Introduction

Selective leaching is a corrosion process in which one or more constituent of an alloy is preferentially dissolved
by the environment, leaving the dealloyed metal weak and often porous. This “dealloying” may occur uniformly
or locally, often without a measurable change in dimension.

This type of corrosion can occur on numerous metals however the most common examples are:

 Dezincifcation of brass: In the case of dezincification of brass, zinc is preferentially leached out of the
copper-zinc alloy, leaving behind a copper-rich surface layer that is porous and brittle. Most commonly
found in copper-zinc alloys containing less than 85% copper after extended service in water containing
dissolved oxygen.
 Dealuminization of aluminium bronze
 Selective dissolution of tin in phosphor bronze
 Graphite corrosion in grey cast-iron (Mattsson 1989): deterioration of gray cast iron in which the
metallic constituents are selectively leached or converted to corrosion products leaving the graphite
intact.
 Decarburization is the selective loss of carbon from the surface layer of a carbon-containing alloy due to
reaction with one or more chemical substances in a medium that contacts the surface.
 Decobaltification is selective leaching of cobalt from cobalt-base alloys, such as Stellite, or from
cemented carbides.
 Denickelification is the selective leaching of nickel from nickel-containing alloys. Most commonly
observed in copper-nickel alloys after extended service in fresh water.
 Selective leaching of copper alloys involves preferential dissolution of the
alloying element (Zn, Sn, Al, Ni) added to copper to improve its mechanical
properties.

Mechanisms

 Different metals and alloys have different electrochemical potentials (or corrosion potentials) in the
same electrolyte. Modern alloys contain a number of different alloying elements that exhibit different
corrosion potentials. The potential difference between the alloying elements is the driving force for the
preferential attack on the more "active" element in the alloy.

 Three mechanisms have been described for selective leaching:

1. two metals in an alloy are dissolved, and one redeposits on the surface; and
2. one metal is selectively dissolved, leaving the other metals behind. Dezincification of brasses
occurs by the first mechanism; the loss of molybdenum from nickel alloys in the molten sodium
hydroxide occurs by the second. In some alloys, selective leaching takes place by either
mechanism, depending on temperature and on the type, concentration, and flow rate of the
corrodent.
3. Selective attack on inclusions by an environment to which the body of metal is resistant, in
which only small amounts of material (as compared to the massive attack usually encountered in
selective leaching) are preferentially corroded away, is a special case of selective leaching. The
inclusions provide small anodic areas surrounded by large cathodic areas. Where the inclusions
are in the form of elongated stringers and there is end-grain exposure to the environment the
attack is highly directional and deep penetration of the metal is possible.
 The metal in the affected area becomes porous and loses much of its strength, hardness, and
ductility. Failure may be sudden and unexpected because dimensional changes are not always
substantial and the corrosion sometimes appears to be superficial, although the selective attack
may have left only a small fraction of the original thickness of the part unaffected.

 The environment in which this type of corrosion occurs includes exposure to a stagnant or slow moving
body of water especially if it contains high quantities of O2 , CO2 or chlorides.

 The quantity of a metal in an alloy also determines it’s susceptibility to preferential dissolving which is
highlighted in figure 1. For instance, if zinc content in a brass is less than 15% then dezincification does
not occur significantly. If the zinc content is higher than this and an acidic environment is present
dezincification will occur (Shreir 2013).

Figure 1: Effect of zinc content on dealloying. (Bardal 2007)

 The rate at which dezincification takes place is also affected by the environmental temperature; figure 1
shows that increasing zinc % from 15 to 40 at 80oC increases the rate by over 5 times.

Detecting and Testing Selective Leaching

 Hardness Testing requires cleaning and disassembly of pump casings and valve bodies for access to the
inside diameter. This is considered the most reliable method of detection and is the approach that most
utilities have committed to for License Renewal.

 Visual Examination is also often used and provides a recommended complementary measure to
Hardness Testing. Because selective leaching (especially in cast iron) is difficult to assess due to the
subtleties of color differences, it’s important to have trained and experienced personnel, such as our
experts at Structural Integrity, perform visual inspections.
  The most effective way to test in process for de-alloying is through eddy current testing (Corcoran,
2003). This works by analysing an electric current induced through the surface of the metal. Alloy
compositional changes brought about by de-alloying corrosion will disturb the flow of the induced eddy
currents. This disruption is then represented on the screen of the test equipment as a visual indication.
The limitation of eddy current test is that it can only be used to find surface imperfections of de-
alloying, rather than quantify the depth of any defect.

