Cast irons graphitic corrosion

Cast iron corrodes because of the exposure of graphite content of cast iron (graphitic corrosion), which is cathodic to both low alloy and mild steels. The trim of a valve must be cathodic to the valve body to avoid pitting attack. Thus in aggressive media valve bodies of steel are preferred to cast iron bodies. Steel bolts and nuts coupled to underground mild steel pipes or a weld rod used for steel plates on the hull of a ship should always be of a low nickel, low chromium steel, or from a similar composition to that of the steel pipe (8). 

The selective corrosion of cast iron (graphitization), the preferential corrosion of the steel welding (grooving corrosion), sensitization and knife line attack of welded stainless steels are typical examples of corrosion influenced by metallurgical parameters. 

Impressed-current CP uses an outside power supply such as a rectifier to control the voltage between the pipe and an anode (cast iron, graphite, platinum clad, mixed metal oxide) in such a manner that the pipe becomes the cathode in the circuit and corrosion is mitigated. 

Graphitic Corrosion Graphitic corrosion usually involves gray cast iron in which metalhc iron is converted into corrosion products, leaving a residue of intact graphite mixed with iron-corrosion products and other insoluble constituents of cast iron. 

When the layer of graphite and corrosion products is impervious to the solution, corrosion wdl cease or slow down. If the layer is porous, corrosion will progress by galvanic behavior between graphite and iron. The rate of this attack will be approximately that for the maximum penetration of steel by pitting. The layer of graphite formed may also be effective in reducing the g vanic action between cast iron and more noble alloys such as bronze used for valve trim and impellers in pumps. 

Differences in alloy carbon concentration, heat treatment, and mechanical forming usually produce only small differences in corrosion rate in a pH range of 4—10. It is less certain how corrosion rates vary at high and low pH due to these factors. Cast irons containing graphite particles may experience a unique form of attack called graphitic corrosion (see Chap. 17, Graphitic Corrosion ). 

Changing the pump metallurgy to a more corrosion- and cavitation-resistant material, such as stainless steel, is a potential solution to this type of problem. Note, however, that all other cast iron pump components that have sustained graphitic corrosion should be replaced to avoid the possibility of galvanic corrosion (see Chap. 16) between retained graphitically corroded cast iron components and new components. 

Another form of microstructural galvanic corrosion, graphitic corrosion, is unique to gray and nodular cast irons. It may be encountered in cast iron pumps and other cast iron components. It is a homogeneous form of galvanic corrosion, not requiring connection to a different metal. 

Similarly, graphitically corroded cast iron (see Chap. 17) can assume a potential approximately equivalent to graphite, thus inducing galvanic corrosion of components of steel, uncorroded cast iron, and copper-based alloys. Hence, special precautions must be exercised when dealing with graphitically corroded pump impellers and pump casings (see Cautions in Chap. 17). 

Graphitic corrosion has two distinct features that are useful in distinguishing it from other forms of corrosion. First, it affects an unusually limited number of metals the only metals commonly affected are gray cast iron and nodular cast iron. Second, metal that has experienced graphitic corrosion may retain its original appearance and dimensions. Consequently, graphitic corrosion frequently escapes detection. 

Graphitic corrosion is a slow corrosion process, typically requiring many years to effect significant damage. Complete penetration of thick cross sections has, however, occurred in as little as 2 years in adverse environments. On the other hand, cast iron components can be found in use in Europe after 160 years of service. Although graphitic corrosion causes a substantial reduction in mechanical strength, it is well known that corroded cast iron, when sufficiently supported, may remain serviceable when internal pressure is low and shock loads are not applied. 

The occurrence of graphitic corrosion is not location specific, other than that it may occur wherever gray or nodular cast iron is exposed to sufficiently aggressive aqueous environments. This includes, and is common to, subterranean cast iron pipe, especially in moist soil (Case History 17.1). Cast iron pump impellers and casings are also frequent targets of graphitic corrosion (Case Histories 17.2 through 17.5). 

Note also that graphitic corrosion may occur preferentially in poorly accessible areas, such as the bottom of pipelines. Trouble-free service of cast iron components does not necessarily indicate that all is well, since components suffering severe graphitic corrosion may continue to operate until an inadvertent or intentional (e.g., pressuretesting) shock load is applied. At this point massive, catastrophic failures can occur. 

Graphitically corroded cast irons may induce galvanic corrosion of metals to which they are coupled due to the nobility of the iron oxide and graphite surface. For example, cast iron or cast steel replacement pump impellers may corrode rapidly due to the galvanic couple established with the graphitically corroded cast iron pump casing. In this or similar situations, the entire affected component should be replaced. If just one part is replaced, it should be with a material that will resist galvanic corrosion, such as austenitic cast iron. 

