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Corrosion Science 86 (2014) 285294

Contents lists available at ScienceDirect

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

Degradation behaviour of AZ80E magnesium alloy exposed to phosphate


buffer saline medium
F. El-Taib Heakal a,, O.S. Shehata b, N.S. Tantawy c
a

Chemistry Department, Faculty of Science, Cairo University, Giza 12613, Egypt


Physical Chemistry Department, National Research Centre, Dokki, Giza, Egypt
c
Faculty of Arts, Science and Education, Ain Shams University, Asmaa Fahmi Street, Cairo, Egypt
b

a r t i c l e

i n f o

Article history:
Received 22 April 2014
Accepted 2 June 2014
Available online 11 June 2014
Keywords:
A. Alloy
A. Magnesium
B. EIS
B. SEM
C. Hydrogen overvoltage
C. Passivity

a b s t r a c t
Corrosion behaviour of AZ80E alloy in comparison with pure Mg was investigated in phosphate buffer
saline (PBS) solution in order to assess its bioactivity. Open circuit potential and EIS results reveal that
both samples exhibit self-passivation with time. The higher corrosion resistance of the alloy is discussed
from the perspective of its microstructure. Anodic oxidation for the alloy surface in borate buffer solution
was also attempted potentiostatically to modify its corrosion behaviour. Anodised specimen at controlled
potential of 1.0 V(SCE) can improve the durability of the alloy in PBS medium. The results were further
conrmed by SEM and EDX analyses.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Magnesium and its alloys are light materials possessing suitable
mechanical properties and high strength to weight ratios [1],
which render them valuable candidates for many industrial applications, such as automotive and aerospace parts, electronic
devices, diving gear and sporting goods. Among the various commercial Mg alloys, those developed from the AlZn ternary system,
as named AZ alloys, have found the largest number of industrial
applications [2]. Additionally, the favourable intrinsic biocompatibility and high reactivity of magnesium matrix during service
make magnesium alloys attractive ideal materials to develop
degradable biomedical devices such as orthopaedic tools and vascular stents [311]. The development of biodegradable implants
is one of the important areas in medical science [12]. This is
because when using temporary xation implant materials, which
dissolve in biological environments after a certain time of functional use, a second surgery to remove the implants from the
human body after the tissues have healed may not be necessary
[10,13]. Repeated surgery increases health costs and further morbidity to the patient. Compared with traditional implants such as
stainless steels, cobalt based alloys and titanium alloys as well as
biodegradable polymeric and ceramic materials, magnesium alloys
Corresponding author. Tel.: +20 102449048; fax: +20 235728099.
E-mail address: fakihaheakal@yahoo.com (F. El-Taib Heakal).
http://dx.doi.org/10.1016/j.corsci.2014.06.008
0010-938X/ 2014 Elsevier Ltd. All rights reserved.

are more attractive for their outstanding biological performance


[14]. Moreover, Mg2+ is an essential macro-element for many
metabolism reactions and presents in large amounts in the human
body, being the fourth most abundant cation [15]. It is a co-factor
in many enzymes, and a key component of ribosomal machinery
that translates the genetic information encoded by mRNA into
polypeptide structures [10,16]. The daily intake of Mg for a normal
adult is about 250500 mg, and excess Mg2+ cations is harmless
and can be gradually dissolved, absorbed or consumed by the
human body or excreted in the urine effectively [15]. On the other
hand, current biodegradable implant made of polymer such as
poly-L-lactic acid have an unsatisfactory mechanical strength and
therefore limited applications [11,15]. Moreover, the elastic modulus (4145 GPa) and compressive yield strength (65100 MPa) of
magnesium are closer to those of human bodys bone (320 GPa)
and (130180 MPa) than other implant materials. In addition,
magnesium alloys possess a density of 1.742.0 g cm3, which
is close to that of natural bones (1.82.1 g cm3). All these similarities can minimise or avoid the stress shielding effect which is the
cause for reducing stimulation of new bone growth and decreasing
implant stability [15,16].
Extensive fundamental investigations and evaluations dealing
with the biodegradable behaviours of AZ (MgAlZn) series of
magnesium alloys, such as AZ31 and AZ91 in various physiological
environments are reported in the literatures [1721]. However,
relatively very few work is found on AZ80 alloy [22], which is

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F. El-Taib Heakal et al. / Corrosion Science 86 (2014) 285294

becoming commercially known due to its high strength and low


price [23], and so its degradation activity is still a subject of significant eld of research. Therefore, the present study aimed to investigate the corrosion activity of the biocompatible AZ80E
magnesium alloy at a constant temperature of 37 C in PBS medium relative to its base metal (Mg). PBS is commonly used to simulate the biological solution due to its osmolarity and ion
concentrations which match those of the human body, being an
isotonic and non-toxic medium to living cells. Electrochemical
techniques including open circuit potential (OCP) evolution, electrochemical impedance spectroscopy (EIS) and potentiodynamic
polarisation measurements were employed to compare the corrodibility of AZ80E alloy with its pure Mg metal. Furthermore, to
improve the corrosion resistance which is an important issue for
the application of Mg alloys as biodegradable load-bearing
implants, electrochemical passivation could be employed as a
promising method [24]. Therefore, it was also intended to investigate the corrosion performance of some anodised AZ80E specimens in PBS medium relative to the behaviour of the as-abraded
sample. SEM micrographs of alloy specimens under various
conditions were carried out to further support the electrochemical
information for better understanding the obtained results.

