Liquid mixtures involving fluorinated alcohols: The equation of state (p, r, T, x) of (Ethanol + Trifluoroethanol) Experimental and Simulation

Liquid mixtures involving fluorinated alcohols: The equation of state (p, r, T, x) of (Ethanol + Trifluoroethanol) Experimental and Simulation Pedro Duartea, Djêide Rodriguesa, Marcelo Silvaa, Pedro Morgadoa, Luís Martinsa,b and Eduardo J. M. Filipea* aCentro de Química Estrutural, Instituto Superior Técnico, 1049-001 Lisboa, Portugal bCentro de Química de Évora, Universidade de Évora, 7000-671 Évora, Portugal Fluorinated alcohols are substances with unique properties and high technological value in the pharmaceutical and chemical industries. Trifluoroethanol (TFE), in particular, displays a number of unusual properties as a solvent. For example, it dissolves nylon at room temperature and is effectively used as solvent in bioengineering. The presence of the three fluorines atoms gives the alcohol a high ionization constant, strong hydrogen bonding capability and stability at high temperatures. In the pharmaceutical industry, TFE finds use as the major raw material for the production of inhalation anesthetics. Mixtures of TFE and water (known as Fluorinols®) are used as working fluids for Rankine cycle heat engines for terrestrial and space applications, as a result of a unique combination of physical and thermodynamic properties such as high thermal efficiency and excellent turbine expansion characteristics. Environmentally, TFE is a CFC substitute with an acceptable short lifetime and with small ozone depletion potential. Additionally, TFE is known to induce conformational changes in proteins and it is used as a co-solvent to analyze structural features of partially folded states. The (ethanol + TFE) system displays an interesting and peculiar behaviour, combining a negative azeotrope with high positive excess volumes. In this work, liquid mixtures of (ethanol + TFE) were investigated. The densities of the mixtures were measured as a function of composition between 278K and 338K and at pressures up to 700 bar. The corresponding excess volumes as a function of temperature and pressure, the isothermal compressibilities and thermal expansivities were calculated from the experimental results. The mixtures are highly non-ideal with excess volumes ranging from 0.8 - 1.0 cm3mol-1. Finally, molecular dynamic simulations were performed to model and interpret the experimental results. The Trappe force field was used to simulate the (TFE + ethanol) mixtures and calculate the corresponding excess volumes. The simulation results are able to reproduce the correct sign and order of magnitude of the experimental VE without fitting to the experimental data. Furthermore, the simulations suggest the presence of a particular type of hydrogen bridge between ethanol and TFE, that can help to rationalize the experimental results

Improved magnetodielectric coefficient on polymer based composites through enhanced indirect magnetoelectric coupling

Particulate composites of ferrite and ferroelectric polymer phases with general formula [xCoFe2O4]/[(1-x) PVDF] were prepared for x = 0, 3, 11 and 20 wt.% by solution casting. The dielectric constant, dielectric loss and saturation magnetization of the polymer composite films increase with increasing CoFe2O4 (CFO) content, being 13, 0.13 and 13 emu.g-1 respectively, for x=20. The magnetodielectric (MD) coupling also depend on the CFO content, the change in the dielectric response (MDE(%)) being the highest for the x=20 sample (4.2%). On the other hand, the highest value of the MD coefficient (γ) is higher on the x=3 sample (0.015 emu-2g2). Those values are favourably compared with the ones found in the ceramic-based MD materials, being the highest reported for polymer composites. These facts, together with the flexibility and scalable production of the composites, leads to their large application potential in areas such as filters, magnetic field sensors and actuators, among others.The authors thank the Portuguese Fundação para a Ciência e Tecnologia (FCT) for financial support under projects PTDC/EEI-SII/5582/2014 and PTDC/CTM-ENE/5387/2014.P. M. and M. Silva acknowledges also support from FCT (SFRH/BPD/96227/2013 and SFRH/BD/70303/2010 grants respectively). Financial support from the Basque Government Industry Department under the ELKARTEK Program is also acknowledged. SLM thanks the Diputación Foral de Bizkaia for financial support under the Bizkaia Talent program; European Union’s Seventh Framework Programme; Marie Curie Actions – People; Grant agreement nº 267230