Corrosion Science 55 (2012) 351–362

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

Corrosion behaviour of AZ91D and AM50 magnesium alloys with Nd and Gd

additions in humid environments
R. Arrabal a,⇑, E. Matykina a, A. Pardo a, M.C. Merino a, K. Paucar b, M. Mohedano a, P. Casajús a
a
Departamento de Ciencia de Materiales, Facultad de Ciencias Químicas, Universidad Complutense, 28040 Madrid, Spain
b
Gabinete de Corrosión, Facultad de Ingeniería Química y Textil, Universidad Nacional de Ingeniería, Cod. Postal 25, Lima, Peru

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

Article history: AM50 and AZ91D alloys modified with rare earths (RE) were evaluated under atmospheric conditions. Nd
Received 2 September 2011 and Gd additions resulted in formation of Al2RE and Al–Mn–RE compounds and reduction of the fraction
Accepted 29 October 2011 of b-phase. According to surface potential maps, RE-containing intermetallics were more noble than the
Available online 7 November 2011
b-phase, but less than Al–Mn inclusions. As a result, the action of micro-galvanic couples depended on the
added amount of RE and the initial alloy microstructure. Nd or Gd additions improved the corrosion resis-
Keywords: tance of the AM50 alloy by up to 43%, but had no significant effect on the corrosion resistance of the
A. Magnesium
AZ91D alloy.
A. Rare earth elements
B. Weight loss
Ó 2011 Elsevier Ltd. All rights reserved.
C. Atmospheric corrosion

1. Introduction inhibit the pitting corrosion of magnesium in atmosphere (95%

AM and AZ series alloys are amongst the most attractive struc-
tural magnesium alloys in automotive industry and other indus-
tries concerned with weight reduction of the components due to
a combination of corrosion resistance, strength, and ductility.
However, magnesium alloys are susceptible to severe corrosion
in chloride containing solutions [1], therefore their use is mainly
limited to the atmospheric environment, where magnesium alloys
has been reported to perform comparably to mild steel [2].
Corrosion of magnesium in solutions is influenced by concen-
tration of aluminium in the alloy, its distribution in the a-Mg phase
and the amount/morphology of the b-Mg17Al12 phase [1,3]. Surface
film of Mg–Al alloys enriched in Al2O3 increases the stability and
the corrosion resistance of the passive film [4]. Atmospheric
corrosion of magnesium alloys involves a different mechanism
than the one that takes place in solutions. Water reduction is the
main cathodic reaction in solutions; whereas during atmospheric
corrosion thin electrolyte layers form on the surface [5], and the
main cathodic reaction is oxygen reduction [6]. Further, atmo-
spheric corrosion of magnesium alloys depends strongly on the
impurities of alloys such as Fe, Cu and Ni [7,8]. Magnesium in
atmosphere forms a protective film composed of a mixture of mag-
nesium hydroxide, carbonate and sulfate, which is much influ-
enced by relative humidity (RH) and the temperature, due to the
dissociation of water vapor which induces surface oxidation
process [9]. The presence of CO2 gas (up to 350 ppm) is known to
⇑ Corresponding author. Tel.: +34 91 3945227; fax: +34 91 3944357.
E-mail address: raularrabal@quim.ucm.es (R. Arrabal).
relative humidity) due to formation of Mg2(OH)2CO3
3H2O,
whereas in the absence of CO2 localized attack, strongly related
to distribution of noble inclusions, proceeds with formation of
magnesium hydroxide [10–12].
The authors of the present work previously reported that corro-
sion behaviour of AZ31, AZ80 and AZ91D magnesium alloys is
influenced by the aluminium content and alloy microstructure
for relative humidity (RH) values above 90% [13,14]. The initiation
of corrosion was localized around the Al–Mn inclusions in the AZ31
alloy and at the centre of the a-Mg phase in the AZ80 and AZ91D
alloys. The b-Mg17Al12 phase acted as a barrier against corrosion
[13]. Fraction of magnesium carbonate on the surface was shown
to increase with time whereas fraction of magnesium oxide de-
creased [14], however no substantial enrichment of aluminium in
the corrosion products film on the AZ31 alloy was found after
30 days of testing.
Regarding the b-Mg17Al12 phase, low volume fraction and
agglomerated microstructure of this phase serves as galvanic
cathode and accelerates the corrosion process, whereas nearly con-
tinuous phase of a relatively high volume fraction acts as a barrier
against corrosion [15].
Substantial improvement of corrosion resistance of magnesium
alloys can be achieved through the addition of rare earth (RE)
elements. The refinement of the microstructure and formation of
RE-containing phases that are more stable than the b-Mg17Al12
phase also result in improved mechanical properties at high tem-
peratures [16]. The beneficial effects of RE elements on the corro-
sion behaviour of Mg–Al alloys is determined by three main
factors: (i) reduction of the effect of the impurities due to their

