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Platinum Metals Review PLATINUM METALS REVIEW A quarterly survey of research on the platinum metals and of developments in their applications in industry VOL. 12 APRIL 1968 NO. 2 Contents Lcad-Platinum Bielectrodes for Cathodic Protection 42 A Standard High Purity Platinum 45 Monolithic Ceramic Capacitors 46 Chemistry of Co-ordination Complexes 47 Platinum for Fuel Cells 48 Tcrtiary Phosphine Complexes of the Platinum Metals 50 Palladium Addition Protects Titanium in Hot Concentrated Chloride Solutions 53 Potentiometer Slidewire Materials 54 Frictional Characteristics of the Refractory Platinum Metals 61 Vapour Phase Deposition of Iridium 62 Palladium and Rhodium: Russian Reviews 63 Platinum Sales Problems in the French Revolution 64 Wollaston’s Classic Lecture on Platinum 66 Abstracts 67 New Patents 75 Communications should be addressed to The Editor, Platinum Metals Review Johnson, Matthey & Co., Limited, Hatton Garden, London, E.C.1 Lead-Platinum Bielectrodes for Cathodic Protection ADVANTAGES IN MARINE APPLICATIONS By L. L. Shreir, Ph.D. Department of Metallurgy, Sir John Case College, London The insertion of small pieces of platinum into the surface of lead or lead alloy anodes causes a remarkable change in their behaviour as electrodes. Such lead-platinum bielectrodes are inexpensive, robust and easily fabri- cated and can be used successfully for the cathodic protection of marine structures. In this article the author describes the principles involved and reviews ten years of experience in a variety of applications. It has been established for some years that solutions, as in sea-water, facilities the for- lead and lead alloys can be used as inert mation of PbO,, and anodes of I to 2 per anodes in electrolytic processes provided cent silver-lead and I per cent silver - 6 per that a film of lead peroxide is formed and is cent antimony-lead are used for the cathodic maintained on the surface. protection of marine structures. Lead peroxide, which is a thermodynami- It has been shown however (I), that the cally stable form of lead at elevated electrode insertion of a platinum microelectrode into potentials, can be formed by the oxidation of lead has a remarkable effect on the anodic Pb2+aq in solution at an inert electrode, behaviour of the latter, and that lead- such as platinum, or by the oxidation of lead platinum bielcctrodes can be anodically itself. The oxide is chemically stable and is polarised in chloride solutions at high current characterised by a high electronic conduct- densities (2). Chlorine evolution on platinum ivity (about 50 per cent that of lead) so that takes place at low overpotentials (3), so that lead with a film of PbO, will act as an inert this reaction occurs in preference to oxygen anode, provided the oxide remains in elec- evolution, although the latter is the thermo- trical contact with the metal and is reformed dynamically preferred process; platinum in should a discontinuity be produced in the contact with lead will therefore tend to act film. Thus anodic polarisation of lead in as a potentiostat and to limit the potential sulphuric acid results in the formation of a of the lead/solution interface to about 2.5 thin film of PbO, at the Pb/PbO,-H,SO, volts. It has been shown (4) that the PbO, reversible potential; with further passage of film thickens when anodically polarised at charge the predominant reaction is oxidation high current densities in sea-water, and since of water to oxygen and there is practically the volume ratio of PbO,/Pb is greater than no thickening of the film. unity, the film is under considerable expansive The position in chloride solutions is quite stress. This results in the formation of different, and both PbCl, and PbO, are formed blisters which eventually rupture, with simultaneously, but at low current densities subsequent formation of PbC1, and corrosion a film of the latter gradually consolidates and of the exposed lead and, at constant current the lead can then act as a relatively inert density, the potential of the electrode will electrode. The presence of SO4*-in chloride increase since the PbCI, is nonconductive. Platinum Metals Rev., 1968, 12, (2), 4245 42 dmong the applications for aihich lead-platinum bielectrodes have been found succes.fu1 is the cathodic protertion of the structure and well cnsings of Xorth Sea driZling rigs. liere an electrode - jixed at the lrf-hand end of the steel frame is being installed on one such rig. This electrode will operate at 35 umps per square foot (Photograph by courtesy of Metal and Pipeline Endurance Limited) This can be demonstrated by forming PbO, series of tests on cast lead and lead alloys on a lead-platinum bielectrode and then and on dispersion-hardened lead have been