Rhenium and its Alloys

Biyskhi. B.D. Rhenium and Its Alloys, Advanced Materials Processes, 22... 

There are only a few studies on the electrochemical behaviour of rhenium in molten salts [1-6]. Most investigations dealt with electrodeposition of rhenium and its alloys. The absence of reliable data on the electrochemical reduction of rhenium in molten salts greatly impedes further progress in the field of rhenium galvanoplastics and hinders interpretation of the experimental results. 

The reason for it is not obvious since gold is not a very rare element on earth, and other metals, for example, platinum, rhodium, osmium, and rhenium, are less abundant and more expensive. Its yellow color cannot be the reason either, since other metals, such as copper, and its alloys as bronze or brass, have different colors from the bright silver of most of the metals. Probably, the reason resides in its noble character. In fact, gold does not tarnish with time, and coins and jewelry remain indefinitely unalterable even after long exposure to extremely aggressive conditions. 

Humans have at all times made use of the components of the earth s crust. As a consequence of the discovery that even rare materials may have technically interesting properties, there has been a drive to widen the exploitation of natural resources. New separation methods have made the extraction of desirable elements possible. Such rare elements are often obtained as by-products of the mining of common ores. Gold and platinum, for instance, are present in the anode sludge from electrolytic copper refining. The mineral molybdenite, a sulfide, is roasted at 800°C to the oxide from which molybdenum metal and its alloys are produced. During the roasting process the oxide of a rare element, rhenium, volatilizes and its compounds can be extracted from the gas phase as a by-product. Several examples of this type are treated in the different element chapters of this book. 

For catalysts that were simply dried in air at 110°C after impregnation of the alumina with H2PtClfe and Re207, it was concluded that a platinum-rhenium alloy formed on reduction. This conclusion was based on the observation that the presence of platinum accelerated the reduction of oxygen chemisorbed on the rhenium and on results showing that the frequencies of the infrared absorption bands of carbon monoxide adsorbed on platinum and rhenium sites in platinum-rhenium catalysts were different from those found with catalysts containing only platinum or rhenium. However, for catalysts calcined in air at 500°C prior to reduction in hydrogen, it was concluded that the platinum exhibited much less interaction with the rhenium (66,71). 

Microgram amounts of TcOj can be ascertained by measuring the absorbance of the colored complex, formed with toluene-3,4-dithiol in 2.1 M HCl, after extraction into carbon tetrachloride. One hour must be allowed for the development of the color. ITie molar absorbance index at 410 nm is 1.1-10" mole -1-cm. Beer s law is followed over the range of 1.1 to 16.1 pg Tc/ml. Because many cations interfere, an initial separation of technetium is necessary [73]. The same complex was used for the determination of technetium in uranium fission element alloys after separation of Tc by distillation from sulphuric acid [74j. I hc complex formation of technetium, rhenium, and molybdenum with toluene-3,4-dithiol and its analytical application have been studied in detail [71]. 

Based on TPR results it can be concluded that intimate contact between rhenium and platinum is provided in bimetallic alloy particles on the surface of alumina supported catalysts. Therefore, one can expect that the oxidation of the catalyst followed by reduction at moderate temperature result in the formation of platinum and/or Re-Pt metallic nanoclusters and rhenium ions in atomic closeness. 

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