Corrosion Science 53 (2011) 3299–3308

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Corrosion of heat treated magnesium alloy ZE41

W.C. Neil a,⇑, M. Forsyth b,c, P.C. Howlett b, C.R. Hutchinson c, B.R.W. Hinton c
a
Defence Science and Technology Organisation, Melbourne, Australia
b
Institute for Technology Research & Innovation, Deakin University, Waurn Ponds, Australia
c
Department of Materials Engineering, Monash University, Clayton, Australia

a r t i c l e i n f o a b s t r a c t

Article history: This paper investigates the effect of heat treatment upon the corrosion morphology and mechanism of
Received 4 February 2011 ZE41 alloy. The results of optical and scanning electron microscopy (SEM) together with potentiodynamic
Accepted 6 June 2011 polarisation reveal the importance of the microstructure in the initiation and propagation of corrosion in
Available online 7 July 2011
an aqueous environment. The corrosion of the heat-treated alloy is significantly altered due to changes in
the microstructure, specifically the Zr-rich regions and the grain boundary T-phase.
Keywords: Crown Copyright Ó 2011 Published by Elsevier Ltd. All rights reserved.
A. Magnesium
A. Zirconium
B. Polarisation
B. SEM
C. Pitting corrosion

1. Introduction alloys. In Mg–Y–RE–Zr alloys for example, the presence of Zr-rich

regions within the centre of the grains resulted in a greater corro-
Magnesium alloys have attracted much interest mainly due to sion resistance of these regions as compared with the remainder of
their excellent strength-to-weight ratio – it is the lightest engi- the grain [21–23]. Song and St John [24] also reported similar
neering metal, with a specific density 2/3 that of aluminium and corrosion resistance at Zr-rich regions in a Mg–RE–Zn–Zr alloy. A
1/4 that of steel. However, Mg alloys have an inherently high sus- fine distribution of Zr particles in the alloy was thought to produce
ceptibility to corrosion, which severely limits their usage. As such, a more robust oxide film, leading to increased corrosion protection
improved methods for surface protection are constantly being [22]. Zr was also thought to be beneficial for corrosion resistance as
sought and these include chemical passivation [1–7], anodisation it may combine with impurity elements, namely iron and nickel,
[8,9] and protective coatings [10] and newer techniques such as and form insoluble precipitates, effectively producing higher purity
laser surface modification [11–16]. Despite increased research, alloys [24].
there is still no ideal method for protecting Mg alloy surfaces. As The type of heat treatment is also known to affect the corrosion
new alloys are developed, the effect of the new microstructure rate of Mg alloys containing Zr [25–27]. Kaya et al. [28] have shown
on corrosion behaviour becomes of interest. a difference between the microstructure and corrosion resistance
The Mg–Zn–RE–Zr alloy ZE41 (where RE = rare earth), is used of the as-received and heat treated Mg–Y–Zr–RE alloy. That alloy
for aircraft gearbox and generator housings on military helicopters had Zr-containing particles within the grains, and an elevated tem-
[17,18], which are exposed to severe environments during service, perature heat treatment caused segregation and coalescence of
and corrosion is an ongoing issue. The corrosion of magnesium these Zr-containing particles. Subsequent lower temperature aging
alloys is closely linked to alloy phases in the microstructure. In of the alloy leads to widening of the Zr-containing clusters and a
order to better understand how to provide optimum protection more uniform distribution of Zr bearing microparticles [28]. The
for this alloy in a severe service environment, a better knowledge Zr-enriched central part of the grain and the widening of these
of the relationship between the microstructure and the corrosion Zr-enriched clusters due to aging increased the corrosion resis-
behaviour of ZE41 is needed [19]. tance within the grains.
Zr is added to many Mg alloys as a grain refiner. Previous work It is hypothesised that by heat-treating the ZE41 alloy, the
[19,20] has shown that Zr has a detrimental effect on the corrosion Zr-rich regions and the large Zr-containing particles seen to be
behaviour of the ZE41 alloy. In contrast, there are reports in the responsible for the severe corrosion attack in the as-received
literature that Zr improves the corrosion resistance of other Mg ZE41 (sand cast with a T5 treatment) [19] may be minimised,
or ideally, fully removed. Specifically it was thought that, if
⇑ Corresponding author. Tel.: +61 396267947; fax: +61 396267096. Zr-containing particles could be dissolved back into solid solution,
E-mail address: wayne.neil@dsto.defence.gov.au (W.C. Neil). a microstructure with a more homogenous Zr-distribution could be