0010-938X/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2011.10.038
352 R. Arrabal et al. / Corrosion Science 55 (2012) 351–362

Table 1 casting followed by an extrusion process. Nd and Gd (99.9%) were

Composition of the tested alloys. added to molten alloys at 740 °C protected by a MAGREX 60 slag.
Material Elements (wt.%) Cylindrical casting ingots of 400 mm length and 45 mm diameter
Al Mn Zn Gd Nd Cu Fe Si Mg were homogenised at 350 °C for 24 h and air cooled. The resulting
ingots, rectified to 40 mm in diameter, were extruded at 350 °C
AM50 4.9 0.26 <0.2 – – <0.006 <0.004 <0.06 Bal.
AM50GdB 4.0 0.30 <0.2 0.7 – <0.006 <0.004 <0.06 Bal.
with an extrusion ratio of 4:1 and extrusion rate of 0.4 mm/s. Be-
AM50GdA 4.4 0.24 <0.2 1.0 – <0.006 <0.004 <0.06 Bal. fore cutting the samples of 25 mm thickness, a stress-relieving
AM50NdB 4.4 0.21 <0.2 – 0.8 <0.006 <0.004 <0.06 Bal. treatment at 350 °C for 2 h was performed. The chemical composi-
AM50NdA 4.0 0.24 <0.2 – 1.5 <0.006 <0.004 <0.06 Bal. tions of tested magnesium alloys are given in Table 1. The compo-
AZ91D 8.9 0.19 0.52 – – <0.001 <0.004 <0.01 Bal.
sition of tested alloys was determined using Axios X-ray
AZ91DGdB 8.9 0.15 0.52 0.2 – <0.001 <0.004 <0.01 Bal.
AZ91DGdA 8.0 0.14 0.52 0.7 – <0.001 <0.004 <0.01 Bal. fluorescence instrument (PANalytical).
AZ91DNdB 8.1 0.13 0.52 – 0.7 <0.001 <0.004 <0.01 Bal.
AZ91DNdA 8.1 0.16 0.52 – 1.4 <0.001 <0.004 <0.01 Bal. 2.2. Microstructural characterization

For the metallographic characterization of tested alloys, longi-

entrapment in intermetallic compounds [17]; (ii) formation of
Al-RE phases with low cathodic activity, which reduces the volume
fraction of the Al–Mn intermetallics and, therefore, suppress
micro-galvanic couples [18–21]; (iii) refinement of the microstruc-
ture facilitating the formation of a more uniform b-Mg17Al12 phase
network [22–26].
The present work investigates the corrosion behaviour of AM50
and AZ91D alloys with Nd or Gd additions in laboratory controlled
humid environments with the aim of determination of the role of
RE in atmospheric corrosion of these alloys.
2. Experimental procedure
2.1. Test alloys
The raw original AM50 and AZ91D alloys were supplied by
Magnesium Elektron Ltd. The alloys were fabricated by gravity
tudinal and cross-sections were wet ground through successive
grades of silicon carbide abrasive paper, from P120 to P2000,
followed by diamond finishing to 0.1 lm. Acetic Picral reagent
(4.2 g picric acid + 10 mL acetic acid + 70 mL ethanol + 10 mL
H2O) was used to reveal both constituents and grain boundaries
in the alloys. The constituents were examined by both optical
and scanning electron microscopy (SEM) using a JEOL JSM-6400
microscope equipped with Oxford Link energy dispersive X-ray
(EDX) microanalysis hardware. Quantitative metallography was
performed using the image analysis software ImageJ. For each al-
loy, three different specimens were used. Phase composition was
investigated by low-angle X-ray diffraction (XRD), using a Philips
X’Pert diffractometer (Cu Ka = 1.54056 Å). Surface hardness was
measured, applying a load of 5 kg for 20 s by using an AKASHI
AVK-AII Vickers hardness machine. The cited values are the
average of ten measurements.
Surface potential maps of specimens polished to a 0.1 lm
diamond finish were obtained with a Nanoscope IIIa MultiMode

a b
β-Mg17Al12
Al-Mn

α-Mg

β-Mg17Al12
α -Mg
Al-Mn

c d
β-Mg17Al12
β-Mg17Al12

α-Mg

α-Mg
Al-Mn-Gd/ Al2Gd
Al-Mn-Nd/ Al2Nd

Fig. 1. Optical micrographs of the grain microstructure of (a) AM50, (b) AZ91D, (c) AM50NdB and (d) AZ91DGdA alloys.
 R. Arrabal et al. / Corrosion Science 55 (2012) 351–362 353

