Thermal conductivity Free-electron

This competition between electrons and the heat carriers in the lattice (phonons) is the key factor in determining not only whether a material is a good heat conductor or not, but also the temperature dependence of thermal conductivity. In fact, Eq. (4.40) can be written for either thermal conduction via electrons, k, or thermal conduction via phonons, kp, where the mean free path corresponds to either electrons or phonons, respectively. For pure metals, kg/kp 30, so that electronic conduction dominates. This is because the mean free path for electrons is 10 to 100 times higher than that of phonons, which more than compensates for the fact that C <, is only 10% of the total heat capacity at normal temperatures. In disordered metallic mixtures, such as alloys, the disorder limits the mean free path of both the electrons and the phonons, such that the two modes of thermal conductivity are more similar, and kg/kp 3. Similarly, in semiconductors, the density of free electrons is so low that heat transport by phonon conduction dominates. 

In very dense stellar material, the mean free path of the photon becomes so small that it is no longer the most efficient carrier of energy. Thermal conduction by electrons becomes the dominant transport mechanism, controlled by a conductive opacity Cond in much the same way as conduction by photons is controlled by the radiative opacity. From the diffusion approximation we obtain... 

As described above, quantum restrictions limit tire contribution of tire free electrons in metals to the heat capacity to a vety small effect. These same electrons dominate the thermal conduction of metals acting as efficient energy transfer media in metallic materials. The contribution of free electrons to thermal transport is very closely related to their role in the transport of electric current tlrrough a metal, and this major effect is described through the Wiedemann-Franz ratio which, in the Lorenz modification, states that... 

Conduction. In a solid, the flow of heat by conduction is the result of the transfer of vibrational energy from one molecule to another, and in fluids it occurs in addition as a result of the transfer of kinetic energy. Heat transfer by conduction may also arise from the movement of free electrons, a process which is particularly important with metals and accounts for their high thermal conductivities. 

The free-electron gas was first applied to a metal by A. Sommerfeld (1928) and this application is also known as the Sommerfeld model. Although the model does not give results that are in quantitative agreement with experiments, it does predict the qualitative behavior of the electronic contribution to the heat capacity, electrical and thermal conductivity, and thermionic emission. The reason for the success of this model is that the quantum effects due to the antisymmetric character of the electronic wave function are very large and dominate the effects of the Coulombic interactions. 

The metallic structure essentially consists of atomic nuclei and associated core electrons, surrounded by a sea of free electrons. The high electrical conductivity of metals is derived from the presence of these free electrons. In addition to high electrical conductivity, the free electrons provide the metals with good thermal conductivity as well. The electrical resistivity of a metal increases with temperature. 

Metallic solids have metal atoms occupying the crystal lattice held together by metallic bonding. In metallic bonding, the electrons of the atoms are delocalized and free to move throughout the entire solid. This explains the electrical and thermal conductivity as well as many of the other properties of metals. 

The thermal conductivity of bulk silicon (148 W K m ) is dominated by phonons electronic contributions are negligible. Due to restrictions of the mean free path of phonons in the porous network the thermal conductivity of micro PS is reduced by two or three orders of magnitude at RT, compared to the bulk value. Because of the larger dimensions of its network, meso PS shows a thermal conductivity several times larger than that of micro PS, for the same value of porosity. Thermal oxidation at low temperatures (300°C) is found to decrease the thermal conductivity of meso PS by a factor of about 0.5 [Pe9]. In contrast to bulk Si the thermal conductivity of PS is found to decrease with decreasing temperature [Be21, La4, Ge9, Lyl]. 

This notion of occasional ion hops, apparently at random, forms the basis of random walk theory which is widely used to provide a semi-quantitative analysis or description of ionic conductivity (Goodenough, 1983 see Chapter 3 for a more detailed treatment of conduction). There is very little evidence in most solid electrolytes that the ions are instead able to move around without thermal activation in a true liquid-like motion. Nor is there much evidence of a free-ion state in which a particular ion can be activated to a state in which it is completely free to move, i.e. there appears to be no ionic equivalent of free or nearly free electron motion. 

