International Materials Reviews

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Corrosion of magnesium alloys: the role of alloying

K. Gusieva, C. H. J. Davies, J. R. Scully & N. Birbilis

To cite this article: K. Gusieva, C. H. J. Davies, J. R. Scully & N. Birbilis (2015) Corrosion of
magnesium alloys: the role of alloying, International Materials Reviews, 60:3, 169-194, DOI:
10.1179/1743280414Y.0000000046

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Published online: 22 Oct 2014.

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 Corrosion of magnesium alloys: the role of
alloying
K. Gusieva1, C. H. J. Davies2, J. R. Scully3 and N. Birbilis*1,3
The demand for light-weighting in transport and consumer electronics has seen rapid growth in the
commercial usage of magnesium (Mg). The major use of Mg is now in cast Mg products, as opposed
to the use of Mg as an alloying element in other alloy systems and there is an emerging market of
wrought Mg products and biomedical Mg components – such that the past two decades have seen a
significant number of new Mg-alloys reported. None-the-less, the corrosion of Mg alloys continues to
be a challenge facing engineers seeking weight reductions by deployment of Mg. Herein, authors
review the influence of alloying on the corrosion of Mg-alloys, with particular emphasis on the
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underlying electrochemical kinetics that dictate the ultimate corrosion rate. Such a review focusing
on the chemistry–corrosion link, both in depth and in a holistic approach, is lacking. As such the
authors do not describe aspects such as high-temperature oxidation or cracking, but focus on
delivering the state-of-the-art with regards to alloying influences on corrosion kinetics. It has been
demonstrated that Mg itself will not be thermodynamically passive in environments of pH,11,
regardless of the extent and type of alloying and hence corrosion kinetics require unique attention.
Authors consolidate the presentation to include essentially all commercially available alloys and in
excess of 350 custom alloys with wide variations in composition; in addition to reviewing the range of
intermetallic compounds and impurities that form in such alloys systems. An update is also given
regarding mechanistic advances and the role of grain size on corrosion of Mg. A wider
understanding of the role of chemical effects upon corrosion of Mg is both timely and serves to
highlight metallurgical approaches towards kinetically retarding the corrosion problem. The latter is
of key relevance to next generation lightweight alloys and rational design of wrought Mg and bio-Mg.
Keywords: Magnesium, Magnesium alloys, Corrosion, Intermetallic, Polarisation

Introduction Mg and its alloys rapidly form a surface oxide/

Magnesium (Mg) has the lowest density (1?74 g cm23) of
the engineering metals.1 Mg consumption is growing in
many industrial applications in the present era of light-
weighting,2,3 which is important for energy and fuel
savings, reduced emissions, emerging biomedical applica-
tions, and user satisfaction of portable electronics. Mg
and its alloys are machinable, die castable, non-magnetic
and offer vibration and shock adsorption ability.
However, the two persistent limitations that have
restricted wider Mg use include limited room temperature
ductility and high corrosion rates in aqueous environ-
ments. The former issue, ductility, is undergoing sig-
nificant research in the mechanical metallurgy domain,
and the latter is still an area of active present research.
1
Department of Materials Engineering, Monash University, VIC 3800,
Australia
2
Department of Mechanical and Aerospace Engineering, Monash
University, VIC 3800, Australia
3
Department of Materials Science and Engineering, The University of
Virginia, VA 22904, USA
*Corresponding author, email nick.birbilis@monash.edu
hydroxide layer in moist conditions.4 The high negative
free energy of formation ensures such a layer forms
rapidly, however, this surface layer does not offer
suitable corrosion protection (as say, an oxide layer
does to Al or Cr) on the basis of:
N The oxide/hydroxide layer is soluble in most aqueous
environments, and environments of high humidity.
The primitive E–pH diagram for Mg is seen in Fig. 1
(neglecting hydride formation5). Mg readily dissolves
to form Mg2z, and the corresponding cathodic
reaction is the hydrogen evolution reaction (this
terminology is interchangeable with ‘water reduc-
tion’, because when water is reduced, hydrogen
evolves). It is observed that Mg is prone to dissolu-
tion over a wide pH range extending from 22 to 10?5
and only in highly alkaline conditions, magnesium
hydroxide is insoluble and hence protective (i.e. a
passive film). Mg completely loses its integrity in
acidic conditions or in the presence of chloride,
bromide, and sulphate ions, thereby placing some
practical limits on widespread Mg use6 to alkaline
conditions or situations where suitable coating
systems may be implemented.

ß 2015 Institute of Materials, Minerals and Mining and ASM International

Published by Maney for the Institute and ASM International
Received 11 July 2014; accepted 2 October 2014
DOI 10.1179/1743280414Y.0000000046 International Materials Reviews 2015 VOL 60 NO 3 169
 Gusieva et al. Corrosion of magnesium alloys: the role of alloying
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Labels 0, 22, 24, and 26 are the log of soluble ion activity for the indicated lines, and labels a and b show conditions
of stability for water and its decomposition products, hydrogen and oxygen respectively. Hydride formation has been
neglected.5
1 E–pH diagram for the Mg in water (H2O) system at 25uC adapted from Ref. 8
N Mg surface layers only incompletely cover the metal
surface and are highly defective arising from a Pilling–
Bedworth ratio ,1; meaning the ratio of the volume of
the surface oxide/hydroxide to the underlying (hex-
agonal) metal is not suited for complete coverage.7
N The highly electronegative potential of Mg and
its alloys renders Mg-alloys prone to galvanic and
microgalvanic corrosion (i.e. internal corrosion
between the micro-constituents of the alloy), along
with the possibility of corrosion in deaerated envir-
onments; because oxygen is not required for the
cathodic water reduction reaction that predominates
at such negative potentials.
As a result, thermodynamic stability of Mg is not
considered to be the key issue in determination of Mg
alloy corrosion, with the kinetics of corrosion determin-
ing the ultimate corrosion rate. This review will thus
focus on the factors that determine, and the extent to
which they dictate, the kinetics of corrosion.
The introduction of various alloying elements into Mg
can improve some vital mechanical properties and thus
extend the range of potential engineering applications,
however, this has an attendant influence on the corrosion
of Mg. In regards to Mg-alloys, the main factors in
controlling corrosion rate are chemical composition and
microstructure, hence appropriate attention is given to
the development of Mg microstructures in this review.
The solid solubility of elemental additions in Mg will
dictate the presence of any second phases or impurity
particles. More so than in other commercial metal
systems, the solid solubility of an alloying element is a
key factor in determining its effect on the properties of
Mg; as the majority of elements have either no solubility,
or very limited solubility in Mg. This is an interesting
scenario, as there are concomitantly a large number of
elements that will not form intermetallics with Mg, such
170 International Materials Reviews 2015 VOL 60 NO
that when added to Mg a phase separation occurs to
produce two pure metals (i.e. Mg and Fe in the case of the
Mg–Fe system).9 The solid solubility depends on factors
such as relative atomic size, valency and electronegativity
as well as similarity in crystal structure. A certain liquid
solubility is required to form a homogenous solution at
the alloying temperature.
Table 1 summarises maximum solid solubility values
in Mg based on binary systems9–13 and categorising
elements according to their solubility. The elements
shown in white cells represent elements with solid
solubility (i.e. to levels .0?5 wc), the elements shaded
in orange are defined as slightly soluble (0?05–0?5 wt-%)
and those in grey are insoluble (i.e. ,0?05 wt-%).
Several elements also have an unknown solubility (green
shading). The table also provides the values of the
atomic radius of the elements for general information. A
convenient way of thinking about the insolubility of
elements in Mg is to define the following three scenarios:
1. Complete and full insolubility: Here no solid solution
is formed and no Mg-intermetallic forms with
the particular alloying element. This situation is
typical of Fe, Mo and Nb. When such elements are
present, they form second pure metal phases, with
no mutual solubility. This situation causes dramatic
corrosion.14–17
2. No solubility, but the formation of a Mg-intermetallic:
This is typically what is seen with Si (and Cu, Co,
Ni). In such cases an Mg2X (where X5Si, Cu, Co,
Ni) intermetallic will form. These compounds have
no room temperature solubility and thus the
retention of a homogenous (single phase) micro-
structure is not possible. Elements that form the
Mg2X intermetallic are often very problematic from
a corrosion perspective, as they enhance the
cathodic reaction because of the large exchange
3

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2 Typical Mg-alloy microstructures, all compositions given
in wt-% a Mg–0?4Zn–0?05Sr in the rolled condition. This
alloy has alloying additions below the respective solubi-
lity limits and is a solid solution alloy with uniform matrix
composition. The image is an optical micrograph follow-
ing etching in glycol solution.27; b AZ31 (Al–3Al–1Zn–
0?4Mn) as sectioned from an extruded ingot.
Backscattered electron imaging indicates that this is
close to a solid solution alloy, however, as the Al content
is approaching the solubility limit and solute enrichment
is observed, together with fine second phase particles.
This alloy also includes constituent AlxMn particles, typi-
cal of scenarios with Mn additions; c Mg–6La as high-
pressure die cast. Backscattered electron imaging
reveals that the addition of La well above the solubility
limit results in a large volume fraction of Mg12La phase.28
current density of metals such as Cu and Ni.18
Special attention is nominally given to exclude Si
from commercially produced pure Mg.
Gusieva et al. Corrosion of magnesium alloys: the role of alloying
3. Some solubility with no Mg-intermetallic: It is possible
for elements such as Zr. In such cases, the alloying
element will enter the solid solution to a limited extent,
after which any further alloying will result in a sepa-
rate, pure phase of the element. Again, such phases are
problematic from a corrosion perspective.19,20
The limited solubility of most elements in crystalline Mg
results in only minimal changes to the electrochemical
potential of the Mg (a) phase. As such, the majority of
Mg-alloys have a potential in the close vicinity of about
21?55 VSCE, and essentially all are below 21?4 VSCE.21
During open circuit exposure, the difference in electro-
chemical characteristics between the Mg matrix (a)
phase and any second phase (be it a precipitate or
impurity/insoluble particle) can be defined as the local
current density sustained between microstructural con-
stituents at the iso-potential of the alloy. These locally
sustained current densities dictate whether any micro-
galvanic coupling contributes to corrosion or not.
To orient the reader with the typical microstructures
observed in Mg alloys, a selection of alloy microstruc-
tures are seen in Fig. 2 for alloys with increasing alloy
content. What is generally observed is that increasing
alloy content leads to a rapid increase in the volume
fraction of second phase. The extent and influence of the
second phase will depend on the element added and its
relative solid solubility. The variation in the volume
fraction of second phase is evident in the examples seen
in Fig. 2 with microgalvanic corrosion in Mg-alloys
almost exclusively explained by the accelerated cathodic
activity which arises from intermetallic particles (IMPs)
able to support higher reduction reaction kinetics
compared to pure Mg.16 The fact that most elements
have a greater efficiency at supporting the cathodic
reaction stems from Mg having a low exchange current
density, which is a physical characteristic of Mg itself.
Consequently, IMPs with higher catalytic activity result
in enhanced anodic dissolution of the Mg matrix. One
well documented exception to this was reported by
Kirkland, who indicated that Mg2Ca has a more
negative electrode potential, such that it would be
anodically polarised in the Mg matrix and undergoes
extremely high dissolution rates at the expense of Mg.22
The magnitude of the effect of IMPs on acceleration of
anodic or cathodic kinetics depends on their respective
chemistry (and hence electrochemistry) and volume
fraction, so that the larger the volume fraction of
IMPs in the alloy, the greater the impact on increasing
the corrosion rate of the alloy.23,24 The presence of
impurities (which is the generic name given to insoluble
elements) such as Fe, Ni, and Cu alters corrosion rates
dramatically, even in the ppm range.25,26 For example,
islands of pure Fe or pure Cu in the matrix of Mg create
a mixed potential that assures the Mg is polarised
anodically (dissolves) and the pure insoluble elements
can sustain the cathodic reaction at very high rates, as
they are significantly polarised from their nominal
corrosion potential values (often by .1 V).
Arguably, the biggest single contribution to date with
respect to moderating the corrosion rate of commercial
Mg is the ‘scavenging’ ability of Mn in conjunction with
Al.25,29 By virtue of Mn additions to the Mg–Al systems,
Fe is sequestered in an AlMnFe intermetallic, and hence
the extent of microgalvanic coupling is dramatically
reduced.14 The moderation of corrosion/scavenging
International Materials Reviews 2015 VOL 60 NO 3 171
 Gusieva et al. Corrosion of magnesium alloys: the role of alloying
3 A compilation of the typical potentiodynamic polarisation response of common Mg-alloys. The electrolyte used was
0?1M NaCl and a polarisation scan rate of 1 mV s21.28,33–35 Pure Mg was 99?9% purity
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effect in Al-free alloys remains largely unknown and is
an area of current research20 which will be significant in
the development of creep resistant (i.e. Al-free) Mg-alloys.
Corrosion kinetics of Mg-alloys
Corrosion of Mg-alloys is a kinetic issue, which will
depend on the alloy composition, together with the
component design (i.e. if welded or joined) and environ-
mental factors (such as pH, [Cl2] and temperature).30,31
The half-cell reactions for Mg corrosion are given in
equations (1) and (2). Reaction (1) is Mg dissolution that
produces electrons consumed at the cathode (2) resulting
in generation of hydrogen gas. As will be described in
the subsequent section, this process can be sustained
during anodic polarisation of Mg32
Mg?Mg2z z2e{
2H2 Oz2e{ ?H2 z2OH{
The relative rates of the above reactions, and their
variation as a function of alloy potential, can differ
significantly, as is shown in Fig. 3, which reveals the
typical potentiodynamic polarisation response of the
most common commercial alloys and pure Mg. The
corresponding composition of the alloys shown in Fig. 3
is given in Table 2.
Generally, the potentiodynamic polarisation response
provides information about the relative rates of the
anodic and cathodic kinetics for different alloys. The
method can also provide an instantaneous corrosion rate
(termed the corrosion current density icorr) as approxi-
mated by a Tafel-type fit, usually from the cathodic
polarisation data. This has been verified as a reasonable
approximation to the corrosion rate as it relates to the
rate obtained from other methods.36 However, of key
relevance here is that the polarisation technique, in spite
of not being a long term predictor of corrosion rates
owing to its instant nature, is an important tool in
rationalising alloy behaviour as it is the most effective at
providing information on the effect of a particular
element on anodic or/and cathodic reaction rates.
An archetypal demonstration of this was provided by
172 International Materials Reviews 2015 VOL 60 NO
Kirkland, who revealed that Mg–10Zn ( wt-%) and Mg–
5Ca ( wt-%) show the same corrosion rates from mass
loss tests, however, the origin of corrosion rates could
only be ascertained from polarisation testing, which
revealed that Zn enhanced cathodic kinetics (with little
influence on anodic kinetics), while Ca enhanced anodic
kinetics (with little influence on cathodic kinetics).37
In Fig. 3, the representative polarisation curve for pure
Mg is seen as a thick dark line. It is immediately obvious
that there is a range of movements in the relative anodic
and cathodic curves depending on the respective alloying
additions. One striking feature, however, is that most of
the commercial alloys have significantly more rapid
cathodic kinetics than pure Mg, with the exception of
WE54 and AE44, which both contain appreciable rare
earth (RE) additions, yielding similar cathodic kinetics to
pure Mg. Other features to note include that AM60,
(1)
AZ31, AZ91 and ZE41 showed lower anodic kinetics
than pure Mg, while AE44 and WE54 showed enhanced
(2) anodic kinetics relative to pure Mg.
These simple descriptions are being made to orient the
reader with the form and signatures in such data, while
the effects are treated in a holistic treatise further below.
The data in Fig. 3 provide the classic manifestations
for Mg-corrosion kinetics, which includes
2 Elements that shift the anodic branch to lower rates
nominally do so by solid solution doping, which is
efficiently achieved by Al and Zn. However, this is
countered by a corresponding increase in the cathodic
kinetics. Both of these kinetic changes lead to
ennobled Ecorr values.
2 Significant alloying additions (which in comparison to
other metallurgical systems can in fact be modest) will
lead to second phase development and hence, nominally
more rapid cathodic kinetics (and hence corrosion rates).
2 It can be seen that Al-containing Mg-alloys tend
to show the lowest anodic kinetics and the fastest
cathodic kinetics.
2 Significant alloying with RE elements can reduce the
Ecorr and enhance anodic kinetics on the basis that
REs are themselves ‘active’ elements.
2 Common alloying additions do not result in lower
cathodic kinetics being imparted to Mg. Even REs
3