0010-938X/$ - see front matter Crown Copyright Ó 2011 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2011.06.005
3300 W.C. Neil et al. / Corrosion Science 53 (2011) 3299–3308

produced. Thus the dissolution of the large Zr-particles would lead imen with the pans. The objective of such experiments is to search
to the removal of the cathodic sites within the centre of the grains for signals of phase transformations in the vicinity of 490 °C. The
and an increase in corrosion resistance. graphite pans were baked at 600 °C in the DSC to remove any or-
This paper investigates the effect of altering the bulk micro- ganic contamination from the pans. The DSC was calibrated using
structure of a commercially available ZE41A alloy in the T5 temper a standard indium reference sample. A trial heat treatment of
through subsequent heat treatment, and the resultant changes in ZE41 was performed in the DSC instrument, by holding the speci-
the corrosion behaviour of the alloy. men at a temperature of 490 °C for 48 h under an argon atmo-
sphere. At the completion of the heat treatment, the temperature
within the DSC instrument was lowered to room temperature as
2. Experimental methods
quickly as the instrument allowed. The DSC scan for the as-re-
ceived ZE41 indicated a small exothermic event by the peaks be-
2.1. Material
tween 481 and 482 °C (Fig. 1). This indicates that a phase
transformation occurred in the vicinity of the temperature pre-
The alloy stock used for this investigation was cast 5 mm thick
dicted by the thermodynamic calculations. Based on these trials,
plates of ZE41A heat treated to the T5 temper with a nominal com-
a heat treatment regime of 500 °C for 5 days was chosen.
position shown in Table 1 [29].
The larger scale heat treatment chosen for the dissolution/redis-
Tests were carried out on specimens taken from the as received
tribution of the Zr particles was 500 °C for 5 days. A specimen
plates in the T5 temper (labelled ZE41), and from plates that were
(approximately 15 mm  50 mm) was encapsulated in a vacuum-
subjected to a further heat treatment (labelled HTZE41).
sealed glass ampoule to reduce oxidation during heat treatment.
Heat treatment was performed in a Tetlow™ furnace, initially set
2.2. Heat treatment of ZE41 at 350 °C. The temperature was increased in steps of 50 °C every
2 h to ensure constant heating of the specimen, until the target
In the binary Mg–Zr system, Zr can exist in a solid solution temperature of 500 °C was reached, and to avoid incipient melting
below 650 °C at Zr concentrations of approximately 1 wt.%. To within the alloy. After 5 days, the specimen was quenched in room
obtain an indication of the temperature dependence of the Zr, Zn temperature water, shattering the glass ampoule and providing the
and RE elements solubility in the ZE41 alloy considered in this necessary rapid quench rate.
study requires an accurate thermodynamic assessment of this mul-
ticomponent system. Thermodynamic assessments of commercial
2.3. Constant immersion corrosion tests
Mg alloys are a relatively recent development and are often incom-
plete. In particular, many of the ternary intermetallics that are
Specimens were mounted in an epoxy resin to expose a
observed in these alloys have not yet been incorporated into the
10 mm  7 mm area of alloy. The mounted specimens were ground
databases. To obtain an estimate of the expected temperature
successively to a 4000 grit finish using SiC abrasive papers with
dependence of the equilibrium phase fractions for the ZE41 alloy
water as a lubricant, washed with acetone and dried in a nitrogen
composition, calculations were made both with the Thermo-Calc
stream. Mounted specimens were immersed in a 0.001 M NaCl test
TCCS software package and the Pandat software package, both
solution prepared from analytical grade reagents and distilled
using commercially available Mg databases. It should be empha-
water. Mg alloys are known to corrode rapidly in most aqueous
sised that such calculations provide a starting point only and
environments, which make a study of the development of corro-
should not be interpreted as absolute. Their accuracy is contingent
sion difficult. In order to slow the corrosion rate and allow this
upon the completeness of the databases. The calculations suggest
development to be observed, a mildly aggressive environment of
that at temperatures around 490 °C, for a typical ZE41 composition,
0.001 M NaCl was chosen with a relatively short exposure time
a significant fraction of the Zr and Zn would be dissolved back into
of 18 h, unless otherwise stated.
the solid solution. Some of the RE elements are expected to dis-
After removal from the test solution, the corroded specimens
solve into solid solution with some remaining as constituents of
and corrosion products were examined. The corrosion product
secondary phases. Thus it seemed to be theoretically possible to
was removed by immersion for 60 s in a solution of 200 g CrO3,
treat the as-received ZE41 alloy by means of isothermal heat treat-
10 g AgNO3, 20 g Ba(NO3)2, with 1000 mL of reagent water, in
ment and rapid quenching to produce a microstructure with much
accordance with ASTM Standard G1-90, Designation C5.2 [30].
of the Zr dissolved into the parent Mg phase.
To provide experimental support to the computational thermo-
dynamic calculations, Differential Scanning Calorimetry (DSC) 2.4. Optical microscopy
scans were performed at scan rates of 10 °C/min, from 120 to
600 °C using a Perkin Elmer DSC 7 under an argon atmosphere Specimens were examined using Olympus MX50 and BX61
using specially prepared graphite pans to avoid alloying the spec- optical microscopes. Images were obtained using Spot and
Image-Pro image acquisition software for the MX50 and BX61
microscopes respectively.
Table 1
Nominal composition of Mg alloy ZE41A-T5 [29]. 2.5. Scanning electron microscopy
Element Composition wt.%
Specimens were examined using a JEOL 6490LA SEM with EDX
Minimum Maximum
which incorporated X-ray mapping facilities. Most images were ac-
Zinc 3.5 5.0 quired using an accelerating voltage of 20 keV and a working dis-
Cerium (total rare earths) 0.75 1.75
Zirconium 0.40 1.0
tance of approximately 12 mm. All specimens were grounded to
Manganese – 0.15 the SEM stage using double sided conductive carbon tape. When
Copper – 0.10 using an epoxy mounted specimen, grounding was achieved by
Nickel – 0.01 running a strip of conductive carbon tape across one edge of the
Other impurities – 0.30
metallic specimen, thus ensuring electrical conduction though
Magnesium Remainder
the carbon tape.
 W.C. Neil et al. / Corrosion Science 53 (2011) 3299–3308 3301

