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The Corrosion of Copper and Copper Alloys

Chapter · January 2017

DOI: 10.1016/B978-0-12-409547-2.13429-8

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From Zhou, P.; Ogle, K. 2018. The Corrosion of Copper and Copper Alloys. In: Wandelt, K.,
(Ed.) Encyclopedia of Interfacial Chemistry: Surface Science and Electrochemistry, vol.
6, pp 478–489.
ISBN: 9780128097397
Copyright © 2018 Elsevier Inc. All rights reserved.
Elsevier
 Author's personal copy

The Corrosion of Copper and Copper Alloys

P Zhou and K Ogle, Institut de Recherche de Chimie-Paris, Paris, France
© 2018 Elsevier Inc. All rights reserved.

Introduction 478
Cathodic Reactions on Cu 479
Pure Copper 479
Cu–Sn Alloys 481
Cu–Zn Alloys 482
Dissolution–Redeposition Theory of Dealloying 483
Two- and Three-Dimensional Diffusion Theories of Dealloying 484
In Situ Kinetics of Cu–Zn Dealloying 486
Conclusions 486
References 487

Nomenclature
nCu(aq) Dissolution rate of Cu into the electrolyte (nmol cm
2 s
1)
n*e Convoluted applied current expressed as transfer rate of electrons (nmol cm
2 s
1)
nCu2O Cu2O film formation rate change on a time scale (nmol cm
2 s
1)
jZn Partial Zn current during anodic dissolution (A cm
2)
jCu Partial Cu current during anodic dissolution (A cm
2)

Introduction

Copper, along with gold and rare meteoric alloys, is one of the few metals that are found in nature in the metallic state and is the
only noble metal used as an engineering material. The metallurgy of Cu and its alloys has played a crucial role in the development of
civilization with the successive chalcolithic (copper) and bronze ages preceding the iron age. Interestingly, Cu has also played a role
in the origins of corrosion science, inspiring Plato to write what is perhaps the first speculation on corrosion mechanisms.1 The
Stockholm Papyrus, the earliest known collection of chemical recipes,2 describes a method of corroding Cu using a methodology
that resembles modern accelerated corrosion tests, to synthesize verdigris (Cu(CH3COO)2) with the idea of producing fake emer-
alds. Today, a considerable variety of copper alloy materials are in use in a wide range of environments and many different forms
of Cu corrosion are known.
Understanding the mechanisms of corrosion of Cu alloys is important for many contemporary applications such as in micro-
electronics or as canister material for nuclear waste storage. In these cases, even extremely small corrosion rates may be detrimental
due either to the small amount of material present or the extremely long lifetimes required. In other circumstances, a controlled
corrosion rate may be necessary for applications such as the deliberate release of Cu cations as a biocide or in the preparation of
nanoporous materials by dealloying. Extensive reviews covering many aspects of copper alloy corrosion have been given, for
example by Sequeira3 and Tuck et al.4
Corrosion involves alteration of both the material and the environment and both factors are important for Cu alloys. Material
alteration may take on many forms. The seasonal cracking of brass was one of the earliest recognized forms of stress corrosion
cracking.5 The atmospheric corrosion of Cu alloys is extremely well documented6 due to its use in architectural and artistic construc-
tions and is closely associated with the aesthetically pleasing greenish patinas formed after long time atmospheric exposure. The
abundance of copper-based archeological artifacts provides a database of the long-term stability useful for the validation of corro-
sion models for long-term nuclear waste storage.7
The alteration of the environment mostly concerns the release of Cu cations. The World Health Organization defined the
maximum safe level of Cu ion in drinking water at 2 mg L
1.8 Above 1 mg L
1, Cu ions impart a bitter taste to water, while above
2.5 mg L
1 staining of tissues and discoloration of water may occur. An important danger of dissolved Cu ions is the possibility of
their redeposition as Cu metal by a displacement reaction to form highly localized galvanic couples,9 for example:
Cu2þ ðaqÞ þ FeðsÞ/Fe2þ ðaqÞ þ CuðsÞ (1)
On a positive side, Cu ions have biocidal properties and Cu alloys may be used as self-disinfecting materials.10 For this appli-
cation, it is necessary to find an optimum between ion release and oxide formation: the former being sufficient to generate the

