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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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Download by: [UNAM Ciudad Universitaria] Date: 18 October 2017, At: 10:59
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/


hydroxide layer in moist conditions.4 The high negative
Magnesium (Mg) has the lowest density (1?74 g cm23) of free energy of formation ensures such a layer forms
the engineering metals.1 Mg consumption is growing in rapidly, however, this surface layer does not offer
many industrial applications in the present era of light- suitable corrosion protection (as say, an oxide layer
weighting,2,3 which is important for energy and fuel does to Al or Cr) on the basis of:
savings, reduced emissions, emerging biomedical applica-
tions, and user satisfaction of portable electronics. Mg
N The oxide/hydroxide layer is soluble in most aqueous
environments, and environments of high humidity.
and its alloys are machinable, die castable, non-magnetic The primitive E–pH diagram for Mg is seen in Fig. 1
and offer vibration and shock adsorption ability. (neglecting hydride formation5). Mg readily dissolves
However, the two persistent limitations that have to form Mg2z, and the corresponding cathodic
restricted wider Mg use include limited room temperature reaction is the hydrogen evolution reaction (this
ductility and high corrosion rates in aqueous environ- terminology is interchangeable with ‘water reduc-
ments. The former issue, ductility, is undergoing sig- tion’, because when water is reduced, hydrogen
nificant research in the mechanical metallurgy domain, evolves). It is observed that Mg is prone to dissolu-
and the latter is still an area of active present research. 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
1
Department of Materials Engineering, Monash University, VIC 3800, passive film). Mg completely loses its integrity in
Australia acidic conditions or in the presence of chloride,
2
Department of Mechanical and Aerospace Engineering, Monash
University, VIC 3800, Australia bromide, and sulphate ions, thereby placing some
3
Department of Materials Science and Engineering, The University of practical limits on widespread Mg use6 to alkaline
Virginia, VA 22904, USA conditions or situations where suitable coating
*Corresponding author, email nick.birbilis@monash.edu 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 that when added to Mg a phase separation occurs to
surface and are highly defective arising from a Pilling– produce two pure metals (i.e. Mg and Fe in the case of the
Bedworth ratio ,1; meaning the ratio of the volume of Mg–Fe system).9 The solid solubility depends on factors
the surface oxide/hydroxide to the underlying (hex- such as relative atomic size, valency and electronegativity
agonal) metal is not suited for complete coverage.7 as well as similarity in crystal structure. A certain liquid
N The highly electronegative potential of Mg and solubility is required to form a homogenous solution at
its alloys renders Mg-alloys prone to galvanic and the alloying temperature.
microgalvanic corrosion (i.e. internal corrosion Table 1 summarises maximum solid solubility values
between the micro-constituents of the alloy), along in Mg based on binary systems9–13 and categorising
with the possibility of corrosion in deaerated envir- elements according to their solubility. The elements
onments; because oxygen is not required for the shown in white cells represent elements with solid
cathodic water reduction reaction that predominates solubility (i.e. to levels .0?5 wc), the elements shaded
at such negative potentials. in orange are defined as slightly soluble (0?05–0?5 wt-%)
As a result, thermodynamic stability of Mg is not and those in grey are insoluble (i.e. ,0?05 wt-%).
considered to be the key issue in determination of Mg Several elements also have an unknown solubility (green
alloy corrosion, with the kinetics of corrosion determin- shading). The table also provides the values of the
ing the ultimate corrosion rate. This review will thus atomic radius of the elements for general information. A
focus on the factors that determine, and the extent to convenient way of thinking about the insolubility of
which they dictate, the kinetics of corrosion. elements in Mg is to define the following three scenarios:
The introduction of various alloying elements into Mg 1. Complete and full insolubility: Here no solid solution
can improve some vital mechanical properties and thus is formed and no Mg-intermetallic forms with
extend the range of potential engineering applications, the particular alloying element. This situation is
however, this has an attendant influence on the corrosion typical of Fe, Mo and Nb. When such elements are
of Mg. In regards to Mg-alloys, the main factors in present, they form second pure metal phases, with
controlling corrosion rate are chemical composition and no mutual solubility. This situation causes dramatic
microstructure, hence appropriate attention is given to corrosion.14–17
the development of Mg microstructures in this review. 2. No solubility, but the formation of a Mg-intermetallic:
The solid solubility of elemental additions in Mg will This is typically what is seen with Si (and Cu, Co,
dictate the presence of any second phases or impurity Ni). In such cases an Mg2X (where X5Si, Cu, Co,
particles. More so than in other commercial metal Ni) intermetallic will form. These compounds have
systems, the solid solubility of an alloying element is a no room temperature solubility and thus the
key factor in determining its effect on the properties of retention of a homogenous (single phase) micro-
Mg; as the majority of elements have either no solubility, structure is not possible. Elements that form the
or very limited solubility in Mg. This is an interesting Mg2X intermetallic are often very problematic from
scenario, as there are concomitantly a large number of a corrosion perspective, as they enhance the
elements that will not form intermetallics with Mg, such cathodic reaction because of the large exchange

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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-
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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
2 Typical Mg-alloy microstructures, all compositions given fraction, so that the larger the volume fraction of
in wt-% a Mg–0?4Zn–0?05Sr in the rolled condition. This IMPs in the alloy, the greater the impact on increasing
alloy has alloying additions below the respective solubi- the corrosion rate of the alloy.23,24 The presence of
lity limits and is a solid solution alloy with uniform matrix
impurities (which is the generic name given to insoluble
composition. The image is an optical micrograph follow-
elements) such as Fe, Ni, and Cu alters corrosion rates
ing etching in glycol solution.27; b AZ31 (Al–3Al–1Zn–
dramatically, even in the ppm range.25,26 For example,
0?4Mn) as sectioned from an extruded ingot.
islands of pure Fe or pure Cu in the matrix of Mg create
Backscattered electron imaging indicates that this is
a mixed potential that assures the Mg is polarised
close to a solid solution alloy, however, as the Al content
anodically (dissolves) and the pure insoluble elements
is approaching the solubility limit and solute enrichment
can sustain the cathodic reaction at very high rates, as
is observed, together with fine second phase particles.
they are significantly polarised from their nominal
This alloy also includes constituent AlxMn particles, typi-
corrosion potential values (often by .1 V).
cal of scenarios with Mn additions; c Mg–6La as high-
Arguably, the biggest single contribution to date with
pressure die cast. Backscattered electron imaging
respect to moderating the corrosion rate of commercial
reveals that the addition of La well above the solubility
Mg is the ‘scavenging’ ability of Mn in conjunction with
limit results in a large volume fraction of Mg12La phase.28
Al.25,29 By virtue of Mn additions to the Mg–Al systems,
current density of metals such as Cu and Ni.18 Fe is sequestered in an AlMnFe intermetallic, and hence
Special attention is nominally given to exclude Si the extent of microgalvanic coupling is dramatically
from commercially produced pure Mg. reduced.14 The moderation of corrosion/scavenging