2. Experimental
The working electrodes were chips of pure Mg (99.94%) and
extruded AZ80E magnesium alloy with composition (in wt%) as follows: 8.2 Al, 0.46 Zn, 0.13 Mn, 0.01 Si, 0.004 Fe and <0.001 C, and
were cut into coupons. Extrusion, as one of the bulk-metal forming
processes, is of signicant importance for the production of seminished components. Extruded Mg alloys are more widely used
because of their considerably high plasticity in comparison with
the die-cast Mg alloys [25]. Each coupon has a nominal exposed
area of 0.25 cm2 and was encapsulated into a glass tube with
Araldit epoxy resin, leaving its rectangular cross sectional area to
face the solution. Before each experiment the electrodes were
abraded with sequacious grades of emery papers from 400 grit
down to 1500 grit, rubbed with acetone, rinsed with deionised
water and dried in the air. Anodic oxidation of AZ80E alloy was
performed in borate buffer solution of pH 9.2 containing 0.5 M Na2B4O710H2O and 0.006 M H3BO3 [26], at controlled potential of
1.35 and 1.0 V(SCE) for 10 min in order to attain a steady-state
conditions. The passive electrode was rinsed with deionised water,
dried in air, and quickly transferred to the test medium. The corrosion resistance of AZ80E either with native or a borate passive lm
was monitored with time in the test biological uid consisting
from phosphate buffer saline (PBS) solution of composition (in
g L1) as [20,27]: 8.006 NaCl, 0.201 KCl, 1.420 Na2HPO4 and
0.240 KH2PO4 (pH 7.4). All salts are Analar grade reagents and used
as supplied for preparing the solutions with deionised water.
Measurements were carried out in a typical three-electrode electrolytic cell furnished with a large area platinum sheet of size
40 mm  20 mm  2 mm as a counter electrode and a saturated
calomel (SCE) reference electrode (ESCE = 0.242 V versus SHE). The
tip of the Luggin capillary included in the design was made very
close to the surface of the working electrode to minimise the IR
drop. All potentials were measured and referred to the SCE reference electrode. An electrochemical workstation IM6e Zhaner elektrik, Mebtechnik Kronach, Germany, controlled by personal
computer was used as a measuring instrument for electrochemical
impedance spectroscopy, potentiodynamic and potentiostatic
techniques. Cathodic and anodic polarisation curves were traced
at a scan rate of 1 mV s1. EIS was conducted at the open-circuit
potential (OCP) after different exposure periods extended up to
24 h, by applying 10 mV peak to peak sinusoidal excitation signal

in the frequency domain from 100 kHz down to 100 mHz. Per each
frequency decade, 3, 5 or 9 experimental points were collected
during the measurements. The EIS data were then simulated using
Thales software and an appropriate equivalent electric circuit
(EEC). Corrosion current density (icorr) which is equivalent to the
corrosion rate of the specimen was estimated by extrapolation of
the cathodic Tafel branch of the polarisation curve back to the
active state corrosion potential (Ecorr), namely to the potential at
which the anodic and cathodic reactions at the working
electrode/solution interface were balanced [26,28] using Thales
software for i-E analysis. All experiments were carried out inside
an air thermostat regulated at 37 C. In all cases the tests were conducted in triplicate using a new surface and fresh solution to examine the reliability of the results. SEM micrographs were collected
using JEOL JXA-840A electron probe micro-analyser (Japan)
equipped with EDX micro-analyser, to compare the surface morphologies of specimens after various surface treatments.
3. Results and discussion
3.1. Open circuit potential measurements
The open circuit potential (Eoc) of AZ80E alloy in comparison
with pure Mg was traced over 24 h in phosphate buffer saline
(PBS) medium. As shown in Fig. 1 the evolution of OCP over the
rst hour of immersion reveals a fast decrease in Eoc value for both
materials, which is likely related to partial dissolution of the native
oxide/hydroxide lm on the sample surface. This initial decrease is
followed by a gradual increase in Eoc reaching a maximum value of
1.616 V(SCE) after 12 h for the alloy and 1.582 V(SCE) after 9 h
for the metal before resuming a very less sharp decrease again. The
shift of electrode potential towards the positive direction with
time indicates a propensity for the sample to passivate due to its
interaction with PBS medium and deposition of a protective corrosion products. On the other hand, the decrease in Eoc implies a
natural tendency for the formed surface lm to dissolve at longterm immersion. When the sample is exposed to an aqueous
corrosive medium, the following reactions take place in neutral
range of pH [17]:

Anodic partial reaction Mgs ! Mg2 2e

Cathodic partial reaction 2H2 O 2e ! H2 g 2OH

-1.57
-1.58
-1.59

Eoc / V (SCE)

286

-1.60
-1.61
-1.62
-1.63

Mg
alloy

-1.64
-1.65
0

12

15

18

21

24

27

Time / h
Fig. 1. Evolution of the open circuit potential (Eoc) for pure Mg and AZ80E
electrodes in naturally aerated PBS medium at 37 C.