478
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The Corrosion of Copper and Copper Alloys 479

critical concentration of Cu ions necessary to kill bacteria and the second, low enough to avoid tarnish-forming or passivating oxide
films by hand contact.
In this article, we will focus on the dissolution mechanisms occurring in aqueous solution and we will limit our attention to Cu,
Cu–Zn, and Cu–Sn alloys which have been recently investigated in our laboratory using in situ monitoring of the dissolution reac-
tions.10–12 This choice reflects many of the major applications of copper and its alloys, for example in water distribution
systems,8,13–25 in seawater,26 or exposed to perspiration.10

Cathodic Reactions on Cu

Due to the nobility of Cu, it is most frequently the cathode when in contact with other metallic materials and therefore, the cathodic
properties of Cu are very important. Oxygen reduction by a four-electron mechanism is by far the most important cathodic reaction
for the corrosion of pure Cu27,28:
O2 þ 2H2 O þ 4e
/4OH
(2)
The cathodic properties of Cu are also important for other materials such as high strength Al alloys for which the corrosion rate
may be determined by the presence of Cu intermetallic particles.29 The corrosion may spread via the Cu ions released from the inter-
metallic particles which redeposit at other areas of the surface by a displacement reaction, similar to Eq. (1).30 An important strategy
for the corrosion protection of high strength Al alloys is to block oxygen reduction on Cu with the appropriate inhibitor molecule.31
The removal of surface Cu is an important goal of Al alloy surface pretreatment.32
The spontaneous reaction of Cu with H2O or Hþ is conventionally considered to be thermodynamically impossible. However,
Hultquist33,34 measured hydrogen gas formation, attributed to the reaction of Cu with anoxic pure water; and Cleveland et al.35
measured a corrosion rate of 1 nm/day in water with an O2 concentration on the order of, or less than, 1 ppb. Although this corro-
sion rate is extremely small, it could have important consequences on the choice of Cu for nuclear waste storage, extending the
necessary estimated canister thickness from 0.05 m to 1 m36; and for the use of copper nanostructures as heat exchangers for
liquid-cooling of high-performance electronics. These results have generated some controversy.37

Pure Copper

In aqueous solution, Cu will oxidize to either Cu(II) or Cu(I). The latter is only slightly soluble in water, and therefore a film of
Cu2O is the predominant insoluble product during Cu corrosion11,22,33,36,38 while Cu2 þ is the predominant soluble species. In
the presence of Cl
, or other complexing agents, the solubility of Cu(I) is enhanced and becomes the dominant species in solution
for example in the form of CuCl2
.
In early work, Ives and Rawson39 proposed a two-layer cuprite (Cu2O) film consisting of a compact, epitaxial grown inner layer
and a porous outer layer. A hypothetical structure of the Cu/Cu2O/electrolyte interface based on the Ives and Rawson model is
shown in Fig. 1. The compact cuprite film is a p-type semiconductor in which Cu(II) replaces Cu(I) in the crystal lattice giving
rise to electron transport via a shift between the Cu(II) and Cu(I) species as confirmed by photocurrent measurements.40,41 Ives
and Rawson proposed the existence of a large electrical barrier at the interface between the compact and the porous film, creating
an electrical disconnection of the latter from the metal rendering the porous film susceptible to further oxidation by oxygen reduc-
tion at the oxide/electrolyte interface (Reaction (c) in Fig. 1).
One-electron and two-electron reaction mechanisms for Cu dissolution and film formation have been proposed in the litera-
ture19,42–44 and are illustrated in Fig. 1. The one-electron reaction mechanism (mechanism (a) in Fig. 1) involves the stepwise forma-
tion of slightly soluble cuprite (Cu2O), followed by the subsequent oxidation of cuprite into a soluble Cu(II) species27,28
2Cu þ H2 O/Cu2 O þ 2Hþ þ 2e
(3)

Fig. 1 Mechanisms of film formation at the Cu/cuprite/electrolyte interface.

