Characterization of micro-bubble size distribution and flow configuration in DAF contact zone by a non-intrusive image analysis system and tracer tests

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

Análise do desgaste erosivo por partícula sólida em superligas à base de níquel

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Simulations of physics and chemistry of polar stratospheric clouds with a general circulation model

A polar stratospheric cloud submodel has been developed and incorporated in a general circulation model including atmospheric chemistry (ECHAM5/MESSy). The formation and sedimentation of polar stratospheric cloud (PSC) particles can thus be simulated as well as heterogeneous chemical reactions that take place on the PSC particles. For solid PSC particle sedimentation, the need for a tailor-made algorithm has been elucidated. A sedimentation scheme based on first order approximations of vertical mixing ratio profiles has been developed. It produces relatively little numerical diffusion and can deal well with divergent or convergent sedimentation velocity fields. For the determination of solid PSC particle sizes, an efficient algorithm has been adapted. It assumes a monodisperse radii distribution and thermodynamic equilibrium between the gas phase and the solid particle phase. This scheme, though relatively simple, is shown to produce particle number densities and radii within the observed range. The combined effects of the representations of sedimentation and solid PSC particles on vertical H2O and HNO3 redistribution are investigated in a series of tests. The formation of solid PSC particles, especially of those consisting of nitric acid trihydrate, has been discussed extensively in recent years. Three particle formation schemes in accordance with the most widely used approaches have been identified and implemented. For the evaluation of PSC occurrence a new data set with unprecedented spatial and temporal coverage was available. A quantitative method for the comparison of simulation results and observations is developed and applied. It reveals that the relative PSC sighting frequency can be reproduced well with the PSC submodel whereas the detailed modelling of PSC events is beyond the scope of coarse global scale models. In addition to the development and evaluation of new PSC submodel components, parts of existing simulation programs have been improved, e.g. a method for the assimilation of meteorological analysis data in the general circulation model, the liquid PSC particle composition scheme, and the calculation of heterogeneous reaction rate coefficients. The interplay of these model components is demonstrated in a simulation of stratospheric chemistry with the coupled general circulation model. Tests against recent satellite data show that the model successfully reproduces the Antarctic ozone hole.

Magnetic susceptibility and electric conductivity of marine surficial sediments by benthic electromagnetic profiling

Distribution, accumulation and diagenesis of surficial sediments in coastal and continental shelf systems follow complex chains of localized processes and form deposits of great spatial variability. Given the environmental and economic relevance of ocean margins, there is growing need for innovative geophysical exploration methods to characterize seafloor sediments by more than acoustic properties. A newly conceptualized benthic profiling and data processing approach based on controlled source electromagnetic (CSEM) imaging permits to coevally quantify the magnetic susceptibility and the electric conductivity of shallow marine deposits. The two physical properties differ fundamentally insofar as magnetic susceptibility mostly assesses solid particle characteristics such as terrigenous or iron mineral content, redox state and contamination level, while electric conductivity primarily relates to the fluid-filled pore space and detects salinity, porosity and grain-size variations. We develop and validate a layered half-space inversion algorithm for submarine multifrequency CSEM with concentric sensor configuration. Guided by results of modeling, we modified a commercial land CSEM sensor for submarine application, which was mounted into a nonconductive and nonmagnetic bottom-towed sled. This benthic EM profiler Neridis II achieves 25 soundings/second at 3-4 knots over continuous profiles of up to hundred kilometers. Magnetic susceptibility is determined from the 75 Hz in-phase response (90% signal originates from the top 50 cm), while electric conductivity is derived from the 5 kHz out-of-phase (quadrature) component (90% signal from the top 92 cm). Exemplary survey data from the north-west Iberian margin underline the excellent sensitivity, functionality and robustness of the system in littoral (~0-50 m) and neritic (~50-300 m) environments. Susceptibility vs. porosity cross-plots successfully identify known lithofacies units and their transitions. All presently available data indicate an eminent potential of CSEM profiling for assessing the complex distribution of shallow marine surficial sediments and for revealing climatic, hydrodynamic, diagenetic and anthropogenic factors governing their formation.

Understanding immobilised enzymes by NMR spectroscopy

Enzyme immobilisation is the conversion of a soluble enzyme molecule into a solid particle form. This allows the recovery of the enzyme catalyst for its re-use and avoids protein contamination of the product streams. A better understanding of immobilised enzymes is necessary for their rational development. A more rational design can help enormously in the applicability of these systems in different areas, from biosensors to chemical industry. Immobilised enzymes are challenging systems to study and very little information is given by conventional biochemical analysis such as catalytic activity and amount of protein. Here, solid-state NMR has been applied as the main technique to study these systems and evaluate them more precisely. Various approaches are presented for a better understanding of immobilised enzymes, which is the aim of this thesis. Firstly, the requirements of a model system of study will be discussed. The selected systems will be comprehensibly characterised by a variety of techniques but mainly by solid-state NMR. The chosen system will essentially be the enzyme α-chymotrypsin covalently immobilised on two functionalised inorganic supports – epoxide silica and epoxide alumina – and an organic support – Eupergit®. The study of interactions of immobilised enzymes with other species is vital for understanding the macromolecular function and for predicting and engineering protein behaviour. The study of water, ions and inhibitors interacting with various immobilised enzyme systems is covered here. The interactions of water and sodium ions were studied by 17O and 23Na multiple-quantum techniques, respectively. Various pore sizes of the supports were studied for the immobilised enzyme in the presence of labelled water and sodium cations. Finally, interactions between two fluorinated inhibitors and the active site of the enzyme will be explored using 19F NMR, offering a unique approach to evaluate catalytic behaviour. These interactions will be explored by solution-state NMR firstly, then by solid-state NMR. NMR has the potential to give information about the state of the protein in the solid support, but the precise molecular interpretation is a difficult task.

