Phase behavior, crystallization, and nanostructures in thermoset blends of epoxy resin and amphiphilic star-shaped block copolymers

This article reports thermoset blends of bisphenol A-type epoxy resin (ER) and two amphiphilic four-arm star-shaped diblock copolymers based on hydrophilic poly(ethylene oxide) (PEO) and hydrophobic poly(propylene oxide) (PPO). 4,4'-Methylenedianiline (MDA) was used as a curing agent. The first star-shaped diblock copolymer with 70 wt% ethylene oxide (EO), denoted as (PPO-PEO)(4), consists of four PPO-PEO diblock arms with PPO blocks attached on an ethylenediamine core; the second one with 40 wt% EO, denoted as (PEO-PPO)(4), contains four PEO-PPO diblock arms with PEO blocks attached on an ethylenediamine core. The phase behavior, crystallization, and nanoscale structures were investigated by differential scanning calorimetry, transmission electron microscopy, and small-angle X-ray scattering. It was found that the MDA-cured ER/(PPO-PEO)(4) blends are not macroscopically phase-separated over the entire blend composition range. There exist, however, two microphases in the ER/(PPO-PEO)(4) blends. The PPO blocks form a separated microphase, whereas the ER and the PEO blocks, which are miscible, form another microphase. The ER/(PPO-PEO)(4) blends show composition-dependent nanostructures on the order of 10-30 nm. The 80/20 ER/(PPO-PEO)(4) blend displays spherical PPO micelles uniformly dispersed in a continuous ER-rich matrix. The 60/40 ER/(PPO-PEO)(4) blend displays a combined morphology of worm-like micelles and spherical micelles with characteristic of a bicontinuous microphase structure. Macroscopic phase separation took place in the MDA-cured ER/(PEO-PPO)(4) blends. The MDA-cured ER/(PEO-PPO)(4) blends with (PEO-PPO)(4) content up to 50 wt% exhibit phase-separated structures on the order of 0.5-1 mu m. This can be considered to be due to the different EO content and block sequence of the (PEO-PPO)(4) copolymer. (c) 2006 Wiley Periodicals, Inc.

The effect of ultrasonic waves on the phase behavior of a surfactant-brine-oil system

Acknowledgements The authors would like to gratefully acknowledge and appreciate the School of Engineering, University of Aberdeen, Aberdeen, Scotland, UK, for the provision of the laboratory facilities necessary for completing this work.

The effect of ultrasonic waves on the phase behavior of a surfactant-brine-oil system

Acknowledgements The authors would like to gratefully acknowledge and appreciate the School of Engineering, University of Aberdeen, Aberdeen, Scotland, UK, for the provision of the laboratory facilities necessary for completing this work.

Phase behavior and far-from-equilibrium gelation in charged attractive colloids

In this Rapid Communication we demonstrate the applicability of an augmented Gibbs ensemble Monte Carlo approach for the phase behavior determination of model colloidal systems with short-ranged depletion attraction and long-ranged repulsion. This technique allows for a quantitative determination of the phase boundaries and ground states in such systems. We demonstrate that gelation may occur in systems of this type as the result of arrested microphase separation, even when the equilibrium state of the system is characterized by compact microphase structures.

Systematic characterization of thermodynamic and dynamical phase behavior in systems with short-ranged attraction

In this paper we demonstrate the feasibility and utility of an augmented version of the Gibbs ensemble Monte Carlo method for computing the phase behavior of systems with strong, extremely short-ranged attractions. For generic potential shapes, this approach allows for the investigation of narrower attractive widths than those previously reported. Direct comparison to previous self-consistent Ornstein-Zernike approximation calculations is made. A preliminary investigation of out-of-equilibrium behavior is also performed. Our results suggest that the recent observations of stable cluster phases in systems without long-ranged repulsions are intimately related to gas-crystal and metastable gas-liquid phase separation.

Shape and chemically anisotropic colloidal particles: A theoretical study of their structure, phase behavior, and slow dynamics