atomic force microscope (AFM, Veeco-Digital Instruments) work-
ing in tapping mode. A silicon tip with a platinum-coating of
20 nm thickness was used for simultaneous acquisition of topo-
graphic and surface potential images. The AFM tip was calibrated
by performing a potential ramp on a reference sample consisting
of aluminium coated with a thin gold layer. The tip to sample
distance was kept constant at 20 nm using a two-pass technique,
where the height data is recorded in tapping mode during the first
pass and the tip lifts above the surface to an adjustable lift height
and scans the same line while following the height profile recorded
in the second pass. All measurements were made at room temper-
ature with a relative humidity in the range of 40–65%.
Disc shaped samples with a diameter of 3 mm and 0.1 mm thick
were cut using an Ultrasonic Disk Cutter for transmission electron
microscope (TEM) examination. The thin foils were then ion milled
at room temperature in a Gatan PIPS with a small incident angle
until perforation. The specimens were examined using JEOL
2000-FX TEM instrument operating at 200 keV and equipped with
EDX microanalysis facilities.
2.3. Gravimetric tests
Gravimetric measurements were performed using cylindrical
specimens of working area 7 cm2. The specimens were placed
in the climatic chamber CCK0/81 Dycometal. Mass gain was deter-
mined by measuring mass changes over corrosion time, at regular
intervals of time, at 80, 90 and 98% RH at (50 ± 1) °C for 28 days.
Tests alloys were ground to P1200 grit using series of emery paper
with water as lubricant. Prior to the tests, specimens were mea-
sured and weighed. At the end of the tests, the specimens were
washed with water and then dried with hot air. Later, the samples
were weighed again in order to calculate the mass gain per unit
surface area determined from the expression (Mf–Mi)/A, where Mf
is the final mass, Mi the initial mass, and A the exposed surface
area. Additionally, corrosion rates were calculated using the metal
loss measured by weighing the specimens after removing the cor-
rosion products by pickling in a solution containing 200 g/L CrO3 at
room temperature for 5–10 min. The tests were reproduced twice
to ensure the reliability of the results. Samples were weighed using
a Sartorius BP 211D balance with a precision scale of 0.01 mg.
2.4. Characterization of corrosion products
Once the specimens were evaluated by gravimetric tests, SEM
examination was carried out in order to study the composition,
morphology and evolution of corrosion products formed on the
surface. Likewise, the composition of the corrosion layer was also
analysed by low-angle XRD.
Fourier transform infrared (FTIR) analysis of the materials after
exposure to humid atmosphere was carried out utilising a

Z (0 0 1)
Al10Mn3 200 nm

(1 0 0)

(0 1 0)

a b

Z (0 0 8)
Al2Nd 200 nm

(4 0 0)

(0 2 0)

c d
Fig. 2. Transmission electron micrographs and electron diffraction patterns of the intermetallic particles in (a and b) AM50 alloy; (c and d) AM50NdA alloy.
354 R. Arrabal et al. / Corrosion Science 55 (2012) 351–362

spectrophotometer FTIR Nicolet Magna 750 equipped with Spec-

a 1 1 1 Mg
2 β-Mg17Al12 tra-Tech IR-Plan microscope with Cassgrein 15X objective, refriger-
3 Al-Mn-(Gd,Nd) ated MCT-A detector, KBr beam-splitter and an infrared source
1
4 Al 2Gd EverGlo. The measurement was performed using 128 scans with
3
5 Al 2Nd 1 1 8 cm 1 resolution.
1
Intensity (a.u.)

1
5 25 5 23 1
2 2 2 5 2 12 1 1 1
1 1 AM50NdA
3 11
24 1 4 1 1 1 3. Results
4 2 2 2 23 4 2 2 1 1 1

1 11 AM50GdA 3.1. Microstructural characterization

3
2 1
2 2 23 1 12 1 1
1 Optical micrographs of AM50 and AZ91D alloys reveal equiaxial
AM50
grains of a-Mg phase with an average size of 6.6 and 6.0 lm, respec-
10 20 30 40 50 60 70 80 90 tively, and precipitation of b-phase (Mg17Al12) (Fig. 1a and b). The
Angle (2θ) presence of aluminium and manganese in both alloys results in
the formation of intermetallic Al–Mn phases, such as Al10Mn3 as
b 1 1 1 1 1 Mg shown in TEM micrograph and respective electron diffraction for
2 β-Mg17Al12 AM50 alloy (Fig. 2a and b). The area fraction of Al–Mn intermetallics,
3 Al-Mn-(Gd,Nd) fAl–Mn, in these alloys is 0.2%. A higher area fraction of b-Mg17Al12
1 4 Al 2Gd
phase, fb, is observed in the AZ91D alloy (fb = 7.1%), due to its high-
1 5 Al 2Nd
1 er Al content compared with the AM50 alloy (fb = 0.5%).
Intensity (a.u.)