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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 Kirkland, who revealed that Mg–10Zn ( wt-%) and Mg–
an area of current research20 which will be significant in 5Ca ( wt-%) show the same corrosion rates from mass
the development of creep resistant (i.e. Al-free) Mg-alloys. loss tests, however, the origin of corrosion rates could
only be ascertained from polarisation testing, which
Corrosion kinetics of Mg-alloys revealed that Zn enhanced cathodic kinetics (with little
influence on anodic kinetics), while Ca enhanced anodic
Corrosion of Mg-alloys is a kinetic issue, which will kinetics (with little influence on cathodic kinetics).37
depend on the alloy composition, together with the In Fig. 3, the representative polarisation curve for pure
component design (i.e. if welded or joined) and environ- Mg is seen as a thick dark line. It is immediately obvious
mental factors (such as pH, [Cl2] and temperature).30,31 that there is a range of movements in the relative anodic
The half-cell reactions for Mg corrosion are given in and cathodic curves depending on the respective alloying
equations (1) and (2). Reaction (1) is Mg dissolution that additions. One striking feature, however, is that most of
produces electrons consumed at the cathode (2) resulting the commercial alloys have significantly more rapid
in generation of hydrogen gas. As will be described in cathodic kinetics than pure Mg, with the exception of
the subsequent section, this process can be sustained WE54 and AE44, which both contain appreciable rare
during anodic polarisation of Mg32 earth (RE) additions, yielding similar cathodic kinetics to
pure Mg. Other features to note include that AM60,
Mg?Mg2z z2e{ (1)
AZ31, AZ91 and ZE41 showed lower anodic kinetics
than pure Mg, while AE44 and WE54 showed enhanced
2H2 Oz2e{ ?H2 z2OH{ (2) anodic kinetics relative to pure Mg.
The relative rates of the above reactions, and their These simple descriptions are being made to orient the
variation as a function of alloy potential, can differ reader with the form and signatures in such data, while
significantly, as is shown in Fig. 3, which reveals the the effects are treated in a holistic treatise further below.
typical potentiodynamic polarisation response of the The data in Fig. 3 provide the classic manifestations
most common commercial alloys and pure Mg. The for Mg-corrosion kinetics, which includes
corresponding composition of the alloys shown in Fig. 3 2 Elements that shift the anodic branch to lower rates
is given in Table 2. nominally do so by solid solution doping, which is
Generally, the potentiodynamic polarisation response efficiently achieved by Al and Zn. However, this is
provides information about the relative rates of the countered by a corresponding increase in the cathodic
anodic and cathodic kinetics for different alloys. The kinetics. Both of these kinetic changes lead to
method can also provide an instantaneous corrosion rate ennobled Ecorr values.
(termed the corrosion current density icorr) as approxi- 2 Significant alloying additions (which in comparison to
mated by a Tafel-type fit, usually from the cathodic other metallurgical systems can in fact be modest) will
polarisation data. This has been verified as a reasonable lead to second phase development and hence, nominally
approximation to the corrosion rate as it relates to the more rapid cathodic kinetics (and hence corrosion rates).
rate obtained from other methods.36 However, of key 2 It can be seen that Al-containing Mg-alloys tend
relevance here is that the polarisation technique, in spite to show the lowest anodic kinetics and the fastest
of not being a long term predictor of corrosion rates cathodic kinetics.
owing to its instant nature, is an important tool in 2 Significant alloying with RE elements can reduce the
rationalising alloy behaviour as it is the most effective at Ecorr and enhance anodic kinetics on the basis that
providing information on the effect of a particular REs are themselves ‘active’ elements.
element on anodic or/and cathodic reaction rates. 2 Common alloying additions do not result in lower
An archetypal demonstration of this was provided by cathodic kinetics being imparted to Mg. Even REs

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Gusieva et al. Corrosion of magnesium alloys: the role of alloying
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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 anodic kinetics, when this phenomenon may not be
conditions.38 expected on the basis that the alloying element is (in its
2 Alloying additions nominally only alter Ecorr within a pure form) less active than Mg. This phenomenon is
window of y100 mV. This, however, does not mean common to Al alloys with heavy metals such as Pb and
that corrosion rates cannot be spread over several Sn, which are nominally low melting point elements that
orders of magnitude (as reported in the literature39) segregate to the surface disrupting the surface film and
since large changes in kinetics can be achieved on the allowing dissolution en masse. The phenomenon is also
basis that Mg is ‘weakly polarisable’. This means that observed in Mg (Fig. 4) and occurs with Sn (also with
only small changes in potential can result in large Pb, Sb, and Zr as discussed below). However, this
deviations of current (owing to a very low anodic Tafel phenomenon has not been studied in detail, perhaps
slope in Mg systems, as opposed to say, passivating because of the fact that it has no commercial relevance
systems). to date. Ironically, however, the low melting point
In relation to the aforementioned alloys (Fig. 3), there is elements that lead to anodic activation in Mg are also
ample information in the literature concerning the part of the family of (few) elements that have lower
microstructures developed,40–47 and hence our main cathodic kinetics than Mg (Pb, Sn, and Sb have a low
focus herein is to present their corrosion kinetics exchange current density, which is a physical property of
in respect to the main microstructural constituents. each element18). Unfortunately, the phenomenon of
Mechanical properties will not be covered herein, slowing cathodic reaction kinetics (evident in Fig. 5
however, the authors note that the group of high(er) for the Mg–Sn alloy) is overwhelmed by the anodic
strength Mg-alloys (AE44, WE54, and ZK60) possess activation for reported alloys to date.
the presence of precipitates including Al11RE3, Al10 In the other examples provided that include ternary
RE2Mn7, Al2RE,47 MgxREy,44 and MgZn2,48 with im- additions to Mg–Al alloys, the overriding manifestation
proved mechanical properties at the expense of reduced is the enhanced cathodic kinetics imparted by Al, while
corrosion performance.49 Taking the finite commercial any beneficial effects in reduced anodic kinetics are not
alloys as examples, the microstructural, and hence elec- significant for the cases presented.
trochemical, heterogeneity requires the quantification of In order to provide a synopsis of the electrochemical
microstructure as a requisite effort in the rationalisation kinetics of constituents and precipitates which can
of corrosion performance. populate Mg-alloys, a selection of potentiodynamic
Before discussing the unique effect of specific ele- curves collected by Südholz16 is presented for a finite
ments, a set of polarisation curves depicting the number of Mg-based intermetallics (Fig. 5). Such data
corrosion kinetics of selected experimental alloys is are not inclusive of the entire spectrum of possible Mg-
shown in Fig. 4. The selection of the data in Fig. 4 was based intermetallics, as the collection of such data
deliberate, to indicate instances where anodic reaction necessitates the production of sufficiently large inter-
rates can be rather markedly increased. This phenom- metallics for interrogation via micro-electrochemical
enon occurs for two reasons. The first (Mg–Ca) is when testing.23,51,52 What is observed from Fig. 5 is that the
the alloying element is more reactive (in terms of IMPs are nominally noble with respect to Mg, with the
dissolution kinetics) than Mg, which is the case when exception of Mg2Ca. This, therefore, indicates that such
Ca is alloyed with Mg.22 The second is when an alloying intermetallics, if in an Mg matrix, will be polarised
element triggers ‘anodic activation’. This is the case for cathodically, and will remain cathodically protected at
Mg–Sn. The anodic ‘activation’ is a terminology used the expense of matrix dissolution. Of most interest and
for elements that are able to disproportionally enhance importance, however, is that the rates of reaction on the

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

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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 of contextual relevance to mention that Mg displays a
(i) the relative corrosion rates seen in Mg alloys in units phenomenon known as the ‘negative difference effect’
to which they can compare their own data, be it (NDE). The so-called NDE describes the phenomenon by
corrosion current or mass loss rate, (ii) to indicate that which the amount of hydrogen evolved from an Mg
there is a correlation between tests, in that generally, electrode increases as the electrode potential is polarised
alloys with a high corrosion current density will also anodically to more noble potentials. This is counter-
have a high rate of mass loss, and (iii) to indicate the intuitive to conventional electrochemical wisdom on the
spread of corrosion rates which may arise as a function basis that increasingly anodic polarisation should result in
of alloying. lower rates of the cathodic reaction (which is responsible
This latter point merits some comment, as the authors for the evolution of hydrogen as per equation (2)).
can observe differences in over an order of magnitude in Somewhat controversially, in one study, the origin of
both the corrosion current density and mass loss rate. this phenomenon was proposed by Petty63 to be a result
This spread is rather remarkable, and is perhaps even of the formation of unipositive Mg (Mgz), which was
unique to Mg, in that alloying can have such a marked later popularised by Atrens and co-workers,65,66,69,70
influence on corrosion kinetics for the same environ- who purported that superfluous hydrogen arises from a
ment. A large spread of corrosion rates was also shown chemical reaction of Mgz with water at some unknown
in selected alloys tested in physiological media,39 distance from the metal surface. The claims by Atrens
however, the authors note that the present data and co-workers have led to somewhat of a nuanced
(Fig. 6) only report results for 0?1M NaCl at room tem- understanding of Mg dissolution processes, largely as
perature. To orient readers, the authors note that low the proposed Mgz theory has no reasonable proof of its
corrosion rates (typical of passivating systems, including existence66,70–74 and most recently the Petty experiments
Al-alloys) are nominally y1 mA cm22; noting that the were refuted.75 While the imagined existence of Mgz has
reported rates for the Mg alloys presented are much captured attention and consumed scientific effort, it has
higher than this. Regarding the practical measurement no influence on the content of this review.
and the measurement execution for quantifying of Mg At the time of writing this review, a large number of
corrosion electrochemically, gravimetrically or volume- publications have emerged that provide significant detail
trically (i.e. via hydrogen collection), a study by King regarding the mechanisms of Mg dissolution as well as
et al. abridges and highlights recent developments.54 Ela- physical descriptions of the NDE. Of those studies, the use
boration of the effects seen in Fig. 6 are rationalised from of inductively coupled plasma atomic emission spectro-
the descriptions of unique additions in ‘‘Influence of alloy electrochemistry (AESEC) definitively demonstrated that
composition on corrosion of Mg-alloys’’ section. Mg dissolution occurs with an n52 stoichiometry (i.e.
Mg2z) in both sulphate and chloride solutions.53 This
Update on the mechanistic aspects of observation was recently validated in an independent
study using on-line mass spectroscopy.76 The results
Mg corrosion of AESEC testing are seen in Fig. 7, which show excel-
The mechanism of Mg corrosion is a topic that has been lent agreement between applied current and the Mg2z
studied throughout the past century.53,61–68 While the dissolution current. This echoes the classic notions put
corrosion of Mg is a process occurring at open circuit, it is forth by James and Straumanis,64 albeit with modern