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4 Typical potentiodynamic polarisation response of selected experimental Mg-alloys. The alloy composition is denoted in
the plot, while the pure Mg was 99?9% purity50
tend to serve as local cathodes under free corrosion
conditions.38
2 Alloying additions nominally only alter Ecorr within a
window of y100 mV. This, however, does not mean
that corrosion rates cannot be spread over several
orders of magnitude (as reported in the literature39)
since large changes in kinetics can be achieved on the
basis that Mg is ‘weakly polarisable’. This means that
only small changes in potential can result in large
deviations of current (owing to a very low anodic Tafel
slope in Mg systems, as opposed to say, passivating
systems).
In relation to the aforementioned alloys (Fig. 3), there is
ample information in the literature concerning the
microstructures developed,40–47 and hence our main
focus herein is to present their corrosion kinetics
in respect to the main microstructural constituents.
Mechanical properties will not be covered herein,
however, the authors note that the group of high(er)
strength Mg-alloys (AE44, WE54, and ZK60) possess
the presence of precipitates including Al11RE3, Al10
RE2Mn7, Al2RE,47 MgxREy,44 and MgZn2,48 with im-
proved mechanical properties at the expense of reduced
corrosion performance.49 Taking the finite commercial
alloys as examples, the microstructural, and hence elec-
trochemical, heterogeneity requires the quantification of
microstructure as a requisite effort in the rationalisation
of corrosion performance.
Before discussing the unique effect of specific ele-
ments, a set of polarisation curves depicting the
corrosion kinetics of selected experimental alloys is
shown in Fig. 4. The selection of the data in Fig. 4 was
deliberate, to indicate instances where anodic reaction
rates can be rather markedly increased. This phenom-
enon occurs for two reasons. The first (Mg–Ca) is when
the alloying element is more reactive (in terms of
dissolution kinetics) than Mg, which is the case when
Ca is alloyed with Mg.22 The second is when an alloying
element triggers ‘anodic activation’. This is the case for
Mg–Sn. The anodic ‘activation’ is a terminology used
for elements that are able to disproportionally enhance
Gusieva et al. Corrosion of magnesium alloys: the role of alloying
anodic kinetics, when this phenomenon may not be
expected on the basis that the alloying element is (in its
pure form) less active than Mg. This phenomenon is
common to Al alloys with heavy metals such as Pb and
Sn, which are nominally low melting point elements that
segregate to the surface disrupting the surface film and
allowing dissolution en masse. The phenomenon is also
observed in Mg (Fig. 4) and occurs with Sn (also with
Pb, Sb, and Zr as discussed below). However, this
phenomenon has not been studied in detail, perhaps
because of the fact that it has no commercial relevance
to date. Ironically, however, the low melting point
elements that lead to anodic activation in Mg are also
part of the family of (few) elements that have lower
cathodic kinetics than Mg (Pb, Sn, and Sb have a low
exchange current density, which is a physical property of
each element18). Unfortunately, the phenomenon of
slowing cathodic reaction kinetics (evident in Fig. 5
for the Mg–Sn alloy) is overwhelmed by the anodic
activation for reported alloys to date.
In the other examples provided that include ternary
additions to Mg–Al alloys, the overriding manifestation
is the enhanced cathodic kinetics imparted by Al, while
any beneficial effects in reduced anodic kinetics are not
significant for the cases presented.
In order to provide a synopsis of the electrochemical
kinetics of constituents and precipitates which can
populate Mg-alloys, a selection of potentiodynamic
curves collected by Südholz16 is presented for a finite
number of Mg-based intermetallics (Fig. 5). Such data
are not inclusive of the entire spectrum of possible Mg-
based intermetallics, as the collection of such data
necessitates the production of sufficiently large inter-
metallics for interrogation via micro-electrochemical
testing.23,51,52 What is observed from Fig. 5 is that the
IMPs are nominally noble with respect to Mg, with the
exception of Mg2Ca. This, therefore, indicates that such
intermetallics, if in an Mg matrix, will be polarised
cathodically, and will remain cathodically protected at
the expense of matrix dissolution. Of most interest and
importance, however, is that the rates of reaction on the
International Materials Reviews 2015 VOL 60 NO 3 173
 Gusieva et al. Corrosion of magnesium alloys: the role of alloying

5 Potentiodynamic polarisation curves for intermetallic phase present in, and common to, the Mg-alloys systems. Date
presented along with pure Mg for comparison (40 ppm by wt. Fe), in 0?1M NaCl. From Ref. 16
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different intermetallics are distinctly different, and hence
the chemical entity of the intermetallic is of great
significance to the ultimate corrosion rate of the alloy,
which they occupy. Authors emphasise the salient, but
key point, that it is the kinetics of reaction on
intermetallics that relate to their potency to support
localised corrosion, and not the relative potential
variation from Mg. Potential difference does not
necessarily translate to kinetic effects, as seen in Fig. 5.
Unfortunately, such a consolidated presentation of
intermetallic electrochemistry does not exist for a range
of environments (i.e. pH or [Cl2]), with only reportage
in 0?1M NaCl to date.
In that vein, it is noted that the majority of reports for
Mg corrosion exist in near-neutral chloride environ-
ments. This is considered to be reasonable on the basis
that most atmospheric exposures can be approximated
by dilute chloride solutions. The most common elec-
trolytes appear to be 0?1 and 0?6M (i.e. 3?5 wt-%)
NaCl. Some exceptions include works in more dilute
electrolytes53 and recent work in concentrated chloride
electrolytes on the basis that drying aerosol droplets
will lead to [Cl2] between 1?0 and 5?0M.54 Other
environments in which testing has been conducted
include sulphate solutions53,55 and solutions saturated
with Mg(OH)2.56 Additionally, in the field of Mg as
candidates for bioresorbable implants, testing is exe-
cuted in a variety of physiological environments and
temperatures.57 The pH dependence of pure Mg corro-
sion has been recently extensively covered by Ralston,58
and readers are directed to that dedicated work, while
the focus in this review remains on alloying effects.
Focusing on the electrolyte for which the most data
have been reported for a variety of alloys (0?1M NaCl),
Fig. 6 represents the experimental data collected and
reported over the past decade for a range of Mg-alloys,
commercial and experimental, as subdivided by basic
chemistry. This compilation includes data from 108
alloys and was limited to literature in which the
combination of electrochemically determined corrosion
current and gravimetrically determined corrosion rate
was reported. Confining the representation to such

6 Corrosion rate expressed as corrosion current density (icorr) v mass loss rate (mass loss determined from 1 day expo-
sure in 0?1M NaCl). Inset shows same data, with logarithmic axes. Data from Refs. 16,17,19,27,28,33–35,59,60

