Mesoscopic theories of heat transport in nanosystems (Q896056)

As the authors write in the preface, ``[h]eat transport has been an essential topic in the foundations of thermodynamics since the beginning of the nineteenth century.'' (p.\,vii) Classical thermodynamics is mainly based on Fourier's mathematical description of heat transport, on Fourier transforms. ``Since the end of the 20th century, heat transport has been experiencing a true revolution, enlarging its domain of applicability and finding new regimes and phenomenologies where Fourier's theory is no longer applicable. This new epoch in heat transfer has been stimulated by miniaturization, but it was preceded, in some ways, by the earlier technological frontier of aerospace engineering due to the need of studying heat transfer and cooling of bodies in rarefied gases.'' (p.\,vii) The former theory of heat transport is valid for systems with large Knudson numbers, i.e., large ratios of the mean free path of particles to the characteristic size of the system. In recent nanotechnology with its small system sizes, neither the Fourier law nor classical continuum thermodynamics are strictly applicable. The recent development of heat transport and thermodynamics bases either on several versions of kinetic theory or fluctuation-dissipation theorems, or on detailed computer simulations. Thus, the principal aim of the present book is ``to formulate, from a mesoscopic perspective, generalized transport laws able to keep pace with current microscopic research, and to cope efficiently with new applications. The equations presented [...] are compatible with generalized formulations of nonequilibrium thermodynamics beyond thermal equilibrium.'' (p.\,viii) However, it is tried ``to emphasize the transport equations by themselves. When the mean-free path and relaxation times are negligible with respect to the characteristic size of the system and the rates of phenomena, respectively, these equations reduce to (the) Fourier law, but in other situations they describe other physical features beyond it: heat waves, ballistic transport, and phonon hydrodynamics, for instance.'' (p.\,viii) The authors compare their results with the results of the microscopic theories. For instance, they ``use the concept of photon hydrodynamics as a denomination for a given regime of heat flow where the equations for the heat flux have a form analogous to the hydrodynamic equations for the velocity field.'' (p.\,viii) In fact, this form is derived here from the mesoscopic equations, without kinetic theory and without making reference to the physical nature of the heat carriers, which could be phonons, electrons, or holes. The book consists of seven chapters. Chapter 1 provides a sketch of the extended irreversible thermodynamics (EIT), which represents the general framework within which the generalized heat transport equations are built up. In EIT, one starts with an entropy and an entropy flux which depend on the (thermal, electrical) fluxes \(\vec q\), as well as on the classical thermodynamic variables (density, volume, temperature). Not too far from equilibrium, the entropy equals the local equilibrium entropy minus some quadratic expression in the fluxes \(\vec q\), and the entropy flux is the classical entropy flux plus a correction proportional to the tensor product of the deviatoric part of a flux \(Q\) (of the flux \(\vec q\)) times the flux \(\vec q\) itself. From here, one is led for the entropy production to a quadratic form which is a sum of products of fluxes times generalized thermodynamic forces. There, it is required that the constitutive equations are submitted to the restriction that the entropy production is always positive definite. The main difference with respect to classical irreversible thermodynamics (CIT) are: (1) The thermodynamic forces are more general than their local equilibrium counterparts, and in them appear the time derivatives and the gradients of the fluxes, as the consequence of using an entropy and entropy flux which depend on the fluxes. (2) Since the fluxes are considered as independent variables, the constitutive equations do not aim to express the fluxes in terms of thermodynamic forces, but to express the evolution equations for the fluxes, i.e., to give the time derivative of the fluxes in terms of classical thermodynamic forces, fluxes \(\vec q\), and gradients of the fluxes \(\nabla\vec q\). (p.\,xi) ``After the evolution equations for the fluxes have been formulated, one is able to give a physical interpretation to the several coefficients appearing in such equations [...] in terms of the classical transport coefficients, the relaxation times of the fluxes, the correlation lengths of the fluxes'' (p.