcalino (1,05 Ga) e bacias deposicionais, como a que acolheu os sedimentos que originaram as supracrustais do Cinturão Araguaia. No Neoproterozoico, através da inversão nas condições geodinâmicas, ocorreu novo processo de encurtamento/espessamento crustal com fusões que originaram expressivas massas batolíticas (Granitos Matança e Santa Luzia). O Cinturão Araguaia foi edificado a partir dessa movimentação tectônica. O transporte de massas tectônicas no sentido do Cráton Amazônico teria ocorrido, resultando na atual arquitetura em que se encontram as várias unidades lito-estratigráficas, organizadas sob a forma de lascas imbricadas.

Estudo da fluidodinâmica de uma mistura de sólidos em um leito fluidizado gás-sólido

Fluidization consists in a bed of solid particles acquire fluid behavior by using a fluid (in this case air) flowing through the solid particles. Because of this, it can be a good mix of these materials, as well as to show increased rates of heat and mass transport. The fluid flowing through the spaces between the particles gives an interstitial velocity, that if is too low does not cause movement of the particulates. The gradual increase in speed will generate small vibrations between the particles promotes its fluidization. Our study focus in the fluid state of solid bed , when the fluid velocity reaches a state where the drag forces are sufficient to support the weight of the solid particles making these solids behave like fluids . Knowledge of the minimum velocity required to fluidize that particles is of great importance since below this speed there is no fluidization, and far above it, the solids are carried out of the bed. The fluidized bed reactor is widely used in physics and engineering, particularly in gas-solid fluidization, with emphasis on thermochemical processes

Espectroscopia de impedância eletroquímica da biodissolução da calcopirita na presença de íons ferrosos

Pós-graduação em Química - IQ

Higher education in evening courses in Brazil: history, growth and public policies at the beginning of the XXI Century

There are three distinct and complementary objectives in this article in order to clarify the higher education outline in Brazil, specifically evening courses (classes are held on weekdays, generally from 7:00 pm to 10:30 pm) and thesecurrent sector policies. The first objective is to present a short historical overview on the establishment of evening courses in Brazil, including those in the higher education level, occurred on the middle of last century. The second objective is to demonstrate the growth of evening higher education in Brazil, considering that in 1998, of the 2.1 million college enrollments, 55.3% were enrolled in evening courses; in 2010, twelve years later, of the 5.4 million students enrolled, there were 63.5% enrolled in evening courses. This expansion is due to the growing need of many students who must work while attending college, to defray costs of the study as well as personal and family costs. The reality of the working student is hostile considering external factors, such as transport problems, public security and lack of legislation for flexible working hours. The third objective is to discuss current public policies to expand eveningopenings in public institutions which represent nowadays only 16.1% of the 3.4 million enrollments for evening classes, including federal (6.8%), state (7.0%) and municipal (2.3%) institutions. In the third objective it is included the discussion of programs for scholarships and tuition loans. The methodology applied was to rescue historical information on the establishment and the expansion of evening courses in Brazil, analyzing the current general Brazilian policies and the specific ones from the State of São Paulo. The research results pointed to the importance of federal programs for scholarships and tuition loans for students from private institutions such as the 1,382,484 scholarships since 2004 (PROUNI Program) and the 847,000 tuition loans since 1999 (FIES Program). Important steps have been made by the Brazilian government. Considering that there are 3,987,424 enrollments in private institutions, the effectiveness of the programs for scholarships and tuition loans is still insufficient to meet the universal benefits for the student’s needs. Evening courses became the real instrument of social inclusion for many Brazilian youths and must be expanded quantitatively and qualitatively, with aggressive public policies, including also, scholarships and tuition loans.

Estudo do efeito do transporte de massa nas curvas de polarização potenciodinâmica em ligas de alumínio da série 7XXX de aplicação aeronáutica

Aluminum Alloys are widely used as structural materials in the aerospace industry due to low weight, high mechanical strength and enduring corrosion resistance. Their resistance to corrosion is attributed to the rapidly formed stable oxide film (Al2O3) which spontaneously forms itself on the surface of the material. However, in the presence of aggressive ions, such as halide, Aluminum Alloys are subject to a localized process of corrosion. The electrochemical behavior of 7081-T73511 and 7050-T7451 Aluminum Alloys employed in the aerospace industry was investigated using a 0.6 M NaCl solution under the conditions of a controlled mass transport employing a rotating disk electrode. The theoretical limiting current density was determined by the Kouteki-Levich equation. The results confirmed that the inter-metallic Al7Cu2Fe acts as preferential cathode generating the galvanic coupling and the dissolution of the Aluminummatrix around it.

