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

503
CHINA FOUNDRY Research & Development
Vol.11 No.6 November 2014

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

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

504
 Research & Development CHINA FOUNDRY
Vol.11 No.6 November 2014

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 densities (Icorr) obtained from Fig. 2(b) of Mg 66Zn 30Ca 4,
for the Nd-containing Mg alloy is higher than that of the Mg- Mg65.5Zn30Ca4Nd0.5, Mg65Zn30Ca4Nd1 and Mg64.5Zn30Ca4Nd1.5
Zn-Ca amorphous alloy. That is to say, the overpotential of amorphous alloys (Table 1) are 1.964×10-5 A·cm-2, 1.345×10-5
the cathodic hydrogen evolution reaction is lower for the Nd- A·cm-2, 8.579×10-6 A·cm-2 and 4.564×10-6 A·cm-2, respectively. It
containing Mg-based amorphous alloys as compared to that is clearly seen that Icorr values decrease greatly with increasing
of Nd-free Mg-based amorphous alloy. This also reveals that Nd content. It can therefore be concluded that the corrosion
the cathodic reaction is kinetically easier for the Nd-containing resistance of the Mg-based alloys is enhanced by microalloying
amorphous specimen, which may be due to the existence of the Nd to the alloys.
Nd element. On the other hand, the anodic polarization curves
of the Mg-based alloys with and without Nd addition show a
2.2 Surface morphologies and
wide passivation-like region, indicating the protective films are
electrochemical properties of alloys after
formed on the alloy surface via anodic polarization. Moreover,
immersion in SBF
microalloying Nd element to the alloys leads to an ennoblement Figure 3(a-d) shows SEM micrographs of the Mg-Zn-Ca(-Nd)
of the open circuit potentials of the alloys, which is in agreement amorphous alloys after immersion in the SBF at 37 °C for 1 day.
with the result shown in Fig. 2(a), Meanwhile, it is found that When the Mg66Zn30Ca4 sample is immersed in the simulated
the anodic current densities of the Mg-based amorphous alloys body fluids [Fig. 3(a)], the anodic dissolution of magnesium
decrease with an increase in the Nd content during the applied occurs, and the magnesium hydroxide layer is formed on the
potentials up to -1.06 V (vs. Ag/AgCl). The corrosion current 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.)

505
CHINA FOUNDRY Research & Development
Vol.11 No.6 November 2014

Cl - occurs at the weak sites of the magnesium hydroxide the crack. The corrosion resistance of the reticular structure is
layer and transforms the magnesium hydroxide into soluble weak and could not protect the fresh alloy substrate from the
magnesium chloride. The fresh substrate, directly exposed to the corrosion fluids attack. Microalloying 0.5at.% Nd to the alloy
medium, suffers further corrosion companied with the release gives rise to the great change in the surface morphology during
of Mg2+ and Zn2+ cations [15]. From Fig. 3(a), it is observed that the 7 day-immersion. The surface of the 0.5at.% Nd-containing
a large number of spot corrosion pits appear on the immersed alloy is covered with the corrosion products showing flake-like
surface. At the same time, the apatite begins to be formed on structures [21,22], as shown in Fig. 4(b). The SEM image [Fig.
the surface. The upwarping ‘skin’ on the sample surface is 4(b)] shows that a large amount of the flakes with thin walls are
formed by the surface shrinking during drying, as shown in perpendicular to the alloy substrate, while a few of them are
Fig. 3(a). On the other hand, for the 0.5at.% and 1at.% Nd- tilted or parallel to the substrate [23,24]. It seems that this kind of
containing alloys immersed in SBF for 1 day (Fig. 3b and 3c), the structure is more effective in preventing the corrosion fluids
there are some white particles to be precipitated on the alloy against the alloy as compared with the reticular structure in Fig.
surfaces. The elemental compositions of the white particles 4(a). When the Nd content reaches 1at.%, shown in Fig. 4(c),
in Fig. 3 mainly consist of Ca, P and O, which indicate Ca-P the wall of the flake becomes stronger than that of the 0.5at.%
apatite granules nucleate and grow on the alloy surface. Figure Nd addition. Additionally, most of the flakes turn to be parallel
3(e) shows the typical EDS spectra of the white particles in to the substrate surface. Previous research [25] demonstrated that
Fig. 3 (Note: the Au in EDS spectra comes from the sample the flakes paralleling to the surface could prevent the corrosion
preparation). No corrosion pits are observed on the surface of process more effectively. Moreover, Fig. 4(d) shows that
the Nd-containing alloys, indicating that the pitting corrosion the 1.5at.% Nd-containing amorphous alloy suffers uniform
is inhibited effectively with the Nd addition. Figure 3(d) shows corrosion during the SBF immersion for 7 days, accompanied
that the surface structure of the 1.5at.% Nd-containing Mg- by a very low corrosion dissolution. As a result, the addition of
based amorphous alloy maintains good integrity, in addition to Nd element to the Mg-Zn-Ca amorphous alloys is effective in
a small amount of apatite on the surface, demonstrating that improving the corrosion performance of the Mg-based alloys
the corrosion resistance is enhanced with an increase in the Nd in SBF by modifying the corrosion morphology and surface
content. structure [26].
Further immersing the Mg-Zn-Ca(-Nd) amorphous alloys After immersion in the SBF at 37 °C for 3 and 7 days, the
in the SBF at 37 °C for 7 days, the surface morphologies of polarization curves of the as-immersed Mg-Zn-Ca-Nd alloys
these alloys are shown in Fig. 4. In Fig. 4(a), it is found that are further measured in the SBF, displayed in Fig. 5. The
the reticular structure of the Mg66Zn30Ca4 amorphous alloy polarization curves of the as-spun alloys are also shown for
immersed in the SBF for 7 days is formed at the bottom of comparison. The open circuit potential (Ecorr) and corrosion