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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, properties for Mg-alloys to date. Although Al is soluble to
the notion of superfluous hydrogen evolution during y12 wt-% in Mg, this is dependent on temperature, and
anodic polarisation (i.e. a parasitic cathodic reaction) the room temperature solubility is much lower, with alloys
was proposed by Frankel67 to be the result of the catho- richer in Al than AZ31 showing the presence of b-phase
dic reaction being catalysed by Mg dissolution, which (Mg17Al12). The extent of b-phase will depend on the
is consistent with the classic works noting enhanced time–temperature history of the alloy, with the relative
‘reducing ability’17 and has also recently shown by proportion of b-phase for the same given composition also
scanning vibrating electrode (SVET) measurements.32 varying rather widely depending on alloy cooling rate
The atomistic origins of this enhanced catalytic activity or subsequent heat treatment (i.e. whether sand-cast, die
are the goal of active studies.77 It is, however, empha- cast, or high-pressure die cast).82–92 Above y3 wt-%, Al
sised, that the alloying effects described herein are not additions tend to enhance the cathodic reaction, which
dependent on the elucidation of the origins of enhanced although further93 ennobles Ecorr, is associated with an
catalytic activity in a first order sense, and hence this increase in corrosion rate. In open circuit conditions,
section will not be elaborated further in the present review. b-phase serves as a local cathode. As such, cathodic
kinetics of the following alloys increase in the order of
Influence of alloy composition on AZ31,AZ61,AZ91#AM60. Al has been reported to
increase the susceptibility to stress corrosion cracking in
corrosion of Mg-alloys cases where b-phase exists in appreciable fractions.78 It is
An attempt has been made to present an abridged also noted that the AZ alloy system undergoes solid-state
summary of the influence of specific elements upon the phase changes at moderate temperatures, and hence its
corrosion kinetics of Mg. In many cases, the effect of an utility in more demanding modern applications is leading
element is over and above that of an existing system (i.e. to the proliferation of Al-free Mg alloys.
the effect of Mn, on say, the Mg–Al system). However,
such scenarios are described in words and the relevant Silver (Ag)
references provided in order to yield a unique con- The effect of Ag additions on the corrosion of Mg was
solidation of information not available elsewhere. studied by Hanawalt more than 70 years ago, who
suggested a tolerance limit for Ag in Mg to be
Aluminium (Al) y0?5 wt-%.15 Above this concentration the mass loss
Al is the most common addition to Mg, by virtue that it is rate increased monotonically from y1 mg cm22 day21
(relatively) cheap, light, soluble, and considerably im- for 1 wt-% Ag, to y12 mg cm22 day21 for 5 wt-% Ag.
proves strength of Mg (i.e. from y70 to y250 MPa).78 In contrast, the effect of Ag on accelerating the corrosion
Additions of Al below the solubility limit tend to reduce of Mg is therefore as dramatic as that as Ca on Mg.15 In
the anodic kinetics of Mg. The addition of Al to Mg more complex alloys, however, lower level quaternary
ennobles the corrosion potential, with Mg–Al alloys additions of Ag (to ,y2 wt-%) in the Mg–RE–Zr family
tending to be ennobled by y100 mVSCE compared to of alloys are reported, because Ag improves the age
pure Mg, in Cl2 environments.65,66,79–81 The Mg–Al alloys hardening response and thus provides substantial incre-
nominally have the lowest corrosion rates of the com- ment in strength.13 However, it is prudent to note at this
mercial Mg-alloys,13 particularly AZ31 (Fig. 6), which point that although Ag has been added to the high
gives an optimum balance between physical and corrosion strength Mg alloy family (which can be considered ultra

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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.

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

3VOL
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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 led to increased corrosion rate because of co-formation
avenue that can be exploited. For example, trace Mg4Ag precipitates that can stimulate microgralva-
additions of Ag (y0?1 wt-%) to AZ91 were recently nic corrosion.34,94 In addition, micro-additions of Ag
shown to stimulate an interaction between Ag and the (,0?5 wt-%) to Mg–Zn–Ca systems facilitate grain refine-
Mg17Al12 phase, providing an increment in hardness 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 shown to bring about the acceleration of both the anodic
basis of the potential to kinetically limit the cathodic and cathodic reactions rates.99 In spite of the negative
reaction, with As known to be a cathodic ‘poison’ influence on corrosion, Bi-containing particles seem to
preventing hydrogen recombination96 and restricting have a positive effect on enhancing tensile and creep
the completion of the reaction in equation (2). The properties via restricting grain boundary sliding.100
metallurgical influence of As has been recently reported
by Birbilis et al.,97 whereby relatively small additions of Calcium (Ca)
sparingly soluble As (y0?37 wt-%) result in formation In the binary context, Ca additions in low levels (less
of Mg3As2 phase. In spite of this second phase presence, than 0?35 wt-%) are essentially inert.101 In general,
a decrease in Mg corrosion rate (five times lower than however, Ca additions dramatically increase corrosion
that of pure Mg) was determined by simultaneous rates in Mg when added near to, or above the solubility
hydrogen collection and 7 day mass loss tests, as well as limit (of y1?35 wt-%). Ca-containing Mg alloys result
lower cathodic kinetics determined by potentiodynamic in exceptionally high corrosion rates. According to
polarisation. The reduction in corrosion rates was Hanawalt, the mass loss rate of Mg–Ca binary alloys
associated with the ability of As to slow down the increases from y1 mg cm22 day21 for 0?5 wt-% Ca to
cathodic reaction rate of pure Mg. about 6 mg cm22 day21 for 5 wt-% Ca. This is almost
six times higher than the corrosion rate of Mg–5 wt-%
Bismuth (Bi) Al.15 In addition to possessing the highest corrosion
The addition of Bi to Mg–Al alloys has the effect of rates of any candidates for structural alloys ever
refining Mg17Al12 and is accompanied by co-formation reported, Ca-containing Mg alloys dissolve to yield a
of needle-shaped Mg3Bi2 particles, even for Bi concen- voluminous corrosion product that is insoluble.39 Owing
trations below the solubility limit.98 When added to to the biocompatibility of Ca, however (along with Zn),
AZ91, Südholz reported that the presence of Mg3Bi2 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 giving rise to what was described as a pseudo-passiva-
functional Ca additions are being explored in Al-free tion effect by incorporation of Er into the Mg(OH)2.
Mg-alloys,102 in attempt to exploit the fact that Ca is However, there is still a lack of evidence to support this
one of the few soluble elements in Mg. Provided that Ca assumption. Furthermore, the testing of Mg in a buffer
concentrations are kept below the solubility limit to is likely to impose an unrealistic scenario of surface film
avoid Mg2Ca formation, the corrosion rate will not evolution, which is nominally influenced by natural
sharply accelerate, while solid solutions of Mg–Ca can surface alkalinisation.
display appreciable ductility.103–105
Iron (Fe)
Copper (Cu) Fe is the most common impurity in Mg-alloys. Fe
The addition of Cu to Mg and Mg-alloys is generally contamination can be present because of the quality the
avoided because of the insolubility of Cu, and the starting ‘pure’ Mg as well as because ofpickup from the
resultant formation of Cu islands in the microstructure. casting process. Owing to its low solubility in Mg
Cu is highly detrimental for corrosion,78 rationalised on (y0?001 wt-%) Fe largely remains in its pure (body
the basis that Cu has a high exchange current density, centred cubic) form. To date, the literature reports a
and hence an efficient cathode. The tolerance limit of number of tolerance limits for Fe, which is nominally
0?1 wt-% was established by Hanawalt, however, the restricted to as low a level as economically feasible.13,113
limit is sharply reduced to 0?01 wt-% when Al and Mn The notion of an Fe tolerance limit dates back several
are present in the alloy composition.15 When added to decades, where the proposed limit of 150 ppm by weight
AZ series alloys it forms an Mg–Al–Cu–Zn phase, which was commonly accepted.114,115 Recent works have
is also a relatively strong local cathode resulting in local focused more specifically on the role of Fe, as its ability
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corrosion.106 In general, Cu is avoided in the production to be scavenged by sequestration to AlMnFe particle