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The overall corrosion reaction can thus be described as follows:


2

Mgs 2H2 O ! Mg

2OH H2 g

When the solubility limit is exceeded, Mg(OH)2(s) will precipitate (Ksp = 1.8  1011) [22,29] and the corrosion product lm
formed on the sample surface can be attributed to this dissolutionprecipitation mechanism. As can be recognised, during the
whole testing time the potential of Mg electrode is kept higher
than the alloy. This may be related to the difference in the nature
of the surface lm on each sample either chemically or physically
(such as its thickness and/or microstructure). Perhaps, the lower
electrode potential of the alloy may suggest that hydrogen
evolution on the alloy (as a main cathodic partial reaction in the
corrosion process) occurs at lower overpotential than on pure
Mg. This will be further explored using the following ac and dc
electrochemical results.
3.2. EIS measurements
Impedance spectroscopy is an extremely powerful nondestructive investigative technique which can provide essential
information about the assessment of in vitro bioactivity of AZ80E
alloy during immersion in articial bio-uid. In these experiments
the immersion of Mg and its alloy was carried out continuously in
PBS medium, which is used to simulate the biochemical reactions
of degradable magnesium materials in physiological conditions at

the pH level of body uid (7.47.6). Figs. 2 and 3 present the


impedance spectra recorded after different time intervals of electrode immersion for pure Mg and AZ80E alloy, respectively as Bode
and Nyquist plots in PBS solution. In both cases the impedance
spectra show two merged time constants that are typically
observed in the impedance spectra of the Mg alloys [22,3032].
As can be clearly seen, on the Bode format the impedance spectra
show two resistive regions at high and low frequency ranges (HF
and LF), where log |Z| tends to become constant (horizontal segment) with phase angle value falling towards zero degree
(h  0). At the HF range solution resistance (Rs) dominates, whilst
at the LF range both (Rs + Rct) are the dominant parameters, where
Rct is the charge transfer resistance at the metal/solution interface.
However, in the middle frequency range (MF) the Bode plots are all
characterised by a capacitative contribution, which corresponds to
a maximum in the phase angle h versus log f plot [33]. The impedance modulus (|Z|) as well as the phase angle (h) for both materials
are clearly found to depend on the immersion time. It is of interest
to observe that |Z| experiences a continuous and sharp increase in
its value from the incipient of immersion up to 9 h for Mg
(Fig. 2(a)) and 12 h for the alloy (Fig. 3(a)), afterwards its value
decreases when the immersion time is extended to 24 h. This

-80

4.0

-70

3.6

3.5

-70

-60
-60

2.4

-30
2.0

-30

-10

0
-1

z'' / cm 2

0.4434

z'' / cm2

30 min
1h
3
6
9
12
24

-1000

30 min
1h
3h
6h
9h
12 h
24 h

-2000

0.8514

0.8514

1.5210

-1000
-500

-3000

-1500

log (f / Hz)

log (f / Hz)

b -2000

-10

1.0
0

0.8

-1

-20

1h
3
6
9
12
24

1.5

1.6

1.2

-40

2.5

2.0

-20
1h
3
6
9
12
24

-50

phase / degree

-40

phase / degree

-50

2.8

log (|Z| / k cm 2 )

3.0

log (|Z| / k cm 2)

3.2

3.3858

0.2154

0
0

500

1000 1500 2000 2500 3000 3500 4000

z' / cm2
Fig. 2. Impedance spectra of pure Mg as a function of immersion time in PBS
medium (a) in Bode format and (b) in Nyquist format.

1000

2000

3000

4000

5000

6000

z' / cm2
Fig. 3. Impedance spectra of AZ80E alloy as a function of immersion time in PBS
medium: (a) in Bode format and (b) in Nyquist format.

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behaviour indicates a continuous decrease in the capacitive behaviour of the interface [34]. However, the phase angle maximum
(hmax) exhibits a monotonic decrease from 63 to 40 for Mg spectra, whilst for AZ80E spectra it shows a less sharp increase from 67
to 73, with a concomitant shift to lower frequencies in both cases.
Moreover, at any immersion time the values of |Z| or hmax are
always higher for AZ80E alloy as compared to pure Mg, suggesting
that the formed corrosion products lm on the alloy in PBS medium is more stable and offers considerable protection to the alloy
than that formed on Mg metal. On the other hand, all Nyquist plots
recorded on pure Mg (Fig. 2(b)) and AZ80E alloy (Fig. 3(b)) reveal
an obvious tendency to form two scarcely depressed capacitive
loops, which increase their diameters from the start of immersion
up to 9 h for Mg and 12 h for the alloy, then the plot begins to
shrink afterwards, in agreement with the trend of their Bode modules (log|Z|log f spectra). The results also display the behaviour of
two relaxation time constants at HF and LF ranges, that vary quantitatively with the immersion time and the electrode composition.
The results are generally in good agreement with EIS data previously reported for other AZ alloys in SBF [19,21]. Moreover, the
EIS spectra of each sample are similar to one another except for
the diameters of the loops, implying that the corrosion mechanisms of the two materials in PBS medium are similar, but they
have different corrosion rates.
It is worthwhile to notice that the main damage of magnesium
materials immersed in most aqueous solutions, especially in chloride-containing environment, is localised corrosion due to the
micro-galvanic effect. Pitting can be clearly seen on the surface,
where the surrounding region is relatively shiny and protected
by a surface lm of the corrosion products. Based on that, the evolution of the corrosion resistance of the tested samples were quantied by analysing the impedance spectra using an appropriate
equivalent electrical circuit (EEC), which is taken as a metric to
characterise the corrosion resistance of the sample. A good tting
was obtained using EEC drawn in Fig. 4, which denes two processes in parallel with two time constants for an electrode/electrolyte solution interface. This EEC is typical of porous lms formed on
Mg materials, as has been demonstrated experimentally
[30,3539]. The model is essentially the classic Randles circuit of
parallel resistorcapacitor (R1C1) combination in series with the
solution resistance (Rs) between the working specimen and the reference electrodes. Addition of another parallel resistorcapacitor
(R2C2) combination to the circuit was made to account for the time
constant at the HF region that can be attributed to the formed protective lm covered the sample surface. In this way, the diameter
of the capacitive loop in the HF region represents the resistance
(R2) of the corrosion product lm on the sample surface [30]. For
both samples, as hmax values are found to be far from the ideal
behaviour of 90, the capacitance associated with the surface lm
is not represented in the model by a pure capacitive element, instead
a constant phase element (CPE) is introduced in the model. This gave