5 25 2 1
5 5 2 1 1 1 The additions of Nd or Gd into AM50 alloy induce the decrease
2 5 25 1
AZ91DNdA of the proportion of the b-phase down to 0.1–0.2%, while the
2 11 grain size of a-phase remains relatively unchanged (6.1–7.7 lm)
1
4 4 42 2 1 1
2 3 4 4 2 12 1 1 compared with the AM50 alloy. At low concentration (0.8 wt.%),
1 AZ91DGdA Nd is mainly present in Al–Mn–Nd inclusions (Fig. 1c). A higher
1
3 2 1 concentration of Nd (1.5 wt.%) leads to formation of both Al2Nd,
1 1
2 2 2 23 2 1 2 2 1 1 as indicated by TEM, (Fig. 2c and d) and Al–Mn–Nd intermetallic
AZ91D compounds. The area fraction of Nd-containing intermetallics is
10 20 30 40 50 60 70 80 90 higher than that of Al–Mn inclusions in the unmodified AM50 alloy
with values of 1.3% and 2.2% for the AM50NdB and AM50NdA
Angle (2θ)
alloys, respectively. Analogous microstructures are observed for
Fig. 3. Typical X-ray diffraction patterns of the selected alloys before exposure to AM50GdA and AM50GdB alloys, whose area fractions of Gd-con-
humid atmosphere. taining intermetallics are 1.2% and 1.3%, respectively.
Surface Potential (mV)

300
c) Al-Mn
200

100

α-Mg
0
0 2 4 6 8 10 12 14
a Distance (μm) b
Fig. 4. (a) Topographic image; (b) surface potential map; (c) potential profile of Al–Mn inclusion in the AM50 alloy.
 R. Arrabal et al. / Corrosion Science 55 (2012) 351–362 355

Surface Potential (mV)

60
c)

40

β-Mg17Al12
20 α-Mg

0
0.0 0.5 1.0 1.5
Distance (μm)
Fig. 5. (a) Topographic image; (b) surface potential map; (c) potential profile of b-Mg17Al12 phase in the AZ91D alloy.

200
Surface Potential (mV)

d) 5
150

100
1
50
α-Mg
0
0 4 8 12 16 20
a Distance (μm) b

Fig. 6. (a) SEM micrograph; (b) topographic image; (c) surface potential map; (d) potential profile of Nd-containing phases in the AZ91DNdA alloy (See Table 2).
356 R. Arrabal et al. / Corrosion Science 55 (2012) 351–362

Table 2 compared with the mother alloy (Fig. 1d). This significant grain
Results of the local EDX analysis of the intermetallic particles presented in Fig. 6a. coarsening, not observed in the AM50 alloy, was attributed to the
Location Elements (at.%) large reduction in the amount of b-phase, from 7.1% in the
Al Mn Fe Nd unmodified AZ91D alloy down to values as low as 2.6% in case
of AZ91DNdA alloy. Nd and Gd additions in AZ91D alloy are located
1 68.5 – 0.6 30.9
2 77.6 – 0.4 22.0
in Al–Mn–Nd, Al–Mn–Gd, Al2Nd and Al2Gd intermetallic particle
3 72.6 0.4 0.4 26.6 inclusions. The area fractions of these intermetallics are between
4 70.7 – 0.6 28.8 0.3–0.6% and 1.2–2.1% in Gd- and Nd-containing alloys,
5 68.1 26.1 0.5 5.3 respectively.
6 62.8 13.2 0.8 23.2
As indicated by XRD analysis, Al2Nd and Al2Gd are the main
composition for the Al–Nd and Al–Gd intermetallic particles in
the alloys with higher concentration of Nd and Gd (Fig. 3).
The addition of Nd or Gd into AZ91D alloy resulted in a micro- The information about the local nobility of the different micro-
structure with larger grain size of a-Mg phase (10.8–11.9 lm) structural phases on a submicron scale was obtained using AFM

80 80
98%-50ºC AM50
70 70 98%-50ºC AZ91

Mass change (μg/cm2 )

Mass change (μ g/cm2 )

90%-50ºC
60 60 90%-50ºC
80%-50ºC
50 50 80%-50ºC
μ

40 40
30 30
20 20

10 10

0 0
0 10 20 30 0 10 20 30
Time (days) Time (days)

80 80
70 98%-50ºC AM50 GdB 70 98%-50ºC AZ91 GdB
Mass change (μg/cm2 )
Mass change (μ g/cm2 )

90%-50ºC 60 90%-50ºC
60
80%-50ºC 50 80%-50ºC
50
μ

40 40

30 30

20 20

10 10
0
0
0 10 20 30 0 10 20 30
Time (days)
Time (days)

98%-50ºC 80
80
90%-50ºC
AM50 GdA 98%-50ºC AZ91 GdA
70 70
Mass change (μg/cm2 )

80%-50ºC
Mass change (μg/cm2 )

90%-50ºC
60 60
50 50 80%-50ºC

40 40
30 30
20 20
10 10
0
0
0 10 20 30
Time (days) 0 10 20 30
Time (days)

