Comportamento voltamétrico da redução de 2-furfuraldeído em etanol utilizando eletrodo de carbono vítreo

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Sintering of tin oxide and its applications in electronics and processing of high purity optical glasses

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Sintering of ultrafine undoped SnO2 powder

The sintering process of nanometric undoped SnO2 powder was studied. No macroscopic shrinkage was observed during the sintening process. Grain growth kinetics investigation showed that surface diffusion is the dominant mechanism in the temperature range 500-1300 degreesC. For temperatures higher than 1300 degreesC, high weight loss was measured, suggesting evaporation-condensation as the dominant mass-transport mechanism. Thermogravimetric analysis (TG) and mass spectroscopy studies showed that the surface contamination of the SnO2 particles by chemical species like H2O, OH- and CO2, has a strong influence on the role of mass transport controlled by surface diffusion. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Nanocoating of Al2O3 additive on ZrO2 powder and its effect on the sintering behaviour in ZrO2 ceramic

ZrO2 powder was coated with Al2O3 precursor generated by a polymeric precursor method in aqueous solution. The system of nanocoated particles formed a core shell-like structure in which the particle is the core and the nanocoating (additive) is the shell. A new approach is reported in order to control the superficial mass transport and the exaggerated grain growth during the sintering of zirconia powder. Transmission electron microscopy (TEM) observations clearly showed the formation of an alumina layer on the surface of the zirconia particles. This layer modifies the sintering process and retards the maximum shrinkage temperature of the pure zirconia.

Study of Ti-modified columbite route and the effect of lithium doping in 0.9PMN-0.1PT ceramics

The influence of lithium on the structural characteristics of PMN-PT ceramic was studied. The synthesis of PMN-PT powders using this precursor leads to the formation of high amount of perovskite phase. The insertion of Li(+) ions in B-site affects the microstructure because the rise in mass transport changes the mechanical characteristics of sintered ceramic. Higher values of K(m) and T(m) were gotten when lithium is inserted into perovskite phase. Secondary phase was found when lithium content increase beyond 1 mol%, besides the occurrence of transgranular fractures in sintered ceramic. Also, the additive acts increasing the relaxor behavior.

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