Monte Carlo phase diagram for a polydisperse diblock copolymer melt

The phase diagram for an AB diblock copolymer melt with polydisperse A blocks and monodisperse B blocks is evaluated using lattice-based Monte Carlo simulations. Experiments on this system have shown that the A-block polydispersity shifts the order-order transitions (OOTs) towards higher A-monomer content, while the order-disorder transition (ODT) moves towards higher temperatures when the A blocks form the minority domains and lower temperatures when the A blocks form the matrix. Although self-consistent field theory (SCFT) correctly accounts for the change in the OOTs, it incorrectly predicts the ODT to shift towards higher temperatures at all diblock copolymer compositions. In contrast, our simulations predict the correct shifts for both the OOTs and the ODT. This implies that polydispersity amplifies the fluctuation-induced correction to the mean-field ODT, which we attribute to a reduction in packing frustration. Consistent with this explanation, polydispersity is found to enhance the stability of the perforated-lamellar phase.

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.

Phase behavior of the orange essential oil/sodium bis(2-ethylhexyl)sulfosuccinate/water system

The ternary phase diagram for the orange essential oil (OEO)/sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/water system was constructed at 25 degrees C. It indicates a large single phase region, comprising an isotropic water-in-oil (W/O) microemulsion (ME) phase (L(2)), a liquid crystal (LC) (lamellar or hexagonal) and a large unstable emulsion phase that separates in two phases of normal and reverse micelles (L(1) and L(2)). In this communication the properties of the ME are investigated by viscosity, electric conductivity and small angle X-ray scattering (SAXS) indicating that the isotropic ME phase exhibits different behaviors depending on composition. At low water content low viscous ""dry"" surfactant structures are formed, whereas at higher water content higher viscous water droplets are formed. The experimental data allow the determination of the transition from ""dry"" to the water droplet structures within the L(2) phase. SAXS analyses have also been performed for selected LC samples. (C) 2009 Elsevier B.V. All rights reserved.

The magnetic phase diagram of Gd(2)Sn(2)O(7)

Measurements of the magnetic susceptibility of the frustrated pyrochlore magnet Gd(2)Sn(2)O(7) have been performed at temperatures below T = 5 K and in magnetic fields up to H = 12 T. The phase boundaries determined from these measurements are mapped out in an H-T phase diagram. In this gadolinium compound, where the crystal-field splitting is small and the exchange and dipolar energy are comparable, the Zeeman energy overcomes these competing energies, resulting in at least four magnetic phase transitions below 1 K. These data are compared against those for Gd(2)Ti(2)O(7) and will, we hope, stimulate further studies.

Ab initio calculation of the BCC Fe-Al-Mo (Iron-Aluminum-Molybdenum) phase diagram: Implications for the nature of the tau(2) phase

The metastable phase diagram of the BCC-based ordering equilibria in the Fe-Al-Mo system has been calculated via a truncated cluster expansion, through the combination of Full-Potential-Linear augmented Plane Wave (FP-LAPW) electronic structure calculations and of Cluster Variation Method (CVM) thermodynamic calculations in the irregular tetrahedron approximation. Four isothermal sections at 1750 K, 2000 K, 2250 K and 2500 K are calculated and correlated with recently published experimental data on the system. The results confirm that the critical temperature for the order-disorder equilibrium between Fe(3)Al-D0(3) and FeAl-B2 is increased by Mo additions, while the critical temperature for the FeAl-B2/A2 equilibrium is kept approximately invariant with increasing Mo contents. The stabilization of the Al-rich A2 phase in equilibrium with overstoichiometric B2-(Fe,Mo)Al is also consistent with the attribution of the A2 structure to the tau(2) phase, stable at high temperatures in overstoichiometric B2-FeAl. (C) 2009 Elsevier Ltd. All rights reserved.

Phase diagram and spectral properties of a new exactly integrable spin-1 quantum chain

The spectral properties and phase diagram of the exactly integrable spin-1 quantum chain introduced by Alcaraz and Bariev are presented. The model has a U(1) symmetry and its integrability is associated with an unknown R-matrix whose dependence on the spectral parameters is not of a different form. The associated Bethe ansatz equations that fix the eigenspectra are distinct from those associated with other known integrable spin models. The model has a free parameter t(p). We show that at the special point t(p) = 1, the model acquires an extra U(1) symmetry and reduces to the deformed SU(3) Perk-Schultz model at a special value of its anisotropy q = exp(i2 pi/3) and in the presence of an external magnetic field. Our analysis is carried out either by solving the associated Bethe ansatz equations or by direct diagonalization of the quantum Hamiltonian for small lattice sizes. The phase diagram is calculated by exploring the consequences of conformal invariance on the finite-size corrections of the Hamiltonian eigenspectrum. The model exhibits a critical phase ruled by the c = 1 conformal field theory separated from a massive phase by first-order phase transitions.

Phase behavior of the orange essential oil/sodium bis(2-ethylhexyl)sulfosuccinate/water system

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

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.

Oil-in-water lecithin-based microemulsions as a potential delivery system for amphotericin B

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

Phase diagram for freeze-dried persimmon

Phase transitions of freeze-dried persimmon in a large range of moisture content were determined by differential scanning calorimetry (DSC). In order to study this transitions at low and intermediate moisture content domains, samples were conditioned by adsorption at various water activities (a(w) = 0.11-0.90) at 25 degreesC. For the high moisture content region, samples were obtained by water addition. At a(w) less than or equal to 0.75 two glass transitions were visible, with T(g) decreasing with increasing water activity due to water plasticizing effect. The first T(g) is due to the matrix formed by sugars and water, the second one, less visible and less plasticized by water, is probably due to macromolecules of the fruit pulp. At a(w) between 0.80 and 0.90 a devitrification peak appeared after T(g) and before T(m). At this moisture content range, the Gordon-Taylor model represented satisfactorily the matrix glass transition curve. At the higher moisture content range (a(w) > 0.90), the more visible phenomenon was the ice melting. T(g) appeared less visible because the enthalpy change involved in glass transition is practically negligible in comparison with the latent heat of melting. In the high moisture content domain T(g) remained practically constant around T(g)' (-56.6 degreesC). (C) 2001 Elsevier B.V. B.V. All rights reserved.

