Desenvolvimento de microemulsões contendo fotoprotetores inorgânicos nanoparticulador

The inorganic actives, represented mainly by microfine zinc oxide and titanium dioxide, have shown great potential to protect against large UV spectrum. The aim of this study is the development, characterization and analysis of stability in the short term of microemulsions containing inorganic fotoprotection agents. The microemulsions identified by the phases diagram containing the metallic oxides were produced by two different methods and subjected to the centrifugation test and thermal stress cycles, and subsequently characterized by macroscopic evaluation, test dilution, electrical conductivity, pH, particle size, and zeta potential. This study highlights the influence of the metal oxides addition in the structure and distribution of micelles in the microemulsions

Estudo de uma coluna de absorção recheada para desidratação do gás natural utilizando microemulsão como absorvente

During natural gas processing, water removal is considered as a fundamental step in that combination of hydrocarbons and water favors the formation of hydrates. The gas produced in the Potiguar Basin (Brazil) presents high water content (approximately 15000 ppm) and its dehydration is achieved via absorption and adsorption operations. This process is carried out at the Gas Treatment Unit (GTU) in Guamaré (GMR), in the State of Rio Grande do Norte. However, it is a costly process, which does not provide satisfactory results when water contents as low as 0.5 ppm are required as the exit of the GTU. In view of this, microemulsions research is regarded as an alternative to natural gas dehydration activities. Microemulsions can be used as desiccant fluids because of their unique proprieties, namely solubilization enhancement, reduction in interfacial tensions and large interfacial area between continuous and dispersed phases. These are actually important parameters to ensure the efficiency of an absorption column. In this work, the formulation of the desiccant fluid was determined via phases diagram construction, employing there nonionic surfactants (RDG 60, UNTL L60 and AMD 60) and a nonpolar fluid provided by Petrobras GMR (Brazil) typically comprising low-molecular weight liquid hydrocarbons ( a solvent commonly know as aguarrás ). From the array of phases diagrams built, four representative formulations have been selected for providing better results: 30% RDG 60-70% aguarrás; 15% RDG 60-15% AMD 60-70% aguarrás, 30% UNTL L60-70% aguarrás, 15% UNTL L60-15% AMD 60-70% aguarrás. Since commercial natural gas is already processed, and therefore dehydrated, it was necessary to moister some sample prior to all assays. It was then allowed to cool down to 13ºC and interacted with wet 8-12 mesh 4A molecular sieve, thus enabling the generation of gas samples with water content (approximately 15000 ppm). The determination of the equilibrium curves was performed based on the dynamic method, which stagnated liquid phase and gas phase at a flow rate of 200 mL min-1. The hydrodynamic study was done with the aim of established the pressure drop and dynamic liquid hold-up. This investigation allowed are to set the working flow rates at 840 mL min-1 for the gas phase and 600 mLmin-1 for the liquid phase. The mass transfer study indicated that the system formed by UNTL L60- turpentine-natural gas the highest value of NUT

Desenvolvimento de tensoativos e sistemas microemulsionados para recuperação de petróleo

The high concentration of residual oil is one of the greatest problems found in petroleum mature fields. In these reservoirs, different enhanced oil recovery methods (EOR) can be used, highlighting the microemulsion injection. The microemulsion has showed to be efficient in petroleum recovery due to its ability to promote an efficient displacement of the petroleum, acting directly in the residual oil. In this way, this research has as objective the study of microemulsion systems obtained using a commercial surfactant (TP), determining microemulsion thermal stabilities and selecting points inside the pseudoternary phases diagram, evaluating its efficiencies and choosing the best system, that has the following composition: TP as surfactant (S), isopropyl alcohol as co-surfactant (C), kerosene as oil phase, water as aqueous phase, C/S ratio = 1, and 5% sodium p-toluenesulfonate as hydrotope; being observed the following parameters for the selection of the best pseudoternary phases diagram: C/S ratio, co-surfactant nature and addition of hydrotope to the system. The efficiency in petroleum recovery was obtained using two sandstone formation systems: Assu and Botucatu. The study of thermal stabilities showed that as the concentration of active matter in the system increased, the thermal stability also increased. The best thermal stability was obtained using point F (79.56 0C). The system that presented the best recovery percentile between the three selected (3) was composed by: 70% C/S, 2% kerosene and 28% water, with 94% of total recovery efficiency and 60% with microemulsion injection, using the Botucatu formation, that in a general way presented greater efficiencies as compared with the Assu one (81.3% of total recovery efficiency and 38.3% with microemulsion injection)