174 International Materials Reviews 2015 VOL 60 NO 3


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7 Upper plot shows the ICP-AES signal registered (iMg2z) together with current signal (j), along with the signal from dif-
ferent potential steps in the lower plot. The applied potential steps from left to right, are 21?4, 21?3, 21?2, 21?0, 20?8,
20?5, and 20?3 V (Ag/AgCl) applied each time for 240 s in 30mM NaCl electrolyte. From Ref. 53
alloys was deliberate so that the readers could ascertain
(i) the relative corrosion rates seen in Mg alloys in units
to which they can compare their own data, be it
corrosion current or mass loss rate, (ii) to indicate that
there is a correlation between tests, in that generally,
alloys with a high corrosion current density will also
have a high rate of mass loss, and (iii) to indicate the
spread of corrosion rates which may arise as a function
of alloying.
This latter point merits some comment, as the authors
can observe differences in over an order of magnitude in
both the corrosion current density and mass loss rate.
This spread is rather remarkable, and is perhaps even
unique to Mg, in that alloying can have such a marked
influence on corrosion kinetics for the same environ-
ment. A large spread of corrosion rates was also shown
in selected alloys tested in physiological media,39
however, the authors note that the present data
(Fig. 6) only report results for 0?1M NaCl at room tem-
perature. To orient readers, the authors note that low
corrosion rates (typical of passivating systems, including
Al-alloys) are nominally y1 mA cm22; noting that the
reported rates for the Mg alloys presented are much
higher than this. Regarding the practical measurement
and the measurement execution for quantifying of Mg
corrosion electrochemically, gravimetrically or volume-
trically (i.e. via hydrogen collection), a study by King
et al. abridges and highlights recent developments.54 Ela-
boration of the effects seen in Fig. 6 are rationalised from
the descriptions of unique additions in ‘‘Influence of alloy
composition on corrosion of Mg-alloys’’ section.
Update on the mechanistic aspects of
Mg corrosion
The mechanism of Mg corrosion is a topic that has been
studied throughout the past century.53,61–68 While the
corrosion of Mg is a process occurring at open circuit, it is
Gusieva et al. Corrosion of magnesium alloys: the role of alloying
of contextual relevance to mention that Mg displays a
phenomenon known as the ‘negative difference effect’
(NDE). The so-called NDE describes the phenomenon by
which the amount of hydrogen evolved from an Mg
electrode increases as the electrode potential is polarised
anodically to more noble potentials. This is counter-
intuitive to conventional electrochemical wisdom on the
basis that increasingly anodic polarisation should result in
lower rates of the cathodic reaction (which is responsible
for the evolution of hydrogen as per equation (2)).
Somewhat controversially, in one study, the origin of
this phenomenon was proposed by Petty63 to be a result
of the formation of unipositive Mg (Mgz), which was
later popularised by Atrens and co-workers,65,66,69,70
who purported that superfluous hydrogen arises from a
chemical reaction of Mgz with water at some unknown
distance from the metal surface. The claims by Atrens
and co-workers have led to somewhat of a nuanced
understanding of Mg dissolution processes, largely as
the proposed Mgz theory has no reasonable proof of its
existence66,70–74 and most recently the Petty experiments
were refuted.75 While the imagined existence of Mgz has
captured attention and consumed scientific effort, it has
no influence on the content of this review.
At the time of writing this review, a large number of
publications have emerged that provide significant detail
regarding the mechanisms of Mg dissolution as well as
physical descriptions of the NDE. Of those studies, the use
of inductively coupled plasma atomic emission spectro-
electrochemistry (AESEC) definitively demonstrated that
Mg dissolution occurs with an n52 stoichiometry (i.e.
Mg2z) in both sulphate and chloride solutions.53 This
observation was recently validated in an independent
study using on-line mass spectroscopy.76 The results
of AESEC testing are seen in Fig. 7, which show excel-
lent agreement between applied current and the Mg2z
dissolution current. This echoes the classic notions put
forth by James and Straumanis,64 albeit with modern
International Materials Reviews 2015 VOL 60 NO 3 175
 Gusieva et al. Corrosion of magnesium alloys: the role of alloying
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8 Schematic representation of the electrochemical impact of alloying elements studied (data extracted from the papers
cited in ‘‘Influence of alloy composition on corrosion of Mg-alloys’’ section). Plot depicts the ability of alloying addi-
tions to modify anodic or cathodic kinetics (or both), leading to changes in the resultant corrosion rate (icorr), along
with changes in corrosion potential (Ecorr). CS represents the solid solubility
analytical support. With the Mg valency accounted for,
the notion of superfluous hydrogen evolution during
anodic polarisation (i.e. a parasitic cathodic reaction)
was proposed by Frankel67 to be the result of the catho-
dic reaction being catalysed by Mg dissolution, which
is consistent with the classic works noting enhanced
‘reducing ability’17 and has also recently shown by
scanning vibrating electrode (SVET) measurements.32
The atomistic origins of this enhanced catalytic activity
are the goal of active studies.77 It is, however, empha-
sised, that the alloying effects described herein are not
dependent on the elucidation of the origins of enhanced
catalytic activity in a first order sense, and hence this
section will not be elaborated further in the present review.
Influence of alloy composition on
corrosion of Mg-alloys
An attempt has been made to present an abridged
summary of the influence of specific elements upon the
corrosion kinetics of Mg. In many cases, the effect of an
element is over and above that of an existing system (i.e.
the effect of Mn, on say, the Mg–Al system). However,
such scenarios are described in words and the relevant
references provided in order to yield a unique con-
solidation of information not available elsewhere.
Aluminium (Al)
Al is the most common addition to Mg, by virtue that it is
(relatively) cheap, light, soluble, and considerably im-
proves strength of Mg (i.e. from y70 to y250 MPa).78
Additions of Al below the solubility limit tend to reduce
the anodic kinetics of Mg. The addition of Al to Mg
ennobles the corrosion potential, with Mg–Al alloys
tending to be ennobled by y100 mVSCE compared to
pure Mg, in Cl2 environments.65,66,79–81 The Mg–Al alloys
nominally have the lowest corrosion rates of the com-
mercial Mg-alloys,13 particularly AZ31 (Fig. 6), which
gives an optimum balance between physical and corrosion
176 International Materials Reviews 2015 VOL 60 NO
properties for Mg-alloys to date. Although Al is soluble to
y12 wt-% in Mg, this is dependent on temperature, and
the room temperature solubility is much lower, with alloys
richer in Al than AZ31 showing the presence of b-phase
(Mg17Al12). The extent of b-phase will depend on the
time–temperature history of the alloy, with the relative
proportion of b-phase for the same given composition also
varying rather widely depending on alloy cooling rate
or subsequent heat treatment (i.e. whether sand-cast, die
cast, or high-pressure die cast).82–92 Above y3 wt-%, Al
additions tend to enhance the cathodic reaction, which
although further93 ennobles Ecorr, is associated with an
increase in corrosion rate. In open circuit conditions,
b-phase serves as a local cathode. As such, cathodic
kinetics of the following alloys increase in the order of
AZ31,AZ61,AZ91#AM60. Al has been reported to
increase the susceptibility to stress corrosion cracking in
cases where b-phase exists in appreciable fractions.78 It is
also noted that the AZ alloy system undergoes solid-state
phase changes at moderate temperatures, and hence its
utility in more demanding modern applications is leading
to the proliferation of Al-free Mg alloys.
Silver (Ag)
The effect of Ag additions on the corrosion of Mg was
studied by Hanawalt more than 70 years ago, who
suggested a tolerance limit for Ag in Mg to be
y0?5 wt-%.15 Above this concentration the mass loss
rate increased monotonically from y1 mg cm22 day21
for 1 wt-% Ag, to y12 mg cm22 day21 for 5 wt-% Ag.
In contrast, the effect of Ag on accelerating the corrosion
of Mg is therefore as dramatic as that as Ca on Mg.15 In
more complex alloys, however, lower level quaternary
additions of Ag (to ,y2 wt-%) in the Mg–RE–Zr family
of alloys are reported, because Ag improves the age
hardening response and thus provides substantial incre-
ment in strength.13 However, it is prudent to note at this
point that although Ag has been added to the high
strength Mg alloy family (which can be considered ultra
3
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Table 1 Maximum solubility of elements (at any temperature) in magnesium presented in wt-%: atomic radius of elements also given in picometeres8–12
Gusieva et al.

International Materials Reviews

2015
Atomic radius of elements also given in picometeres.9–13

3VOL
60
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Corrosion of magnesium alloys: the role of alloying
 Gusieva et al. Corrosion of magnesium alloys: the role of alloying

9 The relationship between corrosion rate and grain size a pure Mg for current densities measured in 0?1M NaCl225 and
b for ZK60 processed by a combination of extrusion and equal channel angular pressing (ECAP)219

high strength when considering specific strength), this has without any significant loss of corrosion properties, i.e. a
not been an alloy design with corrosion considerations in slight increase in cathodic kinetics is counterbalanced by
mind. None the less, addition of elements such as Ag that decrease in anodic kinetics.33 High concentrations of Ag
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have the ability to modify nucleation/precipitation is an
avenue that can be exploited. For example, trace
additions of Ag (y0?1 wt-%) to AZ91 were recently
shown to stimulate an interaction between Ag and the
Mg17Al12 phase, providing an increment in hardness
led to increased corrosion rate because of co-formation
Mg4Ag precipitates that can stimulate microgralva-
nic corrosion.34,94 In addition, micro-additions of Ag
(,0?5 wt-%) to Mg–Zn–Ca systems facilitate grain refine-
ment and in cast and wrought alloys.95

10 Back scattered SEM images (a, c, e) of polished specimens and the corresponding optical profilometry images follow-
ing 330 min of exposure to 0?1M NaCl for ZK60: Each micrograph corresponds to different extents of processing and
imaged on the ND–TD plane for a and b initial, unprocessed condition; c and d intermediate, extrusion processed
condition; and e and f the extrusionzECAP processed condition219

178 International Materials Reviews 2015 VOL 60 NO 3

 Gusieva et al. Corrosion of magnesium alloys: the role of alloying

11 (left) Corrosion rates as a function of approximate crystallinity for two Mg-based bulk metallic glass (BMGs),
Mg65Cu25Y10 and Mg70Zn25Ca5 measured from potentiodymamic polarisation testing in 0?1M NaCl. The 0% crystallinity
designated the fully amorphous condition, while the increase in crystallinity to the fully devitrified state was achieved
by heat treatment. (right) corresponding SEM micrographs from specimens denoted on the left plot following 12 h
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immersion in 0?1M NaCl. It is observed that Mg65Cu25Y10 in the fully amorphous condition (i) undergoes filiform-like
corrosion, while in the fully crystalline form, undergoes localised corrosion (ii) that is driven by the chemical entity of
microstructural features (active particle dissolution). In the amorphous condition, Mg70Zn25Ca5 is rather uniformly
attacked (iii), forming ‘blisters’, while in the crystalline condition (iv) undergoes localised corrosion that is driven by
the chemical entity of microstructural features (active particle dissolution). The figure is adapted from Ref. 107

Arsenic (As) ennobles the corrosion potential of the alloy34 and is

The effect of As on Mg corrosion was explored on the
basis of the potential to kinetically limit the cathodic
reaction, with As known to be a cathodic ‘poison’
preventing hydrogen recombination96 and restricting
the completion of the reaction in equation (2). The
metallurgical influence of As has been recently reported
by Birbilis et al.,97 whereby relatively small additions of
sparingly soluble As (y0?37 wt-%) result in formation
of Mg3As2 phase. In spite of this second phase presence,
a decrease in Mg corrosion rate (five times lower than
that of pure Mg) was determined by simultaneous
hydrogen collection and 7 day mass loss tests, as well as
lower cathodic kinetics determined by potentiodynamic
polarisation. The reduction in corrosion rates was
associated with the ability of As to slow down the
cathodic reaction rate of pure Mg.
Bismuth (Bi)
The addition of Bi to Mg–Al alloys has the effect of
refining Mg17Al12 and is accompanied by co-formation
of needle-shaped Mg3Bi2 particles, even for Bi concen-
trations below the solubility limit.98 When added to
AZ91, Südholz reported that the presence of Mg3Bi2
shown to bring about the acceleration of both the anodic
and cathodic reactions rates.99 In spite of the negative
influence on corrosion, Bi-containing particles seem to
have a positive effect on enhancing tensile and creep
properties via restricting grain boundary sliding.100
Calcium (Ca)
In the binary context, Ca additions in low levels (less
than 0?35 wt-%) are essentially inert.101 In general,
however, Ca additions dramatically increase corrosion
rates in Mg when added near to, or above the solubility
limit (of y1?35 wt-%). Ca-containing Mg alloys result
in exceptionally high corrosion rates. According to
Hanawalt, the mass loss rate of Mg–Ca binary alloys
increases from y1 mg cm22 day21 for 0?5 wt-% Ca to
about 6 mg cm22 day21 for 5 wt-% Ca. This is almost
six times higher than the corrosion rate of Mg–5 wt-%
Al.15 In addition to possessing the highest corrosion
rates of any candidates for structural alloys ever
reported, Ca-containing Mg alloys dissolve to yield a
voluminous corrosion product that is insoluble.39 Owing
to the biocompatibility of Ca, however (along with Zn),
Mg–Zn–Ca alloys are being explored as potential

Table 2 Precise chemical composition of commercial Mg-alloys for which polarisation data are given in Fig. 3, as
determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES)28,33–35

Mg Al Zn Mn Zr Fe Gd Y La Ce Nd

Alloy wt-%

AZ31 Bal. 3.06 0.91 0.38 – 0.006 – – – – –

AZ91E Bal. 8.82 0.81 0.3 – 0.004 – – – – –
AE44 Bal. 3.98 0.2 0.35 – 0.005 ,0.005 ,0.005 y2 y1 y1
AM60 Bal. 6 0.1 0.45 – 0.003 – – – – –
ZE41 Bal. 0.009 4 0.011 0.7 0.001 ,0.005 ,0.005 0.33 0.64 0.2
ZK60 Bal. 0.006 5.41 0.010 0.61 0.006 ,0.005 ,0.005 ,0.005 ,0.005 ,0.005
WE54 Bal. 0.023 0.002 0.008 0.53 0.001 0.29 4.86 0.11 0.4 1.72