of Mg-alloys, with measures in place to avoid Cu formation is not possible in emerging Al-free Mg
contamination and pick-up. Unfortunately, from a alloys.17 The role of thermal history on the Fe tolerance
corrosion perspective, Cu is, however, a popular element limit has also been recently discussed on the basis of
in the formation of Mg metallic glasses,107 where the calculated phase diagrams.116,117 The experimental
influence of Cu on the resultant corrosion mechanism validation and robustness of the related thermodynamic
has been described as incongruent dissolution and databases for Mg–Fe remain open questions without
discussed further below. further empirical work, particularly because it was seen
that calculated phase predictions can vary from the
Cerium (Ce) structures characterised by electron microscopy.17
When added as a binary addition (i.e. Mg–Ce) the
formation of Mg12Ce occurs in increasing volume fraction Gadolinium (Gd)
with Ce additions, which can monotonically accelerate Of the elements that Mg may be alloyed with, Gd is
corrosion by enhancing cathodic kinetics.24 In spite of the unique on the basis that it has high solubility (.10 wt-
chemical reactivity of Ce, Mg12Ce is more noble than Mg, %) in Mg, forming binary Mg–Gd solid solutions over a
and Mg12Ce sustains the cathodic reaction at higher rates wide range of compositions. Such solid solutions can be
than Mg over the range of potentials typical of Mg-alloys. used as a basis for further loading of the matrix with
On the other hand, Ce additions to Al-containing Mg- solute elements – in the case of wrought Mg alloys, or
alloys can refine microstructure by formation of Al4Ce for carefully controlled precipitation processes in the
or Al11Ce3 intermetallics.108,109 These compounds are, family of Gd-containing precipitation-hardened Mg-
however, more deleterious for corrosion than Mg12Ce. alloys.118–121 In regards to this latter class of alloys,
Rare earth elements are typically not combined with Al- corrosion characterisation remains scarce. The addition
containing Mg alloys, with the exception of the commer- of Gd in Mg–Al alloys results in the precipitation of
cial alloy AE44. In the more modern wrought series of Mg Al2Gd and Al–Mn–Gd phases that consumes Al and
alloys, RE and Al are not combined, because of the ease reduces the volume fraction of Mg17Al12 phase.122 These
of formation of AlxREy compounds that reduce alloy phases may contribute to a minor decrease in the total
ductility. Some reports suggest that Ce contributes to the rate of cathodic reaction.123 This tendency is commonly
surface film and stabilises Mg hydroxide.110 Südholz, observed for Mg–Al alloys modified with REs.
however, revealed via XPS analysis that RE elements were However, the effect of Gd is more complex because
not seen to dope the surface oxide of Mg–Al alloys.28 The it leads to more heterogeneous microstructures and
notion of oxide modification of Mg-alloys is an area diminished Al content in the Mg matrix. Therefore long
of mixed reports, and one that is an open question. term corrosion tests show a greater corrosion for Mg-
Irrespectively, elements with thermodynamic ability to alloys containing Gd.124 Other studies have also
replace Mg-oxides/hydroxide generally do not offer a indicated that the influence of Gd on corrosion is
wider window of passivity than Mg.111 generally defined as detrimental.125
Erbium (Er) Mercury (Hg)
In favour of more cost effective RE elements, Er has Alloying with Hg is nominally only reserved for the
not been well studied in Mg. In one study, however, production of high voltage anode materials for sea water
Er, when added in 2–3 wt-%, was found to decrease batteries.126 The Mg3Hg phase can form in binary Mg–
corrosion rates in Mg–2 to 3Al (wt-%) alloys compared Hg alloy at concentrations of Hg at around 4–6
to commercial AM60 [nominal Mg–6Al–0?13Mn (wt- wt-%.126,127 Thermomechanical processing of Mg–Hg
%)] when tested in borate buffer solution.112 The alloys can promote the redissolution of Mg3Hg into the
assumption was made that Er facilitates an apparently Mg matrix, which subsequently retards microgalvanic
enhanced protective effectiveness to the surface oxide corrosion and thus lowers corrosion rates.128 Feng

180 International Materials Reviews 2015 VOL 60 NO 3


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

compared the electrochemical response of Mg–5Hg (wt- Lithium (Li)


%) and Mg–6Hg (wt-%) in 3?5% NaCl solution, and Mg–Li alloys because of their ultra-lightweight and
concluded that Hg accelerates anodic reaction rates and superplastic behaviour remain promising materials for
leads to very negative corrosion potentials (Ecorr, Mg– many critical engineering applications,134 in spite of
5Hgy22?3 VSCE), in fact representing the most nega- limited use to date. The microstructure of binary Mg–Li
tive corrosion potential reported of any Mg alloys. This alloys depending on the Li content may consist of either
was concomitant with high corrosion rates with icorr of a single hexagonal a (HCP) phase, at 0–5?7 wt-% Li;
Mg–5Hg being y27 mA cm22, compared to two phase – a and body-centred b (HCP and BCC)
y20 mA cm for pure Mg.127 The role of Hg in struc-
22
at 5?7–10?3 wt-% Li; or a single b (BCC) phase at
tural Mg alloys has not been explored. Li concentrations greater than 10?3 wt-%.135,136 There-
fore, high additions of Li (.10?3 wt-%) can produce a
Holmium (Ho) uniform b phase that is cubic. Li is the only researched
The limited research to date regarding Ho has suggested element able to impart a change in the crystal structure,
that a Ho addition of 0?24 and 0?44 wt-% can decrease which has major implications for ductility. Early work
the rate of corrosion in an Mg–Al alloy (AZ91D) by by Frost in 1955 and a later published report from
decreasing the volume fraction of Mg17Al12 owing to the Battelle in 1964 indicate superior corrosion resistance of
formation of Ho-containing intermetallic phases with binary Mg–11Li alloy compared to the alloys with lower
Al. In one study, inspection of the reported data indicate Li content, for example, the mass loss rate of the alloys
a minor decrease in the cathodic reaction rate, along measured in 3% NaCl solution (at 35uC) over 8 days was
with as much as 10 times lower mass loss rates compared Mg–2Li (4?92).Mg–4Li (4?44).Mg–9?3Li (0?77).Mg–
to that of the base Mg–Al alloy.129 This, however, is 11Li (0?57), mg cm22 day21.135,137 The greater corro-
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likely to lead to decrease in alloy strength and may be sion resistance of Mg–11Li alloy was attributed to the
manifest as the same outcome as lowering of the alloy Al BCC structure. More recent studies have also validated
content. It has been posited that Ho presumably aspects of the early research by reporting that Li addi-
contributes to more uniform and compact layer of tions below the bcc transition increase the corrosion rate
corrosion product because of the higher content of Al of Mg (from 19 mA cm22 for pure Mg to 45 mA cm22
present in the surface film; however, more evidence is for Mg–8Li138). Li was also seen to increase the corro-
needed to support such assertions. sion rate of an Mg-alloy, from 12 mg cm22 h21 for
AZ80 to about 200 mg cm22 h21 for AZ80–1?95Li.139
Lanthanum (La) In addition, over long exposure periods the corrosion
As a binary addition, La forms the Mg12La phase24 rates of Mg–Li alloys are more likely to remain con-
when added above its solubility limit. This phase is stant or decrease much more slowly in contrast to AZ31
a more efficient cathode than pure Mg leading to for instance, for which corrosion rate decreases with
an overall increase in corrosion rates (from 10 to time.135,138 Although some information on the effect of
30 mA cm22 at concentrations varying from y0?5 Li on bulk Mg corrosion exists, there is still a gap in
to y3 wt-% La).28 However, as an elemental addition regards to electrochemical effect of Li on corrosion
to Mg–Al alloys, La modifies the alloy microstructure kinetics of Mg and its alloys.
(in a manner analogous to Ce), forming needle-like Al–
La compounds and alters Mg17Al12 from discontinuous Manganese (Mn)
to continuous with a fine polygonal-shape.130,131 Liu The influence of Mn additions on Mg has been studied
et al. reported a drop in corrosion rate (icorr) of AZ91 in detail as far back as almost a century.15,25 Its role is
from y603 to y3 mA cm22 in 3?5% NaCl solution therefore well characterised and generally well under-
when 0?5 wt-% of La was added. This phenomenon was stood. As a binary addition to Mg, Mn has been
attributed to a refined microstructure and allegedly more reported to show no significant effect on corrosion rate
protective corrosion product film. It should be noted, at concentrations up to y5 wt-%.15 Mn is essentially
however, that the reported icorr of the base AZ91 was always added to the Mg–Al and Mg–Al–Zn systems
much higher than any other reports for AZ91; while the (i.e. the commodity Mg-alloys). Compounds such as
evidence for any La in the surface film was also not Al8Mn5, Al6Mn or Al4Mn are formed, and the addition
provided. In a separate study, Südholz also tested the of Mn helps to reduce corrosion rate via the incorpora-
effect of 0?3 wt-% of La on corrosion rate of AZ91E. In tion of lowly soluble metals in Al–Mn intermetallic
that study, however, the reduction in the icorr value phases. The classic example of this behaviour is the
was only by 0?3 mA cm22 (from 7 mA cm22 of AZ91E incorporation of Fe into Al–Mn–Fe.140
to 6?7 mA cm22 of AZ91E–0?3La).28 It is generally It has been reported that the amount of Mn to
observed that any excess addition of La, above the effectively mitigate the effect of Fe must be in the range
solubility limit, reduces corrosion resistance because that satisfies the maximum Fe/Mn ratio of 0?032,
coarse Al–La precipitation in Mg–Al alloys.130,132 In the whereas greater ratios will sharply increase corrosion
context of Mg–RE earth alloys, containing only Mg and rates.6 Although Mn is known to improve corrosion
REs, the presence of La in concert with Ce and Nd will resistance, a low ratio between Al/Mn leads to higher
lead to a different morphology and microchemistry of cathodic potency. Therefore corrosion rate gradually
the second phase; transitioning from a lamellar eutectic increases with an increase in Mn content,25,141 indepen-
to a divorced eutectic.133 The relative proportions of La, dent of the Fe sequestration aspect of Mn. More
Ce and Nd are important in the ultimate corrosion rate, recently, the work of Gandel et al. reports the corrosion
as depicted in a combined electrochemical and micro- behaviour of Mg–Mn binary alloys where the corrosion
structural study.133 It was determined that Nd is less rate icorr reduces from 40 to about 22 mA cm22 in 0?1M
detrimental than La (or Ce) on the corrosion of Mg. NaCl with Mn content ranging from 0?2 to 2 wt-%,