Fig. 7. Dependence of mass change on time for materials exposed to high humidity environments at 50 °C.
 R. Arrabal et al. / Corrosion Science 55 (2012) 351–362 357

80 80
70
98%-50ºC AM50 NdB 70
98%-50ºC AZ91 NdB

Mass change (μ g/cm2 )

Mass change (μ g/cm2 )

90%-50ºC 60 90%-50ºC
60
50 80%-50ºC 50 80%-50ºC

μ
μ

40 40
30 30
20 20
10 10
0 0
0 10 20 30 0 10 20 30
Time (days) Time (days)

80 80
70
98%-50ºC AM50 NdA 98%-50ºC AZ91 NdA
70
Mass change (μ g/cm2 )

Mass change (μ g/cm2 )

90%-50ºC 90%-50ºC
60 60
50 80%-50ºC 80%-50ºC
50
μ

μ
40 40
30 30
20 20
10 10
0 0
0 10 20 30 0 10 20 30
Time (days) Time (days)

Fig. 7 (continued)

(Figs. 4–6). The topographical images, surface potential images and
potential profiles of the AM50 alloy show that Al–Mn particles are
by 220 mV more cathodic compared with the surrounding mag-
nesium matrix (Fig. 4), whereas the b-Mg17Al12 phase reveals only
20–40 mV of potential difference with the matrix (Fig. 5), sug-
gesting a stronger galvanic couple between the Al–Mn inclusions
and the a-Mg phase. These values were similar to those observed
for the AZ91D alloy and other Mg–Al alloys [27].
Fig. 6 shows the SEM micrograph, topographic image, surface
potential map and potential profile of a selected area of the
AZ91DNdA alloy, corresponding to Nd-containing intermetallic
particles. Table 2 shows the results of EDX local analysis of the
particles in Fig. 6. Al–Mn–Nd particles (location 5, Table 2,
Fig. 6d) reveal a potential about 160 mV more cathodic than
the magnesium matrix, whereas the behaviour of Al2Nd particles
(location 1, Table 2, Fig. 6d) is similar to that of the b-Mg17Al12
phase, with a potential difference of 30 mV. The data in Table 2
and Fig. 6c indicates that Mn content reduces with the incorpora-
tion of Nd and consequently the nobility of Al–Mn particles de-
creases. In case of intermetallic compounds containing Gd,
potential differences with the matrix were also below those ob-
served for the Al–Mn inclusions and close to or slightly higher than
those observed for the b-phase.
3.2. Gravimetric results
Fig. 7 shows the mass gain versus time for the alloys tested at
different RH over 28 days. All the mass gain dependencies followed
a parabolic law indicating initial dissolution of magnesium fol-
lowed by the formation of a protective corrosion products layer.
All the alloys exhibited a similar behaviour at 80% RH, with the
average mass gain of about 15 lg/cm2, possibly associated with
the water adsorption in the surface of the alloy and the formation
of a corrosion layer of Mg(OH)2. Variation of the mass gain
becomes notable at increased RH values, more so for AM50 alloys
than for AZ91D alloy; the mass gain increased from 3.3 to 4.7
times. The effect of the additions of Gd and Nd to the AM50 alloy
becomes evident at the 90% and 98% RH and leads to a reduction
in the mass gain by approximately 43–55%.
The additions of the lanthanides into the AZ91D alloy led to a
greater differentiation in corrosion behaviour of the alloy at 90%
and 98% RH, compared with the mother alloy. The mass gains ob-
tained at the same values of RH for various concentrations of Nd
and Gd were very similar between each other and similar to (or
slightly higher than) that for the mother alloy. These results are
opposite to those of the AM50 alloy and indicate that Nd and Gd
additions have a different effect on the corrosion behaviour of
AM50 and AZ91D alloys.
The corrosion rates, PW, calculated from weight loss measure-
ments after removing the corrosion products by pickling in a solu-
tion containing 200 g/L CrO3 at room temperature for 5–10 min are
shown in Fig. 8. At 98% RH, the AZ91D alloy exhibited lower corro-
sion rate than the AM50 alloy by a factor of 2.1. Further, reduction
of RH from 98% to 80% reduced the PW values from 4.5 to 1.6 lm/
year for the AM50 alloy and from 2.1 to 0.2 lm/year for the AZ91D
alloy. Gd and Nd additions clearly improved the atmospheric cor-
rosion behaviour of the AM50 alloy. In most cases, AM50GdB and
AM50NdB alloys reveal the lowest corrosion rates (between 3.6
and 0.3 lm/year, depending on the relative humidity) (Fig. 8a). A
less clear effect is observed in case of the AZ91D alloy since corro-
358 R. Arrabal et al. / Corrosion Science 55 (2012) 351–362
a 5
o AZ91DNdA alloys (1.4 wt.% and 1.5 wt.% of Nd, respectively) were
98% HR-50 C
o
90% HR-50 C
4 o
80% HR-50 C
PW (μm/year)
3
2 compared with the surface appearance of the mother alloys
1 uous protective corrosion layer in the areas without localized
0 sure to the atmposphere with 98% RH/50 °C for 28 days revealed
AM50 AM50GdB AM50GdA AM50NdB AM50NdA
b 5
98% HR-50 C
o corrosion products formed on AM50, AM50NdA, AM50GdA, and
o AZ91DNdA alloys, in accordance with their macro- and micro-
90% HR-50 C
o scopic surface appearance.
4 80% HR-50 C
PW (μm/year)
3
2
1
0
AZ91 AZ91GdB AZ91GdA AZ91NdB AZ91NdA
Fig. 8. Corrosion rates for the alloys determined after exposure to high humidity