International Materials Reviews 2015 VOL 60 NO 3 179

 Gusieva et al. Corrosion of magnesium alloys: the role of alloying
biomaterials.22 More recently, very low levels of
functional Ca additions are being explored in Al-free
Mg-alloys,102 in attempt to exploit the fact that Ca is
one of the few soluble elements in Mg. Provided that Ca
concentrations are kept below the solubility limit to
avoid Mg2Ca formation, the corrosion rate will not
sharply accelerate, while solid solutions of Mg–Ca can
display appreciable ductility.103–105
Copper (Cu)
The addition of Cu to Mg and Mg-alloys is generally
avoided because of the insolubility of Cu, and the
resultant formation of Cu islands in the microstructure.
Cu is highly detrimental for corrosion,78 rationalised on
the basis that Cu has a high exchange current density,
and hence an efficient cathode. The tolerance limit of
0?1 wt-% was established by Hanawalt, however, the
limit is sharply reduced to 0?01 wt-% when Al and Mn
are present in the alloy composition.15 When added to
AZ series alloys it forms an Mg–Al–Cu–Zn phase, which
is also a relatively strong local cathode resulting in local
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corrosion.106 In general, Cu is avoided in the production
of Mg-alloys, with measures in place to avoid Cu
contamination and pick-up. Unfortunately, from a
corrosion perspective, Cu is, however, a popular element
in the formation of Mg metallic glasses,107 where the
influence of Cu on the resultant corrosion mechanism
has been described as incongruent dissolution and
discussed further below.
Cerium (Ce)
When added as a binary addition (i.e. Mg–Ce) the
formation of Mg12Ce occurs in increasing volume fraction
with Ce additions, which can monotonically accelerate
corrosion by enhancing cathodic kinetics.24 In spite of the
chemical reactivity of Ce, Mg12Ce is more noble than Mg,
and Mg12Ce sustains the cathodic reaction at higher rates
than Mg over the range of potentials typical of Mg-alloys.
On the other hand, Ce additions to Al-containing Mg-
alloys can refine microstructure by formation of Al4Ce
or Al11Ce3 intermetallics.108,109 These compounds are,
however, more deleterious for corrosion than Mg12Ce.
Rare earth elements are typically not combined with Al-
containing Mg alloys, with the exception of the commer-
cial alloy AE44. In the more modern wrought series of Mg
alloys, RE and Al are not combined, because of the ease
of formation of AlxREy compounds that reduce alloy
ductility. Some reports suggest that Ce contributes to the
surface film and stabilises Mg hydroxide.110 Südholz,
however, revealed via XPS analysis that RE elements were
not seen to dope the surface oxide of Mg–Al alloys.28 The
notion of oxide modification of Mg-alloys is an area
of mixed reports, and one that is an open question.
Irrespectively, elements with thermodynamic ability to
replace Mg-oxides/hydroxide generally do not offer a
wider window of passivity than Mg.111
Erbium (Er)
In favour of more cost effective RE elements, Er has
not been well studied in Mg. In one study, however,
Er, when added in 2–3 wt-%, was found to decrease
corrosion rates in Mg–2 to 3Al (wt-%) alloys compared
to commercial AM60 [nominal Mg–6Al–0?13Mn (wt-
%)] when tested in borate buffer solution.112 The
assumption was made that Er facilitates an apparently
enhanced protective effectiveness to the surface oxide
180 International Materials Reviews 2015 VOL 60 NO
giving rise to what was described as a pseudo-passiva-
tion effect by incorporation of Er into the Mg(OH)2.
However, there is still a lack of evidence to support this
assumption. Furthermore, the testing of Mg in a buffer
is likely to impose an unrealistic scenario of surface film
evolution, which is nominally influenced by natural
surface alkalinisation.
Iron (Fe)
Fe is the most common impurity in Mg-alloys. Fe
contamination can be present because of the quality the
starting ‘pure’ Mg as well as because ofpickup from the
casting process. Owing to its low solubility in Mg
(y0?001 wt-%) Fe largely remains in its pure (body
centred cubic) form. To date, the literature reports a
number of tolerance limits for Fe, which is nominally
restricted to as low a level as economically feasible.13,113
The notion of an Fe tolerance limit dates back several
decades, where the proposed limit of 150 ppm by weight
was commonly accepted.114,115 Recent works have
focused more specifically on the role of Fe, as its ability
to be scavenged by sequestration to AlMnFe particle
formation is not possible in emerging Al-free Mg
alloys.17 The role of thermal history on the Fe tolerance
limit has also been recently discussed on the basis of
calculated phase diagrams.116,117 The experimental
validation and robustness of the related thermodynamic
databases for Mg–Fe remain open questions without
further empirical work, particularly because it was seen
that calculated phase predictions can vary from the
structures characterised by electron microscopy.17
Gadolinium (Gd)
Of the elements that Mg may be alloyed with, Gd is
unique on the basis that it has high solubility (.10 wt-
%) in Mg, forming binary Mg–Gd solid solutions over a
wide range of compositions. Such solid solutions can be
used as a basis for further loading of the matrix with
solute elements – in the case of wrought Mg alloys, or
for carefully controlled precipitation processes in the
family of Gd-containing precipitation-hardened Mg-
alloys.118–121 In regards to this latter class of alloys,
corrosion characterisation remains scarce. The addition
of Gd in Mg–Al alloys results in the precipitation of
Al2Gd and Al–Mn–Gd phases that consumes Al and
reduces the volume fraction of Mg17Al12 phase.122 These
phases may contribute to a minor decrease in the total
rate of cathodic reaction.123 This tendency is commonly
observed for Mg–Al alloys modified with REs.
However, the effect of Gd is more complex because
it leads to more heterogeneous microstructures and
diminished Al content in the Mg matrix. Therefore long
term corrosion tests show a greater corrosion for Mg-
alloys containing Gd.124 Other studies have also
indicated that the influence of Gd on corrosion is
generally defined as detrimental.125
Mercury (Hg)
Alloying with Hg is nominally only reserved for the
production of high voltage anode materials for sea water
batteries.126 The Mg3Hg phase can form in binary Mg–
Hg alloy at concentrations of Hg at around 4–6
wt-%.126,127 Thermomechanical processing of Mg–Hg
alloys can promote the redissolution of Mg3Hg into the
Mg matrix, which subsequently retards microgalvanic
corrosion and thus lowers corrosion rates.128 Feng
3

compared the electrochemical response of Mg–5Hg (wt-
%) and Mg–6Hg (wt-%) in 3?5% NaCl solution, and
concluded that Hg accelerates anodic reaction rates and
leads to very negative corrosion potentials (Ecorr, Mg–
5Hgy22?3 VSCE), in fact representing the most nega-
tive corrosion potential reported of any Mg alloys. This
was concomitant with high corrosion rates with icorr of
Mg–5Hg being y27 mA cm22, compared to
y20 mA cm for pure Mg.127 The role of Hg in struc-
22
tural Mg alloys has not been explored.
Holmium (Ho)
The limited research to date regarding Ho has suggested
that a Ho addition of 0?24 and 0?44 wt-% can decrease
the rate of corrosion in an Mg–Al alloy (AZ91D) by
decreasing the volume fraction of Mg17Al12 owing to the
formation of Ho-containing intermetallic phases with
Al. In one study, inspection of the reported data indicate
a minor decrease in the cathodic reaction rate, along
with as much as 10 times lower mass loss rates compared
to that of the base Mg–Al alloy.129 This, however, is
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likely to lead to decrease in alloy strength and may be
manifest as the same outcome as lowering of the alloy Al
content. It has been posited that Ho presumably
contributes to more uniform and compact layer of
corrosion product because of the higher content of Al
present in the surface film; however, more evidence is
needed to support such assertions.
Lanthanum (La)
As a binary addition, La forms the Mg12La phase24
when added above its solubility limit. This phase is
a more efficient cathode than pure Mg leading to
an overall increase in corrosion rates (from 10 to
30 mA cm22 at concentrations varying from y0?5
to y3 wt-% La).28 However, as an elemental addition
to Mg–Al alloys, La modifies the alloy microstructure
(in a manner analogous to Ce), forming needle-like Al–
La compounds and alters Mg17Al12 from discontinuous
to continuous with a fine polygonal-shape.130,131 Liu
et al. reported a drop in corrosion rate (icorr) of AZ91
from y603 to y3 mA cm22 in 3?5% NaCl solution
when 0?5 wt-% of La was added. This phenomenon was
attributed to a refined microstructure and allegedly more
protective corrosion product film. It should be noted,
however, that the reported icorr of the base AZ91 was
much higher than any other reports for AZ91; while the
evidence for any La in the surface film was also not
provided. In a separate study, Südholz also tested the
effect of 0?3 wt-% of La on corrosion rate of AZ91E. In
that study, however, the reduction in the icorr value
was only by 0?3 mA cm22 (from 7 mA cm22 of AZ91E
to 6?7 mA cm22 of AZ91E–0?3La).28 It is generally
observed that any excess addition of La, above the
solubility limit, reduces corrosion resistance because
coarse Al–La precipitation in Mg–Al alloys.130,132 In the
context of Mg–RE earth alloys, containing only Mg and
REs, the presence of La in concert with Ce and Nd will
lead to a different morphology and microchemistry of
the second phase; transitioning from a lamellar eutectic
to a divorced eutectic.133 The relative proportions of La,
Ce and Nd are important in the ultimate corrosion rate,
as depicted in a combined electrochemical and micro-
structural study.133 It was determined that Nd is less
detrimental than La (or Ce) on the corrosion of Mg.
Gusieva et al. Corrosion of magnesium alloys: the role of alloying
Lithium (Li)
Mg–Li alloys because of their ultra-lightweight and
superplastic behaviour remain promising materials for
many critical engineering applications,134 in spite of
limited use to date. The microstructure of binary Mg–Li
alloys depending on the Li content may consist of either
a single hexagonal a (HCP) phase, at 0–5?7 wt-% Li;
two phase – a and body-centred b (HCP and BCC)
at 5?7–10?3 wt-% Li; or a single b (BCC) phase at
Li concentrations greater than 10?3 wt-%.135,136 There-
fore, high additions of Li (.10?3 wt-%) can produce a
uniform b phase that is cubic. Li is the only researched
element able to impart a change in the crystal structure,
which has major implications for ductility. Early work
by Frost in 1955 and a later published report from
Battelle in 1964 indicate superior corrosion resistance of
binary Mg–11Li alloy compared to the alloys with lower
Li content, for example, the mass loss rate of the alloys
measured in 3% NaCl solution (at 35uC) over 8 days was
Mg–2Li (4?92).Mg–4Li (4?44).Mg–9?3Li (0?77).Mg–
11Li (0?57), mg cm22 day21.135,137 The greater corro-
sion resistance of Mg–11Li alloy was attributed to the
BCC structure. More recent studies have also validated
aspects of the early research by reporting that Li addi-
tions below the bcc transition increase the corrosion rate
of Mg (from 19 mA cm22 for pure Mg to 45 mA cm22
for Mg–8Li138). Li was also seen to increase the corro-
sion rate of an Mg-alloy, from 12 mg cm22 h21 for
AZ80 to about 200 mg cm22 h21 for AZ80–1?95Li.139
In addition, over long exposure periods the corrosion
rates of Mg–Li alloys are more likely to remain con-
stant or decrease much more slowly in contrast to AZ31
for instance, for which corrosion rate decreases with
time.135,138 Although some information on the effect of
Li on bulk Mg corrosion exists, there is still a gap in
regards to electrochemical effect of Li on corrosion
kinetics of Mg and its alloys.
Manganese (Mn)
The influence of Mn additions on Mg has been studied
in detail as far back as almost a century.15,25 Its role is
therefore well characterised and generally well under-
stood. As a binary addition to Mg, Mn has been
reported to show no significant effect on corrosion rate
at concentrations up to y5 wt-%.15 Mn is essentially
always added to the Mg–Al and Mg–Al–Zn systems
(i.e. the commodity Mg-alloys). Compounds such as
Al8Mn5, Al6Mn or Al4Mn are formed, and the addition
of Mn helps to reduce corrosion rate via the incorpora-
tion of lowly soluble metals in Al–Mn intermetallic
phases. The classic example of this behaviour is the
incorporation of Fe into Al–Mn–Fe.140
It has been reported that the amount of Mn to
effectively mitigate the effect of Fe must be in the range
that satisfies the maximum Fe/Mn ratio of 0?032,
whereas greater ratios will sharply increase corrosion
rates.6 Although Mn is known to improve corrosion
resistance, a low ratio between Al/Mn leads to higher
cathodic potency. Therefore corrosion rate gradually
increases with an increase in Mn content,25,141 indepen-
dent of the Fe sequestration aspect of Mn. More
recently, the work of Gandel et al. reports the corrosion
behaviour of Mg–Mn binary alloys where the corrosion
rate icorr reduces from 40 to about 22 mA cm22 in 0?1M
NaCl with Mn content ranging from 0?2 to 2 wt-%,
International Materials Reviews 2015 VOL 60 NO 3 181
 Gusieva et al. Corrosion of magnesium alloys: the role of alloying
respectively.20 The role of Mn additions in Al-free
(wrought Mg alloy) systems is likely to be a productive
avenue of future work. Of such works, Mn has been
recently observed to ‘encapsulate’ Fe in Al-free magne-
sium alloys,20 which is a very positive result on the basis
that Mn may remain an effective sequestration tool for
Fe even in the absence of Al.
Neodymium (Nd)
In binary Mg–Nd alloys, the Mg3Nd phase is formed.24
Mg3Nd is a more efficient cathode than pure Mg and
therefore serves as a local cathode leading to continually
increased cathodic kinetics (and hence corrosion rates)
with an increase in Nd content.28 It is noted that the
increase in corrosion arising from Nd is less than that
arising from Ce or La. This is an important point, as the
Mg3Nd phase also possesses a much higher atomic per
cent of RE than either Mg12Ce or Mg12La, which are the
phases that form in the case of the latter. From a
corrosion standpoint, if RE elements are preferable in
isolation, Nd is thus the most suitable; unfortunately,
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however, Nd is also the most expensive of the common
REs and its concentration is therefore often limited. In
AZ and AM alloys, Nd forms an Al–Nd phase as well as
replacing the Al–Mn phase with an Al–Mn–Nd inter-
metallic compound.142 Nd was noted to improve
corrosion resistance of Mg–Al alloys by minimising
the effect of galvanic coupling that exists in Nd-free AZ
or AM alloys.143 In addition, Nd was reported to be
beneficial in contributing into formation of protective
surface oxide film consisting of Mg and RE,132 however,
this is one of many such claims that requires further
investigation. The replacement of, or contribution to,
more robust surface films is a common claim in many
Mg-corrosion studies, however, the finding is often
speculative and ultimately not proven. As with Ce and
La, the influence of Nd on Mg–RE alloys was captured
in a recent combined study.133
Lead (Pb)
In the binary context, Pb was historically reported to be
quite inert to Mg and not detrimental for corrosion when
added up to 5 wt-%.15 Generally, Pb is added to Mg for
production of anode materials, with the AP65 alloy
having a nominal composition of 5 wt-% Pb serving as a
common example.144 The addition of Pb to structural Mg
alloys has not been explored, perhaps on the basis that Pb
has a significantly higher density than Mg (logically
negating the light-weighting opportunities).
However, generally speaking the effect of Pb on
corrosion of Mg-alloys has received contradictory
reports overall. On one hand, Pb was reported to
allegedly modify the microstructure of AZ series alloys
by means of refining and a more homogenous distribu-
tion of Mg17Al12.145–147 Another example of the
beneficial effect of Pb was found in Mg–10Al–12Si
alloys, where the additions of 0?2, 0?5 and 1 wt-% of Pb
led to lower cathodic reaction rates and subsequently
resulted in a reduction of mass loss rate from
1 g cm22 day21 for 0 wt-% of Pb to 0?4 g cm22 day21
with 1 wt.% Pb.145 In contrast to this, works have
suggested that low levels of Pb (#0?5 wt.%) to AZ91
stimulated more rapid corrosion rates, with the icorr of
Mg-alloys (from 9 mA cm22 of AZ91E to 20 mA cm22
of AZ91–0?5Pb).34 This finding is consistent with what
was reported earlier by Hanawalt, i.e. addition of Pb to
182 International Materials Reviews 2015 VOL 60 NO
Mg–Al–Mn system results in higher corrosion rates
(exceeding 0?2 mg cm22 day21 at y0?1 wt-% Pb and
0?001 wt-% Fe) because of complex interactions between
Pb and inherent Fe impurity.15 Pb additions are not
common in structural Mg alloys, and its role in Mg-
alloy corrosion is not well established, in spite of its use
in sacrificial Mg anodes.
Praseodymium (Pr)
In Mg–Al alloys, the addition of Pr leads to the formation
of Al2Pr in preference to Mg17Al12. Increasing Pr loading
results in grain size reduction concomitant with an
increase in the volume fraction of secondary phases.146
Salt spray testing has indicated that corrosion was
reduced with increased Pr concentration from 1 wt-% to
maximum of 4 wt-% in a base Mg–4Al–0?4Mn alloy.
However, there are few corroborating reports of the role
of Pr in Mg alloy corrosion, and of the limited works,
there are some unfounded claims that relate to ‘compact-
ness’ of the corrosion product layer increasing with Pr
content and an improvement in corrosion resistance
attributed to the potential of Al–Pr phases to passivate
over the wide range of pH.148 Such aspects would need
further validation by independent methods.
Antimony (Sb)
Owing to the insolubility of antimony (Sb) in Mg,
second phase formation is expected, and the second
phase will appear in a large volume fraction. It was seen
that the rod-shaped Mg3Sb2 compound forms along
grain boundaries when Sb was added to AZ91.34 As an
example, alloying of AZ91 with 0?5 wt-% Sb leads to a
significantly faster cathodic reaction rate and results in
increased overall corrosion rate by y50%.34,149 The
limited work to date clearly indicates that Sb has also
been noted to have negative effect on the corrosion
resistance of the AZ91D,99 where 0?4 wt-% Sb was
reported to increase the alloy corrosion rate from 8?6 to
19?91 mm year21. Sb, however, is a known cathodic
poison, and based on the recent findings on the
poisoning effect of As,97 the revisiting of Sb presents
an avenue of future work.
Scandium (Sc)
The effect of Sc on corrosion properties of Mg and its
alloys is yet to be fully explored, however, the
information available to date reports that Sc additions
to AZ91 alloys refine microstructure through the
formation of the Al3Sc compound that suppresses
Mg17Al12 phase formation.150 Sc has also been noted
to comparatively retard cathodic kinetics, resulting in
the reduction of the corrosion rate of AZ91E in 0?1M
NaCl from y8 mA cm22 to 2 mA cm22 at 0?1 wt-% of
Sc. In contrast, a higher Sc content was shown to not be
as effective.34 Sc is an extremely expensive metal
(.US$100 g21), which significantly limits its wider use,
and therefore few studies exist. The comparatively low
catalytic activity of the Al3Sc compound in isolation was
reported by Cavanaugh.151
Silicon (Si)
There exist commercial Mg–Si alloys, the most common
of which are AS21 and AS41 with Si additions of
y1 wt-%. Si additions to Mg result in formation of
magnesium silicide (Mg2Si) intermetallics. Depending
on the shape and distribution of this intermetallic, it
3

