Direct metallization Other methods

These have been known for many years.1052-1054 Chromium(III) is approximately octahedral ( ie(f = 3.69-4.1 BM) the compounds have a layer structure. In the chloride, r(Cr—Cl) is 5.76 A between layers and 3.46 A within layers. The iodide is isomorphous with the chloride and the bromide has a similar but distinct structure. All may be prepared by the direct halogenation of the metal. Other methods are available, e.g. CrCl3 may be prepared by heating Cr203-xH20 in CCU vapour at 650 °C.1055 The anhydrous halides are insoluble in water, however reducing agents such as zinc catalyze dissolution. The trichloride reacts with liquid ammonia to form ammine complexes. 

A complete set of trihalides for arsenic, antimony and bismuth can be prepared by the direct combination of the elements although other methods of preparation can sometimes be used. The vigour of the direct combination reaction for a given metal decreases from fluorine to iodine (except in the case of bismuth which does not react readily with fluorine) and for a given halogen, from arsenic to bismuth. 

Surface Modification. Plasma surface modification can include surface cleaning, surface activation, heat treatments, and plasma polymerization. Surface cleaning and surface activation are usually performed for enhanced joining of materials (see Metal SURFACE TREATMENTS). Plasma heat treatments are not, however, limited to high temperature equiUbrium plasmas on metals. Heat treatments of organic materials are also possible. Plasma polymerization crosses the boundaries between surface modification and materials production by producing materials often not available by any other method. In many cases these new materials can be appHed directly to a substrate, thus modifying the substrate in a novel way. 

Titanium Silicides. The titanium—silicon system includes Ti Si, Ti Si, TiSi, and TiSi (154). Physical properties are summarized in Table 18. Direct synthesis by heating the elements in vacuo or in a protective atmosphere is possible. In the latter case, it is convenient to use titanium hydride instead of titanium metal. Other preparative methods include high temperature electrolysis of molten salt baths containing titanium dioxide and alkalifluorosiUcate (155) reaction of TiCl, SiCl, and H2 at ca 1150°C, using appropriate reactant quantities for both TiSi and TiSi2 (156) and, for Ti Si, reaction between titanium dioxide and calcium siUcide at ca 1200°C, followed by dissolution of excess lime and calcium siUcate in acetic acid. 

Other Pyrochemical Processes. The chemistry of pyrochemi-cal separation processes is another fertile area of research e.g., new molten salt systems, scrub alloys, etc. and the behavior of plutonium in these systems. Studies of liquid plutonium metal processes should also be explored, such as filtration methods to remove impurities. Since Rocky Flats uses plutonium in the metal form, methods to convert plutonium compounds to metal and purify the metal directly are high-priority research projects. 

More direct and successful methods for the preparation of non-aqueous metal sols are desirable. Especially valuable would be a method that avoids the metal salt reduction step (and thus avoids contamination by other reagents), avoids electrical discharge methods which decompose organic solvents, and avoids macromolecule stabilization. Such a method would provide pure, non-aqueous metal colloids and should make efficient use of precious metals employed. Such colloids would be valuable technologically in many ways. They would also be valuable to study so that more could be learned about particle stabilization mechanisms in non-aqueous media, of which little is known at the present time. 

Although the sputter deposition technique can provide a cheap and directly controlled deposition method, the performance of PEM fuel cells with sputtered CLs is still inferior to that of conventional ink-based fuel cells. In addition, other issues arise related to the physical properties of sputtered catalyst layers, such as low lateral electrical conductivity of the thin metallic films [96,108]. Furthermore, the smaller particle size of sputter-deposited Ft can hinder water transport because of the high resistance to water transport in a thick, dense, sputtered Ft layer [108]. Currently, the sputter deposition method is not considered an economically viable alternative for large-scale electrode fabrication [82] and further research is underway to improve methods. 

Most of our understanding of the marine chemistry of trace metals rests on research done since 1970. Prior to this, the accuracy of concentration measurements was limited by lack of instrumental sensitivity and contamination problems. The latter is a consequence of the ubiquitous presence of metal in the hulls of research vessels, paint, hydrowires, sampling bottles, and laboratories. To surmount these problems, ultra-clean sampling and analysis techniques have been developed. New methods such as anodic stripping voltammetry are providing a means by which concentration measurements can be made directly in seawater and pore waters. Most other methods require the laborious isolation of the trace metals from the sample prior to analysis to eliminate interferences caused by the highly concentrated major ions. 

The time-resolved studies of the cluster formation achieved by pulse radiolysis techniques allow one to better understand the main kinetic factors which affect the final cluster size found, not only in the radiolytic method but also in other reduction (chemical or photochemical) techniques. Generally, reducing chemical agents are thermodynamically unable to reduce directly metal ions into atoms (Section 20.4) unless they are complexed or adsorbed on walls or dust particles. Therefore, we explain the higher sizes and the broad dispersity obtained in this case by in situ reduction on fewer sites. A classic... 

It is likely that more silicon-carbon bonds are produced by the hydrosilylation of olefins than by any other method except the direct process. This deceptively simple addition of an Si-H bond to a C-C multiple bond can be promoted by a variety of means, but transition metal catalysis is by far the most significant. Two relatively old catalysts, H2PtCl6 ( Speier s catalyst ) and Pt2(Me2ViSiOSiMe2Vi)3 ( Karstedt s catalyst ), remain the most effective, and the remarkable rates and turnover numbers observed in these systems are among the most impressive in all of organometallic chemistry. The bulk of the literature on hydrosilylation falls outside the scope of this review, and readers are directed to the comprehensive work on hydrosilylation edited by Marciniec.93... 

Other methods of synthesis are widely reviewed by Dayagi and Degani.2 However, it must be observed that few Schiff bases commonly used as ligands have been prepared and characterized in the uncomplexed state, since the corresponding metal complexes have been directly obtained by other procedures. For example, many metal complexes containing salenH2 may be obtained directly by reaction between metal ions, salicylaldehydes and ethylenediamine.3... 

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