environments at 50 °C: (a) AM50 alloys; (b) AZ91D alloys.
sion rate values of modified alloys are similar or even higher than
those of the mother alloy.
3.3. Morphology, composition and microstructure of corrosion
products
Fig. 9 shows the surface appearances of test alloys after expo-
sure to an atmosphere with 80–98% RH at 50 °C for 28 days. The
surface degradation for all alloys at 80–90% RH and 50 °C was less
significant than the one observed at 98% RH, as it can be seen on
the example of AM50 and AZ91D alloys (Fig. 9a). At 98% RH and
50 °C a duller surface appearance and signs of localized surface
corrosion are readily visible (Fig. 9b). The unmodified AZ91D alloy,
with higher aluminium content, exhibited lower degree of corro-
sion than the AM50 alloy. Small additions of Nd (0.8 wt.%) or Gd
(0.7 wt.%) considerably decreased the surface degradation of
AM50 alloy. However, the appearance of the AM50 alloys with fur-
ther additions of Nd and Gd (1.5 wt.% and 1.0 wt.%, respectively)
slightly deteriorated compared with the AM50NdB and AM50GdB
alloys, as the areas with localized corrosion have extended. Com-
pared with unmodified AM50 alloy, elevated content of Gd and
Nd offered negligible improvement in corrosion resistance
(Fig. 9b). A less obvious trend was observed in case of the modified
AZ91D alloys. The AZ91DNdA alloy with higher addition of Nd
(1.4 wt.%) clearly revealed a higher level of corrosion than the
mother alloy, whereas the rest of the materials shown a similar
surface appearance compared with AZ91D alloy.
To reveal the initiation of corrosion attack, AM50NdA and
polished and exposed to 98% RH atmosphere at 50 °C for 1 h.
SEM examination of the materials (Fig. 10) indicates that corrosion
attack commenced in the centre of a-Mg grains and is often asso-
ciated with Al–Mn inclusions. After 28 days of exposure of ground
samples at 98% RH and 50 °C the surface examination of AM50GdB
(0.7 wt.% Gd) and AZ91DGdB (0.2 wt.% Gd) alloys reveals that the
addition of Gd has considerably reduced localized corrosion
(Fig. 11). Cross-sectional backscattered electron micrograph of
the AZ91GdA alloy (0.7 wt.% Gd) reveales about 2 lm-thick contin-
corrosion (Fig. 12).
The low-angle (1°) X-ray diffractograms of the alloys after expo-
peaks corresponding to the substrate and corrosion products in
the form of brucite (Mg(OH)2) and hydromagnesite (Mg5(CO3)4
(OH)2
4H2O) (Fig. 13). Higher intensity peaks were observed for
X-ray findings were confirmed by the results of FTIR analysis of
the corrosion products: all of the materials exhibited a peak at
3683 cm 1, corresponding to brucite as the main corrosion prod-
uct, more readily visible for the AM50 alloys (Figs. 14 and 15).
The presence of hydromagnesite was manifested through a group
of peaks at 3435, 1646, 1118, 879, 852 and 794 cm 1. In particular,
the stretch of 3645–3509 cm 1 represents the vibration bands of
OH–/H2O group of hydromagnesite and the asymmetric bending
peaks at 1477 and 1411 cm 1 correspond to (CO3)2 groups. The
intensity of the latter peaks is particularly prominent in the mate-
rials with Nd and Gd additives, suggesting that hydromagnesite
constitutes a significant fraction of the corrosion products in the
presence of these lanthanides. Conversely, these hydromagnesite
peaks are practically absent in AM50 alloy, indicating that brucite
is the main corrosion product. These differences could be associ-
ated with an easier CO2 diffusion through the corrosion products
in the modified alloys, although a more quantitative study is
needed in order to confirm this.
4. Discussion
All materials have demonstrated an excellent corrosion perfor-
mance with no or negligible visible signs of surface degradation in
atmospheres with RH of 80% and 90% at 50 °C. Notable changes and
differentiation in corrosion behaviour of various alloys manifested
themselves at 98% RH in the form of localized corrosion. Firstly, as
expected, AZ91D alloy revealed smaller surface degradation than
AM50 alloy due to higher aluminium content in its a-phase and
a b-phase acting as physical barrier against corrosion attack
[28–30]. The main corrosion products consisted of Mg(OH)2 and
Mg5(CO3)4(OH)2
4H2O, which are common for atmospheric corro-
sion of Mg alloys [14].
The addition of Nd and Gd into AM50 and AZ91D magnesium
alloys led to formation of Al2Nd, Al2Gd, Al–Mn–Nd and Al–Mn–
Gd instead of Mg–RE intermetallic compounds due to a larger
difference in electronegativity between the RE and Al than that
between RE and Mg [31]. As the melting point of Al2RE and Al–
Mn–RE phases is much greater than that of the b-Mg17Al12 phase
(Tm = 435 °C), the incorporation of Al into these phases reduced
the volume fraction of b-Mg17Al12 phase from 0.5% and 7.1%
down to 0.1% and 2.6% in the AM50 and AZ91D alloys, respec-
tively. These microstructural characteristics are in agreement with
those previously reported for similar Mg–Al alloys with addition of
 R. Arrabal et al. / Corrosion Science 55 (2012) 351–362 359