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480 The Corrosion of Copper and Copper Alloys

Cu2 O þ 2Hþ /2Cu2þ þ H2 O þ 2e
(4)

The two-electron mechanism (mechanism (b) in Fig. 1), also known as the dissolution–redeposition mechanism, involves the
direct formation of Cu2 þ17 followed by a synproportionation between Cu(0) and Cu(II)2,4,8,45–47
Cu/Cu2þ þ 2e
(5)

Cu þ Cu2þ þ H2 O/Cu2 O þ 2Hþ (6)

Time-resolved kinetic measurements are helpful in identifying the mechanisms of interfacial reactions. Atomic emission spec-
troelectrochemistry (AESEC) has been used to measure the release of Cu (and other alloying elements such as Zn and Sn) as a func-
tion of time during free corrosion and electrochemical polarization of pure Cu,11 brass,12 and bronze.10 The technique involves
exposing the material to an electrolyte in a small volume flow cell. The electrolyte composition is continuously analyzed down-
stream from the cell using inductively coupled plasma atomic emission spectroscopy which gives a simultaneous measurement
of up to 50 different species. The downstream composition of the electrolyte is converted into partial elemental dissolution.
With this technique, cation release is measured directly and oxide film formation is measured indirectly by mass balance.
Fig. 2 shows a typical example of the dissolution kinetics of pure Cu in synthetic tap water at pH ¼ 7.5 with an applied anodic
current of 10 mA cm
2 replotted from ref.11 Shown are the convoluted electrical current expressed in nmol cm
2 s
1 (n*), e the rate
of Cu ion release (nCu(aq)), and the rate of formation of Cu2O (nCu2O) layer as a function of time. Note that the convolution of the
electrical current with the experimentally determined residence time distribution in the electrochemical flow cell allows us to make
a rigorous comparison of the electrochemical and spectroscopic data as the former is essentially instantaneous while the latter is
broadened by mass transfer in the cell and capillaries. See ref.102 The release of Cu2 þ accounts for only about 5% of the total
current, the remainder going to Cu2O formation. We note that in Fig. 2, Cu dissolution was more intense at shorter times and
appears to decrease with time. The final Cu2O film thickness, after 1200 s, is estimated to be approximately 13 nm assuming
a uniform film and the typical density of Cu2O. In this way, it is possible to obtain a complete kinetic profile of dissolution and
film growth as a function of time.
In the original Ives and Rawson model,39 Cu dissolution was attributed to the oxidation of the Cu2O film on the outer surface
(reaction (d), Fig. 1). Other authors27 attribute Cu dissolution to the solubility of Cu2O (reaction (e), Fig. 1). The first mechanism
seems unlikely as under galvanostatic conditions (as in Fig. 2), the ratio of Cu2 þ to Cu2O formed increased from near zero at an
applied current of zero, to about 0.7 at an applied current of 80 mA cm
2.11 The second mechanism also seems unlikely in the
absence of complexing anions or accelerated hydrodynamic conditions due to the very limited solubility of Cu(I) in neutral
pure water varying between 10
8 and 10
10 molality at pH 7 and 9.3, respectively (1–0.01 ppb).48 Therefore, we would favor
the direct formation of Cu2 þ at the Cu/Cu2O interface, either simultaneously with Cu2O formation, or more likely coupled
with the dissolution–redeposition mechanism of Eqs. (5) and (6).
In addition to cuprite (Cu2O), precipitated Cu(II) species such as Cu(OH)2 and malachite(Cu2CO3(OH)2)19,49 may occur in an
outer layer. The duplex nature of the passive film formed in alkaline electrolytes has been extensively characterized50 with the p-type
semiconducting Cu2O inner layer, Cu(OH)2/CuO outer layer, and other types of CuOy oxides present.51 The growth of the Cu(I)/
Cu(II) duplex passive layers grown on Cu(111) and Cu(001) in 0.1 M NaOH has been observed directly by in situ electrochemical
scanning tunneling microscopy.51
Under atmospheric conditions, a large variety of corrosion products is possible and a patina with a complex structure may be
formed. Leygraf and Graedel listed 20 solid copper species that have been documented during atmospheric corrosion.52 Oxide films
may be characterized qualitatively by surface analytical techniques including X-ray photoelectron spectroscopy,19 Raman

Fig. 2 AESEC kinetic profile of pure Cu in synthetic tap water at þ10 mA cm
2. Shown are the convoluted electrical current expressed in
nmol cm
2 s
1 (n*),
e the rate of Cu ion release (nCu(aq)), and the rate of formation of Cu2O (nCu2O) layer as a function of time. The galvanostatic
pulse began at t ¼ 0 s. After Zhou, P.; Hutchison, M. J.; Scully, J. R.; Ogle, K. The Anodic Dissolution of Copper Alloys: Pure Copper in Synthetic
Tap Water. Electrochim. Acta 2016, 191, 548–557.

