Re-entrant phase behaviour of network fluids: A patchy particle model with temperature-dependent valence

We study a model consisting of particles with dissimilar bonding sites ("patches"), which exhibits self-assembly into chains connected by Y-junctions, and investigate its phase behaviour by both simulations and theory. We show that, as the energy cost epsilon(j) of forming Y-junctions increases, the extent of the liquid-vapour coexistence region at lower temperatures and densities is reduced. The phase diagram thus acquires a characteristic "pinched" shape in which the liquid branch density decreases as the temperature is lowered. To our knowledge, this is the first model in which the predicted topological phase transition between a fluid composed of short chains and a fluid rich in Y-junctions is actually observed. Above a certain threshold for epsilon(j), condensation ceases to exist because the entropy gain of forming Y-junctions can no longer offset their energy cost. We also show that the properties of these phase diagrams can be understood in terms of a temperature-dependent effective valence of the patchy particles. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3605703]

Nonmonotonic Magnetic Susceptibility of Dipolar Hard-Spheres at Low Temperature and Density

We investigate, via numerical simulations, mean field, and density functional theories, the magnetic response of a dipolar hard sphere fluid at low temperatures and densities, in the region of strong association. The proposed parameter-free theory is able to capture both the density and temperature dependence of the ring-chain equilibrium and the contribution to the susceptibility of a chain of generic length. The theory predicts a nonmonotonic temperature dependence of the initial (zero field) magnetic susceptibility, arising from the competition between magnetically inert particle rings and magnetically active chains. Monte Carlo simulation results closely agree with the theoretical findings. DOI: 10.1103/PhysRevLett.110.148306

Density measurements of compressed dipropyl, dibutul, bis (2-ethylhexyl) adipates from (293 to 373K) at pressures up to about 68MPa

The article reports density measurements of dipropyl (DPA), dibutyl (DBA) and bis(2-ethylhexyl) (DEHA) adipates, using a vibrating U-tube densimeter, model DMA HP, from Anton Paar GmbH. The measurements were performed in the temperature range (293 to 373) K and at pressures up to about 68 MPa, except for DPA for which the upper limits were 363 K and 65 MPa, respectively. The density data for each liquid was correlated with the temperature and pressure using a modified Tait equation. The expanded uncertainty of the present density results is estimated as 0.2% at a 95% confidence level. No literature density data at pressures higher than 0.1 MPa could be found. DEHA literature data at atmospheric pressure agree with the correlation of the present measurements, in the corresponding temperature range, within +/- 0.11%. The isothermal compressibility and the isobaric thermal expansion were calculated by differentiation of the modified Tait correlation equation. These two parameters were also calculated for dimethyl adipate (DMA), from density data reported in a previous work. The uncertainties of isothermal compressibility and the isobaric thermal expansion are estimated to be less than +/- 1.7% and +/- 1.1%, respectively, at a 95% confidence level. Literature data of isothermal compressibility and isobaric thermal expansivity for DMA have an agreement within +/- 1% and +/- 2.4%, respectively, with results calculated in this work. (C) 2014 Elsevier B.V. All rights reserved.

Tris(2-Ethylhexyl) trimellitate (TOTM) a potential reference fluid for high viscosity. Part II: density measurements at temperatures from (293 to 373)K and pressures up to 85MPa

In Part I of the present work we describe the viscosity measurements performed on tris(2-ethylhexyl) trimellitate or 1,2,4-benzenetricarboxylic acid, tris(2-ethylhexyl) ester (TOTM) up to 65 MPa and at six temperatures from (303 to 373)K, using a new vibrating-wire instrument. The main aim is to contribute to the proposal of that liquid as a potential reference fluid for high viscosity, high pressure and high temperature. The present Part II is dedicated to report the density measurements of TOTM necessary, not only to compute the viscosity data presented in Part I, but also as complementary data for the mentioned proposal. The present density measurements were obtained using a vibrating U-tube densimeter, model DMA HP, using model DMA5000 as a reading unit, both instruments from Anton Paar GmbH. The measurements were performed along five isotherms from (293 to 373)K and at eleven different pressures up to 68 MPa. As far as the authors are aware, the viscosity and density results are the first, above atmospheric pressure, to be published for TOTM. Due to TOTM's high viscosity, its density data were corrected for the viscosity effect on the U-tube density measurements. This effect was estimated using two Newtonian viscosity standard liquids, 20 AW and 200 GW. The density data were correlated with temperature and pressure using a modified Tait equation. The expanded uncertainty of the present density results is estimated as +/- 0.2% at a 95% confidence level. Those results were correlated with temperature and pressure by a modified Tait equation, with deviations within +/- 0.25%. Furthermore, the isothermal compressibility, K-T, and the isobaric thermal expansivity, alpha(p), were obtained by derivation of the modified Tait equation used for correlating the density data. The corresponding uncertainties, at a 95% confidence level, are estimated to be less than +/- 1.5% and +/- 1.2%, respectively. No isobaric thermal expansivity and isothermal compressibility for TOTM were found in the literature. (C) 2014 Elsevier B.V. All rights reserved.

Constrains on the structure of Maio Island (Cape Verde) by a three-dimensional gravity model: Imaging partially exhumed magma chambers

We propose a 3-D gravity model for the volcanic structure of the island of Maio (Cape Verde archipelago) with the objective of solving some open questions concerning the geometry and depth of the intrusive Central Igneous Complex. A gravity survey was made covering almost the entire surface of the island. The gravity data was inverted through a non-linear 3-D approach which provided a model constructed in a random growth process. The residual Bouguer gravity field shows a single positive anomaly presenting an elliptic shape with a NWSE trending long axis. This Bouguer gravity anomaly is slightly off-centred with the island but its outline is concordant with the surface exposure of the Central Igneous Complex. The gravimetric modelling shows a high-density volume whose centre of mass is about 4500 m deep. With increasing depth, and despite the restricted gravimetric resolution, the horizontal sections of the model suggest the presence of two distinct bodies, whose relative position accounts for the elongated shape of the high positive Bouguer gravity anomaly. These bodies are interpreted as magma chambers whose coeval volcanic counterparts are no longer preserved. The orientation defined by the two bodies is similar to that of other structures known in the southern group of the Cape Verde islands, thus suggesting a possible structural control constraining the location of the plutonic intrusions.

Properties of patchy colloidal particles close to a surface: a Monte Carlo and density functional study

We investigate the behavior of a patchy particle model close to a hard-wall via Monte Carlo simulation and density functional theory (DFT). Two DFT approaches, based on the homogeneous and inhomogeneous versions of Wertheim's first order perturbation theory for the association free energy are used. We evaluate, by simulation and theory, the equilibrium bulk phase diagram of the fluid and analyze the surface properties for two isochores, one of which is close to the liquid side of the gas-liquid coexistence curve. We find that the density profile near the wall crosses over from a typical high-temperature adsorption profile to a low-temperature desorption one, for the isochore close to coexistence. We relate this behavior to the properties of the bulk network liquid and find that the theoretical descriptions are reasonably accurate in this regime. At very low temperatures, however, an almost fully bonded network is formed, and the simulations reveal a second adsorption regime which is not captured by DFT. We trace this failure to the neglect of orientational correlations of the particles, which are found to exhibit surface induced orientational order in this regime.