Fig. 4. Equivalent circuit model representing two parallel time constants for an
electrode/electrolyte interface.

consistency overall the frequency range and reduced the error to an


average of <2.5% in the tting procedure. The CPE is used to account
for the non-uniform current distribution from the pure capacitive
behaviour and the deviation due to surface inconsistencies [40].
The impedance of the CPE can be represented by:

Z CPE

1
x
Q jx

where Q (F cm2 s(x1)) is the general admittance function of CPE,


will be identical to the idealised capacitance of the lm (C2) at the
angular frequency x = 1 (x = 2pf rad s1). j is the square root of
1 and f is the frequency in Hz (=s1) of applied ac signal in the
impedance scan. x is a coefcient related to the dispersive behaviour, and its value varies between 1 for a pure capacitive behaviour
associated with ideally at surface and 0.5 for a porous surface [38].
It is to be noted that appearance of LF time constant (R1C1) indicates
that the formed lm of corrosion products layer exhibits certain
degree of porosity as corrosion process occurs on spots where electrolyte penetrates through the pores of the lm to the metal surface.
Using Thales software provided with the workstation, the tted
characteristics circuit parameters for both Mg and AZ80E alloy in
PBS medium as a function of immersion time were all computed.
Table 1 summaries the tted EIS data whilst solid lines in Figs. 2
and 3 represent the simulated curves.
It is well established that the phase diagram of an AZ type alloy
(such as the model AZ91 alloy) is a typical MgAl binary phase diagram [41]. The alloy is formed from two main phases: a Mg-rich a
phase and Al-rich b phase (the intermetallic Mg17Al12) located at
the grains boundaries of the matrix [28,42] and acts as a cathodic
centre for the a phase, being 150 mV nobler than the a phase
[43,44]. Note that depending on the distribution in the a matrix,
the b phase may have passive or active role for the alloy corrosion
behaviour. Thus b phase may act as a protective behaviour layer
when it forms a continuous net over the entire surface. On the
other hand, if the b phase agglomerated in large grain and forms
discontinuous distribution in this case the b phase acts as an active
cathode and accelerate the corrosion of the a matrix [42,43]. Fig. 5a
presents the SEM morphology of the as-abraded extruded AZ80
sample tested in the present investigation, relative to that reported
for Mg [45]. As can be seen in the gure, a clusters of small b phase
particles (bright) are spatially distributed in a stochastic like feature along the grain boundary of the a phase (dark). Some few AlxMnx particles are also randomly embedded in the matrix. The
micrograph manifests fracturing of the intermetallic and some of
bright intermetallics can be observed. This is likely due to the

Table 1
Impedance parameters for both samples in PBS medium as a function of immersion
time.
Time
(h)

R1
(kO cm2)

C1
(lF cm2)

R2
(kO cm2)

C2
(lF cm2)

Rs
(O cm2)

Pure Mg
0.5
0.17
1
0.28
3
0.30
6
0.03
9
2.39
12
1.27
24
0.77

1761.2
1830.8
1713.2
123.44
18.84
21.74
14.72

0.79
0.90
1.27
2.39
1.53
0.92
0.60

14.59
18.44
17.82
8.14
1.95
1.90
2.19

7.2
8.8
12.9
15.6
9.3
16.3
19.7

0.83
0.85
0.81
0.69
0.57
0.58
0.61

AZ80E alloy
0.5
0.26
1
0.37
3
0.66
6
0.87
9
0.98
12
1.08
24
1.16

5024.0
2936.0
1840.0
1494.8
1416.8
1317.2
1362.0

0.74
0.99
1.81
3.74
4.80
5.45
4.81

14.92
10.83
9.11
7.02
7.31
8.04
11.12

13.2
12.6
13.4
6.5
13.4
13.5
11.5

0.89
0.87
0.84
0.81
0.82
0.83
0.86

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F. El-Taib Heakal et al. / Corrosion Science 86 (2014) 285294

AZ80E

AZ80

c
Mg

40 m

50 m

289

40 m

Fig. 5. (a) Surface morphology of the as-received AZ80E sample after grinding. (b) and (c) Microstructures of AZ80 and Mg according to Ref. [45].

