Research & Development CHINA FOUNDRY

Vol.11 No.6 November 2014

Corrosion behavior of Mg-Zn-Ca amorphous

alloys with Nd addition in simulated body fluids
Qin Chunling1, Xiao Tongna1, Li Yongyan1, Wang Zhifeng1, Liu Li1, Xiong Hanqing2, and *Zhao Weimin1
1.School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130, China;
2. School of Materials Science and Engineering, Central South University, Changsha 410083, China

Abstract: The effects of Nd addition on corrosion behavior of Mg66Zn30Ca4 amorphous alloys in simulated body
fluids (SBF) were studied in this paper. Electrochemical properties of the samples before and after corrosion were
determined. Surface morphologies of samples after immersion in SBF at 37 ºC for different times were observed
under scanning electron microscope (SEM). Results show that the corrosion resistance of Mg-based alloys in
SBF is improved with the addition of Nd element. The electrochemical properties indicate that microalloying Nd
element to the alloys leads to an ennoblement in the open circuit potentials of the alloys and a decrease in the
anodic current density in SBF, especially for the Mg66-xZn30Ca4Ndx alloys with Nd content of 1.0at.%-1.5at.%. It
was observed that the surface morphologies of the alloys immersed in SBF change with the Nd addition. A flake-
like structure parallel to the alloy substrate formed on the surface of 1.0at.% Nd-containing alloy immersed in
SBF for 7 days improves the corrosion resistance of the amorphous alloys by blocking the corrosion liquid from
attacking the alloys.

Key words: Mg alloy; amorphous alloy; corrosion behavior; SBF; electrochemical measurements
CLC numbers: TG139+.8 Document code: A Article ID: 1672-6421(2014)06-503-07

I n recent years, magnesium alloys have attracted

considerable attention as potential biomedical
materials especially for implant applications such as bone
substitutes[1] and intravascular stents[2]. This interest in
magnesium alloys has been particularly motivated by
their good mechanical properties [3,4], biocompatibilities
and biodegradation properties[5]. Magnesium is the fourth
most abundant cation in the human body and an essential
element for many biochemical functions in the living
processes of the human body [6]. Many studies involving
animal experiments and clinical reports indicate that the
degradation products of magnesium in the body are non-
toxic, and that excess magnesium would be excreted
out via the kidneys. Indeed, magnesium has stimulatory
effects on the growth of new bone tissue [5]. Additionally,
the density and elastic modulus of magnesium are much
closer to human bones and can avoid the stress shielding
effects which will reduce the stability of implants [7].
Therefore, Mg-based biomaterial is a new kind of
biodegradable biomaterial [8]. In addition, one group
* Zhao Weimin
Male, born in 1959, Ph.D, Professor.
His research interests mainly focus on light metals and their industrialization.
He has published more than 50 technical papers.
E-mail: wmzhao@yahoo.com
Received: 2013-11-24; Accepted: 2014-06-10
of magnesium alloys, containing the human-essential
elements Zn and Ca, has been especially studied with
reference to biosafety and biocompatibility of released
alloying elements [9,10]. For example, Zhang et al.[11]
reported that a Mg-Zn alloy had high tensile strength
(279.5 MPa) and no adverse effect had been caused
by the released zinc. The results [12] indicated that Mg-
1Ca alloy degraded gradually within the bone at the
corrosion rate of 2.28 mg·mm-2·year-1. Moreover, an
enhanced bone formation was visible around implanted
pins.
However, biodegradable Mg alloys are facing serious
challenges in practical applications. Pitting corrosion is
the typical corrosion mode of Mg alloys even in neutral
or alkaline salt solutions [13]. Subsequently, the pits
tend to spread laterally resulting in the disintegration
of the alloys during the corrosion period [12,14]. Pitting
corrosion, resulting from the surface defects, will also
lead to rapid strength loss of magnesium alloys [15]. At
the same time, the release of hydrogen and localized
alkalization caused by the fast corrosion [16,17] may be
deleterious to the surrounding tissues. Therefore, it
is very important to explore a new magnesium alloy
with a lower degradation rate and uniform corrosion.
The Mg60+xZn35-xCa5(x = 0, 3, 6, 9, 12, 14, 15 at.%)
amorphous alloys were implanted into the abdominal