Estudo do crescimento, eficiência de biofiltração e cinética de absorção de nutrientes (N-NH, N-NO e P-PO4³) da macroalga Gracilaria cervicornis (Turner) J. Agardh

The objective of this study was to examine the growth of Gracilaria cervicornis cultured in a shrimp (Litopenaeus vannamei) pond and to determine the absorption efficiency and the kinetics parameters (Vmax, Ks e Vmax:Ks) of this macroalgae for the nutrients N-NO3-, N-NH4+ and P-PO4-3, aiming at its use as bioremediatory of eutrophicated environments. For this study, two experiments (field and laboratory) were developed. In the field study, the seaweed was examined in relation to the growth and the biomass. In the laboratory experiment, the absorption efficiency of G. cervicornis was measured through the monitoring of the concentration of the three nutrients (N-NO3-, N-NH4+ e P-PO4-3) during 5 hours and the kinetic parameters were determined through the formula of Michaelis-Menten. The results obtained in this study demonstrated that G. cervicornis benefited from the available nutrients in the pond, increasing 52.4% of its biomass value after 30 days of culture. It was evidenced that the variability of the biomass could be explained through the salinity, availability of light (transparency and solid particle in suspension) and concentration of N-NO3- in the environment. In the laboratory experiment, the highest absorption efficiency was found in the treatments with low concentration (5 µmol.L-1), being evidenced a reduction of up to 85,3%, 97,5% and 81,2% of N-NH4+, N-NO3- and P-PO43-, respectively. Regarding the kinetic parameters, G. cervicornis presented better ability in absorbing N-NH4+ in high concentrations (Vmax = 158,5 µmol g-1 dry wt h-1) and P-PO43- in low concentrations (Ks = 5 µmol.L-1 e Vmax:Ks = 10,3). The results of this study show that G. cervicornis could be cultivated in shrimp ponds, presents a good capacity of absorption for the tested nutrients and is a promising candidate for biorremediation in shrimp pond effluent

Avaliação do efeito de particulados sólidos na eficiência de um inibidor de corrosão recomendado para meios salinos com CO2

The main problem on the exploration activity on petroleum industry is the formation water resulted on the fields producing. The aggravating of this problem is correlated with the advancing technologies used on the petroleum extractions and on its secondary approach objecting the reobtainment of this oil. Among the main contaminants of the water formation are corrosives gases such as: O2, CO2 and H2S, some solids in suspension and dissolved salts. Concerning to those gases the CO2 is the one that produce significant damage for carbon steel on corrosion process of the petroleum and gas industries. Corrosion inhibitors for carbon steel in formation water is one of the most used agents in control of those damages. In this context, the poor investigations of carbon steel corrosion proceeding from solids in suspension is an opened field for studies. On this work the inhibitor effect of the commercial CORRTREAT 703 was evaluated on some specific solids in suspension at saline medium containing 10.000 ppm of de-aerated chloride using CO2 until non oxygen atmosphere been present. For that, quartz, calcium carbonate, magnetite and iron sulphide were subjected to this investigation as the selected solids. The effect of this inhibitor on corrosion process correlated with those specific solids, was measured using electrochemical (resistance of linear polarization and galvanic pair) and gravimetrical techniques. During all the experimental work important parameters were monitored such as: pH, dissolved oxygen, temperature, instantaneous corrosion rate and galvanic current. According to the obtained results it was proved that the suspension solids calcium carbonate and iron sulphide decrease the corrosion process in higher pH medium. Meanwhile the quartz and magnetite been hardness increase corrosion by broking of the passive layer for erosion. In the other hand, the tested inhibitor in concentration of 50 ppm, showed to be effective (91%) in this corrosion process

Estudo do crescimento, eficiência de biofiltração e cinética de absorção de nutrientes (N-NH, N-NO e P-PO4³) da macroalga Gracilaria cervicornis (Turner) J. Agardh