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
 Research & Development CHINA FOUNDRY
Vol.11 No.6 November 2014

current density (Icorr) data obtained from the polarization structure of the 0.5at% Nd-containing alloy during the 7 days of
curves (Fig. 5) are listed in Table 1. The as-immersed alloys immersion changes to the thin wall flake-like structure, which
in the SBF exhibit a similar polarization behavior, which could more effectively prevent the corrosion fluids against the
shows much higher open circuit potentials and lower corrosion alloy than the reticular structure. Moreover, when the alloys
current densities as compared with the as-spun alloys. It can immersed for 3 and 7 days, respectively, Figure 5(c) shows that
be found that the corrosion current density of the Mg66Zn30Ca4 the 1at.% Nd alloy exhibits higher corrosion potential than the
amorphous alloy slightly increases after immersion in the SBF 0.5at.% Nd alloy, which is probably due to the formation of the
for 7 days compared with that for 3 days, as shown in Fig. 5(a). parallel flake-like structure for the 1at.% Nd alloy. Although the
The corrosion resistance of the Mg66Zn30Ca4 amorphous alloy Mg64.5Zn30Ca4Nd1.5 amorphous alloy after immersion for 3 and
immersed in the SBF for 7 days is reduced due to the formation 7 days shows slightly lower open circuit potentials and higher
of reticular structures on the alloy surface [Fig. 4(a)]. On the corrosion current density as compared to the 1.0at.% Nd alloy,
other hand, for 0.5at% Nd-containing alloy immersed in the the 1.5at.% Nd alloy with the uniform corrosion morphology
SBF for 7 days shown in Fig. 5(b) and Table 1, the corrosion shown in Fig. 4(d) would provide a better biomaterial candidate
potential of the alloy containing a small amount of Nd increases in the future. As a result, the addition of the Nd element to the
and its corrosion current density decreases as compared to the Mg-Zn-Ca alloys results in the enhanced corrosion resistance
Nd-free alloy at the same conditions. of the alloys by changing the morphology of the corrosion
As we discussed in the SEM image [Fig. 4(b)], the surface products.
I