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walls and cavities of domestic pigs [18]. The in vivo tests
showed that hydrogen evolution can be dramatically reduced
in biodegradable Mg-based alloys with Zn content exceeding
28%. Actually, some RE elements (such as Nd, Dy, and Gd) are
beneficial in terms of mechanical and corrosion properties, and
have acceptable toxicity [19]. Yuan et al.[20] studied the cytotoxicity
of the Mg-3Nd-0.2Zn-0.4Zr alloys and found that most cells
showed a healthy morphology. As the culture time increased,
some cells exhibited a round shape due to the proliferation and
concentration of the cells, which was also healthy. In the present
work, the effects of the Nd addition on the corrosion behavior of
the Mg66Zn30Ca4 amorphous alloy are studied. For the Mg-based
amorphous alloys containing different amounts of Nd immersed
in the simulated body fluids (SBF), the electrochemical
properties, corrosion morphologies and surface characterization
were examined by electrochemical measurements, scanning
electron microscope (SEM) and Fourier Transform Infrared
Spectroscopy (FTIR), respectively.
NaCl 8.00 g·L-1, MgSO4·7H2O 0.20 g·L-1, Na2HPO4·12H2O 0.09
g·L-1, KH2PO4 0.06 g·L-1 and glucose 1.00 g·L-1. The immersion
times were 1 day, 3 days, and 7 days, respectively. The Fourier
Transform Infrared (FTIR) spectrum of the samples was placed
in the FTIR spectrophotometer (Bruker Vertex 80V) with a
spectral resolution of 4 cm-1 and accumulation of 16 scans.
2 Results and discussion
2.1 Nd microalloying effect on microstructure
and electrochemical properties
Figure 1 shows the XRD patterns of the as-spun Mg66-xZn30Ca4Ndx
(x=0, 0.5, 1, 1.5at.%) ribbons. The typical broad diffraction
peaks were observed for all the Mg-Zn-Ca(-Nd) alloys and no
detectable diffraction peaks corresponding to crystalline phases
are seen within the resolution limit of the XRD, confirming the
fully amorphous structure.

1 Experiment procedure
A mixture of pure elements and master alloys, namely
magnesium (99.95wt.% purity), zinc (99.99wt.% purity) metals,
Mg-19.29wt.%Ca master alloy and Mg-24.31wt.%Nd master
alloy, were used to form the nominal compositions of Mg66-
xZn30Ca4Ndx (x=0, 0.5, 1, 1.5at.%) amorphous alloys. Melting