 More in depth inspection can be achieved by sectioning and microscopic examination. However, as this
is a destructive test, this is usually used in failure analysis or to gain empirical values for reference.
SEM, TEM and optical microscopy are all effectively used to examine sectioned samples, unlike eddy
current testing; this form of examination can measure the depth of attack (Corcoran, 2003).
 Unlike other forms of corrosion, weight loss is not a significant measurement of the impact of de-
alloying. This is due to the extremely small changes in weight loss of an alloying element can have a
massive effect on the mechanical characteristics of the metal. The impact of de-alloying on the strength
of the material can be evaluated through mechanical testing (Beavers, 1983)

Prevention
Dealloying, selective leaching and graphitic corrosion can be prevented through the following methods:

 Select metals/alloys that are more resistant to dealloying that is to limit the proportions of alloying
elements. In brasses for example, inhibited brass containing arsenic and tin can be added (around 1%) to
stop the leaching of zinc (Herro, 1993). This gives superior resistance to de-alloying when compare to
alpha brass. In cast irons, ductile iron has a higher resistance to graphite corrosion than gray cast iron.
 Another method of prevention is to control the environment described above to minimize the effect of de
alloying, however, this is not always possible. The design of the component will also dramatically affect
the ability to resist de-alloying. By reducing turbulence in pipe line applications and areas of high stress
in structures, this will reduce the rate of corrosion
 A final measure of corrosion protection to de-alloying is the use of a sacrificial anode to protect the
alloy. This can be done by selecting a material that has a higher level of electrochemical reactivity to
corrode, protecting the main component. This anode can then be replaced periodically. Another system
of corrosion prevention is to implement an impressed current cathodic protection induce a controlled
current into the alloy to counteract the flow of electrons found in the corrosion cell.
Most Common Selective Leaching Processes

1. DEZINCIFICATION

Within dezincification, zinc is the preferential and removed from the alloy leaving the copper. This process
usually results in a colour change across the metal as the areas which zinc has become depleted in appear
copper red (Bardal 2007). The problem associated with this corrosion is that a weak porous metal is usually left
after the selective leaching out of the alloy (Davis 2001). Dezincification can occur in two ways:

 Plug
 Layering

Plug dezincification can be seen in figure 1. This type of attack occurs when the alloy is exposed to waters
which are either neutral or alkaline and contain a high salt content and the zinc content is low (NACE 2015).
Plug dezinification is a localised attack and penetration into the metal tends to be deeper.

Figure 1 : Plug dezincification (NACE 2015)

Layer zincification on the other hand occurs relatively uniformly across the material (figure 3). Layered
dezincification is more common in acidic environments and more common in the alloy if the zinc content is
higher (Bardal 2007).

Figure 2: comparing a) layered b) plug forms of dealloying. (Bardal 2007)

A common example is the dezincification of unstabilized brass, whereby a weakened, porous copper structure is
produced. The selective removal of zinc can proceed in a uniform manner or on a localized (plug-type) scale. It
is difficult to rationalize dezincification in terms of preferential Zn dissolution out of the brass lattice structure.
Rather, it is believed that brass dissolves with Zn remaining in solution and Cu replating out of the solution.

Dezincification can be prevented by:

 Keeping copper content above 85%

 Alloy substitution e.g. adding 1% tin to the brass

2. GRAPHITIC CORROSION

 Graphite corrosion in grey cast irons is also a common example of dealloying. This corrosion
mechanism takes a galvanic approach as a galvanic cell is produced as the graphite becomes cathodic to
the iron (Davis 2001).
 Similarly to dezincification a weakened structure is also left as a result of this corrosion technique.
Figure 3 demonstrates the weekend structure where the iron has preferentially corroded leaving a less
dense graphite structure with low mechanical strength.
 Unlike dezincification it is almost always uniform across the metal and is sometimes not detected and
can cause unexpected failures. It can be prevented by altering the environment by raising the pH of the
water (Davis 2001) however this isn’t always possible in applications.
 Therefore a different material selection should be made by substituting the gray cast iron for white iron
without graphite, or a ductile cast iron which is also less prone to graphitic corrosion as there is a lack of
graphite flakes in the microstructure. If changing material selection is also not appropriate then
inhibitors can be added to the iron.
 During cast iron graphitic corrosion the porous graphite network, that makes up 4-5% of the total mass
of the alloy, is impregnated with insoluble corrosion products.
 Graphitic corrosion should not be confused with another term graphitization, which is used to describe
the formation of graphite in iron or steel, usually from decomposition of iron carbide at elevated
temperatures.
Testing and identification of graphitic corrosion is accomplished by scraping through the surface with a knife to
reveal the crumbling of the iron beneath.
Where extensive graphitic corrosion occurs, usually the only solution is replacement of the damaged element.
Figure 3: Graphitic corrosion at a microscopic level. (Anderson Materials Evaluation Inc 2015)

Example : Steel part of a car (optional)

The part has been covered with a layer of paint to stop the steel from oxidizing with the atmosphere. However,
over time this surface has become damaged and the steel has started to corrode. This is primarily due to the
environment that the suspension leg is exposed to.

It is positioned directly behind the wheel of the car where it can be damaged by stone chips and debris. This
causes the paint to be chipped and worn causing the steel to become exposed. Also, by being located next to the
car’s wheel, it is also subjected to cyclic wet and dry conditions, creating a electrolyte for corrosion to occur. In
winter months, salt from the roads can also be transferred onto the surface of the component; this will also
increase the rate of corrosion.

The design of the suspension leg has also contributed to the corrosion. The area of corrosion has occurred in the
cup of the damper. This creates a seat where the spring is located. As the spring is free to move in the cup, this
then leads to wear of the paint surface exposing the steel. This, combined with the shape of the cup that creates
a place for water, salt and other contaminants to gather, creates a design that could be improved to stop the
corrosion.

All these factors have contributed to the suspension leg corroding.