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

respectively.20 The role of Mn additions in Al-free Mg–Al–Mn system results in higher corrosion rates
(wrought Mg alloy) systems is likely to be a productive (exceeding 0?2 mg cm22 day21 at y0?1 wt-% Pb and
avenue of future work. Of such works, Mn has been 0?001 wt-% Fe) because of complex interactions between
recently observed to ‘encapsulate’ Fe in Al-free magne- Pb and inherent Fe impurity.15 Pb additions are not
sium alloys,20 which is a very positive result on the basis common in structural Mg alloys, and its role in Mg-
that Mn may remain an effective sequestration tool for alloy corrosion is not well established, in spite of its use
Fe even in the absence of Al. in sacrificial Mg anodes.
Neodymium (Nd) Praseodymium (Pr)
In binary Mg–Nd alloys, the Mg3Nd phase is formed.24 In Mg–Al alloys, the addition of Pr leads to the formation
Mg3Nd is a more efficient cathode than pure Mg and of Al2Pr in preference to Mg17Al12. Increasing Pr loading
therefore serves as a local cathode leading to continually results in grain size reduction concomitant with an
increased cathodic kinetics (and hence corrosion rates) increase in the volume fraction of secondary phases.146
with an increase in Nd content.28 It is noted that the Salt spray testing has indicated that corrosion was
increase in corrosion arising from Nd is less than that reduced with increased Pr concentration from 1 wt-% to
arising from Ce or La. This is an important point, as the maximum of 4 wt-% in a base Mg–4Al–0?4Mn alloy.
Mg3Nd phase also possesses a much higher atomic per However, there are few corroborating reports of the role
cent of RE than either Mg12Ce or Mg12La, which are the of Pr in Mg alloy corrosion, and of the limited works,
phases that form in the case of the latter. From a there are some unfounded claims that relate to ‘compact-
corrosion standpoint, if RE elements are preferable in ness’ of the corrosion product layer increasing with Pr
isolation, Nd is thus the most suitable; unfortunately, content and an improvement in corrosion resistance
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however, Nd is also the most expensive of the common attributed to the potential of Al–Pr phases to passivate
REs and its concentration is therefore often limited. In over the wide range of pH.148 Such aspects would need
AZ and AM alloys, Nd forms an Al–Nd phase as well as further validation by independent methods.
replacing the Al–Mn phase with an Al–Mn–Nd inter-
metallic compound.142 Nd was noted to improve Antimony (Sb)
corrosion resistance of Mg–Al alloys by minimising Owing to the insolubility of antimony (Sb) in Mg,
the effect of galvanic coupling that exists in Nd-free AZ second phase formation is expected, and the second
or AM alloys.143 In addition, Nd was reported to be phase will appear in a large volume fraction. It was seen
beneficial in contributing into formation of protective that the rod-shaped Mg3Sb2 compound forms along
surface oxide film consisting of Mg and RE,132 however, grain boundaries when Sb was added to AZ91.34 As an
this is one of many such claims that requires further example, alloying of AZ91 with 0?5 wt-% Sb leads to a
investigation. The replacement of, or contribution to, significantly faster cathodic reaction rate and results in
more robust surface films is a common claim in many increased overall corrosion rate by y50%.34,149 The
Mg-corrosion studies, however, the finding is often limited work to date clearly indicates that Sb has also
speculative and ultimately not proven. As with Ce and been noted to have negative effect on the corrosion
La, the influence of Nd on Mg–RE alloys was captured resistance of the AZ91D,99 where 0?4 wt-% Sb was
in a recent combined study.133 reported to increase the alloy corrosion rate from 8?6 to
19?91 mm year21. Sb, however, is a known cathodic
Lead (Pb) poison, and based on the recent findings on the
In the binary context, Pb was historically reported to be poisoning effect of As,97 the revisiting of Sb presents
quite inert to Mg and not detrimental for corrosion when an avenue of future work.
added up to 5 wt-%.15 Generally, Pb is added to Mg for
production of anode materials, with the AP65 alloy Scandium (Sc)
having a nominal composition of 5 wt-% Pb serving as a The effect of Sc on corrosion properties of Mg and its
common example.144 The addition of Pb to structural Mg alloys is yet to be fully explored, however, the
alloys has not been explored, perhaps on the basis that Pb information available to date reports that Sc additions
has a significantly higher density than Mg (logically to AZ91 alloys refine microstructure through the
negating the light-weighting opportunities). formation of the Al3Sc compound that suppresses
However, generally speaking the effect of Pb on Mg17Al12 phase formation.150 Sc has also been noted
corrosion of Mg-alloys has received contradictory to comparatively retard cathodic kinetics, resulting in
reports overall. On one hand, Pb was reported to the reduction of the corrosion rate of AZ91E in 0?1M
allegedly modify the microstructure of AZ series alloys NaCl from y8 mA cm22 to 2 mA cm22 at 0?1 wt-% of
by means of refining and a more homogenous distribu- Sc. In contrast, a higher Sc content was shown to not be
tion of Mg17Al12.145–147 Another example of the as effective.34 Sc is an extremely expensive metal
beneficial effect of Pb was found in Mg–10Al–12Si (.US$100 g21), which significantly limits its wider use,
alloys, where the additions of 0?2, 0?5 and 1 wt-% of Pb and therefore few studies exist. The comparatively low
led to lower cathodic reaction rates and subsequently catalytic activity of the Al3Sc compound in isolation was
resulted in a reduction of mass loss rate from reported by Cavanaugh.151
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 Silicon (Si)
suggested that low levels of Pb (#0?5 wt.%) to AZ91 There exist commercial Mg–Si alloys, the most common
stimulated more rapid corrosion rates, with the icorr of of which are AS21 and AS41 with Si additions of
Mg-alloys (from 9 mA cm22 of AZ91E to 20 mA cm22 y1 wt-%. Si additions to Mg result in formation of
of AZ91–0?5Pb).34 This finding is consistent with what magnesium silicide (Mg2Si) intermetallics. Depending
was reported earlier by Hanawalt, i.e. addition of Pb to on the shape and distribution of this intermetallic, it