was conducted in an electronic resistance furnace under Ar +

0.2%SF6 gas in a graphite crucible. Melting temperature was
set at 700 °C for 40 min. The first 30 min was for melting and
the remaining 10 min for complete melt homogenization. Then
the melt was cast into a stainless steel mold to obtain the Mg-
Zn-Ca(-Nd) alloys. Small pieces of Mg-based alloys were
ultrasonically cleaned in absolute ethanol and distilled water.
The Mg-Zn-Ca(-Nd) amorphous alloys were fabricated by
the single roller spinning method. In brief, small pieces of Mg
alloys were placed in a quartz tube and induction-melted under
an argon atmosphere, then the melt was quickly injected into a
copper wheel to obtain melt-spun samples of 1.5 mm width and
25-35 μm thickness.
X-ray diffraction (XRD) was performed to verify the
amorphous structure of the samples using a Bruker D8 X-ray
diffractometer with Cu Kα radiation. Corrosion morphologies
were observed using a Hitachi S4800 field emission scanning
electron microscope (SEM) coupled with an energy dispersive
X-ray Spectrometer (EDS). Electrochemical measurements were
set using a typical three-electrode system including a stationary
specimen, a Pt net counter electrode and an Ag/AgCl reference
electrode. A LK2005A electrochemical workstation was used for
the polarization curves tests at 37 °C. A wire lead was attached
to one end of each sample and was closely sealed with epoxy
resin leaving an end surface exposed to solution. The immersion
test and the electrochemical measurements were performed
in the SBF solution at 37 °C. The SBF solution was prepared
by pipetting calculated amounts of concentrated solutions of
NaHCO3 0.35 g·L-1, KCl 0.4 g·L-1, CaCl2·2H2O 0.19 g·L-1,
Fig.1: XRD patterns of as-spun Mg66-xZn30Ca4Ndx(x = 0,
0.5, 1, 1.5 at.%) amorphous alloys, showing fully
amorphous structure
Figure 2 shows the changes in the open circuit potential
(corrosion potentials) and potentiodynamic polarization curves
for the as-spun Mg66-xZn30Ca4Ndx (x = 0, 0.5, 1, 1.5at.%) in SBF
at 37 °C open to air. In Fig. 2(a), it was observed that the open
circuit potential values (Ecorr) of the Mg-Zn-Ca(-Nd) samples
rapidly shift toward the positive potential in the initial 200 s, and
then decrease quickly. The open circuit potentials of the Mg-
Zn-Ca(-Nd) amorphous alloys increase slowly after 300 s and
become stable at about 2,400 s. On the other hand, it is clearly
seen that the open circuit potentials of the Nd-containing Mg-
based amorphous alloys, especially, with Nd content of 1.0 at.%-
1.5at.%, are higher than that of the Nd-free alloy. This implies
that the Nd addition improves the surface stability of the Mg-
based amorphous alloys in SBF solutions.
Representative electrochemical polarization curves of as-spun
Mg-Zn-Ca(-Nd) amorphous alloys in SBF are displayed in Fig.
2(b). Generally, the cathodic polarization curves are assumed
to represent the cathodic hydrogen evolution through water
reduction while the anodic ones represent the dissolution of
magnesium. Figure 2(b) shows that the cathodic polarization