H2 PO4 2OH ! PO3


4 2H2 O


3
HPO2
4 OH ! PO4 H2 O

R T / k cm2

5
Mg
alloy

4
3
2
1
0
0

10

15

20

25

30

Time / h
Fig. 6. Variation with time of the total resistance (RT) for the surface lm formed on
pure Mg and AZ80E alloy exposed 24 h to PBS medium.

extrusion process as has been reported by Zhang et al. for AZ91


alloy [46]. In this context, the corrosion properties of AZ80E alloy
in contrast to its base metal Mg in PBS medium can then be visualised. It is well agreed that pH value has a prominent effect in corrosion resistance of magnesium materials [29,47]. Generally,
magnesium alloy has well corrosion resistance in alkali solution
and is active in acidic or neutral environment. Therefore, when
the sample is exposed to PBS solution two competitive processes
occur. The rst one is the partial dissolution of native lm, as well
as the preferential dissolution of the metal Mg in the special locations of boundaries and defects. This process lasts for a very short
period at the beginning of electrode immersion. The second one is
the deposition of corrosion product lm according to Eq. (3). This
process becomes remarkably obvious on extending the immersion
period and thus the total resistance of the corrosion product lm
(RT = R1 + R2) increases with time as depicted in Fig. 6. In the initial
stage, due to surface heterogeneity micro-galvanic cells are quickly
formed between a and b phases on the active Mg sample and the
release of Mg2+ ion from the active sites on the anodic a Mg based
phase deposit as a porous Mg(OH)2 surface layer, which has lower
protective ability. The dissolution is accompanied with hydrogen
evolution and local alkalisation due to the increase in OH ion concentration near the substrate surface in accordance to Eq. (3). This
will induce the following chemical reactions with the predominant
ions in the medium:

Since the solubility product constant (Ksp) for Mg3(PO4)2 is


1.04  1024, which is much lower than Ksp of the other products,
accordingly the produced PO3
ions may be easily incorporated
4
into the lm pores and Mg3(PO4)2 further precipitates leading to
self-healing. White magnesium phosphate particles are also deposited onto the primary corrosion product Mg(OH)2 lm [19,22],
which can be easily seen by the naked eye. This secondary corrosion product covers the reacted surface, reduces the electrochemical activity of the substrate, slows down its corrosion rate and
subsequently enhances its corrosion resistance leading to RT
increase. On prolonging the immersion time, it seems that lm
healing and growth are the major effective processes for both samples, which spawn a continuous increase in the resistance of the
corrosion product layer deposited on the sample. The diffusion of
ions inside this layer is thus restricted. After a threshold exposure
period of about 12 h for the alloy and 9 h for Mg, the rate of lm
dissolution exceeds the rate of its growth and partial depassivation
process sets up until nally a quasi steady state is achieved, which
mirror completely the trend for the open circuit potential (Fig. 1).
This behaviour is likely due to an increase in the amount of
adsorbed aggressive Cl ion on the weak parts of the lm layer
with a preferential formation of the more soluble magnesium chloride via the following reaction [19,48]:


Mg 2Cl ! MgCl2

Thus as found experimentally, RT value for the alloy concomitantly experiences a slight decreases with time compared to its
base metal Mg. The breakdown in the initially formed layers can
be also explained from point of view of microstructure changes,
wherein the increased density of dislocation, pores and grain
boundary in the growing lm layer increase the anodic dissolution
of AZ80E and to a larger extent the dissolution of Mg metal. Additionally, rearrangement of b phase accelerate the rate of the anodic
and cathodic process as well [46]. Generally, PBS improves the corrosion resistance of AZ80E and Mg with time, and spawning a selfprotection effect. Table 1 and Fig. 6 indicate that RT value increases
from 1 kX cm2 for both samples at the beginning of immersion
and reaching a maximum values of 6 kX cm2 and 4 kX cm2
for the alloy and its base metal, respectively. The improvement
and self-protection against corrosion for the alloy can withstand
for longer time than for the metal. Also, as shown in Fig. 6 the value
of RT at any given time, being equivalent to the polarisation resistance of the sample (Rpol), is higher for AZ80E than for Mg, proving
that the alloy is more resistant than its base metal in PBS medium.