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The Corrosion of Copper and Copper Alloys 481

spectroscopy,53 infrared reflection absorption spectroscopy,54 and X-ray diffraction.55 Quantitative characterization can be per-
formed using a galvanostatic reduction technique.56

Cu–Sn Alloys

The addition of Sn to Cu forms the tin-bronze family of alloys, often containing other metals such as Zn, Si, Al, Ni, Fe, and Pb. The
addition of Sn has two main effects on Cu. Firstly because the Cu–Sn bond is weaker than the Cu–Cu bond, it actually accelerates
Cu dissolution.10,57 However, as Sn forms a semipassive SnO2 film, it will ultimately slow the corrosion rate of Cu. Therefore, Cu
loss is the most common corrosion phenomenon, the Sn remaining behind as an oxide film. The overall structure is shown in
Fig. 3 (after Hutchison et al.10) for the corrosion of Cu–9.7Sn–0.1Zn. The main difference as compared to pure Cu is that the
defective cuprite Cu2O layer is separated from the bulk alloy by an inner cassiterite (SnO2) layer that has a protective effect on
the metallic substrate.
SnO2 should be formed preferentially to Cu2O due to the large difference of their standard Gibbs energies:
519 kJ mol
1
versus
146 kJ mol
1, respectively.58 SnO2 is usually stable over a wide range of pH and embedded in the cuprous layer. The
primary oxide layer thickens and grows inwardly toward the bulk while the outermost oxide starts to dissolve, releasing Cu into
the electrolyte.58 The first step of bronze corrosion is therefore the formation of the SnO2 layer:
Sn þ 2H2 O/SnO2 þ 4Hþ þ 4e
(7)
This is followed by the oxidation of Cu, the rate-determining step being the migration of Cu cations through the SnO2 layer.59
2Cu þ H2 O/Cu2 O þ 2Hþ þ 2e
(8)

Cu2 O þ 2Hþ /2Cu2þ þ H2 O þ 2e
(9)

In the presence of Cl , an outer layer of nantokite (CuCl) is sometimes obtained, for example in artificial perspiration for
Cu–4.5Sn–0.1Zn.10 The artificial perspiration is composed of NaCl (85.6 mM), urea (16.7 mM), lactic acid (11.1 mM), and ammo-
nium hydroxide ( 11 mM).
A kinetic profile of the galvanostatic dissolution of Cu–9.7Sn–0.1Zn at þ 20 mA cm
2 is shown in Fig. 4. In this case, Cu(I) is
soluble as CuCl2
due to the high chloride content of the electrolyte. In the later stages of this experiment, Cu dissolution accounts
for about 96% of the total electrical current suggesting that SnO2 formation occurs mainly in the early stages and that the formation
of an Sn-rich dealloyed layer occurs. In this case, it is impossible to measure the Cu2O formation rate from a mass balance because
of the nonnegligible corrosion rate. However, the formation of Cu2O is very small as compared to the situation in Fig. 2 due to the
solubility of Cu(I) in the chloride containing electrolyte. This was confirmed by a subsequent analysis with a citrate buffer solution
which selectively dissolves Cu2O. After the experiment of Fig. 4, approximately 29 nmol cm
2 of Cu were detected, corresponding
approximately to an equivalent 7 nm layer of Cu2O.
At longer exposure time and under atmospheric conditions, the outer oxide layer thickens and transforms into a multilayered
structure by (a) the deposition of Cu(II) salts back onto cathodic sites and ion exchange (mass transportation of cations from the
bulk to the electrolyte or anions in reverse direction).58 Layers of various Cu-containing salts may also appear such as CuO, brochan-
tite (Cu4SO4(OH)6, atmospheric corrosion), malachite (Cu2CO3(OH)2, usually in soil corrosion), and atacamite (Cu2Cl(OH)3, sea
water corrosion).26 The third step corresponds to the aging of the layers: the transformation of the cuprous oxides into cupric ones,60
and/or the resumption of the corrosion process due to the cracking of the layers and/or localized corrosion. The structure of the
cupric salts layer is sensitive to the environment, the porosity, and stratification change significantly under various conditions.