Fig. 1. DSC curve of as-received ZE41 showing a exothermal peak between 481 and 482 °C.

2.6. Potentiodynamic polarisation size of 60 lm. A phase thought to be T-phase (Mg7Zn3RE) [32] is
clearly visible at the grain boundaries. Some larger intermetallic
Potentiodynamic polarisation (PP) was carried out using a EG&G particles were also observed within the grains. The same micro-
PAR VMP2/Z Potentiostat, using a Saturated Calomel (SCE) refer- structural features were observed in the SEM (Fig. 2b) with the grain
ence electrode, and a mixed metal oxide mesh counter electrode. boundary T-phase appearing as a white network. The zones rich in
Specimens were mounted in an epoxy resin with a 10 mm  7 mm Zr (interaction zones), as identified by EDX, were clearly visible in
area of alloy exposed, with an electrical wire attached to the reverse the centres of the grains when imaged in SEM (Fig. 2b).
face of the specimen. This wire was soldered onto a piece of conduc- Fig. 3a is an optical micrograph showing the microstructure of
tive-adhesive backed copper tape and adhered to the specimen. The HTZE41 after heat-treating for 5 days at 500 °C. A dispersion of
epoxy mounted specimens were ground successively to a 4000 grit the T-phase (Mg7Zn3RE) at the grain boundaries, and larger, darker
finish using SiC abrasive papers, washed with acetone and dried in a ‘‘cloudy’’ regions associated with Zr-rich areas in the grains are
nitrogen stream. The PP was performed after recording the open clearly visible. The grain boundaries are well defined, seen as lines
circuit potential for 10 min at a scan rate of 0.167 mV s 1 sweeping in the HTZE41, whereas in the as-received ZE41 (Fig. 2a), the grain
from 100 mV vs. open circuit over a range of 500 mV. boundaries were defined by the semi-continuous network of T-
A borate buffer was used as the test solution to distinguish the phase. The SEM image (Fig. 3b) shows clearly a large reduction in
effect of the microstructure on the corrosion kinetics without the the volume fraction of grain boundary secondary phases after the
complicating effects of added chloride ions. The borate buffer solu- elevated temperature heat treatment (cf. Fig. 2) as expected from
tion consisted of 0.15 mol/L of boric acid and 0.05 mol/L of sodium the thermodynamic calculations. The SEM image also revealed a
tetraborate, at pH 8.5 [31]. light coloured zone within most of the grains, which was revealed
by EDX analysis to be a Zr-rich region. Particles were clearly pres-
3. Results ent within these zones, EDX point analyses of several particles
indicated that they were rich in Zr with some Zn but contained
3.1. Microstructure of ZE41 and HTZE41 very little Mg, as was previously found in the as-received ZE41
[19]. For HTZE41, the majority of the Zr–Zn intermetallic particles
The optical micrograph (Fig. 2a) taken from a ZE41 plate shows were smaller in size (compared to ZE41) and were not visible in
an equiaxed grain structure of a-Mg typical of a casting, with a grain some of the grains. As expected, the elevated temperature heat
3302 W.C. Neil et al. / Corrosion Science 53 (2011) 3299–3308