may have a minor or major influence on enhancing the
corrosion rates of the commercial AS alloys. A recent
report has revealed that Mg2Si acts as a local cathode in
Mg alloy AS31 and thus promotes the dissolution of
surrounding matrix.152 Fine and evenly distributed
polygonal-shaped Mg2Si was reported to be more inert
to corrosion of AZ91 alloy compared to coarse Chinese
script-like Mg2Si.149 It is however, important to mention
that Si has an adverse effect on corrosion in the pre-
sence of Fe contamination,15,113 which was recognised
early in the twentieth century. As such, besides the AS
series of alloys which are used in some automotive
applications,153 Si is not a typical alloying element in Mg
alloys and its level in commercial purity Mg is very
carefully controlled.
Samarium (Sm)
Samarium is known to be beneficial in improving the
mechanical properties in binary Mg alloys,154 however,
there is a limited number of studies regarding the effect of
Sm on corrosion of Mg. Wu and co-workers reported that
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additions of about 1 wt-% Sm to AZ92 led to formation of
an Al–Mn–Sm and Al–Sm phase, along with a more
refined b (Mg17Al12) phase, accompanied with a decrease
in the b volume fraction which contributed to decreased
corrosion rate of AZ92 by y40% in 3?5% NaCl.155
Moreover Sm has also been reported to refine the
microstructure of Mg–Al–RE alloys and somewhat
decrease the mass loss rate from 2?6 to 1?95 mm year21
in 3?5% NaCl when added at 0?5 wt-%.156
Tin (Sn)
Tin has a tendency to form Mg2Sn along grain
boundaries. The volume fraction of Mg2Sn increases
with Sn content.157 As Sn has a low exchange current
density it does not enhance cathodic kinetics, but leads
to a significant increase in anodic activity – akin to the
notion of anodic activation – which Sn also imposes
when added to Al.158 The anodic activation phenomena
in Mg alloys is not understood nor studied at the nano-
scale to date. In the work of Wang et al., additions of 1–
3 wt-% Sn to AP65 alloy decreased the corrosion
potential of the alloys by about 120 mV in 3?5%
NaCl and increased the icorr from 6?3161024 to
7?961021 mA cm22 at 1–3 wt-% Sn.159 This is synon-
ymous with anodic activation. In an early study, binary
additions of Sn to Mg were reported to be negligible for
corrosion for concentrations up to as high as 5 wt-%
Sn.15 It is therefore worthwhile to mention that some
misinterpretations of the role of Sn in Mg binary alloys
exist. For instance, the recent report by Ha suggested
that Sn increases cathodic reaction rates and thus
increases hydrogen evolution rate which in turn pro-
motes passivity in Mg–Sn alloys (2–8 wt-% of Sn
added).160 This effect was not demonstrated by the
presence of a passive region or a passive current density.
As such, the effect of Sn appears to be more deleterious
in alloyed Mg, than pure Mg, either alone, or depending
on the interaction of Sn with the elements present in
the Mg alloy. More specifically, the experimental alloy
of Mg–5Al–1Sn exhibits the icorr value of about
51 mA cm22 in comparison to icorr of Mg–7Sn that is
about 27 mA cm22 in 0?1M NaCl.50 The mechanism of
anodic activation is not understood, but its manifestation
has been depicted rather markedly in Fig. 4 for the
example of heavy Sn loadings.
Gusieva et al. Corrosion of magnesium alloys: the role of alloying
Strontium (Sr)
Strontium has low solid solubility in Mg (y0?1 wt-%)
and in binary context forms Mg17Sr2 along grain
boundaries.27 Sr significantly increases cathodic reaction
rates and corrosion potentials of Mg that results in high
overall corrosion rates. Xia reported the corrosion rate
(icorr) of commercially pure Mg of about 20 mA cm22 in
contrast to 38 and 60 mA cm22 when 0?2 and 2 wt-% of
Sr, respectively, were added.27 In the Mg–Al–Zn system,
when added above solubility limit, Sr decreases grain size
forming the and binary eutectic Al4Sr,148 Mg17Sr2 and
Mg2Sr. These particles lower the volume fraction
of Mg17Al12 and homogenise its distribution.161 Sr is
reported to improve corrosion resistance of AZ91 by a
purported retardation of anodic activity concomitant
with an increase in corrosion potential (Ecorr) by about
150 mV and reducing the icorr by y50%.162 This agrees
with results by Fan where the additions of up to 2 wt-%
Sr led to ennoblement of Ecorr by y80 mVSCE and
decrease in the icorr of AZ91D alloy from about 24 to
12 mA cm22.163 More so, the recent study by Xia reveals
an increased cathodic reaction rates and ennoblement of
corrosion potential of binary Mg–2Sr alloy compared to
pure magnesium (Ecorr, Mg––2Sr521?64 VSCE, Ecorr,
Mg521?725 VSCE).27 Subsequently the icorr of Mg–2Sr
increased from 21 of pure Mg to 58 mA cm22, whereas
the icorr of Mg–0?2Sr increased to 38 mA cm22.
Titanium (Ti)
The literature indicates that Ti has so far only been added
to AZ91 alloys. As a result, the effect of Ti on other alloy
systems is not known. However, it is reported that Ti
addition in AZ91 alloy, progressively improves corrosion
performance (to the reported maximum values of 0?8 wt-
% Ti). This effect of Ti is associated with (1) changes in
morphology and distribution of b phase from coarse and
semi-continuous to fine, uniform and rodlike, and (2) an
increase of Al in the solid solution of a-phase.164 Südholz
tested the effect of 0?1 wt-% Ti addition to AZ91E in
0?1M NaCl and found that although anodic activity was
slightly increased in the presence of Ti, the cathodic
reaction rate was somewhat decreased. However, this did
not have a significant impact on the overall corrosion rate
icorr.34
Candan and co-workers measured the corrosion
potential and corrosion rate of AZ91 alloy with 0?2, 0?3,
0?4, 0?5 wt-% Ti additions in 3?5% NaCl solution, and
reported somewhat unrealistic corrosion potential values
(Ecorr) and corrosion current densities (icorr) for commercial
and alloyed AZ91 alloys (i.e. Ecorr, AZ91520?821
VSCE and Ecorr, AZ91–0?5Ti520?980 VSCE, icorr, AZ915
153 mA cm22 and icorr, AZ91–0?5Ti543 mA cm22).165
Such high potentials are synonymous with potentials in
which the cathodic reaction would be oxygen reduction,
and not water reduction – and cannot be realistic or relied
upon. The corrosion potential of AZ91 alloy is typically
around 21?5 VSCE.
Yttrium (Y)
In binary Mg–Y alloys, Y additions monotonically
increase corrosion rate because of the increasing volume
fraction of Mg24Y5 and a concomitant enhancement of
cathodic kinetics.166 An increase in corrosion rates
reported from 17 to 65 mA cm22 when 2–18 wt-% Y
was added to Mg. Y as an elemental addition to AZ series
alloys forms Al2Y phase, refines a (Mg) grains and
International Materials Reviews 2015 VOL 60 NO 3 183
 Gusieva et al. Corrosion of magnesium alloys: the role of alloying
contributes to a lower fraction of, and more homo-
geneous distribution of b (Mg17Al12). As a result, the
corrosion properties of AZ91 have been reported
to improve with Y additions ranging from 0 to
0?8 wt-%;167 the mass loss rate of AZ91 dropping
from 7?5 mg cm22 day21 to about 0?5 mg cm22 day21
at 0?8 wt-% Y. This was not mechanistically analysed in
detail by the authors, however, the electrochemical
response showed slightly slower cathodic reaction rates.
The improvement in corrosion was mainly because of the
refined microstructure, and a change in the morphology
of the Mg17Al12 phase from continuous to discontinu-
ously dispersed with a concomitant decrease in its volume
fraction.168 However, in contrast, with heavier loadings
of Y, the work of Südholz indicated a significant increase
in corrosion when 2 wt-% Y was added to AZ91E (an
increase in icorr from 8 mA cm22 at 0 wt-% Y to about
60 mA cm22 at 2 wt-% Y in 0?1M NaCl).34 The notion
that Y is problematic for pure Mg, along with its ability to
serve as a local cathode,16 has resulted in the conclusion
that Y is deleterious to the corrosion of Mg. That said,
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however, the high solubility of Y in Mg has resulted in
increased use in the modern age hardenable alloys, such
that Y is a major component of the commercial alloys
WE54 and WE43. In addition, the magnetron co-sputter
deposited non-equilibrium thin film Mg–22 at-% Y alloy
was reported to exhibit the lowest corrosion rate
(icorr50?9 mA cm22) in 0?1M NaCl (pH 12) compared
to commercial purity Mg and bulk WE43 alloy.169 This
significant reduction in corrosion rate was attributed to
passivity enhancement by Y via incorporation in the
surface film, and also because of this method of alloy
fabrication not resulting in formation of MgxYy phase
and Y remaining in solid solution.169 Physical vapour
deposition (PVD) techniques are both challenging and
not up-scalable, but have been able to reveal compara-
tively corrosion resistant Mg-based thin film alloys and
coatings,170 indicating how important microstructural
heterogeneity (and retention of solid solutions) can be in
limiting the kinetics of corrosion,171 unfortunately this
requires specialist fabrication due to the limited solubility
of metals in Mg prepared by conventional casting.
Zinc (Zn)
Zinc is the second most frequently used alloying element
in Mg alloy production after Al. In the binary context, Zn
forms MgxZny phases (depending on precise composition)
that provide and age hardening response.27,172,173
However, this phase serves as a local cathode to the Mg
matrix and has been reported to be responsible for overall
increase in corrosion rates due to accelerated cathodic
reaction rates22,88,174 when present in concentrations
above y1 wt-%. Although Hanawalt established a
threshold limit for Zn of up to 2?5 wt-% in his early study
in 1941,15 Kirkland reported a substantial increase in
corrosion rates when Zn concentration rises from 1 to
3 wt-%.22 In addition, increasing the Zn content has been
shown to lead to a higher susceptibility to stress corrosion
cracking.175 Zinc is often used in combination with Mg–Al
and Mg–Zr–(RE) alloys and hence the role of Zn in
synergy with other elements has been described along with
those specific elements.
Zirconium (Zr)
Zirconium has low solubility in Mg and does not form
intermetallic phases with Mg.176 Zr is added to Mg
184 International Materials Reviews 2015 VOL 60 NO
because of its potent ability to refine the grain size of Mg
alloys, improving both the casting quality and mechanical
properties of Mg. Usually Zr is added to Zn- and RE-
containing alloys such as ZE and ZK series alloys.
Corrosion of these alloys is generally more rapid than the
AZ (Al–Zn) class of alloys. It has been reported that
corrosion resistance may be improved by heat treat-
ment,13 while there are even reports that Zr addition up to
0?42 wt-% may have positive influence (i.e. decrease)
corrosion of Mg-alloys.177 However, of the systematic
studies to date, they have indicated that Zr is rather
detrimental for Mg corrosion.20,178 A systematic study of
Zr additions was also able to indicate that the assertions
made regarding the role of Zr in higher order (multi-
element) alloys, is difficult to ascertain – as the corrosion
response may be dictated or overwhelmed by the role of
the other elements (present in a much higher proportion).
There are reports that suggest Zr can purify Mg-alloys
by combining with Fe to form Fe2Zr which settles to the
bottom of the melt (by gravity) resulting in higher purity
castings. This potential beneficial effect, however, was
also recently described by Gandel, who revealed that
overall, the influence of Zr on corrosion was by in large
negative and unique.20 It was indicated (from carefully
prepared binary alloys) that Zr imparted an ‘activation’
effect where it could accelerate the anodic reaction by
destabilising the surface film. This led to rapid general
dissolution rates corroborated by SEM. Furthermore,
the ratio of soluble to insoluble Zr was also a key factor
(as following the limited solubility in the Mg matrix, any
excess Zr phase separates to form pure Zr). While a
potent grain refiner, Zr content should be balanced so as
to not be deleterious to corrosion. Zr is nominally not
added to Mg–Al alloys as it combines with Al to form an
Al3Zr intermetallic that negates the grain refining effect
of Zr. Even in commercial Zr-containing alloys such as
ZE41, the presence of Zr particles was seen by electron
microscopy to be responsible for the accumulation of
corrosion damage.179,180 Neil and co-researchers pro-
posed the corrosion mechanism of ZE41 that initiates
with localised attack of the regions beside Mg7Zn3RE
intermetallic, followed by deep attack at Zr-rich regions.
Other elements (Au, B, Ba, Be, Cd, Co, Eu, Ga,
Ge, In, Nb, Ni, Se, Tb, Th, V)
Boron as a trace addition to AZ series alloys from 0?008
to 0?032 wt-% provides significant grain refinement,
which is attributed to the presence of AlB2 particles that
serve as Mg grain nucleation sites.181 Studies suggest
that B improves the fluidity and die casting properties of
AZ alloys,182 however, the presence of 0?05–0?2 wt-% B
in AZ31 and AZ91E alloys leads to higher corrosion
rates by a factor of about 234,183 compared to the B-free
base alloy.
Barium has been noted to improve the age hardening
response of Mg–Zn alloys, with dispersed particles of
Mg7Zn2Ba forming within grains and at grain bound-
aries.184 Ba has, however, been shown to have an
adverse effect on corrosion properties of AZ91. The only
corrosion study related to Ba additions to date indicates
the addition of 0?1 wt-% Ba to AZ91E,34 increased
corrosion rates increased by y50%, concomitant with a
decrease in Ecorr of y25 mVSCE.
Beryllium has an ability to control melt oxidation of
Mg during melting, casting or welding.185,186 However,
3

