Exploring the free energy surfaces of clusters using reconnaissance metadynamics

A new approach is proposed for exploring the low-energy structures of small to medium-sized aggregates of atoms and molecules. This approach uses the recently proposed reconnaissance metadynamics method [G. A. Tribello, M. Ceriotti, and M. Parrinello. Proc. Natl. Acad. Sci. U.S.A. 107(41), 17509 (2010)] in tandem with collective variables that describe the average structure of the coordination sphere around the atoms/molecules. We demonstrate this method on both Lennard-Jones and water clusters and show how it is able to quickly find the global minimum in the potential energy surface, while exploring the finite temperature free energy surface. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3628676]

Nonequilibrium Quantum Landauer Principle

Using the operational framework of completely positive, trace preserving operations and thermodynamic fluctuation relations, we derive a lower bound for the heat exchange in a Landauer erasure process on a quantum system. Our bound comes from a nonphenomenological derivation of the Landauer principle which holds for generic nonequilibrium dynamics. Furthermore, the bound depends on the nonunitality of dynamics, giving it a physical significance that differs from other derivations. We apply our framework to the model of a spin-1/2 system coupled to an interacting spin chain at finite temperature.

Landauer’s Principle in Multipartite Open Quantum System Dynamics

We investigate the link between information and thermodynamics embodied by Landauer’s principle in the open dynamics of a multipartite quantum system. Such irreversible dynamics is described in terms of a collisional model with a finite temperature reservoir. We demonstrate that Landauer’s principle holds, for such a configuration, in a form that involves the flow of heat dissipated into the environment and the rate of change of the entropy of the system. Quite remarkably, such a principle for heat and entropy power can be explicitly linked to the rate of creation of correlations among the elements of the multipartite system and, in turn, the non-Markovian nature of their reduced evolution. Such features are illustrated in two exemplary cases.

Reconsidering the Origins of Forsbergh Birefringence Patterns

In 1949, P. W. Forsbergh Jr. reported spontaneous spatial ordering in the birefringence patterns seen in flux-grown BaTiO3 crystals [1], under the transmission polarized light microscope [2]. Stunningly regular square-net arrays were often only found within a finite temperature window and could be induced on both heating and cooling, suggesting genuine thermodynamic stability. At the time, Forsbergh rationalized the patterns to have resulted from the impingement of ferroelastic domains, creating a complex tessellation of variously shaped domain packets. However, evidence for the intricate microstructural arrangement proposed by Forsbergh has never been found. Moreover, no robust thermodynamic argument has been presented to explain the region of thermal stability, its occurrence just below the Curie Temperature and the apparent increase in entropy associated with the loss of the Forsbergh pattern on cooling. As a result, despite decades of research on ferroelectrics, this ordering phenomenon and its thermodynamic origin have remained a mystery. In this paper, we re-examine the microstructure of flux-grown BaTiO3 crystals, which show Forsbergh birefringence patterns. Given an absence of any obvious arrays of domain polyhedra, or even regular shapes of domain packets, we suggest an alternative origin for the Forsbergh pattern, in which sheets of orthogonally oriented ferroelastic stripe domains simply overlay one another. We show explicitly that the Forsbergh birefringence pattern occurs if the periodicity of the stripe domains is above a critical value. Moreover, by considering well-established semiempirical models, we show that the significant domain coarsening needed to generate the Forsbergh birefringence is fully expected in a finite window below the Curie Temperature. We hence present a much more straightforward rationalization of the Forsbergh pattern than that originally proposed, in which exotic thermodynamic arguments are unnecessary.

Nonlinear numerical modelling of lightning strike effect on composite panels with temperature dependent material properties

This paper presents a physics based modelling procedure to predict the thermal damage of composite material when struck by lightning. The procedure uses the Finite Element Method with non-linear material models to represent the extreme thermal material behaviour of the composite material (carbon/epoxy) and an embedded copper mesh protection system. Simulation predictions are compared against published experimental data, illustrating the potential accuracy and computational cost of virtual lightning strike tests and the requirement for temperature dependent material modelling. The modelling procedure is then used to examine and explain a number of practical solutions to minimize thermal material damage. © 2013 Elsevier Ltd.

NONLINEAR NUMERICAL MODELLING OF LIGHTENING STRIKE EFFECT ON COMPOSITE PANELS WITH TEMPERATURE DEPENDANT MATERIAL PROPERTIES

Lightning strike is one of the challenges that the aerospace industry is facing in an effort to increase the percentage of composite materials used in aircraft structures. Lightning strike damage is due to high orthotropic electric resistivity of the composite panels, which leads to high thermal loads that cause decomposition of the epoxy and delimitations of the laminates. Yet, experimental testing of lightning strike on aircraft panels is expensive due to the large number of design parameters that can control the inflicted damage. A coupled thermal-electrical finite element analysis is used to investigate the design variables space that can affect lightning strike damage on epoxy/graphite composite panels. The contribution of this study is modeling the composite panels’ material properties as temperature dependent, which was excluded by other researchers. A number of practical solutions to minimize the damage effect are proposed. Two set of experimental results are used to verify the numerical ones. One experimental set for plain composite panel, and second one for composite panels with joints

Coupled Temperature-Displacement Modelling of Injection Stretch Blow Moulding of PET bottles using Buckley Model