Fig. 3 Mechanisms of film formation at the Cu–Sn/SnO2/Cu2O electrolyte interface in artificial perspiration. After Hutchison, M. J.; Zhou, P.; Ogle,
K.; Scully, J. R. (2017). Enhanced Electrochemical Cu Release Form Commercial Cu–Sn Alloys: Fate of the Alloying Elements in Artificial Perspiration.
Electrochim. Acta 2017, 24, 73–88.

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482 The Corrosion of Copper and Copper Alloys

Fig. 4 AESEC kinetic profile of Cu–9.7Sn-0.1Zn in synthetic tap water at þ10 mA cm
2. Shown are the convoluted electrical current (ne *)
expressed in nmol cm
2 s
1, the rate of Cuþ release (nCu(aq)), and the difference n*–nCu
e as a function of time. The galvanostatic pulse began at
t ¼ 0 s. The dashed curve gives n*e offset by the open circuit corrosion rate to allow a visual comparison with nCu.

Cu–Zn Alloys

The Cu–Zn family comprises the brass family of alloys. Dealloying is of considerable consequence for these alloys due to the large
equilibrium potential difference of Cu and Zn. Dealloying may occur either as a generalized form of corrosion or during the prop-
agation step of stress corrosion cracking.61 The dealloying of other Cu alloys is also important for example, the selective removal of
either Cu from Cu–Sn alloys or Al from aluminum bronze. During the corrosion of many technical Al alloys, the dealloying of
Cu-rich intermetallic particles (i.e., the q phase, Al2Cu, or the S phase, Al2CuMg) may occur as a first step.62,63 The process of deal-
loying may also be exploited for the preparation of functional, nanoporous Cu-based materials.64–66 In fact, the dealloying of
Cu–Au alloys has a long history as pre-Colombian Indians developed the process of depletion gilding by selectively removing Cu
as a means of decoration.67
For Cu–Zn alloys, the mechanisms of dezincification68–80 and the characterization of the dezincification structure54,81–83 have
been thoroughly investigated during the past decades. The situation is simplest in acidic media where little oxide is formed.84–86
However, in neutral electrolyte a more severe dezincification may be observed despite a lower corrosion rate.87 This is due to
the formation of a multilayered dezincification structure (Fig. 5) consisting of a Zn depleted layer and a corrosion product layer
composed of Zn and Cu corrosion products.12,78,79 The composition and structure vary with testing condition, chemical compo-
sition of the alloy and the electrolyte, but typically Cu2O, CuO, Cu(OH)2, ZnO, and Zn(OH)2 are the most representative species
that constitute the altered layer.
The susceptibility for dezincification increases directly with the Zn content, yellow brass with 33% Zn, being among the most
susceptible. Admiralty brass has a similar composition (30% Zn) with an addition of 1% Sn to specifically inhibit dezincification.
This rule extends to the microstructure of the alloy, the Zn-rich b0 (CuZn) phase being the most sensitive to dezincification due to
a high Zn content in this phase. The electrochemistry of the individual phases has been investigated by Seuss et al.80 using a micro-
electrochemical technique. From the polarization curves of a (Cu3Zn), g (Cu4ZnSi), and k (Cu8Zn2Si) phase in a Si-brass (CuZn21-
Si3P) they concluded that g and k phase underwent a preferential dezincification.
The idea of a critical potential for dealloying was developed based on the determination of partial polarization curves of Cu–Zn
alloys70 as shown in Fig. 6. Below the critical potential, region A in Fig. 6, Zn dissolution occurs selectively across a Cu-rich film. This
film inhibits Zn dissolution more or less equivalent to a passive oxide film and the anodic current is essentially independent of
potential. Above the critical potential, region B, there is an abrupt increase in the porosity of the Cu-enriched film which enhances

Fig. 5 Hypothetical dezincification structure of a Cu–Zn alloy.

