Metals, properties

Small metal clusters are also of interest because of their importance in catalysis. Despite the fact that small clusters should consist of mostly surface atoms, measurement of the photon ionization threshold for Hg clusters suggest that a transition from van der Waals to metallic properties occurs in the range of 20-70 atoms per cluster [88] and near-bulk magnetic properties are expected for Ni, Pd, and Pt clusters of only 13 atoms [89] Theoretical calculations on Sin and other semiconductors predict that the stmcture reflects the bulk lattice for 1000 atoms but the bulk electronic wave functions are not obtained [90]. Bartell and co-workers [91] study beams of molecular clusters with electron dirfraction and molecular dynamics simulations and find new phases not observed in the bulk. Bulk models appear to be valid for their clusters of several thousand atoms (see Section IX-3). 

The change from non-metallic to metallic properties of the Group V elements as the atomic mass of the element increases is shown in their reactions with alkalis. 

Polymers. The Tt-conjugated polymers used in semiconducting appHcations are usually insulating, with semiconducting or metallic properties induced by doping (see Flectrically conductive polymers). Most of the polymers of this type can be prepared by standard methods. The increasing use of polymers in devices in the last decade has led to a great deal of study to improve the processabiUty of thin films of commonly used polymers. 

Vessel heads can be made from explosion-bonded clads, either by conventional cold- or by hot-forming techniques. The latter involves thermal exposure and is equivalent in effect to a heat treatment. The backing metal properties, bond continuity, and bond strength are guaranteed to the same specifications as the composite from which the head is formed. AppHcations such as chemical-process vessels and transition joints represent approximately 90% of the industrial use of explosion cladding. 

The physical and chemical properties of sufficiently small particles, in particular their magnetism, must depend on their size, whence the idea of using NMR to study them. Because of the theoretical and technical difficulties associated with the NMR detection of metals, and specially since only a few can be detected, NMR work has been mainly devoted to the indirect study of metallic properties, by the intenuediary of easily detected chemisorbed phases ( F1, C) or of physically adsorbed probes ( Xe). We will develop the cases of Pt and Pd. 

The actual shape of the curve illustrated in Fig. 12.4 can vary according to factors such as metal properties and cavitation intensity. (Cavitation intensity relates to the number of bubbles created in a unit volume of fluid and the amount of energy transferred during the col-... 

Potassium (metal). Properties and applications are similar to those for sodium but as the reactivity is greater than that of sodium, the hazards are greater than that of sodium. Handle with extreme care. 

Tin finds widespread use beeause of its resistanee to eorrosion, or as foil or to provide proteetive eoats/plates for other metals. Properties of lead whieh make industrial applieation attraetive surround its soft, plastie nature permitting it to be rolled into sheets or extruded through dies. In the finely-divided state lead powder is pyrophorie in bulk form the rapidly-formed proteetive oxide layer inhibits further reaetion. It dissolves slowly in mineral aeids. Industrial uses inelude roofing material, piping, and vessel linings, e.g. for aeid storage. 

Although it is required to refine the above condition I in actuality, this rather simple but impressive prediction seems to have much stimulated the experiments on the electrical-conductivity measurement and the related solid-state properties in spite of technological difficulties in purification of the CNT sample and in direct measurement of its electrical conductivity (see Chap. 10). For instance, for MWCNT, a direct conductivity measurement has proved the existence of metallic sample [7]. The electron spin resonance (ESR) (see Chap. 8) [8] and the C nuclear magnetic resonance (NMR) [9] measurements have also proved that MWCNT can show metallic property based on the Pauli susceptibility and Korringa-like relation, respectively. On the other hand, existence of semiconductive MWCNT sample has also been shown by the ESR measurement [ 10], For SWCNT, a combination of direct electrical conductivity and the ESR measurements has confirmed the metallic property of the sample employed therein [11]. More recently, bandgap values of several SWCNT... 

The optimised interlayer distance of a concentric bilayered CNT by density-functional theory treatment was calculated to be 3.39 A [23] compared with the experimental value of 3.4 A [24]. Modification of the electronic structure (especially metallic state) due to the inner tube has been examined for two kinds of models of concentric bilayered CNT, (5, 5)-(10, 10) and (9, 0)-(18, 0), in the framework of the Huckel-type treatment [25]. The stacked layer patterns considered are illustrated in Fig. 8. It has been predicted that metallic property would not change within this stacking mode due to symmetry reason, which is almost similar to the case in the interlayer interaction of two graphene sheets [26]. Moreover, in the three-dimensional graphite, the interlayer distance of which is 3.35 A [27], there is only a slight overlapping (0.03-0.04 eV) of the HO and the LU bands at the Fermi level of a sheet of graphite plane [28,29],... 