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F. El-Taib Heakal et al. / Corrosion Science 86 (2014) 285294

This suggests that spontaneously formed lm on Mg is more porous and therefore less passive than that formed on the alloy. Moreover, compared with Mg sample, AZ80E alloy undergoes a more
effective self-repair and even self-strengthen in PBS medium. The
higher corrosion resistance of the alloy is actually related to the
higher amount of Al-rich b phase that rests on its surface after corrosion. This can be corroborated by previously reported results,
which conrm via XPS analysis that the corroded surface of
AZ91D in wet environment presents an enrichment in mixed magnesium and aluminium oxides and hydroxides [42].
3.3. Polarisation measurements
Cathodic and anodic polarisation behaviour of AZ80E alloy relative to its base metal Mg was studied after 24 h exposure in PBS
medium using potentiodynamic linear scan at a rate of 1.0 mV s1.
Fig. 7 shows that the two samples exhibit the same shape of the
polarisation curve Elog i. Where over the anodic trace up to
0.8 V(SCE) no activepassive transition peak can be discerned,
instead the active region of potential is directly followed by a passivation zone that ends with a certain transition potential value at
which the dissolution rate turns abruptly from slow to rapid as the
anodic potential is raised. Generally, this critical potential value
assigns the breakdown potential (Eb) of a given electrode material
in corrosive environments and is considered as an indication for
the capability of its anodic passive lm to deter localised corrosion
attack [22,29,33,48]. Over the potential domain of the anodic plateau the metal is in a state of pseudo passivation. As can be seen
in Fig. 7, the alloy registers breakdown potential of 1.256 V(SCE),
whilst Mg shows a more active breakdown potential of
1.422 V(SCE). Therefore, the difference (DE) between the corrosion potential and the breakdown potential in the anodic region
(DE = Eb  Ecorr) for the alloy (364 mV) is much larger than for
Mg (178 mV). This implies that the alloy can form anodic passive
lm in PBS medium with inherent better protecting ability than
Mg. On the other hand, the cathodic trace which assumes to represent the cathodic hydrogen gas evolution via water reduction (Eq.
(2)) follows Tafel behaviour. Where each material provides an
extensive linear region in the cathodic branch. Additionally, several
authors refer to the possibility of the following reaction to produce
also hydrogen gas evolution in the anodic sites [43,4952]:

Mg ! Mg e

1
Mg H2 O ! Mg2 OH H2 g
2

Thus, the origin of the copious hydrogen gas evolution in the


anodic defects may be due to reaction (3) or reaction (9) or most
probably both of them.
As can be seen in Fig. 7, in comparison with Mg the cathodic
curve for the alloy shifts to less negative potential and higher
cathodic current density, indicating that hydrogen evolution reaction (HER) is more facilitated on AZ80E surface, in good agreement
with the OCP results. However, when the applied potential exceeds
the corrosion potential, Mg substrate becomes vulnerable to pitting corrosion more easily than the alloy as marked by the lower
values for both Eb and DE. In case of magnesium materials, electrochemical technique might not be the best for estimating their corrosion rates. Nevertheless, Tafel extrapolation method is widely
used for the evaluation of the corrosion rate of Mg alloy, at least
partly after long exposure period which is the case in the present
work, because it is quick and easy technique [48,52,53]. Reasons
are given due to the fact that the polarisation curves are not symmetrical in the anodic and cathodic branches, when the polarisation curves are measured immediately after specimen immersion
in the solution. This is ascribed to the complicate nature of the anodic polarisation curves, most likely due to the simultaneous combination of both anodic dissolution and cathodic hydrogen evolution
in the anodic region [54]. Also, due to the occurrence of localised
corrosion, which could make the anodic process unstable [28]. In
addition, it is well established that [55,56] only pure charge transfer controlled current can be accepted as true Tafel data. Therefore,
assessment of the corrosion current density (icorr) can be often possible from the polarisation curves by Tafel extrapolation using the
cathodic branch which is linear in nearly all cases over the
extended time with an accuracy of 9496% for the points more
negative to Ecorr by 50 mV. This was done using Thales Software
for iE analysis provided with the electrochemical workstation.
The value of icorr is inversely related to the corrosion or polarisation
resistance (Rpol) of the sample as given from the SternGeary relation through cathodic and anodic Tafel slopes (bc and ba) as follows
[5759]:



1
1
1
2:303icorr

Rpol
jbc j ba

10

-4

The estimated icorr values for the alloy and Mg samples are
25.11 and 38.36 lA cm2, which indicate that alloying Mg with
Al and Zn not only improve its strengthening effectiveness, but also
cause a decease to some extent in its susceptibility for degradation
[60]. This further suggests that AZ80E has better corrosion resistance than its base metal in PBS medium, in good agreement with
the EIS results. It is also reported that icorr in mA cm2 derived from
Tafel extrapolation method is related to the average penetration
rate (Pi) in mm y1 via the correlation [12,28,52]: Pi = 22.85icorr.
Therefore, lower icorr value means lower penetration rate for the
alloy relative to its base metal in PBS medium.

-5

3.4. Effect of anodic oxidation

-6

Surface treatment can be used to impart active corrosion protective properties to Mg alloys. They can also serve as a base for
further improvement of surface properties by applying a suitable
coating on the alloy [8,61]. Among the typical surface modication
techniques electrochemical anodising is one of the most promising
methods for magnesium alloys [52,62]. Therefore, the present
experiments were attempted to investigate the effect of anodic
oxidation on the corrosion resistance of AZ80E alloy in PBS

0
-1

-2

log (i / A cm-2)

Followed by hydrolysis of Mg+ via its chemical reaction with


water,

1
2

-3

-7
-2.8

-2.6 -2.4

-2.2 -2.0

-1.8 -1.6

-1.4 -1.2

-1.0

-0.8

E / V (SCE)
Fig. 7. Potentiodynamic polarisation curves of (1) pure Mg and (2) AZ80E alloy after
24 h immersion in BPS medium.