because of its low solubility and effective grain coarsen-
ing effect, the addition of Be is nominally restricted to
the parts per million range (y,30 ppm).78 In addition,
there are significant safety risks with Be such that it is
not presently commercially viable.
Cadmium additions to Mg have not been widely
explored, however, an early report suggests that addi-
tions of Cd up to 5 wt-% do not have a detrimental
effect on corrosion.15 More recently, a study by Xu
indicated decreased corrosion rates with Cd additions,
concomitant with a reduced corrosion potential of
y20 mV when 2?04 wt-% Cd was added to Mg.
Hydrogen evolution measurements showing Mg–Cd
lowered corrosion rate three times (3?44 mm year21
with 0 wt-% Cd v 1?06 mm year21 at 2?04 wt-% Cd).187
In a separate study by Südholz, the addition of 0?2 wt-%
Cd to an AZ91Ez0?2Au alloy resulted in a lower
overall corrosion current density compared with similar
alloys including AZ91Ez0?05Au and AZ91Ez0?001Au
(icorr, AZ91E–0?2Au–0?2Cd53?1 mA cm22; icorr, AZ91E–
0?05Au55 mA cm22; icorr, AZ91E–0?001Au513 mA cm22).34
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In the binary context, addition of Cd may also im-
prove tensile strength and provides an increment in
elongation.187 As Cd is 100% soluble in Mg it does not
form any intermetallic compounds and as a binary
addition to Mg, is perhaps in no way detrimental to
corrosion performance; unfortunately, however, Cd is
hazardous to human health and its widespread use as an
alloying element in Mg will remain unlikely.188
Cobalt is mainly used as an alloying addition in the
production of lightweight load sensitive materials with
sensory properties, allowing for on-line monitoring of
mechanical forces applied to components made of Mg–
Co.189 Co has no solid solubility in Mg and forms
intermetallic compounds of the types Co2Mg and Mg2–
Cox in binary Mg–Co alloys. Micro-additions of Co
(y0?1 wt-%) result in extremely high corrosion rates of
Mg, with the corrosion rates being comparable to those
Mg alloys loaded with common impurities such as Fe,
Ni.15 In the early study of Hanawalt, the tolerance limit of
Mg for Co was reported to be 0?017 wt-%, the
concentrations exceeding this limit drastically increase
corrosion rate of Mg.15 More recently, Co additions have
also been studied in the pursuit of ultra high strength Mg
alloys.190 Such alloys have been largely based on the Mg–
Zn system with both heavy and complex multi-alloying to
stimulate heterogeneous microstructures. Co-containing
Mg alloys display among the highest corrosion potentials
of any Mg alloys ever reported, owing to the significant
enhancement of cathodic kinetics that Co imposes. As
such, the more noble potential values are linked with very
high rates of corrosion. For Mg–8Zn–1Co, an Ecorr of
21419 mVSCE and icorr 194 mA cm22 were recorded. This
icorr is about 20 times more rapid than AZ31. The same
alloy with 0?02 wt-% Ti added, resulted in a decrease of
icorr to y70 mA cm22, which is the same icorr measured in
the case of more Zn, in a Mg–10Zn–1Co alloy. Finally,
the lowest icorr recorded for a Co-containing alloy was in
Mg–8Zn–1Co–0?5Ag–0?3Ca, with an icorr of 47 mA cm22
and retention of an ennobled potential of about
21416 mVSCE. These are comparatively higher icorr
values, than all the commercial Mg alloys as measured
under similar conditions.
Dysprosium assists grain refinement and solid solution
strengthening in Mg–Dy binary alloys, while it enhances
Gusieva et al. Corrosion of magnesium alloys: the role of alloying
compression and tensile properties to ZK alloys when
added below the solubility limit.191–193 As Dy has a high
maximum solid solubility in Mg (25?34 wt-%9), it largely
dissolves in the Mg matrix with only low concentrations
departing the matrix in precipitation of second phases,
which increases in volume fraction with an increase in
Dy content. It is reported that corrosion of Mg–Dy
binary alloys is of the filiform-type and localised, and
the corrosion rate does not notably increase or decrease
with differing Dy contents between 5 and 20 wt-%.194
Although the Mg–Dy system appears to be promising
for research on the basis that Dy is not studied in
complex alloy systems, Dy did not appear to adversely
influence corrosion, while Dy has excellent promise for
improvement of mechanical properties due to age-
hardening; however, Dy is a rather heavy and expensive
metal to be used industrially.195
Gallium as a binary addition forms rod-shaped
Mg5Ga2 along grain boundaries.196 Mg–Ga alloys were
found to have good ductility and owing to a good
response to aging, show substantial increases in tensile
strength compared to pure Mg (i.e. UTS5180?1 MPa,
TYS5107?4 MPa, e58?2% for Mg–2 wt-% Ga).196
However, the low melting point of Ga (27uC), its
relative rarity, and the embrittlement risk to Al-alloys
posed by Ga makes such additions unsuitable for
commercial structural alloy use. On the other hand,
Ga has been pursued as an alloying addition in Mg–Hg
alloys that are used as a material for sea water batteries.
Low concentrations of Ga (1 wt-%) show a reduction of
the anodic reaction rate (which is increased owing to the
Hg) improving the overall corrosion resistance of the
Mg–5Hg system (icorr, Mg–5Hg526?98 mA cm22, icorr,
Mg–5Hg–1Ga52?34 mA cm22).127
Germanium forms rod-shaped Mg2Ge precipitates in
Mg binary alloys and can effectively refine the grain size
of Mg.197 Of the few corrosion studies regarding Ge
additions, it was seen that additions of 0?5–2 wt-% Ge in
Mg increase the cathodic kinetics accompanied by an
ennoblement of Ecorr by about 100 mV. Ge was observed
to suppress the anodic reaction rates and thereby reduce
the overall corrosion rate when tested in 3?5% NaCl.198
The lowest overall corrosion rate (relative to pure Mg)
was achieved at 1?5 wt-% Ge, claimed to be an order of
magnitude lower than that of Mg. The explanation for
this reduction in corrosion rate was given as being a result
of the finer grain structure that promoted more uniform
corrosion product film formation,198 however, such a
mechanism is in need of further validation.
Gold because of its relatively high cost has not received
much attention as an alloying element for Mg. The
literature review shows that the trace amount of gold in
AZ91E alloy can improve creep response,199 with only
small increases in corrosion current density with 0?001,
0?05, 0?1 wt-% Ag added (AZ91Ey6 mA cm22, AZ91E–
0?001Auy8 mA cm22, AZ91E–0?05Auy5 mA cm22, AZ91E–
0?1Auy12 mA cm22).34
Indium additions were studied several decades ago by
Hiroki, who reported the corrosion of Mg–47 at-% In
both dry and humid environments.200 Although the
corrosion was not measured either electrochemically or
by mass loss, a negative effect of In on accelerated
corrosion of Mg was established. According to the
proposed mechanism, the Mg–In alloy surface immedi-
ately oxidises once exposed to dry air. MgO film forms on
International Materials Reviews 2015 VOL 60 NO 3 185
 Gusieva et al. Corrosion of magnesium alloys: the role of alloying
the surface and it contains isolated In. As the melting
point of In is very low (156?6uC) the In crystals continue to
grow at room temperature. These crystals were posited to
induce the stress in the corrosion product film that
subsequently results in the film breakdown. In humid
environment (30uC, 70% RH), the corrosion product was
composed of the mixture of Mg(OH)2 and isolated In
crystals. The isolated In is purported to serve as a local
cathode to Mg. The role of In is in need of further
research, particularly at lower alloy loadings and non-
binary systems.
Lutetium: The influence of Lu on Mg or Mg-alloys has
not been explored yet. The recent study by Samaniego is
the only report on the effect of Lu on Mg-alloys. In
particular the low level of Lu (0?21 wt-%) was added to
AZ31 alloy. Lutetium incorporates into Al–Mn consti-
tuent particle, however, this does not change the Volta
potential of these particles. Lu was found to reduce the
corrosion rates of AZ31 in the as-cast condition. This
was achieved by reducing the cathodic kinetics of Mg.
The overall corrosion rate was therefore decreased from
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12?3 to 7?25 mA cm22, the mass loss rate from 0?36
to 0?14 mg cm22 per day. XPS analysis showed no
appreciable amount of Lu on the alloy surface implying
that Lu does not promote a more protective corrosion
film. Although Lu seems to have a positive effect on
corrosion resistance of AZ31 alloy, it negatively resulted
in larger grain structure of this alloy leading to an
increase in grain size from 100 to 700 mm.201
Molybdenum is not a typical elemental addition into
Mg because of its insolubility. However, low-level
additions of Mo to AZ91E (0?1 wt-% Mo), studied by
Südholz, indicated that microalloying with Mo leads to
a significant increase (about a factor of 10) in the
corrosion current density values icorr.34
Nickel is regarded as an impurity in Mg alloys and has
an adverse effect on corrosion. A tolerance limit of only
0?0005 wt-% Ni is reported for Mg.15,78
Niobium is not a common alloying addition for Mg.
Nb is not soluble in Mg and its alloying would only be
possible via methods such as magnetron sputtering,
limiting its utility to that of thin films. One attempt has
been made to add Nb to Mg composites.202
Palladium has recently been explored as an alloying
addition to heavily alloyed versions of biodegradable
Mg–Ca–Zn alloys.203,204 Pd additions (y2, 6 at-%) to
Mg–Zn–Ca amorphous alloys were reported to retard
the anodic reaction rate in simulated body fluid.
However, given the insolubility of Pd and its high
exchange current density, this effect is concomitant with
enhanced cathodic activity leading to higher corrosion
current densities (icorr, Mg–23Zn–5Ca51?7 mA cm22;
icorr, Mg–23Zn–5Ca–2Pd52?1 mA cm22; icorr, Mg–23Zn–
5Ca–6Pd52?7 mA cm22203), however, it should be noted
that the baseline corrosion current density of the Mg–
23Zn–5Ca alloy is very high to begin with, at least an
order of magnitude higher than that of pure Mg in the
same solution.39
Selenium has not been widely used in Mg alloy
production, likely because of its toxicity. A study
conducted by Südholz indicates that small amount of
Se (0?1 wt-%) in AZ91 alloy can reduce the corrosion
current density values (icorr) from y8 to 2 mA cm22.34
The solubility of Se in Mg is unknown, and its use in
conventional alloy production is hazardous.
186 International Materials Reviews 2015 VOL 60 NO
Terbium has a high solubility in Mg (24 wt-%),
however, the use of Tb in Mg alloys is not widespread.
Binary Mg–Tb alloys show a good age hardening
response and the hardness values increase with an
increase of Tb concentration (up to 93 HB at 20 wt-%
Tb).205 One study by Neubert suggested that Tb has a
deleterious effect on corrosion of a Mg–4Tb-2?5Nd
alloy.206 That study reported accelerated cathodic
kinetics with addition of 4 wt-% Tb and higher overall
corrosion rate in 300 ppm NaCl solution compared to
WE43 (where icorr, Mg–4Tb–2?5Ndy7?4 mA cm22 and
icorr, WE43y2. mA cm22).
Thorium is the most effective elemental addition for
imparting high-temperature strength and creep resis-
tance up to 350uC. In addition, it improves casting and
welding properties. Unfortunately, because of the radio-
active nature of thorium, it is not commercially
viable,113 and the influence of Th on corrosion is not
widely reported.
Vanadium in the context of influencing corrosion of
Mg or Mg alloys is yet to be reported. However, V-
containing Mg-alloys have been studied, with trace
additions indicating notable grain refinement for both
Mg–Zn207 and Mg–Al alloy systems.208 In the AZ series
alloys, V forms Al3V phase that apparently results in
high grain boundary density and refines grains and the
distribution of b-phase (Mg17Al12).
Consolidation of alloying effects
Following the descriptive interpretations of the influence
of alloying elements above, an attempt has been made to
graphically present the information for quantification of
the kinetic effects upon corrosion. Based on processing
of the literature to date, and the interpretation of data
therein, it is possible to extract the electrochemical effect
of the elements in a holistic sense. Figure 8 shows a
schematic of the polarisation curve of Mg and the
relative influence of alloying elements on anodic and
cathodic kinetics.
The interpretation of Fig. 8 can be made on the basis
of the relative movement of cathodic and anodic
branches of polarisation curve. The distance associated
with the relative movement (along the length of the
schematic arrow) is a representation of how significant
the effect is. The information in Fig. 8 is a valuable map
as far as corrosion engineering is concerned, as the
authors emphasise that the issue of Mg corrosion is one
of the kinetics, and the map in Fig. 8 provides an
attempt at consolidating this notion. The figure has been
constructed by using the polarisation and interpretable
data extracted from the literature as summarised by the
reference list accompanying this review. Some of the
most significant observations included in Fig. 8 are
briefly summarised below:
N Al retards anodic dissolution rates when added below
or at the effective solubility limit. This effect becomes
overwhelmed when the Al content exceeds the
effective solubility limit (the word effective is used,
because the solubility is time–temperature and
processing dependent), forming Al-rich zones and
Al-containing intermetallics that enhance cathodic
reaction rates.
N The addition of Mn below the solubility limit to pure
Mg has a minor effect on decreasing the cathodic
reaction rates, the additions exceeding the solubility
3
 Gusieva et al. Corrosion of magnesium alloys: the role of alloying