504

Fig. 2: Changes in open circuit potentials with immersion time (a) and potentiodynamic polarization curves (b) for as-
spun Mg66-xZn30Ca4Ndx(x = 0, 0.5, 1, 1.5 at.%) amorphous alloys in SBF solution at 37 °C open to air
current corresponding to the hydrogen evolution reaction
for the Nd-containing Mg alloy is higher than that of the Mg-
Zn-Ca amorphous alloy. That is to say, the overpotential of
the cathodic hydrogen evolution reaction is lower for the Nd-
containing Mg-based amorphous alloys as compared to that
of Nd-free Mg-based amorphous alloy. This also reveals that
the cathodic reaction is kinetically easier for the Nd-containing
amorphous specimen, which may be due to the existence of the
Nd element. On the other hand, the anodic polarization curves
of the Mg-based alloys with and without Nd addition show a
wide passivation-like region, indicating the protective films are
formed on the alloy surface via anodic polarization. Moreover,
microalloying Nd element to the alloys leads to an ennoblement
of the open circuit potentials of the alloys, which is in agreement
with the result shown in Fig. 2(a), Meanwhile, it is found that
the anodic current densities of the Mg-based amorphous alloys
decrease with an increase in the Nd content during the applied
potentials up to -1.06 V (vs. Ag/AgCl). The corrosion current
Research & Development CHINA FOUNDRY
Vol.11 No.6 November 2014
densities (Icorr) obtained from Fig. 2(b) of Mg 66Zn 30Ca 4,
Mg65.5Zn30Ca4Nd0.5, Mg65Zn30Ca4Nd1 and Mg64.5Zn30Ca4Nd1.5
amorphous alloys (Table 1) are 1.964×10-5 A·cm-2, 1.345×10-5
A·cm-2, 8.579×10-6 A·cm-2 and 4.564×10-6 A·cm-2, respectively. It
is clearly seen that Icorr values decrease greatly with increasing
Nd content. It can therefore be concluded that the corrosion
resistance of the Mg-based alloys is enhanced by microalloying
Nd to the alloys.
2.2 Surface morphologies and
electrochemical properties of alloys after
immersion in SBF
Figure 3(a-d) shows SEM micrographs of the Mg-Zn-Ca(-Nd)
amorphous alloys after immersion in the SBF at 37 °C for 1 day.
When the Mg66Zn30Ca4 sample is immersed in the simulated
body fluids [Fig. 3(a)], the anodic dissolution of magnesium
occurs, and the magnesium hydroxide layer is formed on the
surface of the Mg66Zn30Ca4 alloy. Meanwhile, the attack of
Fig. 3: SEM images of the surface of
Mg66-xZn30Ca4Ndx(x = 0, 0.5, 1, 1.5
at.%) amorphous alloys immersed
in SBF at 37 °C for 1 day:
(a) Mg66Zn30Ca4,
(b) Mg65.5Zn30Ca4Nd0.5,
(c) Mg65Zn30Ca4Nd1,
(d) Mg64.5Zn30Ca4Nd1.5, (e) typical
EDS spectra of white particles in
(b) and (c) (Note: the element Au in
EDS spectra comes from the sample
preparation.)
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Cl - occurs at the weak sites of the magnesium hydroxide
layer and transforms the magnesium hydroxide into soluble
magnesium chloride. The fresh substrate, directly exposed to the
medium, suffers further corrosion companied with the release
of Mg2+ and Zn2+ cations [15]. From Fig. 3(a), it is observed that
a large number of spot corrosion pits appear on the immersed
surface. At the same time, the apatite begins to be formed on
the surface. The upwarping ‘skin’ on the sample surface is
formed by the surface shrinking during drying, as shown in
Fig. 3(a). On the other hand, for the 0.5at.% and 1at.% Nd-
containing alloys immersed in SBF for 1 day (Fig. 3b and 3c),
there are some white particles to be precipitated on the alloy
surfaces. The elemental compositions of the white particles
in Fig. 3 mainly consist of Ca, P and O, which indicate Ca-P
apatite granules nucleate and grow on the alloy surface. Figure
3(e) shows the typical EDS spectra of the white particles in
Fig. 3 (Note: the Au in EDS spectra comes from the sample
preparation). No corrosion pits are observed on the surface of
the Nd-containing alloys, indicating that the pitting corrosion
is inhibited effectively with the Nd addition. Figure 3(d) shows
that the surface structure of the 1.5at.% Nd-containing Mg-
based amorphous alloy maintains good integrity, in addition to
a small amount of apatite on the surface, demonstrating that
the corrosion resistance is enhanced with an increase in the Nd
content.
Further immersing the Mg-Zn-Ca(-Nd) amorphous alloys
in the SBF at 37 °C for 7 days, the surface morphologies of