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medium. Anodisation was carried out for 10 min prior to the


immersion test under potentiostatic mode in borate buffer solution
of pH 9.2 [26,52]. Two potential values were chosen with reference
to the characteristics features of the polarisation curve in borate
solution of our previous reported work [52], namely, 1.350 and
1.0 V(SCE). After anodic oxidation at the prescribed potential the
passive surface was rinsed with deionised water, air dried and
immersed quickly in the test PBS medium at 37 C to monitor its
impedance spectra with time. During the 10 min anodising process
the cell current at a potential of 1.0 V(SCE) decreases with time fast
at rst and then slowly until achieving a steady current value, indicating formation of a protective oxide layer. On the other hand,
anodic surface treatment at 1.350 V(SCE) leads to an increase in
the current with time until reaching the steady state value. This
behaviour obviously indicates a continuous dissolution of Mg leading to an enrichment of the b phase in the surface.
Fig. 8(a and b) presents the evolution of Nyquist plots for a
borate anodised AZ80E electrode at the two tested potentials.
The impedance responses are all similar to those recorded for the
as-abraded pristine sample at OCP (cf. Fig. 3b). Hence, at any
immersion period the corrosion resistance of an oxidised specimen
(Rpol) is associated with the combined diameters of the two merged
capacitive loops controlling the corrosion process [8,63]. The
impedance data were analysed and the estimated impedance
parameters presented in Table 2 were found to give the best t
with the model shown in Fig. 4. Generally, C1 value assigning the
pseudo-capacitance of double layer for the metal/solution interface, decreases signicantly with increasing anodic potential for
oxidation, whilst the capacitance of the formed lm (C2) decreases
slightly. Fig. 9 compares the trend of the total resistance (RT) for the
two oxidised samples after immersion in PBS medium for various
time intervals, relative to the trend of the as-abraded pristine sample. The results reveal that anodic oxidation not necessarily leads
to improvement in the corrosion resistance of AZ80E surface. In

Z'' / cm2

a -2500

30 min
1h
3

-2000
-1500

6
9
12

-1000

24

Table 2
Impedance parameters of both anodized AZ80E samples as a function of immersion
time.
Time
(h)

C1
(lF cm2)

R2
(kO cm2)

C2
(lF cm2)

Rs
(O cm2)

At 1.35 V(SCE)
0.5
0.28
1
0.27
2
0.32
3
0.36
6
0.56
9
0.54
12
0.90
24
0.57

3447.2
2240.0
1949.2
1937.2
1566.0
1666.4
802.0
1032.0

1.37
1.48
1.92
1.93
2.84
2.57
3.45
2.94

7.28
8.46
8.54
9.27
9.74
10.56
2.95
10.20

10.7
10.9
10.7
10.1
12.1
12.1
14.1
10.6

0.88
0.87
0.85
0.85
0.86
0.86
0.85
0.86

At 1.0 V(SCE)
0.5
0.05
1
0.09
2
0.15
3
0.19
6
0.18
9
0.21
12
0.20
24
0.25

39.80
27.11
19.84
16.56
12.75
10.30
8.49
6.76

1.32
2.03
3.21
3.91
3.79
4.46
4.37
5.35

10.73
7.92
7.25
7.48
8.65
9.29
9.97
11.88

15.6
12.8
9.4
8.9
9.0
10.2
10.3
11.5

0.81
0.77
0.76
0.79
0.82
0.83
0.84
0.85

R1
(kO cm2)

general, oxidised specimens have nearly comparable corrosion


resistance with the as-abraded alloy, whilst at any time interval
the specimen anodised at 1.0 V always exhibits higher RT value
than the other one anodised at 1.350 V. As can be seen, during
the rst hour of immersion there is little enhancement in RT value
for the two oxidised samples. However, with immersion time
increase passive samples versus the pristine AZ80E alloy demonstrate lower RT values, most likely due to difference in the extent
of porosity for those cases. In the meantime, there is a continuous
self-healing as evidenced from the monotonic increase in RT value
up to 24 h exceptionally for 1.0 V sample, and to 12 h only for the
other two samples. The increased durability of the 1.0 V oxidised
sample may be ascribed to change in the distribution, conguration and size of the b Mg17Al12 phase, which may result in different
corrosion rate and different RT value. The SEM micrographs shown
in Fig. 10(ac) after 24 h immersion in PBS medium support the EIS
results. It appears that oxidised specimen at 1.0 V in borate solution demonstrates the best dense and compact microstructure.
On the other hand, Fig. 11a presents the SEM image for the

-500
7
0
0

1000

2000

3000

4000

5000

1h
6
12
24

Z' / cm2

30 min
1h
2
6
12
24

Z'' / cm2

-3000
-2500
-2000

R T / k cm 2

b -3500

0.9203

0.6043

-1500
-1000

2
1.5210

-500

0.1585

0
0

1000

2000

3000

4000

5000

6000

Z' / cm2

0
As-abraded

Fig. 8. Nyquist plots of anodised AZ80E samples in borate buffer solution at two
different potentials as a function of immersion time in PBS medium: (a) at
1.350 V(SCE), and (b) at 1.0 V(SCE).