Τ-phase
(Mg7Zn3RE)
Intermetallic
particle
Zr Interaction
Zone
α-Mg

(a) (b)
Fig. 2. Microstructure of ZE41 (a) optical micrograph and (b) SEM micrograph.

Τ-phase
(Mg7Zn3RE)

“Cloudy”
Zr-rich region

Intermetallic
particle
(a) (b)
Fig. 3. Microstructure of HTZE41 (a) optical micrograph and (b) SEM micrograph.

treatment has dissolved many of the Zr-containing particles within optical micrographs of ZE41 (Fig. 5a inset) and HTZE41 (Fig. 5b in-
the grains (on average leading to smaller particles) but not all of set). For ZE41 (Fig. 5a inset) there were large regions of attack
them were fully dissolved. The Zr may not have been fully within the centre of the grains (dark regions), and some attack
dissolved because (a) the homogenization treatment was not long around the grain boundaries. This is seen clearly in the SEM micro-
enough, (b) the Zr content of the alloy exceeds the solubility limit graph (Fig. 5a). The dark regions in the centre of the grains have the
at 500 °C, or (c) the fine Zr particles may have formed during cool- appearance of deep craters, along with fine pitting covering the
ing from the homogenization treatment. Based on the particles size remainder of the surface within the grains.
and the quenching rate, option (c) is unlikely. Neither of the com- With the HTZE41 (Fig. 5b inset) the attack on the surface chan-
mercial Mg databases used to estimate the equilibrium constitu- ged significantly with the corrosion taking the form of filaments
tion of the alloy at 500 °C contained the ternary T-phase. It is and very little evidence of any deep pitting or craters. The SEM
therefore not possible, at this stage, to differentiate between option micrograph of the HTZE41 surface (Fig. 5b) shows more clearly
(a) or (b). the filiform-like filaments and lack of general pitting over the sur-
The EDX scans in Fig. 4a and b show that the particles present face within the grains.
within the grains were rich in Zr, although the size and distribution It was found that the T-phase was preferentially attacked by the
had been altered compared to as-received ZE41, by the heat treat- corrosion product removal solution in ZE41. However, this solution
ment. It can be seen that the ‘‘cloudy’’ region surrounding Zr-rich did not attack the other features of the microstructure, and inter-
particles (in HTZE41) covers more of the grain, in contrast to the estingly did not attack the altered T-phase in the HTZE41 speci-
‘‘cloudy’’ region in the as-received ZE41 (cf. Fig. 2b). This ‘‘cloudy’’ mens. It should be emphasized that the corrosion morphology
region appears to have been made up from very small (approxi- seen in ZE41 was not the result of the corrosion product removal
mately 1 lm) Zr-rich particles, as seen in Fig. 4c. process, which has been verified through comparison of as-pol-
The distribution of the T-phase (Mg7Zn3RE) which was present ished surfaces exposed to corrosion product removal solution.
at the grain boundaries of the as-received ZE41 had been affected Cross-sectional micrographs of both the as-received and
by the heat treatment process, resulting in a smaller phase fraction HTZE41 revealed how the microstructural features were involved
and less homogeneous coverage of the grain boundaries, which is in the corrosion of the surface. Fig. 6a shows a SEM micrograph
in agreement with the optical and SEM micrographs in Fig. 3. This of the as-received surface after immersion in 0.001 M NaCl for
is seen in Fig. 4b by the greater intensity of RE elements (Ce and La) 18 h, and inset, a cross-sectional optical micrograph of the cor-
and negligible amounts of Zr, as opposed to particles interrogated roded as-received ZE41. The cross-sectional micrograph (corrosion
in Fig. 4a and c that show large intensity peaks of Zr and Zn, and product not removed) reveals that the attack at the grain bound-
only trace amounts of RE elements. A consequence of the dissolu- aries is directly adjacent to the T-phase.
tion of a fraction of the T-phase is that the concentration of RE’s in Fig. 6b is a SEM micrograph of the surface of HTZE41 after
the matrix has increased and the distribution will be more homo- immersion in 0.001 M NaCl for 18 h, and inset, a cross-sectional
geneous than in the as-received ZE41. optical micrograph of the corroded HTZE41. The cross-sectional
micrograph (corrosion product not removed) shows that the fila-
3.2. Corrosion morphology of HTZE41 alloy compared to ZE41 ments appeared to follow the grain boundaries, and spread into
the a-Mg matrix until they reach the dark Zr-rich zone present
Fig. 5 shows typical SEM micrographs of the surface of ZE41 and in the HTZE41.
HTZE41 (Fig. 5a and b, respectively), after immersion in 0.001 M A series of SEM micrographs taken at different time intervals
NaCl for 18 h, and the corrosion product removed. Fig. 5 also shows during immersion of HTZE41 in 0.001 M NaCl is shown in Fig. 7.
 W.C. Neil et al. / Corrosion Science 53 (2011) 3299–3308 3303