The Azores Current System and the Canary Current from CTD and ADCP data

Se han eliminado páginas en blanco

A communication infrastructure to support knowledge level agents on the web

Agent Communication Languages (ACLs) have been developed to provide a way for agents to communicate with each other supporting cooperation in Multi-Agent Systems. In the past few years many ACLs have been proposed for Multi-Agent Systems, such as KQML and FIPA-ACL. The goal of these languages is to support high-level, human like communication among agents, exploiting Knowledge Level features rather than symbol level ones. Adopting these ACLs, and mainly the FIPA-ACL specifications, many agent platforms and prototypes have been developed. Despite these efforts, an important issue in the research on ACLs is still open and concerns how these languages should deal (at the Knowledge Level) with possible failures of agents. Indeed, the notion of Knowledge Level cannot be straightforwardly extended to a distributed framework such as MASs, because problems concerning communication and concurrency may arise when several Knowledge Level agents interact (for example deadlock or starvation). The main contribution of this Thesis is the design and the implementation of NOWHERE, a platform to support Knowledge Level Agents on the Web. NOWHERE exploits an advanced Agent Communication Language, FT-ACL, which provides high-level fault-tolerant communication primitives and satisfies a set of well defined Knowledge Level programming requirements. NOWHERE is well integrated with current technologies, for example providing full integration for Web services. Supporting different middleware used to send messages, it can be adapted to various scenarios. In this Thesis we present the design and the implementation of the architecture, together with a discussion of the most interesting details and a comparison with other emerging agent platforms. We also present several case studies where we discuss the benefits of programming agents using the NOWHERE architecture, comparing the results with other solutions. Finally, the complete source code of the basic examples can be found in appendix.

Caratterizzazione di membrane metalliche e ionomeriche per applicazioni energetiche

The work of this thesis has been focused on the characterization of metallic membranes for the hydrogen purification from steam reforming process and also of perfluorosulphonic acid ionomeric (PFSI) membranes suitable as electrolytes in fuel cell applications. The experimental study of metallic membranes was divided in three sections: synthesis of palladium and silver palladium coatings on porous ceramic support via electroless deposition (ELD), solubility and diffusivity analysis of hydrogen in palladium based alloys (temperature range between 200 and 400 °C up to 12 bar of pressure) and permeation experiments of pure hydrogen and mixtures containing, besides hydrogen, also nitrogen and methane at high temperatures (up to 600 °C) and pressures (up to 10 bar). Sequential deposition of palladium and silver on to porous alumina tubes by ELD technique was carried out using two different procedures: a stirred batch and a continuous flux method. Pure palladium as well as Pd-Ag membranes were produced: the Pd-Ag membranes’ composition is calculated to be close to 77% Pd and 23% Ag by weight which was the target value that correspond to the best performance of the palladium-based alloys. One of the membranes produced showed an infinite selectivity through hydrogen and relatively high permeability value and is suitable for the potential use as a hydrogen separator. The hydrogen sorption in silver palladium alloys was carried out in a gravimetric system on films produced by ELD technique. In the temperature range inspected, up to 400°C, there is still a lack in literature. The experimental data were analyzed with rigorous equations allowing to calculate the enthalpy and entropy values of the Sieverts’ constant; the results were in very good agreement with the extrapolation made with literature data obtained a lower temperature (up to 150 °C). The information obtained in this study would be directly usable in the modeling of hydrogen permeation in Pd-based systems. Pure and mixed gas permeation tests were performed on Pd-based hydrogen selective membranes at operative conditions close to steam-reforming ones. Two membranes (one produced in this work and another produced by NGK Insulators Japan) showed a virtually infinite selectivity and good permeability. Mixture data revealed the existence of non negligible resistances to hydrogen transport in the gas phase. Even if the decrease of the driving force due to polarization concentration phenomena occurs, in principle, in all membrane-based separation systems endowed with high perm-selectivity, an extensive experimental analysis lack, at the moment, in the palladium-based membrane process in literature. Moreover a new procedure has been introduced for the proper comparison of the mass transport resistance in the gas phase and in the membrane. Another object of study was the water vapor sorption and permeation in PFSI membranes with short and long side chains was also studied; moreover the permeation of gases (i.e. He, N2 and O2) in dry and humid conditions was considered. The water vapor sorption showed strong interactions between the hydrophilic groups and the water as revealed from the hysteresis in the sorption-desorption isotherms and thermo gravimetric analysis. The data obtained were used in the modeling of water vapor permeation, that was described as diffusion-reaction of water molecules, and in the humid gases permeation experiments. In the dry gas experiments the permeability and diffusivity was found to increase with temperature and with the equivalent weight (EW) of the membrane. A linear correlation was drawn between the dry gas permeability and the opposite of the equivalent weight of PFSI membranes, based on which the permeability of pure PTFE is retrieved in the limit of high EW. In the other hand O2 ,N2 and He permeability values was found to increase significantly, and in a similar fashion, with water activity. A model that considers the PFSI membrane as a composite matrix with a hydrophilic and a hydrophobic phase was considered allowing to estimate the variation of gas permeability with relative humidity on the basis of the permeability in the dry PFSI membrane and in pure liquid water.