D. Jou

Temperature in non-equilibrium states: a review of open problems and current proposals

The conceptual problems arising in the definition and measurement of temperature in non-equilibrium states are discussed in this paper in situations where the local-equilibrium hypothesis is no longer satisfactory. This is a necessary and urgent discussion because of the increasing interest in thermodynamic theories beyond local equilibrium, in computer simulations, in non-linear statistical mechanics, in new experiments, and in technological applications of nanoscale systems and material sciences. First, we briefly review the concept of temperature from the perspectives of equilibrium thermodynamics and statistical mechanics. Afterwards, we explore which of the equilibrium concepts may be extrapolated beyond local equilibrium and which of them should be modified, then we review several attempts to define temperature in non-equilibrium situations from macroscopic and microscopic bases. A wide review of proposals is offered on effective non-equilibrium temperatures and their application to ideal and real gases, electromagnetic radiation, nuclear collisions, granular systems, glasses, sheared fluids, amorphous semiconductors and turbulent fluids. The consistency between the different relativistic transformation laws for temperature is discussed in the new light gained from this perspective. A wide bibliography is provided in order to foster further research in this field.

Extended irreversible thermodynamics revisited (1988-98)

We review the progress made in extended irreversible thermodynamics during the ten years that have elapsed since the publication of our first review on the same subject (Rep. Frog. Phys. 1988 51 1105-72). During this decade much effort has been devoted to achieving a better understanding of the fundamentals and a broadening of the domain of applications. The macroscopic formulation of extended irreversible thermodynamics is reviewed and compared with other non-equilibrium thermodynamic theories. The foundations of EIT are discussed on the bases of information theory, kinetic theory, stochastic phenomena and computer simulations. Several significant applications are presented, some of them of considerable practical interest (non-classical heat transport, polymer solutions, non-Fickian diffusion, microelectronic devices, dielectric relaxation), and some others of special theoretical appeal (superfluids, nuclear collisions, cosmology). We also outline some basic problems which are not yet completely solved, such as the definitions of entropy and temperature out of equilibrium, the selection of the relevant variables, and the status to be reserved to the H-theorem and its relation to the second law. In writing this review, we had four objectives in mind: to show (i) that extended irreversible thermodynamics stands at the frontiers of modern thermodynamics; (ii) that it opens the way to new and useful applications; (iii) that much progress has been achieved during the last decade, and (iv) that the subject is far from being exhausted.

Memory and nonlocal effects in heat transport: From diffusive to ballistic regimes

The authors discuss a generalized transport model including memory and nonlocal effects, which aims to describe the transition of heat transport from the diffusive regime to the ballistic regime. By using an effective thermal conductivity depending on the Knudsen number, they describe in a single equation the behavior of conductivity in terms of the system size and a reduction in the limit flux through nanoscale devices.

Non-equilibrium thermodynamics and anomalous diffusion

The convenience of a new thermodynamic frame for the description of anomalous diffusion is explored. Our research, which makes use of a recent new definition for entropy arising from multifractal analysis, shows that both dynamical and thermodynamical effects may contribute to non-classical diffusion.

Diffuse-interface model for rapid phase transformations in nonequilibrium systems

A thermodynamic approach to rapid phase transformations within a diffuse interface in a binary system is developed. Assuming an extended set of independent thermodynamic variables formed by the union of the classic set of slow variables and the space of fast variables, we introduce finiteness of the heat and solute diffusive propagation at the finite speed of the interface advancing. To describe transformations within the diffuse interface, we use the phase-field model which allows us to follow steep but smooth changes of phase within the width of the diffuse interface. Governing equations of the phase-field model are derived for the hyperbolic model, a model with memory, and a model of nonlinear evolution of transformation within the diffuse interface. The consistency of the model is proved by the verification of the validity of the condition of positive entropy production and by outcomes of the fluctuation-dissipation theorem. A comparison with existing sharp-interface and diffuse-interface versions of the model is given.

Phonon hydrodynamics and phonon-boundary scattering in nanosystems

We use phonon hydrodynamics with a surface slip flow as a simplified macroscopic model accounting for a reduction in lateral thermal conductivity in nanosystems. For high Knudsen numbers, the corresponding effective thermal conductivity decreases linearly with the radius or the width, in contrast with the quadratic dependence predicted by usual phonon hydrodynamics. The linear dependence is accounted for by the surface slip flow. The difference in the expressions for the surface tangential flow in the hydrodynamic and the diffusive regimes is commented on and the influence of boundary conditions on the form of the effective thermal conductivity is explored.

Thermodynamics of fluids under flow

From the contents: Non-equilibrium Thermodynamics and Rheology.- Ideal Gases.- Non-ideal Fluids.- Polymeric Solutions.- Non-equilibrium Chemical Potential and Shear-Induced Effects.- Comparison Between Thermodynamical and Dynamical Approaches.- Thermodynamic Couplings Between Flow and Diffusion.- Chemical Reactions Under Flow.- Concluding Remarks and Perspectives.- Appendices: A. Survey of Experimental Information.- B. Liquid Crystals.- C. Summary of Vector and Tensor Notation.- D. Useful Integrals in the Kinetic Theory of Gases.- E. Some Physical Constants.- Subject Index.

An extension of the local equilibrium hypothesis

In order to extend the range of application of classical irreversible thermodynamics far from equilibrium, an extension of the Gibbs equation is presented. The new Gibbs equation is assumed to contain, besides its usual contributions, supplementary terms equal to the thermodynamic fluxes. The entropy flux and the entropy production also take more general forms than in classical non-equilibrium thermodynamics. As an illustration of the formalism, an isotropic viscous and non-isothermal two-fluid mixture is considered. The results are shown to be in agreement with the Boltzmann kinetic theory.

Pore-size dependence of the thermal conductivity of porous silicon: A phonon hydrodynamic approach

Phonon hydrodynamics is used to analyze the influence of porosity and of pore size on reduction in thermal conductivity in porous silicon, with respect to crystalline silicon. The expressions predict that the thermal conductivity is lower for higher porosity and for smaller pore radius, as a consequence of phonon ballistic effects. The theoretical results describe experimental data better than the assumption that they only depend on porosity.

Size and frequency dependence of effective thermal conductivity in nanosystems

A single phenomenological expression is proposed to describe thermal transport in a wide variety of nanoscale devices. Size and frequency dependence is studied for some nanosystems from the diffusive to the ballistic regimes. In a single expression we obtain the effective thermal conductivity of cross-plane thin layer experiments where the device has a size limitation in the direction of the flux, and nanowire and in-plane experiments where the size limitation is in a transversal direction from the flux in terms of the effective size of the device. For nonzero frequencies, the size dependence has a maximum which becomes narrower at higher frequencies. For a given size, the effective thermal conductivity decreases for increasing frequency. These features may be limited in the design of nanoscale devices, because of the accumulation of dissipated heat.