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The Corrosion of Copper and Copper Alloys 483

Fig. 6 Partial currents (jM) for M]Zn and Cu from single-phase Cu–Zn alloys: Cu30Zn (a brass); Cu65Zn (g brass), and Cu86Zn (ε brass), in
a buffered (pH 5) Na2SO4 electrolyte. The figure to the right shows the surface structure. Replotted after Pickering, H. W.; Byrne, P. J. Partial
Currents During Anodic Dissolution of Cu–Zn Alloys at Constant Potential. J. Electrochem. Soc. 1969, 116, 1492–1496, Holliday, J. E.; Pickering, H.
W. A Soft X-Ray Study of the Near Surface Composition of Cu30Zn Alloy During Simultaneous Dissolution of its Components. J. Electrochem. Soc.
1973, 120, 470–475.

the dissolution rate of Zn and as a result, the current increases markedly with increasing potential. In both potential domains, selec-
tive Zn dissolution is observed. In region C, both Cu and Zn dissolve leaving a very thin Cu-enriched film on the surface of alloy.
These phenomena have been directly observed by Pareek et al. using scanning tunneling microscopy for CuAu alloys.88
Given its importance in many technical areas, the mechanism of dealloying has been investigated from many different perspec-
tives both experimentally and theoretically. The various mechanisms of dealloying may be divided into two categories: (1) the
dissolution–redeposition model78,79 and (2) the selective dissolution model coupled to either surface diffusion,67,68 volume diffu-
sion 69–75, or percolation.76,77
The selective dissolution of Zn is ensured during the early stages of exposure due to the large equilibrium potential difference of
Cu and Zn. In the absence of solid-state transport processes, however, this interfacial layer would ultimately block the Zn reaction
path, and the Zn depleted Cu layer would retain the physical structure and lattice parameters of the original material. Numerous
investigations have shown that for either the free corrosion or the anodic dissolution of brass, both physical structure89 and surface
phases70 are significantly altered as compared to the original surface state. Therefore, additional atom transport mechanisms have
been introduced to account for the structural alterations.

Dissolution–Redeposition Theory of Dealloying

Dissolution–redeposition (Fig. 7) theory depicts an electrochemical reaction process in which a simultaneous oxidization of both
Cu and Zn is followed closely by Cu deposition back onto the surface78,79 via a displacement reaction with Zn.
Cu/Cu2þ þ 2e
(10)

Cu2þ þ Zn/Cu þ Zn2þ (11)

The large difference of the equilibrium potentials of Zn and Cu should make simultaneous Cu and Zn dissolution unlikely,
however, considering the complex structural and lattice changes induced, the oxidation of Cu below its equilibrium potentials
may be able to proceed under certain circumstances. Polunin and Pchelnikov78,79 used a brass sample labeled with isotopes, aiming
at following the atom transport mechanism. Their results favored the redeposition of Cu as did the results of Heidersbach90 and
Saber91 who found isolated Cu particles in a residual oxide layer, a result which is difficult to interpret by solid transport
mechanisms.
The function of dezincification inhibitors has been described within the framework of the redeposition model. For example,
arsenic (As) may be added to an alloy to inhibit dezincification. Its function has been explained by the following cyclic
mechanism79:
3Cu2þ þ As/3Cuþ þ As3þ (12)

3Cu þ As3þ /3Cuþ þ As (13)

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484 The Corrosion of Copper and Copper Alloys

Fig. 7 Schematic diagram of dissolution–redeposition mechanism.

where the As3 þ serves to catalyze the reaction Cu2 þ þ Cu / 2Cuþ thereby preventing the redeposition via reaction (11). Phos-
phorus, as in the alloy CuZn21Si3P, is also used to inhibit dezincification and is thought to function via an analogous
mechanism.80