This restriction, however, could be circumvented by the doped CNT with either Lewis acid or base [32-36], since such doping, even to semiconductive CNT could enhance the density of states at the Fermi level as well as bring about the metallic property. Appearance of metallic conductivity in helical CNT by such doping process would be of interest in that it could make molecular solenoid of nanometer size [37]. 

We now want to study the consequences of such a model with respect to the optical properties of a composite medium. For such a purpose, we will consider the phenomenological Lorentz-Drude model, based on the classical dispersion theory, in order to describe qualitatively the various components [20]. Therefore, a Drude term defined by the plasma frequency and scattering rate, will describe the optical response of the bulk metal or will define the intrinsic metallic properties (i.e., Zm((a) in Eq.(6)) of the small particles, while a harmonic Lorentz oscillator, defined by the resonance frequency, the damping and the mode strength parameters, will describe the insulating host (i.e., /((0) in Eq.(6)). 

Other hydrides with interstitial or metallic properties are formed by V, Nb and Ta they are, however, very much less stable than the compounds we have been considering and have extensive ranges of composition. Chromium also forms a hydride, CrH, though this must be prepared electrolytically rather than by direct reaction of the metal with hydrogen. It has the anti-NiAs structure (p.. 555). Most other elements... 

Perhaps the most obvious metallic property is reflectivity or luster. With few exceptions (gold, copper, bismuth, manganese) all metals have a silvery white color which results from reflecting all frequencies of light. We have said previously that the electron configuration of a substance determines the way in which it interacts with light. Apparently the characteristic reflectivity of metals indicates that all metals have a special type of electron configuration in common. 

To complete our discussion of metallic bonding we must explain why metallic properties eventually disappear as we proceed from left to right along a row in the periodic table. 

The interest of physicists in the conducting polymers, their properties and applications, has been focused on dry materials 93-94 Most of the discussions center on the conductivity of the polymers and the nature of the carriers. The current knowledge is not clear because the conducting polymers exhibit a number of metallic properties, i.e., temperature-independent behavior of a linear relation between thermopower and temperature, and a free carrier absorption typical of a metal. Nevertheless, the conductivity of these specimens is quite low (about 1 S cm"1), and increases when the temperature rises, as in semiconductors. However, polymers are not semiconductors because in inorganic semiconductors, the dopant substitutes for the host atomic sites. In conducting polymers, the dopants are not substitutional, they are part of a nonstoichiometric compound, the composition of which changes from zero up to 40-50% in... 

Elements on the left of the p block, especially the heavier elements, have ionization energies that are low enough for these elements to have some of the metallic properties of the members of the s block. However, the ionization energies of the p-block metals are quite high, and they are less reactive than those in the s block. The elements aluminum, tin, and lead, which are important construction materials, all lie in this region of the periodic table (Fig. 1.61). 

The elements show increasing metallic character down the group (Table 14.6). Carbon has definite nonmetallic properties it forms covalent compounds with nonmetals and ionic compounds with metals. The oxides of carbon and silicon are acidic. Germanium is a typical metalloid in that it exhibits metallic or nonmetallic properties according to the other element present in the compound. Tin and, even more so, lead have definite metallic properties. However, even though tin is classified as a metal, it is not far from the metalloids in the periodic table, and it does have some amphoteric properties. For example, tin reacts with both hot concentrated hydrochloric acid and hot alkali ... 

Finally, the use of simple valence bond theory has led recently to a significant discovery concerning the nature of metals. Many years ago one of us noticed, based on an analysis of the experimental values of the saturation ferromagnetic moment per atom of the metals of the iron group and their alloys, that for a substance to have metallic properties, 0.72 orbital per atom, the metallic orbital, must be available to permit the unsynchronized resonance that confers metallic properties on a substance.34 38 Using lithium as an example, unsynchronized resonance refers to such structures as follows. 

Successive pivoting resonances of a covalent bond allows for electrical conduction to occur, as shown in Figure 1-1. A test of this theory was provided by gray and white tin. Gray tin is not metallic because all its valence orbitals are used for bonding and there is no metallic orbital available. White tin, on the other hand, has the metallic orbital available and therefore has metallic properties. 

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