Fig. 4. EDX scans of (a) particle in centre of grain; (b) particle at grain boundary; (c) particle inside of ‘‘cloudy’’ region of HTZE41. Arrows indicating location of EDX scans.

Fig. 7a and b are after 1 h immersion, Fig. 7c and d are after 2 h ments were evident along some of the grain boundaries, and there
immersion and Fig. 7e and f are after 5 h immersion. All images was no evidence of any pitting within the grains. After 2 h, there
are with corrosion product removed. After 1 h immersion, fila- was a larger number of filaments, but still no evidence of pitting
3304 W.C. Neil et al. / Corrosion Science 53 (2011) 3299–3308

Fig. 5. (a) SEM micrograph of ZE41 surface, and Inset - optical micrograph of ZE41
Fig. 6. (a) SEM micrograph of the as-received surface after immersion in 0.001 M
surface. (b) SEM micrograph of HTZE41 surface, and inset – optical micrograph of
NaCl for 18 h, and inset, a cross-sectional optical micrograph of the corroded as-
HTZE41 surface after 18 h immersion in 0.001 M NaCl. Corrosion product has been
received ZE41. (b) a SEM micrograph of the surface of HTZE41 after immersion in
removed.
0.001 M NaCl for 18 h, and inset, a cross-sectional optical micrograph of the
corroded HTZE41.
within the grains. After 5 h, a significant fraction of the alloy sur-
face was covered by filaments, but still no obvious pitting within
the grains. Fig. 7b, d, and f are magnified areas of the same speci- fer solution. This solution was chosen to investigate the subtle ef-
men as shown in Fig. 7a, c, and e, respectively (i.e. Fig. 7b is the fect of microstructural changes without the aggressive effect of
same specimen as Fig. 7a, etc.). The difference is that Fig. 7b, d, chloride in the solution. These data clearly show that heat-treating
and f are images of grains not affected by the ‘‘filiform’’ type of cor- of the ZE41 alloy, which has been shown to reduce the phase frac-
rosion attack, revealing that there was no other corrosion visible tion of intermetallic particles along the grain boundary and change
within the grains. the distribution of Zr rich particles within the grains, shifted the
Fig. 8 is a SEM micrograph of HTZE41 taken after 1 h immersion corrosion potential of the HTZE41 to more noble potentials. Tripli-
in 0.001 M NaCl, with the corrosion product removed. There is evi- cate tests were undertaken for both the ZE41 and HTZE41 speci-
dence here of some pitting on the surface of the HTZE41 after the mens. The polarisation data represented in Fig. 10 are the
short immersion period. These areas of pitting are probably con- representative curves, as all the replicate data sets overlayed these
sumed as the filament progresses further into the a-Mg. It can be representative curves.
seen that the centre of the grain (which is associated with the As well as a shift in the corrosion potential (Ecorr), as shown in
Zr-rich region) has less pitting than the outside of the grain. Table 2, to more noble potentials, there was also an apparent
Fig. 9 is a composite SEM image of the surface of HTZE41 after change in the cathodic kinetics with a shift to higher current den-
2 h immersion in 0.001 M NaCl, showing the filament-like corrosion sities. This is possibly due to the increased cathodic area of the
between grains (along the grain boundary region) and the presence HTZE41, with the much larger Zr-rich region acting more noble.
of two large T-phase intermetallic particles. One of the intermetallic
particles (left hand side) appears to extend below the surface, 4. Discussion
which has been exposed by the corrosion filament. The Zr-rich par-
ticles that make up the ‘‘cloudy’’ region can be seen within the areas 4.1. Microstructural differences between as-received ZE41 and HTZE41
of the grains not containing the corrosion filament.
The main microstructural differences between the as-received
3.3. Potentiodynamic polarisation of HTZE41 vs. as-received ZE41 ZE41 and HTE41 are:

