Platinum alloys

Gold and gold-based alloys ate used for corrosion-resistant equipment. Gold—platinum alloys, 75 Au-25 Pt or 84 Au-15 Pt-1 Rh, ate used as cmcible material for many molten salts (98). Spinnerets for rayon manufacture ate based on the Au—Pt system which exhibits a broad miscibility gap in the soHd state so that the alloys can be age-hardened. Spinneret alloys contain 30—40% or mote platinum modified by small additions of usually rhodium (99). Either gold or gold—platinum alloys ate used in mpture disks for service with corrosive gases (100). 

Plating and Coatings. Thin surface coatings of platinum and platinum alloys are used as decorative finishes and in critical appHcations where it is necessary to provide finishes resistant to corrosion or high temperature, eg, coatings on jet-engine turbine components (258). Compounds used in the electro deposition of platinum are based on Pt(Il) and Pt(IV) and include H2[PtCl3] and its salts, eg, Pt—P—Salt, [Pt(NH3)2(N02)2] H2[Pt(S04)(N02)2] ... 

Iridium [7439-88-5] Ir, and rhodium [7440-16-6] Rh, iadividually iacrease corrosion resistance, hardness, and strength of platinum alloys. They can be used to reduce grain size (140). 

Platinum and Platinum Alloys. Platinum has excellent resistance to strong acids and, at elevated temperatures, to oxidation. Under reducing conditions at high temperatures it must be protected from low-fusing elements or their oxides. Easily reduced metals at high temperatures may form low-fusing alloys with platinum. 

The electrolyte is a perfluorosulfonic acid ionomer, commercially available under the trade name of Nafion . It is in the form of a membrane about 0.17 mm (0.007 in) thick, and the electrodes are bonded directly onto the surface. The elec trodes contain veiy finely divided platinum or platinum alloys supported on carbon powder or fibers. The bipolar plates are made of graphite or metal. 

Phosphoric Acid Fuel Cell This type of fuel cell was developed in response to the industiy s desire to expand the natural-gas market. The electrolyte is 93 to 98 percent phosphoric acid contained in a matrix of silicon carbide. The electrodes consist of finely divided platinum or platinum alloys supported on carbon black and bonded with PTFE latex. The latter provides enough hydrophobicity to the electrodes to prevent flooding of the structure by the electrolyte. The carbon support of the air elec trode is specially formulated for oxidation resistance at 473 K (392°F) in air and positive potentials. 

Alloys with rhodium Rhodium alloys readily with platinum in all proportions, although the workability of the resulting alloy decreases rapidly with increasing rhodium content. Alloys containing up to about 40% rhodium, however, are workable and find numerous applications. The principal physical and mechanical properties of rhodium-platinum alloys are listed in Table 6.3. 

The resistance of rhodium-platinum alloys to corrosion is about the same as or slightly better than that of pure platinum, but they are much more stable at high temperatures. They have excellent resistance to creep above 1 000°C, a factor which largely determines their extensive use in the glass industry, where continuous temperatures sometimes exceeding 1 500°C are encountered. Rhodium additions to platinum reduce appreciably the volatilisation of pure platinum at high temperatures. 

Table 6.3 Physical and mechanical properties of rhodium-platinum alloys...

Alloys with iridium Iridium alloys with platinum in all proportions, and alloys containing up to about 40% iridium are workable, although considerably harder than pure platinum. The creep resistance of iridium-platinum alloys is better than that of rhodium-platinum alloys at temperatures below 500°C. Their stability at high temperatures, however, is substantially lower, owing to the higher rate of formation of a volatile iridium oxide. 

Alloys with ruthenium Additions of ruthenium have a most marked effect upon the hardness of platinum, but the limit of workability is reached at about 15% ruthenium, owing to the fact that ruthenium belongs to a crystallographic system different from that of platinum. Apart from a somewhat greater tendency to oxide formation at temperatures above 800°C, the resistance to corrosion of ruthenium-platinum alloys is comparable to that of iridium-platinum alloys of similar composition. 