removing the platinum microelectrode, when carried out in collaboration with D. P. the potential immediately increases. When Peplow of the Central Electricity Generating platinum is in contact with the lead this Board. The illustration overpage shows cast increase in potential cannot occur, and PbO, lead alloys (I inch long by I inch diameter) will re-form at the lead exposed at a ruptured and extruded dispersion-hardened lead (1.5 blister without excessive corrosion. inch long by 0.5 inch diameter) on test in a water box at Marchwood Power Station. Design and Construction These anodes were polarised at 50 A/sq. ft of Rielectrodes for one year in order to assess the effect of The lead-platinum bielectrode consists of the composition on the growth and spalling an extruded bar of lead or lead alloy, I to of the lead peroxide, and the results can be 1.5 inch diameter and up to 12feet in length, summarised as follows: into which are inserted platinum micro- (a)Additions of silver are beneficial, and 0.1 per cent is almost as effective as I pcr cent. electrodes at 6 to inch intervals. The micro- IZ (b) Additions of antimony, bismuth and tin electrodes consist of small wires of platinum appear to be detrimental. (with a small percentage of an alloying metal (c) Dispersion-hardened lead and lead alloys are unsatisfactory, since pronounced spall- to increase hardness) 0.5 inch long by 0.030 ing occurs in the direction of extrusion. inch diameter, inserted in the lead by drilling a 0.025 inch diameter hole, tapping in the Successful Installations wire until it is flush with the lead surface The use of lead-platinum anodes in cathodic and then peening the surrounding lead to protection installations is largely confined ensure good electrical contact. to Metal and Pipeline Endurance Limited The nature of the lead used in the bielec- (MAPEL) in England, and to Lockheed trode is important and recently an extensive Aircraft Service Corporation of Ontario, Cali- Platinum Metals Rev., 1968, 12, (2) 43 The type of lead or lead alloy for use in platinum bielectrodes is important, and extensive tests have been rarried out with a num- ber of alloys. The anodes shown here were in use for a year. at 50 amps per square foot. in a water box at Marchuiood Pouw Station in order to ussess the effect of composrtion on the grow& and &pallingof the lead peroxide (Photograph by courtesy of the Central Electricity Generating Board) fornia, both of whom, on the basis of over ten Area Rapid Transit Tube, a steel tube four years’ experience, arc using them for a variety miles long and some 130 feet in circumference of marine structures. which will carry rail and road traffic under One of the earliest applications by MAPEL the Bay; this is probably the largest cathodic was for the cathodic protection of the cooling protection installation ever undertaken. water culverts in a power station in Malacca, Malaya. These anodes have now been operat- Advantages of Lead-Platinum ing satisfactorily for ten years at 25 A/sq. ft. Anodes Other examples of large structures protected Lead-platinum bielectrodes are cheap, by MAPEL are the jetties in Europort and robust and easily fabricated, and can be used North Sea gas platforms such as that shown economically in sea-water over a range of in the illustration on page 43. Here the bi- current densities, from 10 to 70 A/sq. ft; electrode is mounted on a steel frame which a large anode operating at a low current is attached to the legs of the platform so density is sometimes an advantage when a that both are protected. uniform current distribution is required on a The Lockheed Aircraft Company have used large structure. The presence of an a.c. these anodes extensively for the protection ripple on the d.c. produced by transformer- of bulk carriers, tankers, liners, offshore rectifiers causes the slow corrosion of plati- drilling rigs and oil-wells and this company num, which can be serious when the platinum has recently been awarded the contract (5) is in the form of a very thin coating on a valve for the protection of the San Francisco Bay metal. The effect of a.c. corrosion on the Platinum Metals Rev., 1968, 12, (2) 44 relatively massive platinum microelectrode i.s References insignificant, and this has the advantage that I L.L. Shreir and A. Weinraub, Chcm. and Ind., 1958, 1326; L. L. Shreir, Platinum Metals single-phase equipment produces no problems Rev., 19~9,3, 44 when lead-platinum anodes are used in a 2 E. L. Littauer and L. L. Shreir, Proc. First Int. Congr. Metall. Corros., p. 374, Butter- cathodic protection system. worths, London, (1961); L. L. Shreir, The experience gained over the past ten Corrosion, 1961, 17, 90; E. L. Littauer and years has shown that the lead-platinum L.
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