The pump has experienced graphitic corrosion. Figures 17.10, 17.12, and 17.14 illustrate typical appearances of graphitically corroded cast iron. In addition, cavitation damage (see Chap. 12) has produced severe metal loss in specific areas (see Fig. 17.13). The soft, friable corrosion products produced by graphitic corrosion are susceptible to cavitation damage at relatively low levels of cavitation intensity. 

Graphitic corrosion of the cast iron produced a soft, mechanically weak corrosion product that is highly susceptible to cavitation damage, even at relatively low cavitation intensities. The black coating on the impeller surface is visual evidence of graphitic corrosion. The spongelike surface contours are typical of cavitation damage (see Chap. 12). 

Figure 17.15 Section of a cast iron pump impeller that has suffered graphitic corrosion followed by cavitation damage.

Austenitic cast irons (either flake graphite irons or nodular graphite irons) are produced by mixing in nickel from 13-30%, chromium from 1-5% and copper from 0.5-7.5 (to lower nickel-containing grades to augment the corrosion resistance at lower cost). 

See Figure 12-8. Pistons may be of aluminum, built-up carbon or graphite, cast iron, cast steel, fabricated and metaUzed steel, stainless steel, or forged carbon or stainless steel. The selection involves the corrosive nature of the gas plus the weight-balancing problem of the compressor manufacturer. 

Borehole waters are generally very hard and cast iron pipes are still used because of the low internal corrosion rates permitted by the scaling which occurs naturally. Acidic waters cause graphitic attack on cast irons. 

Limitations on the use of cast irons are similar to those for steel, since in many environments most cast iron has poor corrosion resistance. Most grades are also susceptible to graphitization (the loss of iron, leaving a weak structure of graphite) in acidic environments below a pH of approximately 5.5. This attack occurs in soils. 

In principle the selective dissolution of the less noble component of a singlephase alloy would perhaps be expected and is in fact observed (dezincification of an a-brass, etc.) even though the details of the mechanism by which it occurs is not yet fully understood. In contrast, the preferential attack of the less noble phase of a two-phase alloy is not only expected and observed —the mechanism by which it occurs in practice is also quite clear. Selective dissolution of the more active phase of a two-phase alloy is best exemplified by the graphitic corrosion (or graphitisation) of grey cast iron. 

Local corrosion or pitting is more important for practical purposes than the rate of general corrosion, and may proceed 10 times or so more rapidly than this. Inasmuch as certain types of cast iron are liable to suffer graphitic corrosion, whereas steel does not, steel might theoretically be expected to show to some advantage when used for buried pipelines. In practice, however, a cast-iron pipe has to be of stouter wall than a steel pipe for equal strength, and it is doubtful whether any distinction between the rust resistance of the two materials in the soil is justified. 

The presence of active sulphate-reducing bacteria usually results in graphitic corrosion and this has led to a useful method of diagnosing this cause of corrosion. The leaching out of iron from the graphitic residue which is responsible for the characteristic appearance of this type of corrosion leads to an enriched carbon, silicon and phosphorus content in the residue as compared with the original content of these elements in the cast iron. Sulphur is usually lost to some extent but when active sulphate-reducing bacteria are present, this loss is offset by the accumulation of ferrous sulphide in the residue with a consequent increase in the sulphur content of the residue out... 

One of the outstanding properties of the austenitic irons is their resistance to graphitic corrosion or graphitisation . In some environments ferritic cast irons corrode in such a manner that the surface becomes covered with a layer of graphite. This compact graphite layer, being more noble than the matrix, markedly increases the rate of attack. The austenitic irons rarely form this... 

Water which is used for cooling purposes in refineries and chemical plant can cause severe problems of corrosion and erosion. Ordinary cast irons usually fail in this type of environment due to graphitic corrosion or corrosion/ erosion. Ni-Resist irons however show better corrosion resistance, due to the nobility of the austenitic matrix, and are preferred for use in the more aggressive environments such as those containing appreciable amounts of carbon dioxide or polluted with chemical wastes or sea-water. 

The characteristic mode of corrosion of some alloys may be the formation as a corrosion product of a redeposited layer of one of the alloy constituents, as in the case of the brasses that dezincify, or of a residue of one of the components, as in the case of the graphitic corrosion of cast iron. Particularly in the case of the dezincified brass, the adherent copper is not likely to be removed with the other corrosion products, and therefore the mass-loss determination will not disclose the total amount of brass that has been corroded. This is especially important because the copper layer has very little strength and ductility and the extent of weakening of the alloy will not be indicated by the mass loss. In these cases, also, the mass-loss determinations must be supplemented by, or replaced by, mechanical tests or metallographic examination, or both, to reveal the true extent of damage by corrosion. Difficulties in obtaining accurate mass losses of heavily graphitised specimens have been reported... 

Graphitic Corrosion corrosion of grey cast iron in which the metallic constituents are removed as corrosion products, leaving the graphite. 

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