Platinum and rhodium-platinum and iridium-platinum alloys are frequently employed to line and sheath autoclaves, reactor vessels and tubes, and a wide range of equipment. Linings are generally 0-13 mm to 0- 38 mm thick, and for certain applications co-extruded platinum-lined Inconel or other metal reactor or cooling tubes are fabricated. In such cases the platinum is bonded to the base metal, but in all other instances platinum linings are of the loose type. 

In handling molten glasses at temperatures which sometimes reach 1 500°C, and frequently lie around 1 400°C, platinum alloys fulfil several functions ... 

The most usual forms of platinum or, more frequently, of the platinum alloys containing 5 or 10% of rhodium, are thin protective sheaths contoured to conform with the shape of the underlying refractory. Sheaths of this type, generally 0-25 mm to 0-65 mm thick, are widely employed to protect tank lips, skimmer blocks, stirrers, thermocouple pockets, etc. More substantial —thicknesses-up to 2-5 mm thick —are used to protect orifices whose dimensional accuracy must be maintained to a high degree. 

Rhodium-platinum alloys containing up to 40% Rh are used in the form of wire or ribbon in electrical resistance windings for furnaces to operate continuously at temperatures up to 1 750°C. Such windings are usually completely embedded in a layer of high-grade alumina cement or flame-sprayed alumina to prevent volatilisation losses from the metal due to the free circulation of air over its surface. Furnaces of this type are widely employed for steel analysis, ash fusions and other high-temperature analytical procedures. 

Lead materials lead-antimony-silver, lead with platinum alloy microelectrodes, lead/magnetite, lead dioxide/titanium, lead dioxide/ graphite. 

A typical anode for practical use would be in the order of 25 to 48 mm in diameter, with hard platinum alloy pins of 0-50 mm diameter by 10 mm length, spaced every 150 to 300 mm and progressively positioned around the circumferenceThe pins are a press fit into holes in the lead or lead alloy (approximately 01 mm diametric interference) and lie flush with the surface. The lead is peened around the pins to improve the mechanical and electrical contact. 

Ruthenium nowadays finds many uses in the electronics industry, particularly for making resistor tracks. It is used as an ingredient in various catalysts and, importantly, in electrode materials, e.g. Ru02-coated titanium elements in the chloralkali industry. Osmium tetroxide is a very useful organic oxidant and, classically, is used as a tissue stain. Both elements are employed in making certain platinum alloys. 

Muketjee S, Srinivasan S. 1993. Enhanced electrocatalysis of oxygen reduction on platinum alloys in proton exchange membrane fuel cells. J Electroanal Chem 357 201-224. 

Anderson AB, Roques J, Mukeijee S, Murthi VS, Markovic NM, Stamenkovic V. 2005. Activation energies for oxygen reduction on platinum alloys Theory and experiment. J Phys Chem B 109 1198-1203. 

Mukeijee S, Srinivasan S. 1993. Enhanced electrocatalysis of oxygen reduction on platinum alloys in proton exchange membrane fuel cells. J Electroanal Chem 357 201-224. Mukeijee S, Srinivasan S, Soriaga M, McBreen J. 1995. Role of structural and electronic properties of Pt and Pt alloys on electrocatalysis of oxygen reduction. J Electrochem Soc 142 1409-1422. 

Palladium electrocatalysts, 183 Palladium-alloy electrocatalysts, 298-300 Pareto-optimal plot, 85 Platinum-alloy electrocatalysts, 6, 70-71, 284-288, 317-337 Platinum-bismuth, 86-87, 224 Platinum chromium, 361 362 Platinum-cobalt, 71, 257-260, 319, 321-330, 334-335 Platinum-iron, 319, 321, 334-335 Platinum-molybdenum, 253, 319-320... 

Much of the Pt Mossbauer work performed so far has been devoted to studies of platinum metal and alloys in regard to nuclear properties (magnetic moments and lifetimes) of the excited Mossbauer states of Pt, lattice dynamics, electron density, and internal magnetic field at the nuclei of Pt atoms placed in various magnetic hosts. The observed changes in the latter two quantities, li/ (o)P and within a series of platinum alloys are particularly informative about the conduction electron delocalization and polarization. 

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