Nickel alloys sulphidation

In general, greatly reduced rates of attack are observed for impure or dilute nickel alloys compared with pure nickel when exposed to SO2 + O2 atmospheres. Haflan et al. have attributed this to the segregation of impurities at the sulphide/oxide interface causing breakup of the sulphide network. For example in the case of silicon additions, it has been shown that silicates form and it has been proposed that these alter the wetting characteristics of the sulphide and prevent the establishment of an interconnected sulphide network. 

Meteorites are the grains of meteoroids or meteors that survive the journey through the Earth s atmosphere and reach the surface. Some are almost pure iron-nickel alloy, whereas others contain silicates and sulphides, and yet others (the carbonaceous chondrites) contain organic compounds. 

Copper and copper alloys are highly resistant to atmospheric corrosion because of surface films mainly composed of basic copper salts. The corrosion rate is below 2-3 pm/year [8.9]. Tin as well as nickel and nickel alloys also corrode at similar rates. Lead possesses excellent corrosion resistance in atmospheres due to surface-protecting films (insoluble sulphate, sulphide, carbonate and oxide). 

Steels and stainless steels show preferential nucleation of pits at inclusions, most notably sulphide inclusions ". Other sulphur-rich regions in ferrous and nickel-based alloys may also lead to premature failure. It has been shown that accumulation of sulphur on the surface of these materials retards passivity and enhances dissolution of the metal. These effects occur in any solution in which the metal shows an active region and they are also preferential pitting sites in the presence of chloride. A recent notion for... 

Dilute binary alloys of nickel with elements such as aluminium, beryllium and manganese which form more stable sulphides than does nickel, are more resistant to attack by sulphur than nickel itself. Pfeiffer measured the rate of attack in sulphur vapour (13 Pa) at 620°C. Values around 0- 15gm s were reported for Ni and Ni-0-5Fe, compared with about 0-07-0-1 gm s for dilute alloys with 0-05% Be, 0-5% Al or 1-5% Mn. In such alloys a parabolic rate law is obeyed the rate-determining factor is most probably the diffusion of nickel ions, which is impeded by the formation of very thin surface layers of the more stable sulphides of the solute elements. Iron additions have little effect on the resistance to attack of nickel as both metals have similar affinities for sulphur. Alloying with other elements, of which silver is an example, produced decreased resistance to sulphur attack. In the case of dilute chromium additions Mrowec reported that at low levels (<2%) rates of attack were increased, whereas at a level of 4% a reduction in the parabolic rate constant was observed. The increased rates were attributed to Wagner doping effects, while the reduction was believed to result from the... 

Another factor that determines the long-term stability of the protective oxide layer is its ability to prevent sulphur penetration which would lead to the eventual formation of chromium sulphide beneath the external oxide layer. With most commercial nickel chromium alloys internal sulphidation... 

Extensive studies have been carried out by Giggins and Pettit and by Vasantasree and Hocking on a range of nickel chromium alloys with up to 50% alloying addition. Generally the principles outlined above can be used to interpret the experimental observations, where the thermodynamics of the reaction are a major factor determining the rate of attack, depending upon whether oxide or sulphide is the stable phase. 

Continued exposure of the nickel-chromium alloy to more severely sulphurising and reducing atmospheres results in local depletion of chromium to such an extent that nickel sulphide and the eutectic are formed internally. The latter constituents are not often observed in service failures, but the relative instability of nickel sulphide in the presence of chromium sulphide can result in its reduction to nickel during slow cooling on shut down. That nickel sulphide is formed is suggested by the frequent occurrence of blisters, associated with the formation of molten eutectic on the surface of sulphur-attacked specimens . 

Although iron sulphide also forms a eutectic with the metal this melts at 988°C, and at temperatures in the region of 700 to 800°C alloys with substantial proportions of nickel replaced by iron and a chromium level maintained at about 20% show advantages over nickel-chromium-base alloys in resistance to sulphur attack. 

Low-carbon and chromium-nickel steels, certain copper, nickel and aluminium alloys (which are all widely used in marine and offshore engineering) are liable to exhibit stress-corrosion cracking whilst in service in specific environments, where combinations of perhaps relatively modest stress levels in material exposed to environments which are wet, damp or humid, and in the presence of certain gases or ions such as oxygen, chlorides, nitrates, hydroxides, chromates, nitrates, sulphides, sulphates, etc. 

General corrosion damage was the cause of failure of an A1 alloy welded pipe assembly in an aircraft bowser which was attacked by a deicing-fluid — water mixture at small weld defects . Selective attack has been reported in welded cupro-nickel subjected to estuarine and seawater environments . It was the consequence of the combination of alloy element segregation in the weld metal and the action of sulphate reducing bacteria (SRB). Sulphide-coated Cu-enriched areas were cathodic relative to the adjacent Ni-rich areas where, in the latter, the sulphides were being continuously removed by the turbulence. Sulphite ions seemed to act as a mild inhibitor. 

Phillips and Timms [599] described a less general method. They converted germanium and silicon in alloys into hydrides and further into chlorides by contact with gold trichloride. They performed GC on a column packed with 13% of silicone 702 on Celite with the use of a gas-density balance for detection. Juvet and Fischer [600] developed a special reactor coupled directly to the chromatographic column, in which they fluorinated metals in alloys, carbides, oxides, sulphides and salts. In these samples, they determined quantitatively uranium, sulphur, selenium, technetium, tungsten, molybdenum, rhenium, silicon, boron, osmium, vanadium, iridium and platinum as fluorides. They performed the analysis on a PTFE column packed with 15% of Kel-F oil No. 10 on Chromosorb T. Prior to analysis the column was conditioned with fluorine and chlorine trifluoride in order to remove moisture and reactive organic compounds. The thermal conductivity detector was equipped with nickel-coated filaments resistant to corrosion with metal fluorides. Fig. 5.34 illustrates the analysis of tungsten, rhenium and osmium fluorides by this method. 

The processes involved in the reduction of nickel ores vary considerably, both with the chemical composition of the ore employed and the nature of the product required. For example, the Sudbury (Ontario) ores consist essentially of sulphides of nickel, copper, and iron. When pure nickel is required it is, of course, essential to remove the copper and the iron. Sometimes, however, an alloy of nickel and copper, known as monel metal, is desired, and it is usual then to remove the iron and subsequently reduce the mixed sulphides of copper and nickel to the alloy direct. Monel metal is thus known as a natural alloy, inasmuch as the constituent elements have not been individually isolated. 

Corrosion is further accelerated by the presence of impurities such as oxides, sulphides, carbides, phosphides, and silicates, since these are invariably at a lower potential than the ferrite.3 The influence of alloying elements 4 is particularly interesting. With carbon, for example, cementite or iron carbide, Fe3C, is formed, and as this is electro-negative to ferrite, the latter corrodes at the points of contact. Addition of carbon, therefore, to iron tends to enhance its corrodibility. If a third element is added to the system, its influence upon corrosion is determined largely by the manner in which it distributes itself.5 If it dissolves in the ferrite, reducing its. solution pressure, it reduces the potential difference between the ferrite and cementite, and thus enhances the resistance of the whole to corrosion. Nickel behaves in this manner, the whole of the metal passing into solid solution with the ferrite until the steel contains more than 8 per cent, of nickel. Such steels, therefore, do not readily corrode. 

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