Two- and Three-Dimensional Diffusion Theories of Dealloying

Therefore, a surface diffusion process (Fig. 8) was proposed by Forty et al.67,68 This process involves the initial selective leaching of
the less noble atoms from the surface leaving behind a disordered structure containing vacancies and adatoms of the residual noble
atoms. The adatoms diffuse across the surface, forming small islands.67,92 The interconnection of these islands creates a reordered
porous maze-like structure. This mode of surface rearrangement has been observed experimentally by TEM during the corrosion of
Au–Ag alloy in strong acid.67 Forty et al.68 and Burstein et al.75 concluded that the surface transport of Cu atoms was the rate-
determining step during the early stages of dezincification of brass.
Sieradzki et al.76,77 proposed a percolation mechanism, illustrated in Fig. 9. Following selective leaching of the less noble atoms
from the reaction front, surface rearrangement proceeds via the mobility of several adjacent atoms, rather than a long-range surface
diffusion. Dissolution initiates only within a distance of several atoms from the reaction front. Short-range diffusion and dissolu-
tion allow a kinematic formation of interconnected paths of the less noble elements in a binary phase, constructing an infinite Zn
cluster thereby permitting the continuity of selective leaching from the surface to a certain depth of the bulk.93
The main interest of this mechanism is that it predicts the existence of a percolation threshold, a critical concentration below
which dealloying should not occur. It has been found experimentally that Cu–Zn alloys containing < 20 wt% of Zn are less sensitive

Fig. 8 Schematic diagram of surface diffusion mechanism.

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The Corrosion of Copper and Copper Alloys 485

Fig. 9 Schematic diagram of percolation theory.

to dezincification. A three-dimensional percolation process for Cu–Zn alloy was simulated by Sieradzki et al.76 using a Monte Carlo
model and indeed a dealloying threshold (p) of 0.2 was determined, indicating that a minimum of 20 at% of the less noble atom
was necessary for the dealloying. This theory may be used to interpret the propensity of pitting corrosion of brass alloys with
different Zn content,76 and the function that alloying additions, such as arsenic, boron,77 play in the improvement of dezincification
resistance by a blockage of the continuous Zn reaction clusters.
Pickering et al.69–74 proposed a volume diffusion theory involving a transport mechanism penetrating a certain depth into the
bulk inducing a gradual variation of chemical composition and lattice parameter. In this theory, the interdiffusion/counterdiffusion
of both noble and less noble atoms occur through the migration of vacancies/divacancies. The diffusion of divacancies (diffusion
coefficient of 10
15–10
13 cm2/s94,95) is considerably faster than that of monovacancies (10
19–10
16 cm2/s74,94). A monova-
cancy may be formed through a kink-ledge-terrace model.74 A divacancy may be formed either by the joining of two monovacan-
cies, or directly from the removal of two adjacent atoms (Fig. 10).
The marked difference of mobility between the two kinds of defects ensures an inward diffusion of defects from the interface, the
active atoms are thus transported outwardly through volume diffusion. Pickering used X-ray diffraction to corroborate the volume
diffusion of Cu–Au,69 Cu–Zn74 alloys during anodic dissolution in sulfuric acid, by detecting two characteristic features of the
diffraction patterns: (a) the emergence of new peaks due to the formation of new phases during anodic dissolution, such as the
peak of a phase in the dissolution of b0 brass, g and ε brass70; and (b) the evolvement of the broad diffraction ring, which was
due to the gradual variation of lattice parameterda direct evidence of the existence of a composition transitional region that
was produced by the interdiffusion of atoms.
In support of this model, positron annihilation spectroscopy94–96 was used to correlate the dezincification behavior and the
movement of divacancies. In opposition to this model, during the dissolution of CuZn30, Fort et al.97 found that the diffusion coef-
ficient was 8 orders of magnitude higher than the extrapolated value from high temperature based on Auger electron spectroscopic
depth profiling. They concluded that volume diffusion alone could not be the only transport mechanism for dezincification. Similar
results were reported by Laurent et al.98,99 for the dissolution of CuAu30. The formation of new phases with transitional chemical
composition could also be explained by the percolation theory.76,77
The theories of surface/volume diffusion and percolation have for the most part been derived from experimental results with Au-
based binary alloys, for which Au is considered to not be oxidized. For Cu–Zn alloys, however, both components may be involved
in the electrochemical process and it is reasonable to think that a combined mechanism is possible in which the predominant step
might vary with experimental conditions.