these alloys are shown in Fig. 4. In Fig. 4(a), it is found that
the reticular structure of the Mg66Zn30Ca4 amorphous alloy
immersed in the SBF for 7 days is formed at the bottom of
Fig. 4: SEM images of the surface of Mg66-xZn30Ca4Ndx(x=0, 0.5, 1, 1.5 at.%) amorphous alloys immersed in SBF at
37 °C for 7 days: (a) Mg66Zn30Ca4, (b) Mg65.5Zn30Ca4Nd0.5, (c) Mg65Zn30Ca4Nd1, (d) Mg64.5Zn30Ca4Nd1.5.
506
the crack. The corrosion resistance of the reticular structure is
weak and could not protect the fresh alloy substrate from the
corrosion fluids attack. Microalloying 0.5at.% Nd to the alloy
gives rise to the great change in the surface morphology during
the 7 day-immersion. The surface of the 0.5at.% Nd-containing
alloy is covered with the corrosion products showing flake-like
structures [21,22], as shown in Fig. 4(b). The SEM image [Fig.
4(b)] shows that a large amount of the flakes with thin walls are
perpendicular to the alloy substrate, while a few of them are
tilted or parallel to the substrate [23,24]. It seems that this kind of
the structure is more effective in preventing the corrosion fluids
against the alloy as compared with the reticular structure in Fig.
4(a). When the Nd content reaches 1at.%, shown in Fig. 4(c),
the wall of the flake becomes stronger than that of the 0.5at.%
Nd addition. Additionally, most of the flakes turn to be parallel
to the substrate surface. Previous research [25] demonstrated that
the flakes paralleling to the surface could prevent the corrosion
process more effectively. Moreover, Fig. 4(d) shows that
the 1.5at.% Nd-containing amorphous alloy suffers uniform
corrosion during the SBF immersion for 7 days, accompanied
by a very low corrosion dissolution. As a result, the addition of
Nd element to the Mg-Zn-Ca amorphous alloys is effective in
improving the corrosion performance of the Mg-based alloys
in SBF by modifying the corrosion morphology and surface
structure [26].
After immersion in the SBF at 37 °C for 3 and 7 days, the
polarization curves of the as-immersed Mg-Zn-Ca-Nd alloys
are further measured in the SBF, displayed in Fig. 5. The
polarization curves of the as-spun alloys are also shown for
comparison. The open circuit potential (Ecorr) and corrosion
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current density (Icorr) data obtained from the polarization
curves (Fig. 5) are listed in Table 1. The as-immersed alloys
in the SBF exhibit a similar polarization behavior, which
shows much higher open circuit potentials and lower corrosion
current densities as compared with the as-spun alloys. It can
be found that the corrosion current density of the Mg66Zn30Ca4
amorphous alloy slightly increases after immersion in the SBF
for 7 days compared with that for 3 days, as shown in Fig. 5(a).
The corrosion resistance of the Mg66Zn30Ca4 amorphous alloy
immersed in the SBF for 7 days is reduced due to the formation
of reticular structures on the alloy surface [Fig. 4(a)]. On the
other hand, for 0.5at% Nd-containing alloy immersed in the
SBF for 7 days shown in Fig. 5(b) and Table 1, the corrosion
potential of the alloy containing a small amount of Nd increases
and its corrosion current density decreases as compared to the
Nd-free alloy at the same conditions.
As we discussed in the SEM image [Fig. 4(b)], the surface
I
structure of the 0.5at% Nd-containing alloy during the 7 days of
immersion changes to the thin wall flake-like structure, which
could more effectively prevent the corrosion fluids against the
alloy than the reticular structure. Moreover, when the alloys
immersed for 3 and 7 days, respectively, Figure 5(c) shows that
the 1at.% Nd alloy exhibits higher corrosion potential than the
0.5at.% Nd alloy, which is probably due to the formation of the
parallel flake-like structure for the 1at.% Nd alloy. Although the
Mg64.5Zn30Ca4Nd1.5 amorphous alloy after immersion for 3 and
7 days shows slightly lower open circuit potentials and higher
corrosion current density as compared to the 1.0at.% Nd alloy,
the 1.5at.% Nd alloy with the uniform corrosion morphology
shown in Fig. 4(d) would provide a better biomaterial candidate
in the future. As a result, the addition of the Nd element to the
Mg-Zn-Ca alloys results in the enhanced corrosion resistance
of the alloys by changing the morphology of the corrosion
products.