This study presents a fully coupled temperature–displacement finite element modelling of the injection stretch-blow moulding (ISBM) process of polyethylene terephthalate (PET) bottles using ABAQUS with a view to optimising the process conditions. A physically-based material model (Buckley model) was used to predict the mechanical behaviour of PET at temperatures slightly above its glass transition temperature. A model incorporating heat transfer between the stretch rod, the preform and the mould was built using axisymmetric solid elements. Extensive finite element analyses were carried out to predict the deformation, the distribution and history of strain and temperature during ISBM of a 20 g–330 ml bottle, which was made in an in situ test on a Sidel SB06 machine. Comparisons of numerical results with the measurements demonstrate that the model can satisfactorily model the sidewall thickness and material distributions. It is also shown that significant non-linear differentials exist in temperature and strain in both bottle thickness and length directions during the process. This justifies the employment of a volume approach to accurately predict the final mechanical properties of the bottles governed by the orientation and crystallinity which are highly temperature and strain dependent.

Prediction of ionic liquid properties. I. Volumetric properties as a function of temperature at 0.1 MPa

The prediction of molar volumes and densities of several ionic liquids has been achieved using a group contribution model as a function of temperature between (273 and 423) K at atmospheric pressure. It was observed that the calculation of molar volumes or densities could be performed using the "ideal" behavior of the molar volumes of mixtures of ionic liquids. This model is based on the observations of Canongia Lopes et al. (J. Phys. Chem. B 2005, 109, 3519-3525) which showed that this ideal behavior is independent of the temperature and allows the molar volume of a given ionic liquid to be calculated by the sum of the effective molar volume of the component ions. Using this assumption, the effective molar volumes of ions constituting more than 220 different ionic liquids were calculated as a function of the temperature at 0.1 MPa using more than 2150 data points. These calculated results were used to build up a group contribution model for the calculation of ionic liquid molar volumes and densities with an estimated repeatability and uncertainty of 0.36% and 0.48%, respectively. The impact of impurities (water and halide content) in ionic liquids as well as the method of determination were also analyzed and quantified to estimate the overall uncertainty. © 2008 American Chemical Society.

Liquid-liquid miscibility and volumetric properties of aqueous solutions of ionic liquids as a function of temperature

The volumetric properties of seven {water + ionic liquid} binary mixtures have been studied as a function of temperature from (293 to 343) K. The phase behaviour of the systems was first investigated using a nephelometric method and excess molar volumes were calculated from densities measured using an Anton Paar densimeter and fitted using a Redlich-Kister type equation. Two ionic liquids fully miscible with water (1-butyl-3-methylimidazolium tetrafluoroborate ([CCIm][BF]) and 1-ethyl-3-methylimidazolium ethylsulfate ([CCIm][EtSO])) and five ionic liquids only partially miscible with water (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([CCIm][NTf]), 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([CCIm][NTf]), 1-butyl-3-methylimidazolium hexafluorophosphate ([CCIm][PF]), 1-butyl-3-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([CCPyrro][NTf]), and butyltrimethylammonium bis(trifluoromethylsulfonyl)imide ([N][NTf])) were chosen. Small excess volumes (less than 0.5 cm · mol at 298 K) are obtained compared with the molar volumes of the pure components (less than 0.3% of the molar volume of the pure ionic liquid). For all the considered systems, except for {[CCIm][EtSO] + water}, positive excess molar volumes were calculated. Finally, an increase of the non-ideality character is observed for all the systems as temperature increases. © 2009 Elsevier Ltd. All rights reserved.

Finite ion temperature effects on oblique modulational stability and envelope excitations of dust-ion acoustic waves

Theoretical and numerical investigations are carried out for the amplitude modulation of dust-ion acoustic waves (DIAW) propagating in an unmagnetized weakly coupled collisionless fully ionized plasma consisting of isothermal electrons, warm ions and charged dust grains. Modulation oblique (by an angle theta) to the carrier wave propagation direction is considered. The stability analysis, based on a nonlinear Schrodinger-type equation (NLSE), exhibits a sensitivity of the instability region to the modulation angle theta, the dust concentration and the ion temperature. It is found that the ion temperature may strongly modify the wave's stability profile, in qualitative agreement with previous results, obtained for an electron-ion plasma. The effect of the ion temperature on the formation of DIAW envelope excitations (envelope solitons) is also discussed.

The effect of temperature and strain rate on the deformation behaviour, structure development and properties of biaxially stretched PET-clay nanocomposites.

The inclusion of a synthetic fluoromica clay in PET affects its processability via biaxial stretching and stretching temperature (95 °C and 102 °C) and strain rate (1 s-1 and 2 s-1) influence the structuring and properties of the stretched material. The inclusion of clay has little effect on the temperature operating window for the PET–clay but it has a major effect on deformation behaviour which will necessitate the use of much higher forming forces during processing. The strain hardening behaviour of both the filled and unfilled materials is well correlated with tensile strength and tensile modulus. Increasing the stretching temperature to reduce stretching forces has a detrimental effect on clay exfoliation, mechanical and O2 barrier properties. Increasing strain rate has a lesser effect on the strain hardening behaviour of the PET–clay compared with the pure PET and this is attributed to possible adiabatic heating in the PET–clay sample at the higher strain rate. The Halpin–Tsai model is shown to accurately predict the modulus enhancement of the PET–clay materials when a modified particle modulus rather than nominal clay modulus is used.