\,xi), etc. As a simple illustration, the chapter deals with the so-called Guyer-Krumhansl equation for heat transfer in rigid conductors, which takes into account relaxation effects and nonlocal effects. ``The corresponding entropy depends on the internal energy as well as on the heat flux, and the corresponding entropy flux depends on the gradient of the heat flux, too.'' (p.\,xi) ``Finally, the absolute temperature is given by the reciprocal of the derivative of the entropy with respect to the internal energy (at constant values of the other extensive variables). When the extended entropy is used instead of the local-equilibrium entropy, the resulting absolute temperature differs from the local-equilibrium temperature, and depends on the fluxes.'' (p.\,xii) In Chapter 2, an overview of different generalized heat transport equations is provided, which are able to take into account nonlinear, nonlocal, and memory effects. ``All these models stem from a precise point of view on the problem of heat conduction.'' (p.\,xii) On this subject, the celebrated paper by \textit{C. Cattaneo} [C. R. Acad. Sci. 247, 431--433 (1958; Zbl 1339.35135)], in which it is observed that the classical heat equation leads to the ``paradox'' of infinite speeds of propagation of the thermal disturbances stimulated the formulation of new theories. ``All the presented models are able to reproduce some of the main properties of heat conduction at low temperatures, but none of them leads to an exhaustive description which is free of technical problems. In particular, in the extended thermodynamic theories, in which the fluxes are included in the state space, the higher-order fluxes are necessary in modelling high-frequency processes and the memory effects are modeled by the hierarchical system of equations which is a consequence of kinetic theory, the main problems are due to the rapidly increasing number of unknown quantities.'' (p.\,xii) So, the most important task is the determination of an appropriate number of equations to be solved, i.e., of the step at which the hierarchical system should be truncated. ``A further problem is related to the Guyer-Krumhansl equation, which plays a fundamental role in describing nonlocal and relaxation effects. Such an equation is parabolic, so that finite speeds of propagation, in a strict mathematical sense, cannot be expected. However, finite speeds of propagation can be obtained in a generalized sense as clarified by \textit{G. Fichera} [Rend. Circ. Mat. Palermo, II. Ser. 41, No. 1, 5--28 (1992; Zbl 0756.35035)] and W. A. Day.'' (p.\,xii) Chapter 3 develops a mesoscopic description of boundary effects and effective thermal conductivity in nanosystems by using phonon hydrodynamics. ``Indeed, the rise and the development of nanotechnology requires increasing efforts to better understand the thermal transport properties of nanodevices, as their performance and reliability are much influenced by memory, nonlocal and nonlinear effects. The macroscopic derivation of generalized transport equations represents a very important step in achieving this task. This problem may be tackled by different approaches, the most frequently pursued of which is the microscopic one, based upon the Boltzmann equation. An alternative approach is that based on so-called phonon hydrodynamics, which regards the entire set of heat carriers as a fluid whose hydrodynamic-like equations describe the heat transport. This mesoscopic approach allows for a fast quantitative approximate estimation of the thermal properties and may be a useful complement to microscopic theories in order to select the most promising features of nanosystems. In the linear regime, the phonon hydrodynamics rests on the Guyer-Krumhansl transport equation. However, it is worth observing that in the original proposal of Guyer and Krumhansl a boundary relaxation time was added to the usual relaxation time due to resistive mechanisms by use of the Matthiessen rule. Once the combined resistive-boundary collision time has been obtained, the thermal conductivity (depending on the size of the system through the boundary relaxation time) can be calculated and used in the Guyer-Krumhansl transport equation.'' (p.\,xiii) In Chapter 2, ``instead, a different method is used, which consists in including the boundary collision time not in the differential equation, but in suitable boundary constitutive equations. Particular attention is paid to the modeling of the constitutive equations for a slip heat flux along the walls.'' (p.\,xiii) The application of the model of phonon hydrodynamics to nanoporous materials is described in some detail in Chapter 4. ``In fact, in addition to referring to small systems whose characteristic length is of the order of nanometers, the name `nanosystem' may also refer to those systems characterized by an internal nanostructure that gives them some special mechanical, thermal, electrical and optical properties. Such structures may be nanopores or nanoparticles, or several parallel and very thin layers (graded materials). By regulating the main feaures of such an internal structure, one may control the transport properties of those systems.'' (p.