Fig. 10 shows representative potentiodynamic polarisation data i. The volume fraction of T-phase decorating the grain bound-
for the as-received ZE41 and HTZE41 in a chloride free borate buf- aries, and
 W.C. Neil et al. / Corrosion Science 53 (2011) 3299–3308 3305

Fig. 7. SEM micrographs of HTZE41 after differing immersion times in 0.001 M NaCl, corrosion product removed. (a and b) 1 h; (c and d) 2 h and (e and f) 5 h.

ii. The presence of a ‘‘cloudy’’ region within the grains (as well
as the Zr-rich intermetallic particles contained within these
regions).

4.2.1. Grain boundary decoration

The T-phase (Mg7Zn3RE) which forms at the grain boundaries of
the as-received ZE41 was affected by the heat treatment process.
The T-phase in HTZE41 was not the near-continuous network it
was in the as-received ZE41, but instead it was distributed along
the grain boundaries and was present in a much smaller volume
fraction in HTZE41. The consequence of the dissolution of the T-
phase will be an increase in the Zn and RE concentrations in the
matrix. This solute distribution will also be more homogeneously
distributed in the microstructure as a result of the elevated tem-
perature heat treatment, as compared with the as-received ZE41.
Any Zn and RE solute depleted regions, which for example will
be present around the T-phase in the as-received ZE41, will be re-
moved leading to a more homogeneous solute distribution.

Fig. 8. SEM micrograph after 1 h immersion in 0.001 M NaCl, corrosion product

4.2.2. Cloudy regions within centre of grains
removed, indicating that pitting is present on surface of HTZE41. Arrows highlight The ‘‘cloudy’’ regions that were present in the as-received ZE41
pitting. (Fig. 2) were also present in the HTZE41 (Fig. 3). EDX scans of
3306 W.C. Neil et al. / Corrosion Science 53 (2011) 3299–3308

Fig. 9. Composite SEM image of the surface of HTZE41 after 2 h immersion in 0.001 M NaCl. Yellow arrows highlight intermetallic particles, red arrow highlighting Zr-rich
regions.

Zr-rich particles, so it was assumed that the ‘‘cloudy’’ region in the

1x10 0
as-received ZE41 was similar. These particles were in the order of
1 lm for HTZE41 (Fig. 4c) and sub-micron for as-received ZE41 and
1x10 -1 are consistent with what has been reported in the literature
[22,28]. These are distinct from the large Zr-rich particles observed
I (mA/cm 2 )

in the as-received ZE41 [19,20] that are found in the centre of the
1x10 -2
ZE41 Zr-rich regions (Fig. 2).
HTZE41