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

may have a minor or major influence on enhancing the Strontium (Sr)


corrosion rates of the commercial AS alloys. A recent Strontium has low solid solubility in Mg (y0?1 wt-%)
report has revealed that Mg2Si acts as a local cathode in and in binary context forms Mg17Sr2 along grain
Mg alloy AS31 and thus promotes the dissolution of boundaries.27 Sr significantly increases cathodic reaction
surrounding matrix.152 Fine and evenly distributed rates and corrosion potentials of Mg that results in high
polygonal-shaped Mg2Si was reported to be more inert overall corrosion rates. Xia reported the corrosion rate
to corrosion of AZ91 alloy compared to coarse Chinese (icorr) of commercially pure Mg of about 20 mA cm22 in
script-like Mg2Si.149 It is however, important to mention contrast to 38 and 60 mA cm22 when 0?2 and 2 wt-% of
that Si has an adverse effect on corrosion in the pre- Sr, respectively, were added.27 In the Mg–Al–Zn system,
sence of Fe contamination,15,113 which was recognised when added above solubility limit, Sr decreases grain size
early in the twentieth century. As such, besides the AS forming the and binary eutectic Al4Sr,148 Mg17Sr2 and
series of alloys which are used in some automotive Mg2Sr. These particles lower the volume fraction
applications,153 Si is not a typical alloying element in Mg of Mg17Al12 and homogenise its distribution.161 Sr is
alloys and its level in commercial purity Mg is very reported to improve corrosion resistance of AZ91 by a
carefully controlled. purported retardation of anodic activity concomitant
Samarium (Sm) with an increase in corrosion potential (Ecorr) by about
150 mV and reducing the icorr by y50%.162 This agrees
Samarium is known to be beneficial in improving the with results by Fan where the additions of up to 2 wt-%
mechanical properties in binary Mg alloys,154 however, Sr led to ennoblement of Ecorr by y80 mVSCE and
there is a limited number of studies regarding the effect of decrease in the icorr of AZ91D alloy from about 24 to
Sm on corrosion of Mg. Wu and co-workers reported that 12 mA cm22.163 More so, the recent study by Xia reveals
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additions of about 1 wt-% Sm to AZ92 led to formation of an increased cathodic reaction rates and ennoblement of
an Al–Mn–Sm and Al–Sm phase, along with a more corrosion potential of binary Mg–2Sr alloy compared to
refined b (Mg17Al12) phase, accompanied with a decrease pure magnesium (Ecorr, Mg––2Sr521?64 VSCE, Ecorr,
in the b volume fraction which contributed to decreased Mg521?725 VSCE).27 Subsequently the icorr of Mg–2Sr
corrosion rate of AZ92 by y40% in 3?5% NaCl.155 increased from 21 of pure Mg to 58 mA cm22, whereas
Moreover Sm has also been reported to refine the the icorr of Mg–0?2Sr increased to 38 mA cm22.
microstructure of Mg–Al–RE alloys and somewhat
decrease the mass loss rate from 2?6 to 1?95 mm year21 Titanium (Ti)
in 3?5% NaCl when added at 0?5 wt-%.156 The literature indicates that Ti has so far only been added
to AZ91 alloys. As a result, the effect of Ti on other alloy
Tin (Sn) systems is not known. However, it is reported that Ti
Tin has a tendency to form Mg2Sn along grain addition in AZ91 alloy, progressively improves corrosion
boundaries. The volume fraction of Mg2Sn increases performance (to the reported maximum values of 0?8 wt-
with Sn content.157 As Sn has a low exchange current % Ti). This effect of Ti is associated with (1) changes in
density it does not enhance cathodic kinetics, but leads morphology and distribution of b phase from coarse and
to a significant increase in anodic activity – akin to the semi-continuous to fine, uniform and rodlike, and (2) an
notion of anodic activation – which Sn also imposes increase of Al in the solid solution of a-phase.164 Südholz
when added to Al.158 The anodic activation phenomena tested the effect of 0?1 wt-% Ti addition to AZ91E in
in Mg alloys is not understood nor studied at the nano- 0?1M NaCl and found that although anodic activity was
scale to date. In the work of Wang et al., additions of 1– slightly increased in the presence of Ti, the cathodic
3 wt-% Sn to AP65 alloy decreased the corrosion reaction rate was somewhat decreased. However, this did
potential of the alloys by about 120 mV in 3?5% not have a significant impact on the overall corrosion rate
NaCl and increased the icorr from 6?3161024 to icorr.34
7?961021 mA cm22 at 1–3 wt-% Sn.159 This is synon- Candan and co-workers measured the corrosion
ymous with anodic activation. In an early study, binary potential and corrosion rate of AZ91 alloy with 0?2, 0?3,
additions of Sn to Mg were reported to be negligible for 0?4, 0?5 wt-% Ti additions in 3?5% NaCl solution, and
corrosion for concentrations up to as high as 5 wt-% reported somewhat unrealistic corrosion potential values
Sn.15 It is therefore worthwhile to mention that some (Ecorr) and corrosion current densities (icorr) for commercial
misinterpretations of the role of Sn in Mg binary alloys and alloyed AZ91 alloys (i.e. Ecorr, AZ91520?821
exist. For instance, the recent report by Ha suggested VSCE and Ecorr, AZ91–0?5Ti520?980 VSCE, icorr, AZ915
that Sn increases cathodic reaction rates and thus 153 mA cm22 and icorr, AZ91–0?5Ti543 mA cm22).165
increases hydrogen evolution rate which in turn pro- Such high potentials are synonymous with potentials in
motes passivity in Mg–Sn alloys (2–8 wt-% of Sn which the cathodic reaction would be oxygen reduction,
added).160 This effect was not demonstrated by the and not water reduction – and cannot be realistic or relied
presence of a passive region or a passive current density. upon. The corrosion potential of AZ91 alloy is typically
As such, the effect of Sn appears to be more deleterious around 21?5 VSCE.
in alloyed Mg, than pure Mg, either alone, or depending
on the interaction of Sn with the elements present in Yttrium (Y)
the Mg alloy. More specifically, the experimental alloy In binary Mg–Y alloys, Y additions monotonically
of Mg–5Al–1Sn exhibits the icorr value of about increase corrosion rate because of the increasing volume
51 mA cm22 in comparison to icorr of Mg–7Sn that is fraction of Mg24Y5 and a concomitant enhancement of
about 27 mA cm22 in 0?1M NaCl.50 The mechanism of cathodic kinetics.166 An increase in corrosion rates
anodic activation is not understood, but its manifestation reported from 17 to 65 mA cm22 when 2–18 wt-% Y
has been depicted rather markedly in Fig. 4 for the was added to Mg. Y as an elemental addition to AZ series
example of heavy Sn loadings. alloys forms Al2Y phase, refines a (Mg) grains and