Fig. 9. Surface appearance of the materials after exposure to humid atmosphere (a) AM50 and AZ91D at 50 °C and 80–98% RH; (b) AM50 and AZ91D alloys with additions of
Nd or Gd at 50 °C and 98% RH. Specimen diameter: 20 mm.

a b Al-Mn-Nd
Al-Mn-Nd
Corrosion

Corrosion

100 μm 100 μm

Fig. 10. Secondary electron micrograph of the initial stages of corrosion attack after 1 h exposure to the atmposphere with 98% RH/50 °C: (a) AM50NdA; (b) AZ91DNdA.

RE elements [22,32]. Surface potential maps and EDX analysis of
second-phase particles confirmed that RE-containing intermetallic
inclusions were less cathodic than the Al–Mn particles of the
mother alloys. In particular, greater incorporation of RE element
into the particle accompanied with its depletion in Mn resulted
in decrease of the potential difference between the RE-containing
particles and the a-Mg matrix. In this study, the potential values
of Al2RE intermetallics were comparable to those obtained by Liu
[33] on the AM60 alloy modified with Ce or La.
The effect of Gd and Nd additions on the atmospheric corrosion
behaviour of AM50 and AZ91D alloys is complex and it is closely
related to changes in the microstructure of the alloys, in particular,
to variations in composition and area fraction of secondary phases,
resulting in significant differences between the AM50 and AZ91D
alloys. On the one hand, in view of the fact that atmospheric corro-
sion is an electrochemical process between micro-anodes and
micro-cathodes, the addition of Gd and Nd diminish the effect of
micro-galvanic couples due to complete replacement of Al–Mn
360 R. Arrabal et al. / Corrosion Science 55 (2012) 351–362

a b

100 μm 100 μm

c d

100 μm 100 μm

Fig. 11. Secondary electron micrograph of the surface of the alloys after exposure to the atmposphere with 98% RH/50 °C for 28 d: (a) AM50; (b) AM50GdB; (c) AZ91D; (d)
AZ91DGdB.

a 111 1 Mg
2 β-Mg17Al12
3 Al-Mn
4 Al 2Gd/Al2Nd
Al-Mn-Nd 3 5 Mg(OH)2
Corrosion layer 2 6 Mg5(CO3)4(OH)2.4H2O
Intensity (a.u.)

6 4 4 4 2 21 41 2 1 11 1 1
6 6 3
2 4 1 1 1 AM50NdA
2 1 1 1
6 5 6 3 1 1 1 AM50NdB
2 4 1
2 1 1
3
5 6 2 42 2 1 1 AM50GdA
2 1 1 1
3
5 6 2 2 2 21 1
2 1 1 1 1AM50GdB
AM50

20 40 60 80
Angle (2Θ)

200 μm
b 1 1 1

Fig. 12. Backscattered electron micrograph of the cross-section of AZ91DGdA alloy 1

after exposure to the atmposphere with 98% RH/50 °C for 28 days. 11
1
Intensity (a.u.)