Raman scattering, differential scanning calorimetry and Nd3+ spectroscopy in alkali niobium tellurite glasses

Alkali niobium tellurite glasses have been prepared and some of their properties measured by differential scanning calorimetry and Raman scattering. The vitreous domain was established in the pseudo ternary phases diagram for the system TeO2-Nb2O5-(0.5K(2)O-0.5Li(2)O). Raman scattering shows that for samples in the TeO2 rich part of the phase diagram the vitreous structure is composed essentially of (TeO4) units connected by the vertices, as in the alpha-TeO2 crystal. The addition of alkali and niobium oxides causes depolymerization to occur with structures composed essentially of (TeO3) and (NbO6) units. Samples with the composition (mol%) 80TeO(2)-10Nb(2)O(5)-5K(2)O-5Li(2)O, stable against crystallization, were prepared containing up to 10% mol Nd3+. The addition of this oxide increases the rigidity of the vitreous network shifting characteristic temperatures to higher temperatures. For the 10% Nd3+ sample amorphous phase separation is assumed to exist from the observation of two glass transition temperatures. Spectroscopic properties such as Judd-Ofelt Omega(lambda) intensity parameters, radiative emission probabilities, and induced emission cross sections were calculated. From these results and also from the emission quenching observed as a function of Nd3+ concentration, we suggest that these glasses could be utilized in optical amplifying devices. (C) 1999 Elsevier B.V. B.V. All rights reserved.

New insights on the crystalline forms in binary systems of n-alkanes: Characterization of the solid ordered phases in the phase diagram tricosane + pentacosane

X-ray diffraction analyses of the pure components n-tricosane and n-pentacosane and of their binary mixed samples have enabled us to characterize the crystalline phases observed at low temperature. On the contrary to what was announced in literature on the structural behavior of mixed samples in odd-odd binary systems with D n = 2, the three domains are not all orthorhombic. This work has enabled us to show that two of the domains are, in fact, monoclinic, (Aa, Z = 4) and the other one is orthorhombic (Pca21, Z = 4). The conclusions drawn in this work can be easily transposed to other binary systems of n-alkanes.

Supramolecular polymorphism of DNA in non-cationic L(alpha) lipid phases

The structure of a complex between hydrated DNA and a non-cationic lipid is studied, including its phase diagram. The complex is spontaneously formed by adding DNA fragments (ca. 150 base pairs in length) to non-cationic lipids and water. The self-assembly process often leads to highly ordered structures. The structures were studied by combining X-ray scattering, fluorescence and polarized microscopy, as well as freeze-fracture experiments with transmission electron microscopy. We observe a significant increase of the smectic order as DNA is incorporated into the water layers of the lamellar host phase, and stabilization of single phase domains for large amounts of DNA. The effect of confinement on DNA ordering is investigated by varying the water content, following three dilution lines. A rich polymorphism is found, ranging from weakly correlated DNA-DNA in-plane organizations to highly ordered structures, where transmembrane correlations lead to the formation of columnar rectangular and columnar hexagonal superlattices of nucleotides embedded between lipid lamellae. From these observations, we suggest that addition of DNA to the lamellar phase significantly restricts membrane fluctuations above a certain concentration and helps the formation of the lipoplex. The alteration of membrane steric interactions, together with the appearance of interfacial interactions between membranes and DNA molecules may be a relevant mechanism for the emergence of highly ordered structures in the concentrated regime.

Analysis of the Phase Changes During Evaporation of Emulsions with Different Oil Phases

Emulsions surfer alterations in their microstructure after applied on the skin, because of the interaction with skin constituents and mainly by the evaporation of volatile components. These alterations are not even considered by cosmetic formulators, but they are extremely important because they can act on formulation stability, on delivery and on permeation of actives and also on the ability to build the occlusive film, responsible for skin`s moisturization. This research studied the phase changing during evaporation of emulsions made with three different oil phase: mineral oil, avocado oil, and isocethyl/stearoil stearate, as a function of the decrease on water ratio, using phase diagrams and evaporation test. It was observed the formation of liquid crystalline phases and their transition along the evaporation path for emulsions with the three different oil phases. It was also observed that these transitions occurred in different water ratios.