\,xiii) When the Knudson parameter of the system is vanishing, the thermal properties may be considered in the framework of the classical Fourier theory. For Knudson parameters larger than unity, several new problems emerge. The authors ``briefly furnish in less detail some results from other theories for the thermal conductivity both of nanocomposites and superlattices, and of nanofluids, which are the basis for many outstanding applications.'' (p.\,xiii) Chapter 5 illustrates ``some peculiar phenomena which can be identified when weakly nonlocal and nonlinear heat transport equations are used. As stated above, the thermal behavior of systems whose characteristic length is of the order of a few nanometers is strongly influenced by memory, nonlocal, and nonlinear effects. In one-dimensional steady-state situations, and when modeling the heat transport along nanowires or thin layers, some of these effects may be incorporated into a size-dependent effective thermal conductivity and a Fourier-type equation may still be used with an effective value of the thermal conductivity. However, in fast perturbations, or under strong heat gradients, an effective thermal conductivity is insufficient to overcome the different problems related to the Fourier law and therefore, in modeling heat conduction, it is necessary to go beyond such an equation. In addition to presenting some results that are important from the theoretical point of view, such as the existence of flux limiters,'' (p.\,xiii sqq.) the authors ``also illustrate several applications, including thermal rectification in troncoconical nanowires and axial heat propagation in thin layers and graphene sheets. Also, based on the method of classical hydrodynamics, a~mathematical procedure is developed, which is proven to be useful in studying the stability of the heat flow in nanowires'' (p.\,xiv) In Chapter 6, the authors ``study how to obtain enhanced versions of classical thermoelectric equations, which have meaningful consequences for some well-known classical theoretical results and in practical applications, e.g., for the efficiency of thermoelectric energy generators. In fact, thermoelectric devices offer an attractive source of energy, since they do not have moving parts, do not create pollution, and do not emit noise. Nanomaterials provide an interesting avenue by which to obtain better performing thermoelectric devices, for example, by making nanocomposites, adding nanoparticles to a bulk material, or using one-dimensional nanostructures. '' (p.\,xiv) For the sake of illustration, a one-dimensional thermoelectric nanodevice is considered, the ends of which are put into two heat baths of different constant temperature. It is suggested that an electric current and a quantity of heat per unit time enter uniformly into the hot side of the device and flow through it. ``Further, in Chapter 6, nonlocal and/or nonlinear breaking of Onsager symmetry is studied, which implies modifications of the expression for the maximum efficiency in terms of the transport coefficients and the temperature.'' (p.\,xiv) ``All the results derived herein rest on the basic assumption that in thermoelectric materials the local heat flux has two different contributions, namely, the phonon partial heat flux and the electron partial heat flux. In the simplest situation, the heat carriers (phonons and electrons) may be supposed to have the same temperature. However, in more complex situations, such as in the presence of `hot electrons', or when a laser heat pulse hits a material surface, the phonon and electron temperatures may be different. Thus, in this chapter, the classical results of thermoelectricity are revisited under the hypothesis that phonons and electrons have different temperatures.'' (p.\,xiv) Chapter 7 closes the book with some perspectives on open problems to be further analyzed. Those open problems are, e.g., the detailed microscopic understanding of the generalized transport equations, the comparison of the theory with experiments for a variety of relevant materials, especially with different porosities and for graded materials, the role of phonon hydrodynamics in two-dimensional systems (graphene, silicon thin layers, microporous thin layers), quantum confinement at very low temperatures, devices for the development of phononics (heat rectifiers, heat transistors), and the general understanding of thermoelectric conversions. (All quotations in this review are taken from the Preface and the section ``About this book''.)