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

contributes to a lower fraction of, and more homo- because of its potent ability to refine the grain size of Mg
geneous distribution of b (Mg17Al12). As a result, the alloys, improving both the casting quality and mechanical
corrosion properties of AZ91 have been reported properties of Mg. Usually Zr is added to Zn- and RE-
to improve with Y additions ranging from 0 to containing alloys such as ZE and ZK series alloys.
0?8 wt-%;167 the mass loss rate of AZ91 dropping Corrosion of these alloys is generally more rapid than the
from 7?5 mg cm22 day21 to about 0?5 mg cm22 day21 AZ (Al–Zn) class of alloys. It has been reported that
at 0?8 wt-% Y. This was not mechanistically analysed in corrosion resistance may be improved by heat treat-
detail by the authors, however, the electrochemical ment,13 while there are even reports that Zr addition up to
response showed slightly slower cathodic reaction rates. 0?42 wt-% may have positive influence (i.e. decrease)
The improvement in corrosion was mainly because of the corrosion of Mg-alloys.177 However, of the systematic
refined microstructure, and a change in the morphology studies to date, they have indicated that Zr is rather
of the Mg17Al12 phase from continuous to discontinu- detrimental for Mg corrosion.20,178 A systematic study of
ously dispersed with a concomitant decrease in its volume Zr additions was also able to indicate that the assertions
fraction.168 However, in contrast, with heavier loadings made regarding the role of Zr in higher order (multi-
of Y, the work of Südholz indicated a significant increase element) alloys, is difficult to ascertain – as the corrosion
in corrosion when 2 wt-% Y was added to AZ91E (an response may be dictated or overwhelmed by the role of
increase in icorr from 8 mA cm22 at 0 wt-% Y to about the other elements (present in a much higher proportion).
60 mA cm22 at 2 wt-% Y in 0?1M NaCl).34 The notion There are reports that suggest Zr can purify Mg-alloys
that Y is problematic for pure Mg, along with its ability to by combining with Fe to form Fe2Zr which settles to the
serve as a local cathode,16 has resulted in the conclusion bottom of the melt (by gravity) resulting in higher purity
that Y is deleterious to the corrosion of Mg. That said, castings. This potential beneficial effect, however, was
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however, the high solubility of Y in Mg has resulted in also recently described by Gandel, who revealed that
increased use in the modern age hardenable alloys, such overall, the influence of Zr on corrosion was by in large
that Y is a major component of the commercial alloys negative and unique.20 It was indicated (from carefully
WE54 and WE43. In addition, the magnetron co-sputter prepared binary alloys) that Zr imparted an ‘activation’
deposited non-equilibrium thin film Mg–22 at-% Y alloy effect where it could accelerate the anodic reaction by
was reported to exhibit the lowest corrosion rate destabilising the surface film. This led to rapid general
(icorr50?9 mA cm22) in 0?1M NaCl (pH 12) compared dissolution rates corroborated by SEM. Furthermore,
to commercial purity Mg and bulk WE43 alloy.169 This the ratio of soluble to insoluble Zr was also a key factor
significant reduction in corrosion rate was attributed to (as following the limited solubility in the Mg matrix, any
passivity enhancement by Y via incorporation in the excess Zr phase separates to form pure Zr). While a
surface film, and also because of this method of alloy potent grain refiner, Zr content should be balanced so as
fabrication not resulting in formation of MgxYy phase to not be deleterious to corrosion. Zr is nominally not
and Y remaining in solid solution.169 Physical vapour added to Mg–Al alloys as it combines with Al to form an
deposition (PVD) techniques are both challenging and Al3Zr intermetallic that negates the grain refining effect
not up-scalable, but have been able to reveal compara- of Zr. Even in commercial Zr-containing alloys such as
tively corrosion resistant Mg-based thin film alloys and ZE41, the presence of Zr particles was seen by electron
coatings,170 indicating how important microstructural microscopy to be responsible for the accumulation of
heterogeneity (and retention of solid solutions) can be in corrosion damage.179,180 Neil and co-researchers pro-
limiting the kinetics of corrosion,171 unfortunately this posed the corrosion mechanism of ZE41 that initiates
requires specialist fabrication due to the limited solubility with localised attack of the regions beside Mg7Zn3RE
of metals in Mg prepared by conventional casting. intermetallic, followed by deep attack at Zr-rich regions.
Zinc (Zn)
Other elements (Au, B, Ba, Be, Cd, Co, Eu, Ga,
Zinc is the second most frequently used alloying element
Ge, In, Nb, Ni, Se, Tb, Th, V)
in Mg alloy production after Al. In the binary context, Zn
forms MgxZny phases (depending on precise composition) Boron as a trace addition to AZ series alloys from 0?008
that provide and age hardening response.27,172,173 to 0?032 wt-% provides significant grain refinement,
However, this phase serves as a local cathode to the Mg which is attributed to the presence of AlB2 particles that
matrix and has been reported to be responsible for overall serve as Mg grain nucleation sites.181 Studies suggest
increase in corrosion rates due to accelerated cathodic that B improves the fluidity and die casting properties of
reaction rates22,88,174 when present in concentrations AZ alloys,182 however, the presence of 0?05–0?2 wt-% B
above y1 wt-%. Although Hanawalt established a in AZ31 and AZ91E alloys leads to higher corrosion
threshold limit for Zn of up to 2?5 wt-% in his early study rates by a factor of about 234,183 compared to the B-free
in 1941,15 Kirkland reported a substantial increase in base alloy.
corrosion rates when Zn concentration rises from 1 to Barium has been noted to improve the age hardening
3 wt-%.22 In addition, increasing the Zn content has been response of Mg–Zn alloys, with dispersed particles of
shown to lead to a higher susceptibility to stress corrosion Mg7Zn2Ba forming within grains and at grain bound-
cracking.175 Zinc is often used in combination with Mg–Al aries.184 Ba has, however, been shown to have an
and Mg–Zr–(RE) alloys and hence the role of Zn in adverse effect on corrosion properties of AZ91. The only
synergy with other elements has been described along with corrosion study related to Ba additions to date indicates
those specific elements. the addition of 0?1 wt-% Ba to AZ91E,34 increased
corrosion rates increased by y50%, concomitant with a
Zirconium (Zr) decrease in Ecorr of y25 mVSCE.
Zirconium has low solubility in Mg and does not form Beryllium has an ability to control melt oxidation of
intermetallic phases with Mg.176 Zr is added to Mg Mg during melting, casting or welding.185,186 However,

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

because of its low solubility and effective grain coarsen- compression and tensile properties to ZK alloys when
ing effect, the addition of Be is nominally restricted to added below the solubility limit.191–193 As Dy has a high
the parts per million range (y,30 ppm).78 In addition, maximum solid solubility in Mg (25?34 wt-%9), it largely
there are significant safety risks with Be such that it is dissolves in the Mg matrix with only low concentrations
not presently commercially viable. departing the matrix in precipitation of second phases,
Cadmium additions to Mg have not been widely which increases in volume fraction with an increase in
explored, however, an early report suggests that addi- Dy content. It is reported that corrosion of Mg–Dy
tions of Cd up to 5 wt-% do not have a detrimental binary alloys is of the filiform-type and localised, and
effect on corrosion.15 More recently, a study by Xu the corrosion rate does not notably increase or decrease
indicated decreased corrosion rates with Cd additions, with differing Dy contents between 5 and 20 wt-%.194
concomitant with a reduced corrosion potential of Although the Mg–Dy system appears to be promising
y20 mV when 2?04 wt-% Cd was added to Mg. for research on the basis that Dy is not studied in
Hydrogen evolution measurements showing Mg–Cd complex alloy systems, Dy did not appear to adversely
lowered corrosion rate three times (3?44 mm year21 influence corrosion, while Dy has excellent promise for
with 0 wt-% Cd v 1?06 mm year21 at 2?04 wt-% Cd).187 improvement of mechanical properties due to age-
In a separate study by Südholz, the addition of 0?2 wt-% hardening; however, Dy is a rather heavy and expensive
Cd to an AZ91Ez0?2Au alloy resulted in a lower metal to be used industrially.195
overall corrosion current density compared with similar Gallium as a binary addition forms rod-shaped
alloys including AZ91Ez0?05Au and AZ91Ez0?001Au Mg5Ga2 along grain boundaries.196 Mg–Ga alloys were
(icorr, AZ91E–0?2Au–0?2Cd53?1 mA cm22; icorr, AZ91E– found to have good ductility and owing to a good
0?05Au55 mA cm22; icorr, AZ91E–0?001Au513 mA cm22).34 response to aging, show substantial increases in tensile
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In the binary context, addition of Cd may also im- strength compared to pure Mg (i.e. UTS5180?1 MPa,
prove tensile strength and provides an increment in TYS5107?4 MPa, e58?2% for Mg–2 wt-% Ga).196
elongation.187 As Cd is 100% soluble in Mg it does not However, the low melting point of Ga (27uC), its
form any intermetallic compounds and as a binary relative rarity, and the embrittlement risk to Al-alloys
addition to Mg, is perhaps in no way detrimental to posed by Ga makes such additions unsuitable for
corrosion performance; unfortunately, however, Cd is commercial structural alloy use. On the other hand,
hazardous to human health and its widespread use as an Ga has been pursued as an alloying addition in Mg–Hg
alloying element in Mg will remain unlikely.188 alloys that are used as a material for sea water batteries.
Cobalt is mainly used as an alloying addition in the Low concentrations of Ga (1 wt-%) show a reduction of
production of lightweight load sensitive materials with the anodic reaction rate (which is increased owing to the
sensory properties, allowing for on-line monitoring of Hg) improving the overall corrosion resistance of the
mechanical forces applied to components made of Mg– Mg–5Hg system (icorr, Mg–5Hg526?98 mA cm22, icorr,
Co.189 Co has no solid solubility in Mg and forms Mg–5Hg–1Ga52?34 mA cm22).127
intermetallic compounds of the types Co2Mg and Mg2– Germanium forms rod-shaped Mg2Ge precipitates in
Cox in binary Mg–Co alloys. Micro-additions of Co Mg binary alloys and can effectively refine the grain size
(y0?1 wt-%) result in extremely high corrosion rates of of Mg.197 Of the few corrosion studies regarding Ge
Mg, with the corrosion rates being comparable to those additions, it was seen that additions of 0?5–2 wt-% Ge in
Mg alloys loaded with common impurities such as Fe, Mg increase the cathodic kinetics accompanied by an
Ni.15 In the early study of Hanawalt, the tolerance limit of ennoblement of Ecorr by about 100 mV. Ge was observed
Mg for Co was reported to be 0?017 wt-%, the to suppress the anodic reaction rates and thereby reduce
concentrations exceeding this limit drastically increase the overall corrosion rate when tested in 3?5% NaCl.198
corrosion rate of Mg.15 More recently, Co additions have The lowest overall corrosion rate (relative to pure Mg)
also been studied in the pursuit of ultra high strength Mg was achieved at 1?5 wt-% Ge, claimed to be an order of
alloys.190 Such alloys have been largely based on the Mg– magnitude lower than that of Mg. The explanation for
Zn system with both heavy and complex multi-alloying to this reduction in corrosion rate was given as being a result
stimulate heterogeneous microstructures. Co-containing of the finer grain structure that promoted more uniform
Mg alloys display among the highest corrosion potentials corrosion product film formation,198 however, such a
of any Mg alloys ever reported, owing to the significant mechanism is in need of further validation.
enhancement of cathodic kinetics that Co imposes. As Gold because of its relatively high cost has not received
such, the more noble potential values are linked with very much attention as an alloying element for Mg. The
high rates of corrosion. For Mg–8Zn–1Co, an Ecorr of literature review shows that the trace amount of gold in
21419 mVSCE and icorr 194 mA cm22 were recorded. This AZ91E alloy can improve creep response,199 with only
icorr is about 20 times more rapid than AZ31. The same small increases in corrosion current density with 0?001,
alloy with 0?02 wt-% Ti added, resulted in a decrease of 0?05, 0?1 wt-% Ag added (AZ91Ey6 mA cm22, AZ91E–
icorr to y70 mA cm22, which is the same icorr measured in 0?001Auy8 mA cm22, AZ91E–0?05Auy5 mA cm22, AZ91E–
the case of more Zn, in a Mg–10Zn–1Co alloy. Finally, 0?1Auy12 mA cm22).34
the lowest icorr recorded for a Co-containing alloy was in Indium additions were studied several decades ago by
Mg–8Zn–1Co–0?5Ag–0?3Ca, with an icorr of 47 mA cm22 Hiroki, who reported the corrosion of Mg–47 at-% In
and retention of an ennobled potential of about both dry and humid environments.200 Although the
21416 mVSCE. These are comparatively higher icorr corrosion was not measured either electrochemically or
values, than all the commercial Mg alloys as measured by mass loss, a negative effect of In on accelerated
under similar conditions. corrosion of Mg was established. According to the
Dysprosium assists grain refinement and solid solution proposed mechanism, the Mg–In alloy surface immedi-
strengthening in Mg–Dy binary alloys, while it enhances ately oxidises once exposed to dry air. MgO film forms on