1x10 -3
4.2.3. The corrosion of HTZE41
The corrosion morphology of HTZE41 was significantly different
1x10 -4 to that observed for the as-received alloy. This will be discussed in
-1.7 -1.65 -1.6 -1.55 -1.5 -1.45 -1.4 relation to the role of the Zr-rich regions within the grains and the
E (V vs. SCE) grain boundary phases.
Fig. 10. Polarisation curves for as-received ZE41 and HTZE41 in borate buffer
solution. 4.2.4. Corrosion at the Zr-rich regions with the grains
The attack associated with the Zr-rich regions and the Zr/Zn
intermetallic particles in the as-received ZE41 was not observed
Table 2 in HTZE41. Fig. 4a shows that the large Zr-rich particles present in
Corrosion potential (Ecorr) and corrosion current (icorr) values for ZE41 and HTZE41 ZE41 were significantly reduced in size by the heat treatment. The
from potentiodynamic polarisation. Average and standard deviation (std dev) values distribution of Zr-rich particles in HTZE41 may offer some corrosion
also presented.
protection and appears to hinder corrosion initiation and propaga-
Ecorr (V vs. SCE) icorr (mA/cm2) tion within the grain, although the entire grain would eventually
ZE41 be corroded, as is evident in Figs. 5 and 6b. The observation that
3
1 1.564 3.30  10 the Zr-rich region provided some corrosion resistance is consistent
3
2 1.562 2.92  10 with the literature, where it has been reported that a Zr-rich region
3
3 1.566 3.11  10
3 can be beneficial for corrosion protection due to the formation of a
Average 1.564 3.11  10
Std dev 0.002 1.90  10 4 more robust oxide layer on the surface of the alloy [22,24,28]. It is
clear from the contrasting effects of the Zr-containing particles in
HTZE41
1 1.514 3.66  10 3 the as-received and HTZE41 that control of the size and distribution
2 1.515 6.92  10 3
of the Zr-containing particles is an important feature in the design of
3
3 1.514 7.64  10 these microstructures for corrosion resistance.
3
Average 1.514 6.08  10
3
Std dev 0.001 2.12  10
4.2.5. Corrosion at the grain boundaries
The initiation of corrosion on the surface of the HTZE41 speci-
mens was via attack at the grain boundaries, which is consistent
HTZE41 (Fig. 4) showed that Zr-rich particles were present within with the as-received ZE41 [19,20]. What was different after this
the grains, and that the ‘‘cloudy’’ region surrounding the Zr-rich initial attack at the grain boundaries was the crater like pitting
particles covered a larger area of the grain compared to the as-re- associated with the Zr-rich intermetallic particles in the as-re-
ceived ZE41. The ‘‘cloudy’’ region in HTZE41 consisted of very small ceived ZE41. The attack at the grain boundaries in HTZE41 ap-
 W.C. Neil et al. / Corrosion Science 53 (2011) 3299–3308 3307

Dissolution continues into more protective oxide of the larger Zr-rich region in the HTZE41,
α -Mg up to boundary of Moves along surface as
Zr-rich region corrosion filaments compared with that of the as-received ZE41.
Zr-rich region

5. Conclusions

Dissolution 1. Heat treatment altered the microstructure of sand-cast ZE41A-

1
around T-phase
2
3 T5 by changing the distribution of the grain boundary T-phase,
and by causing an expansion of the ‘‘cloudy’’ Zr-rich zone. Most
Cross-sectional view Top-down view
of the Zr-rich intermetallics observed in the as-received ZE41
were no longer present after the heat treatment, although some
Fig. 11. Schematic diagram of sequence of corrosion in HTZE41. small particles remained.
2. The corrosion morphology on HTZE41 after immersion in
0.001 M NaCl consisted of grain boundary attack propagating
peared to initiate and travel along the surface as a corrosion fila- in the form of corrosion filaments, with no observed pitting in
ment, consistent with what has been observed in other Mg alloys the centre of the grains.
[33] This travelling corrosion filament started along the grain 3. The sequence of corrosion initiation and propagation involved
boundaries, and then spread further into the grain, attacking the corrosion filaments initiating at the grain boundaries, and
portion of the a-Mg grain not rich in Zr (with the Zr-rich region corrosion filaments following along grain boundary paths.
acting as a boundary). In the HTZE41 alloy, the T-phase was still These filaments progress into the a-Mg grain until they meet
present along the grain boundary (albeit less continuously distrib- the Zr-rich regions.
uted) and this still provided preferential cathodic sites [19]. This
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