Pairing in a two-component ultracold Fermi gas: Phases with broken-space symmetries

We explore the phase diagram of a two-component ultracold atomic Fermi gas interacting with zero-range forces in the limit of weak coupling. We focus on the dependence of the pairing gap and the free energy on the variations in the number densities of the two species while the total density of the system is held fixed. As the density asymmetry is increased, the system exhibits a transition from a homogenous Bardeen-Cooper-Schrieffer (BCS) phase to phases with spontaneously broken global space symmetries. One such realization is the deformed Fermi surface superfluidity (DFS) which exploits the possibility of deforming the Fermi surfaces of the species into ellipsoidal form at zero total momentum of Cooper pairs. The critical asymmetries at which the transition from DFS to the unpaired state occurs are larger than those for the BCS phase. In this precritical region the DFS phase lowers the pairing energy of the asymmetric BCS state. We compare quantitatively the DFS phase to another realization of superconducting phases with broken translational symmetry: the single-plane-wave Larkin-Ovchinnikov-Fulde-Ferrell phase, which is characterized by a nonvanishing center-of-mass momentum of the Cooper pairs. The possibility of the detection of the DFS phase in the time-of-flight experiments is discussed and quantified for the case of 6Li atoms trapped in two different hyperfine states.

Étude DFT+U des phases structurales du La2CuO4

Ce mémoire traite des propriétés du La2CuO4 dopé en trous, le premier supraconducteur à haute température critique ayant été découvert. Les différentes phases électroniques du cristal y seront présentées, ainsi que le diagramme de phases en dopage de ce matériau. Les trois structures dans lesquelles on peut retrouver ce cristal seront décrites en détail, et leurs liens présumés avec les phases électroniques seront présentés. Il s’en suivra une étude utilisant la théorie de la fonctionnelle de la densité combinée au modèle de Hubbard (DFT+U) des différentes phases structurales, en plus des phases antiferromagnétiques et paramagnétiques. L’effet de la corrélation électronique sur la structure cristalline sera également étudié par l’intermédiaire du paramètre de Hubbard. Le but sera de vérifier si la DFT+U reproduit bien le diagramme de phases expérimentales, et sous quelles conditions. Une étude des effets de l’inclinaison des octaèdres d’oxygène sur la structure électronique sera également présentée.

Solid phases of cyclopentane: combined experimental and simulation study

The phase diagram of cyclopentane has been studied by powder neutron diffraction, providing diffraction patterns for phases I, II, and III, over a range of temperatures and pressures. The putative phase IV was not observed. The structure of the ordered phase III has been solved by single-crystal diffraction. Computational modeling reveals that there are many equienergetic ordered structures for cyclopentane within a small energy range. Molecular dynamics simulations reproduce the structures and diffraction patterns for phases I and III and also show an intermediate disordered phase, which is used to interpret phase II.

Highly asymmetric phase diagram of a poly(1,2-octylene oxide)-poly(ethylene oxide) diblock copolymer system comprising a brush-like poly(1,2-octylene oxide) block

The phase diagram of a series of poly(1,2-octylene oxide)-poly(ethylene oxide) (POO-PEO) diblock copolymers is determined by small-angle X-ray scattering. The Flory-Huggins interaction parameter was measured by small-angle neutron scattering. The phase diagram is highly asymmetric due to large conformational asymmetry that results from the hexyl side chains in the POO block. Non-lamellar phases (hexagonal and gyroid) are observed near f(PEO) = 0.5, and the lamellar phase is observed for f(PEO) >= 0.5.