-1.35 V(SCE)

1.0 V(SCE)

Fig. 9. The total resistance (RT) of the two anodised AZ80E samples relative to the
as-abraded one after immersion in PBS medium at various time intervals.

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F. El-Taib Heakal et al. / Corrosion Science 86 (2014) 285294

50m

50 m

50 m

Fig. 10. SEM micrographs of AZ80E samples after 24 h immersion in PBS medium: (a) as-abraded, (b) borate anodised at 1.350 V(SCE) and (c) borate anodised at 1.0 V(SCE).

b
Element
Mg
Al
Zn
O

Counts

Atomic %
65.90
5.00
0.18
28.92

Binding Energy / keV

50 m

Fig. 11. (a) SEM micrograph of anodised sample at 1.0 V(SCE) without immersion and (b) EDX spectrum of sample (a).

specimen to the test PBS medium self-passivation occurs due to


its interaction with the anions prevalent in solution. This offers
an increase in RT value, and hence surface lm stability predominates, which leads to a decrease in the degradability of the alloy
with time.
Potentiodynamic polarisation curves were also recorded right
after the EIS measurements for the as-abraded and borate oxidised
samples exposed 24 h to PBS medium as illustrated in Fig. 12.
Table 3 shows the electrochemical corrosion parameters obtained
from those polarisation curves. The data correspond to the mean
values of three different specimens tested at each condition. The
values of icorr and DE corroborate well with the results obtained
from EIS measurements, showing a trend for a marked decrease
in the corrosion resistance of the sample oxidised at 1.350 V versus the as-abraded specimen, whilst the decrease for the other
sample anodically treated at 1.0 V is very little. Another more
important observation for this latter sample is that once the oxide
lm is developed, it starts acting as a barrier to hinder corrosion
attack, and thus exhibits increased durability in PBS medium as

-1

-2

log (i / A cm-2 )

-3

1
-4

-5

-6

-7

1
2
3

-1.35 V (SCE)
1.0
as-abraded

-8
-2.5

-2.0

-1.5

-1.0

-0.5

E / V (SCE)
Fig. 12. Potentiodynamic polarisation curves of borate anodised AZ80E samples at
two different potentials after 24 h immersion in PBS medium relative to the asabraded alloy sample.

anodised lm formed at 1.0 V in as-prepared condition (nonimmersed), and its EDX analysis as given in Fig. 11b reveals that
the oxide lm consists mainly from Mg, O, Al and Zn. This lm cannot provide complete protection for the alloy as it is not covering
completely the surface. Therefore, upon exposing the anodised

Table 3
Electrochemical corrosion parameters of as-abraded and oxidised AZ80E samples at
two different potentials (Ean), after 24 h immersion in PBS medium; DE = Eb  Ecorr, Eb
being the breakdown potential. The same data for as-abraded Mg are also included.
Ean (V(SCE))

Ecorr
(V(SCE))

icorr
(lA cm2)

bc
(mV decade1)

Eb
(V(SCE))

DE
(mV)

As-abraded
alloy
1.35
1.0
As-abraded Mg

1.620

25.11

111

1.256

364

1.693
1.580
1.600

31.99
22.57
38.36

115
85
254

1.624
1.208
1.422

69
372
178

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F. El-Taib Heakal et al. / Corrosion Science 86 (2014) 285294

evidenced from Fig. 9. In summary, the results can infer that


surface lm grown on this specimen during immersion in PBS
medium is more passivating. Perhaps, this is due to its coherent
and protecting properties, giving rise to larger DE and lower icorr
values at longer immersion times. This is a promising result from
the perspective of maintaining sufcient mechanical integrity for
the implant subjected to biodegradation in the high chloride environment of physiological systems, until the tissue has sufciently
healed [21].
4. Conclusions
Degradation behaviour of an extruded AZ80 alloy relative to its
base Mg metal was investigated in phosphate buffer saline (PBS)
medium with the immersion time. Various electrochemical techniques were used to assess their bioactivity at 37 C. For both samples the positive shift in the OCP indicates self-healing and
passivation which extends up to 12 h for AZ80E and 9 h for Mg.
The higher potential values for Mg suggests that hydrogen evolution on the alloy surface occurs at lower overpotential than on
Mg. EIS data reveal that the corrosion or polarisation resistance
(Rpol) for both samples increases with time as evidenced by the
increased total resistance (RT) of the formed corrosion products
layer. However, at any immersion time the alloy always exhibits
higher RT value in PBS medium relative to Mg. This nding is in
agreement with the potentiodynamic polarisation data as marked
by lower corrosion current density (icorr) and higher breakdown
potential (Eb) for the alloy compared to its base metal.
Anodic oxidation of the alloy surface in borate buffer solution of
pH 9.2 was also attempted to modify its corrosion behaviour.
According to the data obtained, the short-term anodisation at a
controlled potential of 1.0 V(SCE) has improved the durability of
AZ80E in PBS medium, as it spawns a monotonic increase in the
corrosion resistance of the alloy with immersion, which extends
over a more time period compared with the pristine abraded sample. SEM and EDX examinations conrm the superior quality of this
lm relative to the other tested oxidised sample at 1.350 V(SCE)
or the as-abraded one.
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