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.

Influence of nearest-neighbor Coulomb interactions on the phase diagram of the ferromagnetic Kondo model

The influence of a nearest-neighbor Coulomb repulsion of strength V on the properties of the ferromagnetic Kondo model is analyzed using computational techniques. The Hamiltonian studied here is defined on a chain using localized S = 1/2 spins, and one orbital per site. Special emphasis is given to the influence of the Coulomb repulsion on the regions of phase separation recently discovered in this family of models, as well as on the double-exchange-induced ferromagnetic ground state. When phase separation dominates at V= 0, the Coulomb interaction breaks the large domains of the two competing phases into small islands of one phase embedded into the other. This is in agreement with several experimental results, as discussed in the text. Vestiges of the original phase separation regime are found in the spin structure factor as incommensurate peaks, even at large values of V. In the ferromagnetic regime close to density n = 0.5, the Coulomb interaction induces tendencies to charge ordering without altering the fully polarized character of the state. This regime of charge-ordered ferromagnetism may be related with experimental observations of a similar phase by Chen and Cheong [Phys. Rev. Lett. 76, 4042 (1996)]. Our results reinforce the recently introduced notion [see, e.g., S. Yunoki et al., Phys. Rev. Lett. 80, 845 (1998)] that in realistic models for manganites analyzed with unbiased many-body techniques, the ground state properties arise from a competition between ferromagnetism and phase-separation - charge-ordering tendencies. ©1999 The American Physical Society.

Enhancement of Nematic Order and Global Phase Diagram of a Lattice Model for Coupled Nematic Systems

We use an infinite-range Maier-Saupe model, with two sets of local quadrupolar variables and restricted orientations, to investigate the global phase diagram of a coupled system of two nematic subsystems. The free energy and the equations of state are exactly calculated by standard techniques of statistical mechanics. The nematic-isotropic transition temperature of system A increases with both the interaction energy among mesogens of system B, and the two-subsystem coupling J. This enhancement of the nematic phase is manifested in a global phase diagram in terms of the interaction parameters and the temperature T. We make some comments on the connections of these results with experimental findings for a system of diluted ferroelectric nanoparticles embedded in a nematic liquid-crystalline environment.

Effectiveness, against tuberculosis, of pseudo-ternary complexes: Peptide-DNA-cationic liposome

We report the effects of a synthetic peptide designed to act as a nuclear localization signal on the treatment of tuberculosis. The peptide contains 21 amino acid residues with the following specific domains: nuclear localization signal from SV 40T, cationic shuttle sequence, and cysteamide group at the C-terminus. The peptide was complexed with the plasmid DNAhsp65 and incorporated into cationic liposomes, forming a pseudo-ternary complex. The same cationic liposomes, composed of egg chicken L-alpha-phosphatidylcholine, 1,2-dioleoyl-3-trimethylammonium-propane, and 1,2-dioleoyl-3-trimethylammonium-propane (2:1:1 M), were previously evaluated as a gene carrier for tuberculosis immunization protocols with DNAhsp65. The pseudo-ternary complex presented a controlled size (250 nm), spherical-like shape, and various lamellae in liposomes as evaluated by transmission electron microscopy. An assay of fluorescence probe accessibility confirmed insertion of the peptide/DNA into the liposome structure. Peptide addition conferred no cytotoxicity in vitro, and similar therapeutic effects against tuberculosis were seen with four times less DNA compared with naked DNA treatment. Taken together, the results indicate that the pseudo-ternary complex is a promising gene vaccine for tuberculosis treatment. This work contributes to the development of multifunctional nanostructures in the search for strategies for in vivo DNA delivery. (C) 2011 Elsevier Inc. All rights reserved.

Microemulsion: prediction of the phase diagram with a modified Helfrich free energy

Microemulsions are thermodynamically stable, macroscopically homogeneous but microscopically heterogeneous, mixtures of water and oil stabilised by surfactant molecules. They have unique properties like ultralow interfacial tension, large interfacial area and the ability to solubilise other immiscible liquids. Depending on the temperature and concentration, non-ionic surfactants self assemble to micelles, flat lamellar, hexagonal and sponge like bicontinuous morphologies. Microemulsions have three different macroscopic phases (a) 1phase- microemulsion (isotropic), (b) 2phase-microemulsion coexisting with either expelled water or oil and (c) 3phase- microemulsion coexisting with expelled water and oil.rnrnOne of the most important fundamental questions in this field is the relation between the properties of the surfactant monolayer at water-oil interface and those of microemulsion. This monolayer forms an extended interface whose local curvature determines the structure of the microemulsion. The main part of my thesis deals with the quantitative measurements of the temperature induced phase transitions of water-oil-nonionic microemulsions and their interpretation using the temperature dependent spontaneous curvature [c0(T)] of the surfactant monolayer. In a 1phase- region, conservation of the components determines the droplet (domain) size (R) whereas in 2phase-region, it is determined by the temperature dependence of c0(T). The Helfrich bending free energy density includes the dependence of the droplet size on c0(T) as