Micelles forming biaxial lyotropic nematic phases

The paper by Yu and Saupe on the first biaxial nematic phase created excitement for a number of reasons. Some theories of biaxial phases already existed, but experimental observation was still lacking. The phase was discovered in a lyotropic system with three components, which in theory is difficult. Lyotropic liquid crystals are composed of supramolecular assemblies of amphiphilic molecules, which may change shape and size as a function of concentration and temperature. The experimental phase diagram of the lyotropic biaxial phase was rather complex, with the biaxial region inserted between nematic cylindrical and nematic discotic phases via second-order transitions. In addition, re-entrant behaviour was evident. Saupe investigated further systems experimentally, observing that the biaxial phase might be absent in cases where a direct transition between the cylindrical and discotic phases occurred. He provided a range of theoretical and experimental contributions on the properties of these lyotropics, but was very cautious regarding the detailed amphiphilic assemblies involved. The present paper reviews this area, focusing on proposals for the structure of the micellar assemblies. Emphasis is placed on recent papers which indicate a transformation of the two uniaxial shapes, in mixing conditions, both from the theoretical and the experimental point of view, and to questions still requiring further study.

Metastable Phase Diagram of Nanocrystalline ZrO(2)-Sc(2)O(3) Solid Solutions

We have investigated the crystal structures and phase transitions of nanocrystalline ZrO(2)-1 to -13 mol % Sc(2)O(3) by synchrotron X-ray powder diffraction and Raman spectroscopy. ZrO(2)-Sc(2)O(3) nanopowders were synthesized by using a stoichiometric nitrate-lysine get-combustion route. Calcination processes at 650 and at 850 degrees C yielded nanocrystalline materials with average crystallite sizes of (10 +/- 1) and (25 +/- 2) nm, respectively. Only metastable tetragonal forms and the cubic phase were identified, whereas the stable monoclinic and rhombohedral phases were not detected in the compositional range analyzed in this work. Differently from the results of investigations reported in the literature for ZrO(2)-Sc(2)O(3) materials with large crystallite sizes, this study demonstrates that, if the crystallite sizes are small enough (in the nanometric range), the metastable t ``-form of the tetragonal phase is retained. We have also determined the t`-t `` and t ``-cubic compositional boundaries at room temperature and analyzed these transitions at high temperature. Finally, using these results, we built up a metastable phase diagram for nanocrystalline compositionally homogeneous ZrO(2)-Sc(2)O(3) solid solutions that strongly differs from that previously determined from compositionally homogeneous ZrO(2)-Sc(2)O(3), Solid solutions with much larger crystallite sizes.

Influence of interlayer tunneling on the quantized Hall phases in intentionally disordered multilayer structures

Stability of the quantized Hall phases is studied in weakly coupled multilayers as a function of the interlayer correlations controlled by the interlayer tunneling and by the random variation of the well thicknesses. A strong enough interlayer disorder destroys the symmetry responsible for the quantization of the Hall conductivity, resulting in the breakdown of the quantum Hall effect. A clear difference between the dimensionalities of the metallic and insulating quantum Hall phases is demonstrated. The sharpness of the quantized Hall steps obtained in the coupled multilayers with different degrees of randomization was found consistent with the calculated interlayer tunneling energies. The observed width of the transition between the quantized Hall states in random multilayers is explained in terms of the local fluctuations of the electron density.

Superfluid Fermi-Fermi mixture: Phase diagram, stability, and soliton formation

We study the phase diagram for a dilute Bardeen-Cooper-Schrieffer superfluid Fermi-Fermi mixture (of distinct mass) at zero temperature using energy densities for the superfluid fermions in one (1D), two (2D), and three (3D) dimensions. We also derive the dynamical time-dependent nonlinear Euler-Lagrange equation satisfied by the mixture in one dimension using this energy density. We obtain the linear stability conditions for the mixture in terms of fermion densities of the components and the interspecies Fermi-Fermi interaction. In equilibrium there are two possibilities. The first is that of a uniform mixture of the two components, the second is that of two pure phases of two components without any overlap between them. In addition, a mixed and a pure phase, impossible in 1D and 2D, can be created in 3D. We also obtain the conditions under which the uniform mixture is stable from an energetic consideration. The same conditions are obtained from a modulational instability analysis of the dynamical equations in 1D. Finally, the 1D dynamical equations for the system are solved numerically and by variational approximation (VA) to study the bright solitons of the system for attractive interspecies Fermi-Fermi interaction in 1D. The VA is found to yield good agreement to the numerical result for the density profile and chemical potential of the bright solitons. The bright solitons are demonstrated to be dynamically stable. The experimental realization of these Fermi-Fermi bright solitons seems possible with present setups.