The objective of this study was to examine the growth of Gracilaria cervicornis cultured in a shrimp (Litopenaeus vannamei) pond and to determine the absorption efficiency and the kinetics parameters (Vmax, Ks e Vmax:Ks) of this macroalgae for the nutrients N-NO3-, N-NH4+ and P-PO4-3, aiming at its use as bioremediatory of eutrophicated environments. For this study, two experiments (field and laboratory) were developed. In the field study, the seaweed was examined in relation to the growth and the biomass. In the laboratory experiment, the absorption efficiency of G. cervicornis was measured through the monitoring of the concentration of the three nutrients (N-NO3-, N-NH4+ e P-PO4-3) during 5 hours and the kinetic parameters were determined through the formula of Michaelis-Menten. The results obtained in this study demonstrated that G. cervicornis benefited from the available nutrients in the pond, increasing 52.4% of its biomass value after 30 days of culture. It was evidenced that the variability of the biomass could be explained through the salinity, availability of light (transparency and solid particle in suspension) and concentration of N-NO3- in the environment. In the laboratory experiment, the highest absorption efficiency was found in the treatments with low concentration (5 µmol.L-1), being evidenced a reduction of up to 85,3%, 97,5% and 81,2% of N-NH4+, N-NO3- and P-PO43-, respectively. Regarding the kinetic parameters, G. cervicornis presented better ability in absorbing N-NH4+ in high concentrations (Vmax = 158,5 µmol g-1 dry wt h-1) and P-PO43- in low concentrations (Ks = 5 µmol.L-1 e Vmax:Ks = 10,3). The results of this study show that G. cervicornis could be cultivated in shrimp ponds, presents a good capacity of absorption for the tested nutrients and is a promising candidate for biorremediation in shrimp pond effluent

Effect of morphology and particle size on the ionic conductivities of composite solid electrolytes

A model incorporating the surface conductivity and morphology of the composite solid electrolytes is envisaged to explain their conduction behaviour. The conductivity data on LinX−50 m/o Al2O3 (X = F−, Cl−, Br−, CO32−, SO42−, PO43−) composites prepared by thermal decomposition of LinX·2nAl(OH)3·mH2O salts and Li2SO4−A (A=Al2O3, CeO2, Y2O3, Yb2O3, Zr2O3, ZrO2 and BaTiO3) composites prepared by mechanical mixing of the components are examined in the light of this model. It is surmised that the particle size of both the dispersoids and the hosts not only influence the ionic conductivity of the host matrix but also affect its bulk properties.

Determination of favorable inter-particle interactions for formation of substitutionally ordered solid phases from a binary mixture of oppositely charged colloidal suspensions

The solid phase formed by a binary mixture of oppositely charged colloidal particles can be either substitutionally ordered or substitutionally disordered depending on the nature and strength of interactions among the particles. In this work, we use Monte Carlo molecular simulations along with the Gibbs-Duhem integration technique to map out the favorable inter-particle interactions for the formation of substitutionally ordered crystalline phases from a fluid phase. The inter-particle interactions are modeled using the hard core Yukawa potential but the method can be easily extended to other systems of interest. The study obtains a map of interactions depicting regions indicating the type of the crystalline aggregate that forms upon phase transition.

A Few Case Studies on the Correlation of Particle Network and Its Stability on the Ionic Conductivity of Solid-Liquid Composite Electrolytes

We discuss here the crucial role of the particle network and its stability on the long-range ion transport in solid liquid composite electrolytes. The solid liquid composite electrolytes chosen for the study here comprise nanometer sized silica (SiO2) particles having various surface chemical functionalities dispersed in nonaqueous lithium salt solutions, viz, lithium perchlorate (LiClO4) in two different polyethylene glycol based solvents. These systems constitute representative examples of an independent class of soft matter electrolytes known as ``soggy sand'' electrolytes, which have tremendous potential in diverse electrochemical devices. The oxide additive acts as a heterogeneous dopant creating free charge carriers and enhancing the local ion transport. For long-range transport, however, a stable spanning particle network is needed. Systematic experimental investigations here reveal that the spatial and time dependent characteristics of the particle network in the liquid solution are nontrivial. The network characteristics are predominantly determined by the chemical makeup of the electrolyte components and the chemical interactions between them. It is noteworthy that in this study the steady state macroscopic ionic conductivity and viscosity of the solid liquid composite electrolyte are observed to be greatly determined by the additive oxide surface chemical functionality, solvent chemical composition, and solvent dielectric constant.

Fluid-Solid Interaction in Particle-Laden Flows

Liu Qingquan, Singh V.P

Laser Doppler velocimetry measurements of particle velocity profiles in gas-solid two-phase flows

The measurement of particle velocities in two-phase gas-solid systems has a wide application in flow monitoring in process plant, where two-phase gas-solids systems are frequently employed in the form of pneumatic conveyors and solid fuel injection systems. Such measurements have proved to be difficult to make reliably in industrial environments. This paper details particle velocity measurements made in a two phase gas-solid now utilising a laser Doppler velocimetry system. Tests were carried out using both wheat flour and pulverised coal as the solids phase, with air being used as the gaseous phase throughout. A pipeline of circular section, having a diameter of 53 mm was used for the test work, with air velocities ranging from 25 to 45 m/s and suspension densities ranging from 0.001 kg to 1 kg of solids per cubic meter of air. Details of both the test equipment used, and the results of the measurements are presented.