Ayesha Malik

Nouman Zubair
Table of Contents
Corrosion
Types of Corrosion
Selective Leaching
De-zincification
De-zincification Mechanism
Prevention
Graphitization
Identification
Case Study
Selective Leaching
Selective leaching or commonly known as de-
alloying is the corrosion process of removal of one
or more components of an alloy
Selective Leaching
Alloys prone to selective corrosion are composed of
components with a great difference between
their Electrode potentials (e.g., Cu-Zn)
The most electronegative element acts as anode,
oxidizes and dissolves in the electrolyte and is leached
away
The most electropositive element behaves as cathode
and is re-plated
Selective Leaching
Alloys prone to selective corrosion:

Brasses (Cu-Zn): dezincification

Silicon bronze: desiliconification

Aluminum bronze: dealuminification

Copper-nickels: denickelification
De-zincification
In the case of dezincification, brass alloys
containing more than approximately 15 wt% zinc
are susceptible to attack

Dezincification of common yellow brass results in

a red copper rich structure
Types of Dezincification
Uniform: The active area is leached out over a broad
area of surface and it is not localized to certain point
of surface. More uniform and shallower loss occurs in
this type. Its found in high brasses (high Zn content)
like acidic environment
Plug Type: Attack is localized at a certain point on
surface. plug-type attack can produce localized
wastage. Its observed in low brasses, alkaline, neutral
or slight acidic environment
Uniform
Localized
Mechanism
There are generally two types of
mechanisms:
Re-deposition Mechanism
Zinc is chemically active element. Its standard
electrode potential is very low (-0.763). Standard
electrode potential of copper is much higher
(+0.337). The difference between the potentials
is the driving force of dezincification

Zn being the electronegative specie will be

leached out and porous Cu will be left behind
Series
Re-deposition Mechanism
Selective dissolution of zinc only according to anodic
reaction:
Zn = Zn2+ + 2e-
Zinc and copper according to anodic reactions:
Zn = Zn2+ + 2e- and
Cu = Cu2+ + 2e-
followed by re-deposition of copper by cathodic
reaction: Cu2+ + 2e- = Cu.
Effects of De-zincification
Dezincification has three effects:
Firstly, the replacement of brass by porous
copper
Secondly, it decreases the corrosion resistance
due to the formation of porous and weak
copper
Thirdly, and often the most important, the
mechanical properties like strength of the brass
are affected
Prevention
Make environment less aggressive e.g. reduce oxygen
content.
Cathodic protection
Use better alloy
REDbrass (<15 percent zinc) almost immune.
Prevention
Admiralty brass ( 70%cu ,29% zn, 1%tin)

Arsenic Admiralty (70%cu, 29% zn, 1%tin,0.04 As)

They act as inhibitors and redeposited on alloy as a

film and prevent the deposition of copper

Cupro Nickel alloys are used for very harsh corrosive

environments where dezincification occurs.
Prevention
Air contact should be prevented through
the use of steam or nitrogen blanketing.
Exposure to soft water, high-pH conditions,
and high concentrations of carbon dioxide
in the water should be avoided.
Surfaces should be kept free of deposits.
Graphitization
Grey cast iron is the cheapest engineering material.
2-4% C, 1-3% Si . Hard, Brittle ,Easy cast. Carbon present
as microscopic flakes of graphite within
microstructure.
Graphitization
Grey cast iron shows effect of selective leaching
particularly in mild , aqueous environments

The cast iron appears to become graphitized in which

the surface has an appearance like graphite and can be
easily cut with penknife. Based on appearance and
behavior phenomenon is known as graphitization
Graphitization
This is a misnomer because graphite is present in the
grey cast iron before corrosion has occurred. It is also
known as graphitic corrosion.
Graphitization process
Selective leaching of iron or steel matrix takes place
leaving behind graphite network.
Graphite is cathode to iron so an excellent galvanic cell
forms.
Iron is dissolved leaving a porous mass consisting of
graphite, voids and rust.
Cast iron loses its strength and metallic properties.
Graphitization Process
It is a slow process.
It does not occur in white cast iron because no free
carbon is present.
It also doesnt occur in malleable cast iron or nodular
iron because graphite network is not present to hold
together the residue.
De-Alloying of other alloy systems
De-alloying most commonly occurs in
copper-containing alloys e.g, Cu Al , Cu Ni,
Cu Si etc
Like in case of brass removal of zinc is
termed as dezincification, for other alloys
it is named as
dealuminification,denickelification,desilicific
ation,destannification etc
Contin
Selective removal of aluminum in aluminum bronzes
has been observed in hydro-floric and other acids.
A two phase or duplex( containing zinc more than 32%
having alpha and beta phases)structures are more
susceptible.
Removal of silicon from Cu Si and cobalt from Co-W-
Cr alloy has also been observed. But these are rare
cases.
Contin
Also there are advantages of selective leaching in
some cases

Enrichment of silicon in oxide film results in

formation of passive layer on stainless steel
results in better passivity and resistance to pitting

Preparation of raney nickel catalyst(used as

catalyst in organic chemistry) by removal of
aluminum from Al Ni alloy by the action of caustic
Identification
De-alloying is most effectively diagnosed
through metallographic examination.
Attacked metal is relatively weak and can
be broken easily by stresses from impact
or bending. Frequently, surfaces will be
riddled with cracks, but will retain original
dimensions. Attacked areas will usually
change to a deep red or salmon color
indicative of elemental copper.
Case Study
Industry: Institutional
Specimen location: Low-pressure boiler
feedwater return piping
Specimen type: Ball valve
Metallurgy: Brass
Years in service: 2
Case study
Chemical analysis of the valve housing
alloy indicated that it was an uninhibited
brass alloy with a zinc content of
approximately 38 wt%. The internal
surfaces of the valve housing and ball were
covered with mounds of light-colored
corrosion products .Chemical analysis of
the corrosion product mounds by SEM-EDS
indicated zinc contents greater than 45
wt% in many areas.
Case study
Beneath the corrosion products, areas of
the metal were copper colored. Microscopic
examinations indicated a duplex
microstructure consisting of alpha and
beta brass, typical of brass alloys
containing greater than 32 wt% zinc Along
the internal surface, porous copper
corrosion products lined the surface in
many places, indicating that dezincification
occurred.
Case study
Cracks penetrated along the porous
corrosion products in threaded regions. It
was recommended that inhibited single-
phase brass alloys with less than 32 wt%
zinc be considered to limit the likelihood of
dezincification. The pH of the water was
reportedly above 10, which most likely
promoted dezincification.
References
Corrosion engineering by Mars G. Fontanna
Principles Of corrosion engineering by Zaki Ahmed
THANK YOU
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