A detailed non-equilibrium state diagram of shape-anisotropic particle fluids is constructed. The effects of particle shape are explored using Naive Mode Coupling Theory (NMCT), and a single particle Non-linear Langevin Equation (NLE) theory. The dynamical behavior of non-ergodic fluids are discussed. We employ a rotationally frozen approach to NMCT in order to determine a transition to center of mass (translational) localization. Both ideal and kinetic glass transitions are found to be highly shape dependent, and uniformly increase with particle dimensionality. The glass transition volume fraction of quasi 1- and 2- dimensional particles fall monotonically with the number of sites (aspect ratio), while 3-dimensional particles display a non-monotonic dependence of glassy vitrification on the number of sites. Introducing interparticle attractions results in a far more complex state diagram. The ideal non-ergodic boundary shows a glass-fluid-gel re-entrance previously predicted for spherical particle fluids. The non-ergodic region of the state diagram presents qualitatively different dynamics in different regimes. They are qualified by the different behaviors of the NLE dynamic free energy. The caging dominated, repulsive glass regime is characterized by long localization lengths and barrier locations, dictated by repulsive hard core interactions, while the bonding dominated gel region has short localization lengths (commensurate with the attraction range), and barrier locations. There exists a small region of the state diagram which is qualified by both glassy and gel localization lengths in the dynamic free energy. A much larger (high volume fraction, and high attraction strength) region of phase space is characterized by short gel-like localization lengths, and long barrier locations. The region is called the attractive glass and represents a 2-step relaxation process whereby a particle first breaks attractive physical bonds, and then escapes its topological cage. The dynamic fragility of fluids are highly particle shape dependent. It increases with particle dimensionality and falls with aspect ratio for quasi 1- and 2- dimentional particles. An ultralocal limit analysis of the NLE theory predicts universalities in the behavior of relaxation times, and elastic moduli. The equlibrium phase diagram of chemically anisotropic Janus spheres and Janus rods are calculated employing a mean field Random Phase Approximation. The calculations for Janus rods are corroborated by the full liquid state Reference Interaction Site Model theory. The Janus particles consist of attractive and repulsive regions. Both rods and spheres display rich phase behavior. The phase diagrams of these systems display fluid, macrophase separated, attraction driven microphase separated, repulsion driven microphase separated and crystalline regimes. Macrophase separation is predicted in highly attractive low volume fraction systems. Attraction driven microphase separation is charaterized by long length scale divergences, where the ordering length scale determines the microphase ordered structures. The ordering length scale of repulsion driven microphase separation is determined by the repulsive range. At the high volume fractions, particles forgo the enthalpic considerations of attractions and repulsions to satisfy hard core constraints and maximize vibrational entropy. This results in site length scale ordering in rods, and the sphere length scale ordering in Janus spheres, i.e., crystallization. A change in the Janus balance of both rods and spheres results in quantitative changes in spinodal temperatures and the position of phase boundaries. However, a change in the block sequence of Janus rods causes qualitative changes in the type of microphase ordered state, and induces prominent features (such as the Lifshitz point) in the phase diagrams of these systems. A detailed study of the number of nearest neighbors in Janus rod systems reflect a deep connection between this local measure of structure, and the structure factor which represents the most global measure of order.

Lipid-Based Liquid Crystals As Carriers for Antimicrobial Peptides: Phase Behavior and Antimicrobial Effect

International audience

Study of the thermal behavior of the transition phase of Co(II)-diclofenac compound by non-isothermal method

The Co(II)-diclofenac complex was evaluated by simultaneous thermogravimetry-differential thermal analysis (TG-DTA) and differential scanning calorimetry (DSC). The DTA curve profile shows one exothermic peak because of the transition phase of the compound between 170 and 180 A degrees C, which was confirmed by X-ray powder diffractometry. The transition phase behavior was studied by DSC curves at several heating rates of a sample mass between 1 and 10 mg in nitrogen atmosphere and in a crucible with and without a lid. Thus, the kinetic parameters were evaluated using an isoconversional non-linear fitting proposed by Capela and Ribeiro. The results show that the activation energy and pre-exponential factor for the transition phase is dependant on the different experimental conditions. Nevertheless, these results indicate that the kinetic compensation effect shows a relationship between them.

Liquid polymorphism, order-disorder transitions and anomalous behavior: A Monte Carlo study of the Bell-Lavis model for water

The Bell-Lavis model for liquid water is investigated through numerical simulations. The lattice-gas model on a triangular lattice presents orientational states and is known to present a highly bonded low density phase and a loosely bonded high density phase. We show that the model liquid-liquid transition is continuous, in contradiction with mean-field results on the Husimi cactus and from the cluster variational method. We define an order parameter which allows interpretation of the transition as an order-disorder transition of the bond network. Our results indicate that the order-disorder transition is in the Ising universality class. Previous proposal of an Ehrenfest second order transition is discarded. A detailed investigation of anomalous properties has also been undertaken. The line of density maxima in the HDL phase is stabilized by fluctuations, absent in the mean-field solution. (C) 2009 American Institute of Physics. [doi:10.1063/1.3253297]

Frustration and anomalous behavior in the Bell-Lavis model of liquid water

We have reconsidered the Bell-Lavis model of liquid water and investigated its relation to its isotropic version, the antiferromagnetic Blume-Emery-Griffiths model on the triangular lattice. Our study was carried out by means of an exact solution on the sequential Husimi cactus. We show that the ground states of both models share the same topology and that fluid phases (gas and low- and high-density liquids) can be mapped onto magnetic phases (paramagnetic, antiferromagnetic, and dense paramagnetic, respectively). Both models present liquid-liquid coexistence and several thermodynamic anomalies. This result suggests that anisotropy introduced through orientational variables play no specific role in producing the density anomaly, in agreement with a similar conclusion discussed previously following results for continuous soft core,models. We propose that the presence of liquid anomalies may be related to energetic frustration, a feature common to both models.