I
I

Fig. 5: Polarization curves of as-immersed and as-spun Mg66-xZn30Ca4Ndx(x=0, 0.5, 1, 1.5 at.%) amorphous alloys in SBF
at 37 °C open to air, respectively: (a) Mg66Zn30Ca4, (b) Mg65.5Zn30Ca4Nd0.5, (c) Mg65Zn30Ca4Nd1, (d) Mg64.5Zn30Ca4Nd1.5

Table 1: Open circuit potential (Ecorr) and corrosion current density (Icorr) obtained from polarization curves of Fig. 5

Ecorr (V) Icorr (Acm-2)

Alloys
As-spun 3 days 7 days As-spun 3 days 7 days
-5 -8
Mg66Zn30Ca4 -1.218 -1.080 -1.053 1.964×10 7.052×10 9.612×10-8
-5 -8
Mg65.5Zn30Ca4Nd0.5 -1.173 -1.124 -1.031 1.345×10 4.585×10 2.173×10-8
-6 -8
Mg65Zn30Ca4Nd1 -1.136 -1.076 -0.985 8.579×10 2.173×10 2.038×10-8
-6 -8
Mg64.5Zn30Ca4Nd1.5 -1.160 -1.078 -1.105 4.564×10 2.316×10 2.316×10-8

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2.3 Surface characteristics as measured by
FTIR
In order to study the surface characteristics of the Mg-Zn-Ca(-Nd)
amorphous alloys immersed in SBF for different times, a group
of FTIR spectra of the alloys immersed in SBF at 37 °C were
measured in this work, as shown in Fig. 6. The absorption peaks
of the spectra located at 1,030 cm-1 and 565 cm−1 are assigned to
the phosphate group, which is related to one type of apatite [24].
The minor carbonate group in corrosion products is confirmed
by the peaks around 1,400 cm−1 and 1,470 cm−1 [27]. In addition,
the broad absorption peaks at 3,400 cm−1 and 1,650 cm−1 are
indicative of bound water or a hydration layer associated
Fig. 6: FTIR spectrum of the surface of Mg66-xZn30Ca4Ndx(x=0, 0.5, 1, 1.5 at.%) immersed in SBF solution at 37 °C for 1,
3 and 7 days, respectively: (a) Mg66Zn30Ca4, (b) Mg65.5Zn30Ca4Nd0.5, (c) Mg65Zn30Ca4Nd1, (d) Mg64.5Zn30Ca4Nd1.5
3 Conclusions
This work demonstrates the effects of microalloying Nd element
on the corrosion behavior and surface morphology of as-spun
Mg66-xZn30Ca4Ndx (x = 0-1.5 at.%) amorphous alloys. The
results obtained are summarized as follows:
(1) The corrosion morphology of the alloys immersed in SBF
for 7 days greatly changes with the Nd content. SEM images
observe that the reticular structure at 0at.% Nd changes to the
surface structure with thin flakes perpendicular to the alloy
substrate at 0.5at.% Nd and the structure with parallel strong
flakes at 1at.% Nd, which is responsible for the corrosion
behavior.
508
with apatite [28,29]. Therefore, the FTIR results suggest that the
corrosion products of the alloy surface are carbonate apatite
mixed with Mg(OH)2[8].
In Fig. 6(a-d), it is observed that the phosphate group peak
intensities increase greatly with the extension of immersion time
of the Mg-Zn-Ca(-Nd) amorphous alloys, indicating that the
amount of the apatite increases with increasing the immersion
time. Moreover, it is also found that the absorption peak
intensities of the phosphate group and carbonate reduce with an
increase in the Nd content. These results demonstrate that the
corrosion resistance of the Mg-Zn-Ca(-Nd) amorphous alloys in
SBF increases effectively with an increase in the Nd content.
(2) The addition of Nd to the Mg-Zn-Ca alloys is effective in
improving the corrosion resistance of the alloys by decreasing
the anodic current density and enhancing the open circuit
potentials in SBF solutions.
(3) FTIR tests reveal that the corrosion products on the
alloy surface are carbonate apatite mixed with Mg(OH)2. The
intensities of the phosphate group peaks increase greatly as the
extension of immersion time of the Mg-Zn-Ca(-Nd) amorphous
alloys. Moreover, the absorption peak intensities of the
phosphate group and carbonate reduce with an increase in the
Nd content.

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