Dezincification mechanism

In certain alloys and under certain environmental conditions, selective removal of one metal (the most electrochemically active) can occur that results in a weakening of the strength of the component. The most common example is dezincification of brass [164, 165]. The residual copper lacks mechanical strength. 

Dezincification Dezincification is corrosion of a brass alloy containing zinc in which the principal product of corrosion is metallic copper. This may occur as plugs rilling pits (plug type) or as continuous layers surrounding an unattacked core of brass (general type). The mechanism may involve overall corrosion of the alloy followed by redeposition of the copper from the corrosion products or selective corrosion of zinc or a high-zinc phase to leave copper residue. This form of corrosion is commonly encountered in brasses that contain more than 15 percent zinc and can be either eliminated or reduced by the addition ox small amounts of arsenic, antimony, or ph osphorus to the alloy. 

Dezincification is explained by two theories. The first is that the alloy dissolves, with a preferential redeposition of copper. The other proposes a selective leaching of the zinc, leaving the copper behind. There is evidence that both mechanisms may operate, depending on the specific environment. 

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. 

Unfortunately, there is no general theory that will explain all the forms of localised attack that occur with the variety of metal/environment systems encountered in practice, e.g. the mechanism of the pitting of stainless steels in Cl -containing solutions is quite different from the dezincification of brass in a fresh natural water. Nevertheless, many of the following factors play an important part in most forms of localised attack ... 

Pitting may be defined as a limiting case of localised attack in which only small areas of the metal surface are attacked whilst the remainder is largely unaffected, and this definition is applicable irrespective of the mechanism involved dezincification, crevice corrosion and impingement attack can all result in pitting, although the mechanisms of these three processes are quite different. 

Dezincification is readily apparent, since the yellow colour of the brass is replaced by the characteristic red of copper, which may take the form of small plugs or of layers that in some cases can extend over the whole of the surface (Fig. 1.60). In plug-type dezincification a mechanically weak, porous residue of copper is produced, which may remain in situ or become removed by the pressure of water, leading to a perforation. In the layer type the transformation of the alloy into a mechanically weak layer of copper results in loss of strength, and failure may occur by splitting when the metal is subjected to water pressure or to external stress. 

Two theories have been proposed to explain dezincification, but since both have considerable support the precise mechanism remains unresolved. One theory proposes that the zinc is selectively leached from the alloy leaving a porous residue of metallic copper in situ (c/. parting of Ag-Au alloys), whilst the other proposes that the whole of brass dissolves and that the copper immediately redeposits at sites close to where the brass was dissolved. 

Dezincification of brasses When dezincihcation occurs, regions of the brass become replaced by a porous mass of copper which, though retaining the shape of the original article, has virtually no strength. There has long been discussion as to whether there is selective corrosion of the zinc in the brass, which leaves the copper behind, or whether complete dissolution of the brass occurs, followed by re-deposition of copper. Possibly both processes occur in different circumstances. The mechanism has been investigated and discussed by Evans, Fink", Lucey , Feller" and Heidersbach , and is referred to in many other papers. ... 

Addition of about 0 04% arsenic will inhibit dezincification of a brasses in most circumstances and arsenical a brasses can be considered immune to dezincification for most practical purposes . There are conditions of exposure in which dezincification of these materials has been observed, e.g. when exposed outdoors well away from the sea , or when immersed in pure water at high temperature and pressure, but trouble of this type rarely arises in practice. In other conditions, e.g. in polluted sea-water, corrosion can occur with copper redeposition away from the site of initial attack, but this is not truly dezincification, which, by definition, requires the metallic copper to be produced in situ. The work of Lucey goes far in explaining the mechanism by which arsenic prevents dezincification in a brasses, but not in a-/3 brasses (see also Section 1.6). An interesting observation is that the presence of a small impurity content of magnesium will prevent arsenic in a brass from having its usual inhibiting effect . 

Brass water fittings give no trouble except that dezincification may occur in acid waters or waters of high chloride content, especially when hot. This dezincification has three effects. Firstly, the replacement of brass by porous copper may extend right through the wall of the fitting and permit water to seep through. Secondly, the zinc which is dissolved out of the brass may form very voluminous hard corrosion products and eventually block the waterway —this is often the case in hot soft waters. Thirdly, and often the most important, the mechanical properties of the brass may deteriorate. For instance, a dezincified screwed union will break off when an attempt is made to unscrew it and a dezincified tap or ball-valve seat is readily eroded by the water. 

As is the case with other types of corrosion testing, mass-loss determinations may fail to indicate the actual damage suffered by specimens that are attacked intergranularly or in such a manner as dezincification. In such cases, mechanical tests will be required as discussed already in the section on evaluation techniques. 

Copper alloys, such as brass, bronze, admiralty, and Muntz metals, can exhibit better corrosion resistance and better mechanical properties than pure copper. In general, high-zinc alloys should not be used with acids or alkalies owing to the possibility of dezincification. Most of the low-zinc alloys are resistant to hot dilute alkalies. 

In addition to ductile iron and PVC, copper and lead are used in pipes, and brass in fixtures and connections. Lead is released because of uniform corrosion. Copper is also released because of uniform corrosion, localized-attack cold water pitting, hot water pitting, MIC, corrosion fatigue, and erosion-corrosion. Lead pipes and lead-tin solder exhibit uniform corrosion. Brass corrosion includes erosion-corrosion, impingement corrosion, dezincification, and SCC. The direct health impacts are because of increased copper, lead, and zinc concentrations in the drinking water. Mechanical problems because of corrosion include leaks from perforated pipes, rupture of pipes, and the loss of water pressure because of blockage of pipes by corrosion products. 

Dezincification, or selective leaching or parting, was first observed on brasses. The zinc is selectively leached out of the alloy, leaving a brittle, weak, and porous mass. It consists predominantly of copper plus copper oxides. The obvious mechanism is solution or corrosion of the brass. The zinc stays in solution, and the copper plates back onto the surface. 

Dezincification can occur, for example, in tap water, river water, seawater, and Uqnid containing chloride. The rate of this corrosion process is increased by plastic deformation of the material. Dezincification can occur by two mechanisms ... 

Alloys of gold with copper or silver retain the corrosion resistance of gold above a critical alloy concentration called the reaction limit by Tammann [1]. Below the reaction limit, the alloy corrodes, for example, in strong acids, leaving a residue of pure gold either as a porous solid or as a powder. This behavior of noble-metal alloys is known as parting and is probably similar in mechanism to dezincification of copper-zinc alloys (see Section 20.2.2). 

A corrosion mechanism similar to brass dezincification, known as dealuminification, can occur to the beta phase or eutectoid structure depending on environmental conditions. Proper quench and temper treatments produce a tempered beta structure with reprecipitated acicular alpha crystals, a combination often superior in corrosion resistance to the normal annealed structure. The nickel component in the more complex nickel aluminum bronzes alters the corrosion characteristics of the beta phase because of the nickel additive and gives greater resistance to deaUoying and cavitation-erosion in most liquids. 

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