Phase diagrams of binary mixtures of patchy colloids with distinct numbers and types of patches: Theempty fluid regime

We investigate the effect of distinct bonding energies on the onset of criticality of low functionality fluid mixtures. We focus on mixtures ofparticles with two and three patches as this includes the mixture where "empty" fluids were originally reported. In addition to the number of patches, thespecies differ in the type of patches or bonding sites. For simplicity, we consider that the patches on each species are identical: one species has threepatches of type A and the other has two patches of type B. We have found a rich phase behavior with closed miscibility gaps, liquid-liquid demixing, and negative azeotropes. Liquid-liquid demixing was found to pre-empt the "empty" fluid regime, of these mixtures, when the AB bonds are weaker than the AA or BB bonds. By contrast, mixtures in this class exhibit "empty" fluid behavior when the AB bonds are stronger than at least one of the other two. Mixtureswith bonding energies epsilon(BB) = epsilon(AB) and epsilon(AA) < epsilon(BB), were found to exhibit an unusual negative azeotrope. (C) 2011 American Institute of Physics. [doi:10.1063/1.3561396]

Metastable liquid-liquid phase transition in a single-component system with only one crystal phase and no density anomaly

We investigate the phase behavior of a single-component system in three dimensions with spherically-symmetric, pairwise-additive, soft-core interactions with an attractive well at a long distance, a repulsive soft-core shoulder at an intermediate distance, and a hard-core repulsion at a short distance, similar to potentials used to describe liquid systems such as colloids, protein solutions, or liquid metals. We showed [Nature (London) 409, 692 (2001)] that, even with no evidence of the density anomaly, the phase diagram has two first-order fluid-fluid phase transitions, one ending in a gas¿low-density-liquid (LDL) critical point, and the other in a gas¿high-density-liquid (HDL) critical point, with a LDL-HDL phase transition at low temperatures. Here we use integral equation calculations to explore the three-parameter space of the soft-core potential and perform molecular dynamics simulations in the interesting region of parameters. For the equilibrium phase diagram, we analyze the structure of the crystal phase and find that, within the considered range of densities, the structure is independent of the density. Then, we analyze in detail the fluid metastable phases and, by explicit thermodynamic calculation in the supercooled phase, we show the absence of the density anomaly. We suggest that this absence is related to the presence of only one stable crystal structure.

Electron transfer by singlet excited state of porphyn and electron acceptor affinity in rigid medium: photoacoustic phase angle analysis

Photoacoustic spectroscopy provides information about both amplitude and phase of the response of a system to an optical excitation process. This paper presents the studies of the phase in the electron transfer process between octaethylporphyn (OEP) and quinone molecules dispersed in a polymeric matrix. It was observed a tendency in the phase behavior to small values only in the spectral region near to 620 nm, while for shorter wavelength did not show any tendency. These measurements suggested that the electron transfer to acceptor occurred with the participation of octaethylporphyn singlet excited state.

Molecular computations for reactions and phase transitions: applications to protein stabilization, hydrates and catalysis

In this work we have made significant contributions in three different areas of interest: therapeutic protein stabilization, thermodynamics of natural gas clathrate-hydrates, and zeolite catalysis. In all three fields, using our various computational techniques, we have been able to elucidate phenomena that are difficult or impossible to explain experimentally. More specifically, in mixed solvent systems for proteins we developed a statistical-mechanical method to model the thermodynamic effects of additives in molecular-level detail. It was the first method demonstrated to have truly predictive (no adjustable parameters) capability for real protein systems. We also describe a novel mechanism that slows protein association reactions, called the “gap effect.” We developed a comprehensive picture of methioine oxidation by hydrogen peroxide that allows for accurate prediction of protein oxidation and provides a rationale for developing strategies to control oxidation. The method of solvent accessible area (SAA) was shown not to correlate well with oxidation rates. A new property, averaged two-shell water coordination number (2SWCN) was identified and shown to correlate well with oxidation rates. Reference parameters for the van der Waals Platteeuw model of clathrate-hydrates were found for structure I and structure II. These reference parameters are independent of the potential form (unlike the commonly used parameters) and have been validated by calculating phase behavior and structural transitions for mixed hydrate systems. These calculations are validated with experimental data for both structures and for systems that undergo transitions from one structure to another. This is the first method of calculating hydrate thermodynamics to demonstrate predictive capability for phase equilibria, structural changes, and occupancy in pure and mixed hydrate systems. We have computed a new mechanism for the methanol coupling reaction to form ethanol and water in the zeolite chabazite. The mechanism at 400°C proceeds via stable intermediates of water, methane, and protonated formaldehyde.