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

the surface and it contains isolated In. As the melting Terbium has a high solubility in Mg (24 wt-%),
point of In is very low (156?6uC) the In crystals continue to however, the use of Tb in Mg alloys is not widespread.
grow at room temperature. These crystals were posited to Binary Mg–Tb alloys show a good age hardening
induce the stress in the corrosion product film that response and the hardness values increase with an
subsequently results in the film breakdown. In humid increase of Tb concentration (up to 93 HB at 20 wt-%
environment (30uC, 70% RH), the corrosion product was Tb).205 One study by Neubert suggested that Tb has a
composed of the mixture of Mg(OH)2 and isolated In deleterious effect on corrosion of a Mg–4Tb-2?5Nd
crystals. The isolated In is purported to serve as a local alloy.206 That study reported accelerated cathodic
cathode to Mg. The role of In is in need of further kinetics with addition of 4 wt-% Tb and higher overall
research, particularly at lower alloy loadings and non- corrosion rate in 300 ppm NaCl solution compared to
binary systems. WE43 (where icorr, Mg–4Tb–2?5Ndy7?4 mA cm22 and
Lutetium: The influence of Lu on Mg or Mg-alloys has icorr, WE43y2. mA cm22).
not been explored yet. The recent study by Samaniego is Thorium is the most effective elemental addition for
the only report on the effect of Lu on Mg-alloys. In imparting high-temperature strength and creep resis-
particular the low level of Lu (0?21 wt-%) was added to tance up to 350uC. In addition, it improves casting and
AZ31 alloy. Lutetium incorporates into Al–Mn consti- welding properties. Unfortunately, because of the radio-
tuent particle, however, this does not change the Volta active nature of thorium, it is not commercially
potential of these particles. Lu was found to reduce the viable,113 and the influence of Th on corrosion is not
corrosion rates of AZ31 in the as-cast condition. This widely reported.
was achieved by reducing the cathodic kinetics of Mg. Vanadium in the context of influencing corrosion of
The overall corrosion rate was therefore decreased from Mg or Mg alloys is yet to be reported. However, V-
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12?3 to 7?25 mA cm22, the mass loss rate from 0?36 containing Mg-alloys have been studied, with trace
to 0?14 mg cm22 per day. XPS analysis showed no additions indicating notable grain refinement for both
appreciable amount of Lu on the alloy surface implying Mg–Zn207 and Mg–Al alloy systems.208 In the AZ series
that Lu does not promote a more protective corrosion alloys, V forms Al3V phase that apparently results in
film. Although Lu seems to have a positive effect on high grain boundary density and refines grains and the
corrosion resistance of AZ31 alloy, it negatively resulted distribution of b-phase (Mg17Al12).
in larger grain structure of this alloy leading to an
increase in grain size from 100 to 700 mm.201 Consolidation of alloying effects
Molybdenum is not a typical elemental addition into Following the descriptive interpretations of the influence
Mg because of its insolubility. However, low-level of alloying elements above, an attempt has been made to
additions of Mo to AZ91E (0?1 wt-% Mo), studied by graphically present the information for quantification of
Südholz, indicated that microalloying with Mo leads to the kinetic effects upon corrosion. Based on processing
a significant increase (about a factor of 10) in the of the literature to date, and the interpretation of data
corrosion current density values icorr.34 therein, it is possible to extract the electrochemical effect
Nickel is regarded as an impurity in Mg alloys and has of the elements in a holistic sense. Figure 8 shows a
an adverse effect on corrosion. A tolerance limit of only schematic of the polarisation curve of Mg and the
0?0005 wt-% Ni is reported for Mg.15,78 relative influence of alloying elements on anodic and
Niobium is not a common alloying addition for Mg. cathodic kinetics.
Nb is not soluble in Mg and its alloying would only be The interpretation of Fig. 8 can be made on the basis
possible via methods such as magnetron sputtering, of the relative movement of cathodic and anodic
limiting its utility to that of thin films. One attempt has branches of polarisation curve. The distance associated
been made to add Nb to Mg composites.202 with the relative movement (along the length of the
Palladium has recently been explored as an alloying schematic arrow) is a representation of how significant
addition to heavily alloyed versions of biodegradable the effect is. The information in Fig. 8 is a valuable map
Mg–Ca–Zn alloys.203,204 Pd additions (y2, 6 at-%) to as far as corrosion engineering is concerned, as the
Mg–Zn–Ca amorphous alloys were reported to retard authors emphasise that the issue of Mg corrosion is one
the anodic reaction rate in simulated body fluid. of the kinetics, and the map in Fig. 8 provides an
However, given the insolubility of Pd and its high attempt at consolidating this notion. The figure has been
exchange current density, this effect is concomitant with constructed by using the polarisation and interpretable
enhanced cathodic activity leading to higher corrosion data extracted from the literature as summarised by the
current densities (icorr, Mg–23Zn–5Ca51?7 mA cm22; reference list accompanying this review. Some of the
icorr, Mg–23Zn–5Ca–2Pd52?1 mA cm22; icorr, Mg–23Zn– most significant observations included in Fig. 8 are
5Ca–6Pd52?7 mA cm22203), however, it should be noted briefly summarised below:
that the baseline corrosion current density of the Mg–
23Zn–5Ca alloy is very high to begin with, at least an
N Al retards anodic dissolution rates when added below
or at the effective solubility limit. This effect becomes
order of magnitude higher than that of pure Mg in the overwhelmed when the Al content exceeds the
same solution.39 effective solubility limit (the word effective is used,
Selenium has not been widely used in Mg alloy because the solubility is time–temperature and
production, likely because of its toxicity. A study processing dependent), forming Al-rich zones and
conducted by Südholz indicates that small amount of Al-containing intermetallics that enhance cathodic
Se (0?1 wt-%) in AZ91 alloy can reduce the corrosion reaction rates.
current density values (icorr) from y8 to 2 mA cm22.34 N The addition of Mn below the solubility limit to pure
The solubility of Se in Mg is unknown, and its use in Mg has a minor effect on decreasing the cathodic
conventional alloy production is hazardous. reaction rates, the additions exceeding the solubility

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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

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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


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

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

190 International Materials Reviews 2015 VOL 60 NO 3


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

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194 International Materials Reviews 2015 VOL 60 NO 3