Hexagonal cobalt

Nanowires of hexagonal cobalt can be grown by the selective adsorption of ligands on all crystal faces except the faces that become the sides of the wires. 

Figure 4.17 Regular layers Inside a cobalt nanoparticle larger than 20 nm in diameter, which are observed after the particle has been exposed to CO at the pressure of 1 bar and temperature 700 K. The light regions are the fine (approximately five atoms in thickness) hexagonal cobalt layers, dark region are the cubic cobalt layers [6].

In the case of cobalt, unstable cubic cobalt was identified as the product of the reduction of standard cobalt catalysts, while hexagonal cobalt was found as a product of the hydrogenation of cobalt carbide. Used cobalt catalysts show no carbide by x-ray examination. Bulk phase carbide decreases the activity of cobalt catalysts. Surface area measurements show no appreciable change when the cobalt of cobalt catalysts was converted to cobalt carbide. Carburization at conditions where free carbon is formed increases the area considerably. 

Cobalt—chromium films (20 at. % Cr) exhibiting strong perpendicular anisotropy, ie, hexagonal i -axis normal to the substrate surface, have been studied (53). Fifty nanometer films are composed of columnar crystaUites and the domain size was found to be a few stmctural columns in diameter. Magnetization reversal was shown to occur by domain rotation in thick films. Thinner (ca 10-nm thick) films do not show the columnar crystaUite... 

The electronic stmcture of cobalt is [Ar] 3i/4A. At room temperature the crystalline stmcture of the a (or s) form, is close-packed hexagonal (cph) and lattice parameters are a = 0.2501 nm and c = 0.4066 nm. Above approximately 417°C, a face-centered cubic (fee) aHotrope, the y (or P) form, having a lattice parameter a = 0.3544 nm, becomes the stable crystalline form. The mechanism of the aHotropic transformation has been well described (5,10—12). Cobalt is magnetic up to 1123°C and at room temperature the magnetic moment is parallel to the ( -direction. Physical properties are Hsted in Table 2. 

Cobalt cannot be classified as an oxidation-resistant metal. Scaling and oxidation rates of unalloyed cobalt in air are 25 times those of nickel. The oxidation resistance of Co has been compared with that of Zr, Ti, Fe, and Be. Cobalt in the hexagonal form (cold-worked specimens) oxidizes more rapidly than in the cubic form (annealed specimens) (3). 

Under deposition of cobalt nanocrystals, self-assemblies of particles are observed and the nanocrystals are organized in a hexagonal network (Fig. 2). However, it can be seen that the grid is not totally covered. We do not have a simple explanation for such behavior. In fact, the size distribution, which is one of the major parameters in controlling monolayer formation, is similar to that observed with the other nanocrystals, such as silver and silver sulfide. One of the reasons could be that the nanocrystals have magnetic properties, but there is at present no evidence for such an assumption. 

Fig. 13 Super-lattice of cobalt nanorods a Top view hexagonal b vue de cote c image k haute resolution...

Aside from the ordered stacking sequences we have considered so far, a more or less statistical sequence of hexagonal layers can also occur. Since there is some kind of an ordering principle on the one hand, but on the other hand the periodical order is missing in the stacking direction, this is called an order-disorder (OD) structure with stacking faults. In this particular case, it is a one-dimensionally disordered structure, since the order is missing only in one dimension. When cobalt is cooled from 500 °C it exhibits this kind of disorder. 

As at room temperature Bragg reflections contain both nuclear and magnetic structure factors, the nuclear structure was refined from a combination of polarized and unpolarized neutron data. Contrary to the ideal structure where only three atomic sites are present, it has been shown [11, 12] that some Y atoms were substituted by pairs of cobalt. These pairs, parallel to the c-axis are responsible for a structure deformation which shrinks the cobalt hexagons surrounding the substitutions. The amount of these substituted Y was refined to be 0.046 0.008. Furthermore, the thermal vibration parameter of Coi site appeared to be very anisotropic. The nuclear structure factors Fn were calculated from this refined structure and were introduced in the polarized neutron data to get the magnetic structure factors Fu. 

Dicyanometalates Dicyanometalates of silver and gold are known. Abrahams et al. [44] have described a cobalt dicyanoaurate. In these compounds, gold ions are carbon coordinated and form linear structures. Cobalt ions are coordinated by four nitrogen atoms of the cyanide group. The unit cell has a hexagonal symmetry. 

It forms glistening crystals of deep green colour. Under the microscope they are dichroie, and appear to crystallise in pointed hexagonal prisms. The salt is soluble in water, yielding a green solution which changes later to -violet. On warming with ammonia, aquo-pentammino-cobaltic chloride is produced. 

The green and violet tetraammines have the same chemical composition, that is, they are isomers and are the only two isomers with this composition. Werner realized that this was possible only if the six ligands were deployed about the cobalt(III) center in an octahedral arrangement (cf. octahedral coordination in solids, Sections 4.3 and 4.4) for example, a flat hexagonal complex Co(NH3)4Cl2+ would have three isomers, like ortho-, meta-, and para-disubstituted benzenes. Werner correctly identified the green compound as the trans isomer (chloro ligands on opposite sides of the octahedron) and the violet as cis (same side), as in Fig. 13.1. 

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