1
4
6 4 6 34 4 2 1 1
particles by less noble Al2RE and Al–Mn–RE intermetallics. How- 5 2 222 4 1 1 1
6 4 6 2 2 1 AZ91DNdA
ever, an excessive addition of Gd and Nd leads to an overall 4
1
increase of the total cathodic area and subsequently to increasing 6 54 3 4 2 2 1 AZ91DNdB
2 4
corrosion rates. This behaviour was evident for the modified 3 2 1 AZ91DGdA
56 2 4 2
AM50 alloy. Indeed, under the majority of tested conditions, 11
5 2 2 21 1 2 1 111 1 AZ91DGdB
AM50NdB and AM50GdB alloys revealed lower corrosion rates
AZ91D
than AM50, AM50NdA and AM50GdA alloys. The same cannot be
said for the AZ91D alloy. In this case, addition of RE elements re-
20 40 60 80
sulted in similar or even higher corrosion rates with respect to
Angle (2Θ)
the mother alloy. Based on surface potential maps and area fraction
measurements, this behaviour is undoubtedly related to a greater Fig. 13. Low angle (1°) X-ray diffractograms of the modified AM50 alloys (a) and
relative diminishment of the b-Mg17Al12 phase in AZ91D alloy than modified AZ91D alloys (b) after exposure to the atmposphere with 98% RH/50 °C for
in AM50 alloy, more so in the presence of Nd than Gd (The fb value 28 d.
 R. Arrabal et al. / Corrosion Science 55 (2012) 351–362 361

a 0.4 a 0.5

3435
3509
3645
3683
AM50NdA

3435
0.4

3509
3645
0.3

3683
AM50NdB AZ91DNdA
AM50GdA

Absorbance
0.3
Absorbance

AZ91DNdB
0.2 AZ91DGdA
AM50GdB 0.2

AZ91DGdB
0.1 0.1
AM50 AZ91D

0.0
0.0 4000 3800 3600 3400 3200 3000
4000 3800 3600 3400 3200 3000 -1
-1
Wavelength (cm )
Wavelength (cm )
b 0.5

1411
b 0.7

1477

1118

794
852
879
1646
0.6 0.4
1411

AZ91DNdA
1477
1646

1118

0.5
794

Absorbance
852
879

0.3
AM50NdA
Absorbance

0.4
AM50NdB
0.2 AZ91DNdB
0.3 AZ91DGdA
AM50GdA
0.2 0.1 AZ91DGdB
AZ91D
0.1 AM50GdB 0.0
AM50 1800 1600 1400 1200 1000 800 600
0.0
-1
1800 1600 1400 1200 1000 800 600 Wavelength (cm )
-1
Wavelength (cm ) Fig. 15. Fourier transform infrared spectra of the AZ91D alloy with and without Gd
and Nd additions after exposure to the atmposphere with 98% RH/50 °C for 28 d: (a)
Fig. 14. Fourier transform infrared spectra of the AM50 alloy with and without Gd 4000–3000 cm 1 and (b) 1800–600 cm 1.
and Nd additions after exposure to the atmposphere with 98% RH/50 °C for 28 d: (a)
4000–3000 cm 1 and (b) 1800–600 cm 1.

in the AZ91D alloy changes from 7.1% down to 4.4% and 2.6%
in the AZ91DGdA and AZ91DNdA alloys, respectively), and to the
concomitant replacement of b-phase by more noble Al2RE and
Al–Mn–RE intermetallics.
In summary, Gd and Nd additions reduce the effect of micro-
galvanic couples and, consequently, the corrosion rate of Mg–Al al-
loys in humid environments as long as Al–Mn inclusions are being
replaced by RE-containing intermetallics. However, if there is a sig-
nificant substitution of b-phase by more noble RE-intermetallics,
the effect of micro-galvanic couples may increase again and result
in similar or even higher corrosion rates of modified alloys with re-
spect to the mother alloys. Hence, these two competing processes
should be considered when adding RE to Mg–Al alloys.
5. Conclusions
1. The addition of Nd or Gd to AM50 and AZ91D alloys has modi-
fied the microstructure of the mother alloys resulting in the for-
mation of Al2RE and Al–Mn-RE intermetallic compounds and
consequent reduction of the fraction of b-Mg17Al12 phase.
2. Gd- and Nd-containing intermetallic particles with increased
content of RE elements and reduced content of Mn are less
noble than Al–Mn inclusions but slightly more noble than the
b-phase.
3. At 80, 90 and 98% RH, the AZ91D alloy revealed lower corrosion
rate than the AM50 alloy. Higher relative humidity leads to
increased surface degradation and formation of corrosion prod-
ucts consisting of brucite (Mg(OH)2) and hydromagnesite
(Mg5(CO3)4(OH)2
4H2O). Corrosion resistance of AM50 alloys
improved with the addition of Nd or Gd by up to 43%. Additions
of Gd and Nd give no significant benefit to corrosion resistance
of AZ91D alloy in high humidity atmospheres.
Acknowledgements
The authors are grateful to the MCYT (Spain, Project MAT 2009-
09845-C02-01) and the MANOEQ of Departamento de Metalurgia
Física of CENIM (CSIC) for supply of the test materials. R. Arrabal
and E. Matykina are grateful to the MICINN (Spain) for financial
support via the Ramon y Cajal Programme (RYC-2008-02038,
RYC-2010-06749). K. Paucar is grateful to the Fundación Carolina
for funding a grant.
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