Classical Free-Electron Theory, Classical free-electron theory assumes the valence electrons to be virtually free everywhere in the metal. The periodic lattice field of the positively charged ions is evened out into a uniform potential inside the metal. The major assumptions of this model are that (1) an electron can pass from one atom to another, and (2) in the absence of an electric field, electrons move randomly in all directions and their movements obey the laws of classical mechanics and the kinetic theory of gases. In an electric field, electrons drift toward the positive direction of the field, producing an electric current in the metal. The two main successes of classical free-electron theory are that (1) it provides an explanation of the high electronic and thermal conductivities of metals in terms of the ease with which the free electrons could move, and (2) it provides an explanation of the Wiedemann-Franz law, which states that at a given temperature T, the ratio of the electrical (cr) to the thermal (k) conductivities should be the same for all metals, in near agreement with experiment ... 

Finally, a special type of primary bond known as a metallic bond is found in an assembly of homonuclear atoms, such as copper or sodium. Here the bonding electrons become decentralized and are shared by the core of positive nuclei. Metallic bonds occur when elements of low electronegativity (usually found in the lower left region of the periodic table) bond with each other to form a class of materials we call metals. Metals tend to have common characteristics such as ductility, luster, and high thermal and electrical conductivity. All of these characteristics can to some degree be accounted for by the nature of the metallic bond. The model of a metallic bond, first proposed by Lorentz, consists of an assembly of positively charged ion cores surrounded by free electrons or an electron gas. We will see later on, when we... 

Recall from Figure 1.15 that metals have free electrons in what is called the valence band and have empty orbitals forming what is called the conduction band. In Chapter 6, we will see how this electronic structure contributes to the electrical conductivity of a metallic material. It turns out that these same electronic configurations can be responsible for thermal as well as electrical conduction. When electrons act as the thermal energy carriers, they contribute an electronic heat capacity, C e, that is proportional to both the number of valence electrons per unit volume, n, and the absolute temperature, T ... 

Returning now to thermal conductivity, Eq. (4.40) tells us that any functional dependence of heat capacity on temperature should be implicit in the thermal conductivity, since thermal conductivity is proportional to heat capacity. For example, at low temperatures, we would expect thermal conductivity to follow Eq. (4.43). This is indeed the case, as illustrated in Figure 4.25. In copper, a pure metal, electrons are the primary heat carriers, and we would expect the electronic contribution to heat capacity to dominate the thermal conductivity. This is the case, with the thermal conductivity varying proportionally with temperature, as given by Eq. (4.42). For a semiconductor such as germanium, there are less free electrons to conduct heat, and lattice conduction dominates—hence the dependence on thermal conductivity as suggested by Eq. (4.41). 

The discussion of the previous section would also lead us to believe that since most ceramics are poor electrical conductors (with a few notable exceptions) due to a lack of free electrons, electronic conduction would be negligible compared to lattice, or phonon, conduction. This is indeed the case, and we will see that structural effects such as complexity, defects, and impurity atoms have a profound effect on thermal conductivity due to phonon mean free path, even if heat capacity is relatively unchanged. 

In summary, metals are good electrical conductors because thermal energy is sufficient to promote electrons above the Eermi level to otherwise unoccupied energy levels. At these levels E > Ef), the accessibihty of unoccupied levels in adjacent atoms yields high mobility of conduction electrons known as free electrons through the solid. 

The sp-valent metals such as sodium, magnesium and aluminium constitute the simplest form of condensed matter. They are archetypal of the textbook metallic bond in which the outer shell of electrons form a gas of free particles that are only very weakly perturbed by the underlying ionic lattice. The classical free-electron gas model of Drude accounted very well for the electrical and thermal conductivities of metals, linking their ratio in the very simple form of the Wiedemann-Franz law. However, we shall now see that a proper quantum mechanical treatment is required in order to explain not only the binding properties of a free-electron gas at zero temperature but also the observed linear temperature dependence of its heat capacity. According to classical mechanics the heat capacity should be temperature-independent, taking the constant value of kB per free particle. 

Fig. 1. Emission and capture processes at a deep level of energy ET. The quantities near the arrows are the rates (in s ) of the processes. Subscripts indicate whether the transition is by an electron (n) or hole (p), and the superscripts indicate a thermal (t) or optical (o) process. The symbol e is an emission rate, c a capture constant, n and p the concentrations of free electrons and holes in the conduction band (at energy Ec) and valence band (at energy ,), and hvt and h 2 photon energies.

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