Fig. 10 Schematic diagram of the volume diffusion mechanism.

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486 The Corrosion of Copper and Copper Alloys

Fig. 11 The dissolution rates of Cu2 þ (aq) and Zn2 þ (aq) and the estimated thickness of the Cu2O Zn depleted layer as a function of time, for
Cu42Zn, in neutral tap water at a constant current of 40 mA cm
2. Data replotted after Zhou, P.; Hutchison, M. J.; Erning, J.W.; Scully, J. R.; Ogle, K.
An In Situ Kinetic Study of Brass Dezincification in Synthetic Tap Water. Electrochim. Acta 2017, 229, 141–154.

In Situ Kinetics of Cu–Zn Dealloying

One of the difficulties encountered in all electrochemical measurements with alloys is the difficulty of decomposing the measured
electrical current into partial elemental currents so as to quantitatively appreciate how different alloy components are reacting in the
system. It was indeed this decomposition of total electrical current into Zn and Cu partial currents that enabled Pickering et al.70 to
define the critical potential (Fig. 6). This was done by analyzing the electrolyte after polarization for a period of time.
Polunin and Pchelnikov78,79 used isotopes to follow the kinetics of Cu and Zn dissolution rates in real time of a and b0 phases:
their results showed that during the dissolution of the b0 phase (CuZn), no Cu was released into the electrolyte whereas for the
a phase (Cu3Zn) both Cu and Zn were released, in agreement with Pickering (Fig. 6).70 The channel flow double electrode is of consid-
erable interest for the investigation of Cu alloys as it permits distinguishing Cu(I) and Cu(II) release in real time during the anodic
dissolution of Cu and Cu–Zn, as shown by Hoshi et al.100,101 This technique has recently been coupled with a video microscopy
system to correlate the elemental dissolution rates with the initiation of pits on Cu.102
The previously described AESEC technique has the advantage of measuring both Cu and Zn dissolution simultaneously. In
recent work, this technique was used to quantitatively monitor the kinetics of dezincification for Cu–Zn alloys under galvano-
static conditions as shown in Fig. 11. The upper curve gives the Cu and Zn dissolution rates and the total current, all three pre-
sented in nmol cm
2 s
1. The formation of the Cu2O and the Zn depleted zone is shown in the lower curve, calculated from
a mass balance. These are expressed in nm assuming the usual density of Cu2O and pure Cu and assuming the films are pure
and uniformly distributed on the surface. The dissolution can be recognized as a two-step process: (a) an initial short period
of around 500 s where both the oxide film and the Zn depleted layer form rapidly; a second period where the thickness of the
Zn depleted layer remains nearly constant ( 15 nm), the release of Cu2 þ and Zn2 þ continues at a steady state, and the Cu2O
film continues to grow.
These results suggest that dezincification continues until Cu and Zn dissolution obtain a steady state at which point the zinc
depleted zone ceases to grow. As with pure Cu, the Cu2O film does not seem to have an effect on the dissolution rates of either
Cu or Zn.

Conclusions

The corrosion of Cu and its alloys has been observed and speculated on for thousands of years. Nevertheless, there are many unre-
solved questions concerning the nature of dissolution, film formation mechanisms, and even whether or not pure copper will
corrode in pure water. For some applications, even very small corrosion rates may be critical due to the small amount of material
present in microelectronic circuits or the extremely long lifetimes required for nuclear waste storage canisters. A controlled corrosion
rate may be important for other applications such as the deliberate release of Cu cations as a biocide or in the preparation of nano-
porous materials by dealloying. The major mechanistic complication is the possible formation of both Cu(I) and Cu(II) oxidation
states coupled with a large variety of possible species that may be formed. The Cu–Sn (bronze) and brass (Cu–Zn) serve as two
extremes of alloy behavior. While Cu is electropositive to both Sn and Zn, the former forms insoluble SnO2 oxides which serve
to passivate the material while Zn is active in most electrolytes.

See also: Corrosion in Electronics; Interaction of Chloride Anions With Copper Surfaces; The Electrode Kinetics of Oxygen Reduction: A Case Study.
The Corrosion of Copper and its Alloys in Aqueous Chloride Solution at a Smooth Rotating Disk Electrode.

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