Table 3 Galvanic series of experimental and commercial

magnesium alloys tested in 0?1M
N Fe, Ni and Cu are the most common impurities in
Mg-alloys because of their insolubility. As local
NaCl20,24,33,34,97,138,166
cathodes, they are heavily polarised at the potential
Average corrosion potential of Mg alloys and dramatically accelerate cathodic
Alloy Ecorr/VSCE (0.1M NaCl) kinetics.16,115,209 Reported threshold limits for these
elements include 170 ppm for Fe, y1000 ppm for Cu
Mg–8Y 21.460 and 5 ppm for Ni and Co.15 Co is exceptionally
Mg–8.85Bi 21.495
efficient at enhancing cathodic kinetics.
AM60 21.495
AZ31–0.48Bi 21.4978 N RE (Ce, La, Nd, Gd) and Y in binary Mg alloys lead
AZ31–0.21Lu 21.500 to increased corrosion potential concomitant with
ZE41 21.52 monotonically increasing cathodic kinetics that
AZ31–0.88Li 21.5235 translate to higher overall corrosion rates. Lu, a
AZ91E–0.1Cr 21.524 heavy RE element, has been suggested to have a
AZ91E–0.1Ag 21.525
minor influence in decreasing anodic kinetics.201
AZ31 21.526
AZ31–0.1Ca 21.5265 N Minor additions of As (the only reported addition
Mg–6La 21.529 being 0?37 wt-%97) can significantly decrease the
AZ91E 21.533 corrosion rate of Mg by suppression of cathodic
AZ31–0.1Sc 21.5345 kinetics.
AZ31–0.005As 21.5345 To also provide a summary of the reported corrosion
AZ31–0.46In 21.5384
potentials of binary, ternary, most common commercial
Mg–2.2Mn 21.540
21.540 magnesium alloys (as well as some commercial alloys
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AZ91D
AZ91E–0.1Sc 21.542 with minor elemental additions) a non-exhaustive
Mg–5Al–1Sn 21.543 galvanic series for Mg-alloys has been compiled and
Mg–4Ce 21.544 presented in Tables 3 and 4. It is seen that the upper
Pure Mg 21.645 values of corrosion potentials are in the vicinity of
Mg–1Nd–2.4La 21.549 approximately 21?4 VSCE, while activating elements can
AZ91E–0.1Ca 21.551
AZ91E–0.1Li 21.551 result in potentials below 22 VSCE. The important
Mg–7Al–0.1Ti 21.557 distinction is made here that alloys with more noble
Mg–3.5Nd 21.565 potentials are nominally more noble because of
Mg–5Al–0.1Sr 21.565 increased cathodic kinetics, and hence the more noble
Mg–1Y 21.57 potentials do not correspond to decreased rates of
Mg–7Bi 21.590 corrosion.
AZ91E–0.1Ce 21.591
ZK60 21.596
AZ91E–0.1Pb 21.602 Grain size and microstructural
Mg–0.5Nd 21.619
Mg–0.3Zr 21.623 influences on the corrosion of Mg-alloys
AE44 21.625 Grain refinement is an effective way to improve the
Mg–2Ca 21.652
Mg–7Sn 21.665
strength of Mg and Mg-alloys. Governed by the Hall–
WE54 21.685 Petch relationship, the room temperature tensile
Mg–2Sr 21.731 strength of Mg and alloys is inversely proportional to
Mg–0.37As 21.765 the square root of grain size according to212,213
Mg–8Li 21.8
sy ~s0 zky d {1=2 (3)
where d is the average grain diameter in meter, s0 is a
limit (2?22 wt-%) have the opposite effect and friction stress, approximately 12 MPa for magnesium
facilitate cathodic activity,25,59 while in multi-element and ky is the Hall–Petch parameter, 0?22 MPa m21/2.214
alloys (i.e. other than pure Mg), Mn can segregate to Mg alloys have an excellent response to grain refine-
elements such as Al forming local cathodes. ment209,215–217 because of a high Hall–Petch coefficient
N Elements including Li and Ca are more electroche- compared to other metals such as Al, ky,Al being 0?01–
mically active than Mg so that when alloyed with Mg, 0?09 MPa m21/2.218 From a corrosion perspective, if the
and either present in the solid solution or in IMPs, strength of a material can be improved with no chemical
increase the rate of anodic reaction39,139 (albeit for Li (alloying) changes, then this is one means for which
the effect is inhibited for Li.y11 wt-% when the corrosion performance is not sacrificed, while strength
alloy crystal structure changes). can be improved.219
N Elements such as Sn, Pb and Zr are seen to promote Grain size has been shown to be a factor in controlling
anodic activation, such that they enhance the rate of the overall electrochemical response of Mg and its
the anodic reaction in a disproportionate manner alloys. A number of studies have shown the effect of
(which may also not be predicted on the basis that grain size on corrosion rate of Mg and Mg-alloys.219–222
they are much noble elements than Mg). From the electrochemical point of view, the reduction in
N Zr, Ag, and Au increase cathodic kinetics. grain size gives an increase in grain boundary density
N Ti shows a positive effect on suppressing the rate of that impacts dissolution and passivation phenomena.58
cathodic reaction in Mg alloys with relatively high Al As a result, this leads to findings of decreased220,221 or
content (e.g. AZ91)34,164 when added in low concen- increased223,224 corrosion, which can, however, be
trations (i.e. %1 wt-%). In a binary sense, Ti has no understood and rationalised on the basis of the role of
functional role. environment and summarised by Ralston, who provided

International Materials Reviews 2015 VOL 60 NO 3 187

 Gusieva et al. Corrosion of magnesium alloys: the role of alloying

Table 4 Galvanic series of experimental and commercial In terms of Mg-alloys, Argade et al. reported almost
magnesium alloys tested in 3?5% NaCl electro- four times lower corrosion rates during immersion of an
lytes122,129,130,139,144,145,149,150,157,159,163,164,174,177,198,210,211
ultra fine grained Mg–Y–RE alloy compared to a coarse
Average corrosion potential grained specimen in 3?5% NaCl.222 In the case of ZK60,
Alloy Ecorr/ VSCE (3.5 wt-% NaCl) the grain size–corrosion relationship is shown in Fig. 9b
for specimens that were processed by a combination of
Mg–10Al–12Si 21.390 extrusion and ECAP. The data in Fig. 9b correspond to
AZ91–0.4Ti 21.4
AZ91–0.5Sb 21.445
different specimen orientations with respect to the
AZ91–0.27Sc 21.45 extrusion direction, revealing a relationship whereby
AZ31–5Sn 21.45 corrosion rate decreased with grain size20?5. In regards
AZ91 21.461 to the grain size-corrosion rate relationship of ZK60,
AZ91–1La 21.47 Orlov et al. reported that the grain refinement of ZK60
AP65–1Sn–0.5RE 21.47 via ECAP had the greatest impact upon anodic reaction
AZ31–9Sn 21.48
Mg–10Gd–3Y–0.5Zr 21.488
kinetics, while chemical redistribution effects had a
Mg–10Al–12Si–1Pb 21.490 greater effect on cathodic reaction kinetics.219
AZ91–0.5Si 21.490 The example in the work of Orlov indicates a very
AZ91–0.2Ti 21.5 important aspect in regards to the corresponding
AZ80 21.5 chemical alterations, which are a consequence of grain
AZ31–1Sn 21.5 refinement, and important in the case of alloys/
AZ31–0.5Sr–0.5Y 21.502
AZ31 21.51
commercial materials; thus the authors feel this point
21.53 merits some comment. In Fig. 10, the original ZK60
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AM50
AZ91–1Ce 21.54 microstructure is observed, along with the correspond-
Mg–10Gd–3Y–1Zr 21.542 ing damage morphology (via optical profilometry)
AZ31–0.5Sr–1Y 21.548 following immersion in 0?1M NaCl. The continued
AZ31–0.5Sr–2Y 21.553 refinement of the grain structure, along with the
AZ91–2Sr 21.556
Mg–2Ge 21.56
attendant chemical redistribution, shows that solute
AZ91–0.5Sr 21.572 can be redissolved into the matrix, with associated
AM50–1Gd 21.58 ramifications (in this case, beneficial) for the subsequent
AP65 21.58 damage morphology. Following the extrusionzECAP
AZ91–0.24Ho 21.58 process, the solute homogenisation leads to less localised
Mg–10Gd–3Y 21.613 corrosion, significantly lower corrosion rates, and higher
Mg–1.5Ge 21.67
AZ80–2Li 21.67 strengths.219 A similar observation was also made in Al-
Mg–1Ge 21.69 alloys,228 and therefore the deformation processing of
Mg–5Zn 21.712 Mg-alloys represents an avenue of future potential.
Mg–2Zn 21.72 Therefore, for a given alloy system, grain size effects
Mg–3Zn 21.728 are of relevance and can effectively reduce the rate of
Mg–0.5Ge 21.74
corrosion. This is one route for perhaps improving the
Pure Mg 21.76
Mg–2Y–3Nd–0.5Zr 21.78 corrosion resistance of the same alloy within a finite
Mg–5Hg–1Ga 21.992 window; however, the distinction of ‘finite’ is made,
Mg–5Hg 22.28 because in general, the influence of changing the
Mg–6Hg 22.28 chemistry of an alloy will contribute over and above
the effect of changing its grain size and solute distribu-
a constitutive relationship for the rate of corrosion as tion – which should be obvious from the preceding
a function of grain size.225 It was noted that any section. This is also evident on the basis that a wide
processing route and elemental additions might impart spread of corrosion rates was observed for say, AZ91
physical or chemical changes to the material in addition with minor alloying additions,34,39 i.e. many orders of
to intentional grain size modification. More so, the magnitude, while a range of grain sizes and solute
nature of the environment or electrolyte will further redistribution may only influence corrosion rate over a
impact corrosion response.225 There exist some reports much smaller range of values.
that grain-refinement treatment appeared to allow Following on from the grain size effect, the emergence
the Mg surface to possess a more pseudo-protective of Mg-based bulk metallic glasses (BMGs) is rapidly
(hydr)oxide layer, so that to withstand large scale evolving.229–232 Bulk metallic glasses are a unique family
breakdown more effectively than coarse grained Mg in of metal alloys that exhibit no crystalline or long-range
dilute NaCl electrolytes,220,221,226 however, this mechan- ordered structure. It is because of this inherent structure
ism is yet to be proven. that BMG possess several unique properties when
Figure 9a illustrates the relationship between corro- compared to their crystalline counterparts, such as high
sion rate and grain size in pure Mg, revealing a trend strengths, high elastic limits, and glass transition phe-
with corrosion rate and the square root of grain size. nomena.233,234 The criteria for a BMG are that it can be
This improvement in corrosion performance with finer produced to be at least 1 mm in thickness, and in the vast
grained Mg was initially reported by Op’t Hoog227 who majority of cases this can only be produced by rapid
studied Mg specimens processed via equal channel solidification.
angular pressing (ECAP), a form of severe plastic While much curiosity surrounded the corrosion
deformation. It was noted that in 0?1M NaCl, the performance of Mg-BMGs following a report of out-
anodic reaction kinetics were reduced with the decrease standing corrosion resistance,235 some peculiarities in
in grain size. that study suggest that the corrosion performance of

