Mercury causing stress-corrosion cracking

Annealed brass, if not subject to a high applied stress, does not stress-corrosion crack. Whether residual stresses in cold-worked brass are sufficient to cause stress-corrosion cracking in an ammonia atmosphere can be checked by immersing brass in an aqueous solution of 100 g mercurous nitrate [Hg2(N03)2] and 13 mL nitric acid (HNO3, specific gravity 1.42) per liter of water. Mercury is released and penetrates the grain boundaries of the stressed alloy. If cracks do not appear with 15 min, the alloy is probably free of damaging stresses. 

There are some differences in the behavior of alloys due to the variations in caustic composition among the three cell processes. These differences occur mostly in lower-grade applications using materials less robust than nickel. Monel, for example, is subject to liquid-metal cracking by mercury and its salts. Stainless steels seem to be equally affected by diaphragm- and mercury-cell caustic, but if the caustic is consumed in some application, the residual chloride from diaphragm-cell NaOH can cause stress corrosion cracking [146]. 

The corrodent is a liquid metal in this form of stress corrosion cracking. Mercury at ambient temperature and metals including zinc (from galvanized steel-work) and copper (from electric cables) when melted during welding or in a fire cause rapid failure of certain metals. 

However, in the case of stress-corrosion cracking of mild steel in some solutions, the potential band within which cracking occurs can be very narrow and an accurately known reference potential is required. A reference half cell of the calomel or mercury/mercurous sulphate type is therefore used with a liquid/liquid junction to separate the half-cell support electrolyte from the process fluid. The connections from the plant equipment and reference electrode are made to an impedance converter which ensures that only tiny currents flow in the circuit, thus causing the minimum polarisation of the reference electrode. The signal is then amplifled and displayed on a digital voltmeter or recorder. 

Only certain specific environments appear to produce stress corrosion of copper alloys, notably ammonia or ammonium compounds or related compounds such as amines. Mercury or solutions of mercury salts (which cause deposition of mercury) or other molten metals will also cause cracking, but the mechanism is undoubtedly differentCracks produced by mercury are always intercrystalline, but ammonia may produce cracks that are transcrystalline or intercrystalline, or a mixture of both, according to circumstances. As an illustration of this, Edmundsfound that mercury would not produce cracking in a stressed single crystal of brass, but ammonia did. 

The behaviour of a wide range of a, a-0 and /3 brasses in various corrosive environments was studied by Voce and Bailey and the results summarised by Whitaker . Penetration by mercury and by molten solder was intercrystalline in all three types of brass. In moist ammoniacal atmospheres the penetration of unstressed brasses of all types was intercrystalline. Internal or applied stresses accelerated the intercrystalline penetration of a brasses and initiated some transcrystalline cracking, and also caused severe transcrystalline cracking of /3 alloys and transcrystalline cracking across the 0 regions in the two-phase brasses. Immersion in ammonia solution, however, caused intercrystalline cracking of stressed 0 brasses. 

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