188 International Materials Reviews 2015 VOL 60 NO 3


Mg-BMGs may not in fact be so promising.107,236–238 A
review of the current state of understanding of the
corrosion behaviour of BMGs was given by Scully
et al.,239 who raised critical issues that serve as a
framework for interpreting the electrochemical response
of BMGs. It was also noted in that review,239 in many
cases metallic glasses in fact do not exhibit superior
corrosion resistance to that of a crystallised metal of
similar composition, and that this is highly dependent on
the context and exposure environment. In the context of
Mg-BMGs, the ‘glass forming’ elements tend to be either
significantly more reactive (i.e. Ca) or significantly more
noble (i.e. Cu), with other elements (at least one other)
required to result in glass formation.240–242 Such a
combination of elements in addition to Mg (which
nominally is present in no more that 70 at-% due to the
requirement of ‘glass forming element’ loading), is a
scenario that is likely to lead to incongruent dissolution.
This implies that the least noble elements will preferen-
tially dissolve at the alloy potential, with the outcome of
leaving behind a porous surface (akin to dealloying).
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This has been classically demonstrated for two Mg-
BMGs107 (in addition to Ca-BMGs237).
To benchmark the corrosion of Mg-BMGs, Fig. 11
reveals the corrosion rates of two Mg-BMGs (Mg65Cu25
Y10 and Mg70Zn25Ca5), measured by polarisation testing,
and as a function of approximate crystallinity. The
variation in crystallinity was achieved by heat treatment
as determined from DSC measurements and reported by
Zhou.107 What is interesting to note from Fig. 11 are
three key points: (i) the Mg-BMGs do not necessarily
show a lower corrosion rate than common crystalline
alloys, (ii) increasing crystallinity tends to increase corro-
sion rates, ascribed to increased microstructural hetero-
geneity, and (iii) the morphology of corrosion is altered
based on the evolving microstructure during devitrifica-
tion. This latter point is rather vivid and was included to
show an obvious demonstration of selective and incon-
gruent dissolution, which is a form of dissolution that is
likely (to a greater or lesser degree) in operation during
the dissolution of all Mg-alloys (be they crystalline or
amorphous).
From a mechanistic perspective, it is noted that
because of the heavy alloying additions in Mg-BMGs
and because of the notion that most other elements have
a higher exchange current density than pure Mg, then
the corrosion kinetics of such alloys are nominally under
cathodic control. This is further validated by not only
the work of Zhou, but also from a recent study by
Wang,243 who revealed that the electrochemical response
during devitrification is dominated by changes in the
cathodic reaction. This is an important point, because
many works in the corrosion of BMGs (generally) give
little, to no, emphasis on the cathodic reaction. None
the less, the interest in Mg-BMGs is likely to continue,
as the applications (touted to be consumer electro-
nics and luxury products) and research into the area
expands.244
Prospects and aspects for retarding the
corrosion kinetics of Mg-alloys
The review herein has intentionally framed the Mg-
corrosion issue as one of the kinetics. The review has
also avoided the aspect of coatings (covered in Refs.
Gusieva et al. Corrosion of magnesium alloys: the role of alloying
245,246), rather focusing on the corrosion metallurgy. It
is prudent to assume, at least in the near term that
thermodynamic approaches to retarding the corrosion
of Mg remain elusive. As a consequence, the framework
for utility of Mg must factor in the control of corrosion
kinetics. The consequence of kinetics is manifest in all
the potential utilisations of Mg alloys, as kinetics will
influence:
(1) The aggressiveness (or lack of aggressiveness) of any
galvanic couple scenarios;
(2) Localised dissolution from microstructural hetero-
geneity, which can perhaps continue to be used to
advantage in the coating pretreatment of Mg-alloys,
whereby surfaces can be homogenised on the basis
of acid–alkaline steps to selectively remove and
passivate Mg-alloy surfaces (and subsequently con-
version or electro/electroless coated);247,248 and
(3) Any attempts to slow the rate of Mg corrosion from
alloy design.
In regard to this last point, the authors believe that this
merits elaboration in the context of the extended
industrial application of Mg alloys . Kinetic restriction
of corrosion may be achieved by:
(a) Careful selection of bulk alloy chemistry and alloy
system. This requires an all-round knowledge of the
alloy application, including mechanical and environ-
mental envelope. However, one example may be that an
equivalent strength target can be met by using Mg–Zn or
Mg–Ca alloys. However, the former possesses at much
lower rates of corrosion.22 Naturally, alloy selection
steps are complex if components are to be extruded, or
high-pressure die cast; nonetheless, bulk alloy composi-
tions can be readily assessed on the basis of Fig. 8.
(b) Alloying for the purposes of altering corrosion
kinetics. For example, specifically altering alloy chem-
istry by (micro- or low level) alloying with additions
is one approach that has not been vigorously pursued
to date. In this context, the aim would be to make
an alteration to an alloy composition that has been
designed for a specific property portfolio with the goal
of reducing the kinetic rate of dissolution while not
altering this portfolio of properties.
There are some examples of this approach in the
literature, albeit not part of systematic studies. The
influence of microalloying additions to AZ91 was shown
by Südholz34 and the beneficial effects of low-level RE
additions to AZ91E alloys were shown to be beneficial in
reducing corrosion rates when added in 0?1 wt-% (Ce,
Y).132,143 Another example is the microalloying addition
of 0?1 wt-% Ag to AZ91, which was able to segregate to
the Mg17Al12 phase, reducing the size fraction and
altering the number density to lead to an increase in
hardness with no increased corrosion rate.
Furthermore, although not tested in a complex alloy
system, the additions of As have been shown to reduce
cathodic kinetics.97 Such additions, however, may not be
industrially feasible because of obvious toxicity, but
reveal the opportunity for similar cathodic poisons to be
explored.
The selection of microalloying additions, while pre-
viously may have been wholly empirical, can nowadays
be rationalised in a desktop manner by the utility of
CALPHAD (calculated phase diagrams) and packages
such as Thermocalc and Pandat (Pandat, Madison, WI,
USA Thermocalc, Stockholm, Sweden). While the
International Materials Reviews 2015 VOL 60 NO 3 189
 Gusieva et al. Corrosion of magnesium alloys: the role of alloying
CALPHAD approach delivers equilibrium phase dia-
grams (for the elements with which calculations are
possible to date), it can provide an important insight
into the solubility of elements in Mg systems of a higher
order than binary alloys, and information regarding
segregation of elements. For example, the solubility of
some elements can decrease dramatically in the presence
of a third element. A classic example is perhaps the
addition of RE elements. In Mg alone, REs have
considerable solubility (see Table 1), however, in the
presence of Al (in the Mg–Al system), AlXREy phases
form immediately. Such design aspects can be screened
using CALPHAD.
If possible to realise, alloying with soluble elements
that remain in solution is desirable in order to retain a
homogeneous microstructure. Also, grain refining is
another factor in realising higher strength and ductility in
Mg-alloys, given their high Hall–Petch coefficient.249–252
The increase strength derived from grain refinement may
be offset with a reduction in microstructural heterogeneity
if the extent of alloying can be decreased. As such, for a
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comparable strength, grain refinement in itself, and in the
alloying modification it subsequently allows, may con-
tribute to lower corrosion kinetics. In regards to grain
refiners, additions of soluble In, Bi, and Sc, as well as the
well documented addition of sparingly soluble Zr, can
reduce grain size in cast Mg alloys.98,253–257 Caution needs
to be exercised to not add too much of such elements,
which can contribute to enhanced corrosion rates when
present beyond low levels. Another factor controlling
ductility and strength of Mg alloys is texture.258,259 It is,
however, still not well understood what role the texture
plays in terms of corrosion performance of Mg alloys.
Although work exists relating texture to corrosion,260,261
the variation with minor changes in texture across a bulk
alloy is likely to not be an overwhelming factor in contrast
to chemical addition.
There are a number of papers that report alloying
elements may contribute to more robust surface oxide/
hydroxide layers.142,232,262 However, quantitative evi-
dence for the presence of dopant elements in the surface
Mg(OH)2 layers has not yet been definitively proven. For
example, it is unknown if elements detected in the surface
layers of Mg arise as a result of (hydr)oxide doping or
because of noble metal enrichment and a presence in the
metallic form (i.e. the other elements are the effect, not
the cause of enrichment, having arisen from higher
surface concentrations from incongruent dissolution
itself). The latter notion was recently supported and
shown by FIB-TEM measurements revealing that surface
Al-enrichment was in the form of metallic Al263,264 –
which arose as a result of accompanying corrosion. As
such, alloying elements at the surface of Mg most likely
arise as the result of corrosion, as opposed to restricting
corrosion. If possible, however, to dope the surface
(hydr)oxide, the doping elements would require a wider
range of stability, i.e. form a more passive film over wider
pH range than Mg.
(c) Thermomechanical processing in order to modify
local alloy chemistry via phase redistribution, and re-
solutionising has been shown to be an effective means for
optimising a property portfolio that includes reduced rates
of corrosion. In addition, thermomechanical processing
may also provide further favourable properties by texture
modification, grain size reduction, and subsequent further
190 International Materials Reviews 2015 VOL 60 NO
grain refinement because of dynamic recrystallisation.265–268
Severe plastic deformation (SPD), in particular, is gaining
popularity in the study of wrought Mg alloys.269 The effect
of SPD (Severe Plastic Deformation) on corrosion is
intrinsically connected to the produced microstructure,
which is temperature sensitive – and therefore needs to be
considered individually for a particular alloy composition.
In addition, parameters such as die geometry, angle, and the
speed of processing will dictate the level of strain a material
receives as well as the presence of the defects (voids, cracks)
and a universal recipe for successful SPD is not, and likely
will not be, established.
Summary
This review has presented the influence of alloying
elements on the corrosion kinetics of magnesium,
drawing widely from the literature to include data from
a large number of commercial and custom alloys.
A deliberately holistic approach was taken, to provide
a comprehensive understanding of the effects of alloy
chemistry, and hence electrochemistry, in dictating the
ultimate corrosion kinetics.
To this end, the electrochemical effect of alloying
elements was summarised according to the relative
influence upon anodic and cathodic kinetics, and the
extent to which such kinetics are catalysed or suppressed
by the addition of a particular element. This was
graphically depicted via an overlay upon a polarisation
schematic. Such a presentation provides a comprehen-
sive foundation for understanding Mg-corrosion
kinetics, also providing a platform for understanding
more complex alloy corrosion, and rationale for alloying
considerations.
In addition to the chemical influence of alloying
elements, attention is given to the important fact that
the presence of second (or third) phases in the micro-
structure, along with their relative volume fraction, will
also contribute to corrosion kinetics. These factors were
addressed by reporting a consolidated table with solubi-
lity of elements in Mg, as well as presenting typical
microstructures for Mg alloys and a galvanic series for a
range of both the common and atypical Mg alloys.
The notions related to alloy design, the influence of
alloy processing, and the prospects for amorphous Mg-
alloys and conventional Mg-alloys with reduced corrosion
rates were touched upon herein. Opportunities to improve
the corrosion resistance of Mg alloys may primarily lie
with elements and processing that retard cathodic kinetics
through poisoning the HER reaction, minimising IMP
formation and solid solution additions that lower anodic
kinetics. Secondary effects may be produced by grain
refinement or texture weakening. Metallic glasses have not
been promising to date owing the detrimental effects of
transition metals, but are less well explored with corrosion
resistance as a chief goal in mind.
Acknowledgement
A very special thanks and gratitude to Emeritus Prof.
Barry Muddle, and thanks to Dr Mark Gibson and Dr
Colleen Bettles for advice and support. Dr Kevin
Ralston is thanked for assistance in the initial assess-
ment of solubility information. Authors also acknowl-
edge and thank those who assisted in providing data for
review and consolidated analysis, along with discussion
3

and assistance in analysis: X. Xia, A. Thornton, D.S.
Gandel, H-Y. Yang, M.K. Cavanaugh, X.B. Chen, A.D.
Südholz, N.T. Kirkland, K.D. Ralston, X. Zhou, N.
Stanford and J-F. Nie. Proof reading and suggestions
from J.P. Labukas, V.H. Hammond and B.E. Placzankis
from the US Army Research Laboratory (Aberdeen,
MD, USA) are also gratefully acknowledged.
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