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

507
CHINA FOUNDRY Research & Development
Vol.11 No.6 November 2014

2.3 Surface characteristics as measured by with apatite [28,29]. Therefore, the FTIR results suggest that the
FTIR corrosion products of the alloy surface are carbonate apatite
In order to study the surface characteristics of the Mg-Zn-Ca(-Nd) mixed with Mg(OH)2[8].
amorphous alloys immersed in SBF for different times, a group In Fig. 6(a-d), it is observed that the phosphate group peak
of FTIR spectra of the alloys immersed in SBF at 37 °C were intensities increase greatly with the extension of immersion time
measured in this work, as shown in Fig. 6. The absorption peaks of the Mg-Zn-Ca(-Nd) amorphous alloys, indicating that the
of the spectra located at 1,030 cm-1 and 565 cm−1 are assigned to amount of the apatite increases with increasing the immersion
the phosphate group, which is related to one type of apatite [24]. time. Moreover, it is also found that the absorption peak
The minor carbonate group in corrosion products is confirmed intensities of the phosphate group and carbonate reduce with an
by the peaks around 1,400 cm−1 and 1,470 cm−1 [27]. In addition, increase in the Nd content. These results demonstrate that the
the broad absorption peaks at 3,400 cm−1 and 1,650 cm−1 are corrosion resistance of the Mg-Zn-Ca(-Nd) amorphous alloys in
indicative of bound water or a hydration layer associated SBF increases effectively with an increase in the Nd content.

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
(2) The addition of Nd to the Mg-Zn-Ca alloys is effective in
This work demonstrates the effects of microalloying Nd element improving the corrosion resistance of the alloys by decreasing
on the corrosion behavior and surface morphology of as-spun the anodic current density and enhancing the open circuit
Mg66-xZn30Ca4Ndx (x = 0-1.5 at.%) amorphous alloys. The potentials in SBF solutions.
results obtained are summarized as follows: (3) FTIR tests reveal that the corrosion products on the
(1) The corrosion morphology of the alloys immersed in SBF alloy surface are carbonate apatite mixed with Mg(OH)2. The
for 7 days greatly changes with the Nd content. SEM images intensities of the phosphate group peaks increase greatly as the
observe that the reticular structure at 0at.% Nd changes to the extension of immersion time of the Mg-Zn-Ca(-Nd) amorphous
surface structure with thin flakes perpendicular to the alloy alloys. Moreover, the absorption peak intensities of the
substrate at 0.5at.% Nd and the structure with parallel strong phosphate group and carbonate reduce with an increase in the
flakes at 1at.% Nd, which is responsible for the corrosion Nd content.
behavior.

508
 Research & Development CHINA FOUNDRY
Vol.11 No.6 November 2014

[16] Witte F, Kaese V, Switzer H, et al. In vivo corrosion of four

References magnesium alloys and the associated bone response.
[1] Yang J X, Cui F Z, Yin Q S, et al. Characterization and degradation Biomaterials, 2005, 26: 3557–3563.
study of calcium phosphate coating on magnesium alloy bone [17] Gu X N, Zheng Y F, Cheng Y, et al. In vitro corrosion and
implant in vitro. Ieee T. Plasma Sci., 2009, 37: 1161 −1168. biocompatibility of binary magnesium alloys. Biomaterials,
[2] Ghimire G, Spiro J R, Kharbanda R K, et al. Evidence for 2009, 30: 484–498.
the return of coronary vasoreactivity following absorption [18] Zberg B, Uggowitzer J P J, Loffler J F. MgZnCa glasses without
of a bioabsorbable magnesium alloy coronary stent. Euro clinically observable hydrogen evolution for biodegradable
Intervention, 2009, 4: 481−484. implants. Nat. Mater, 2009, 8: 887–891.
[3] Ai X L, Quan G F, Liu Z M, et al. Microstructure and tensile [19] Feyerabend F, Fischer J, Holtz J, et al. Evaluation of short-term
properties of thixo-diecast AZ91D magnesium alloy. China effects of rare earth and other elements used in magnesium
Foundry, 2013, 10: 288-293. alloys on primary cells and cell lines. Acta Biomater., 2010, 6:
[4] Zhou K K, Wang H X, Liang W, et al. Microstructure and 1834–1842.
mechanical properties of cast Mg-15Al-xNd alloy by Permanent [20] Zhang X B, Yuan G Y, Niu J L, et al. Microstructure, mechanical
mold. China Foundry, 2013, 10, 315-320. properties, biocorrosion behavior, and cytotoxicity of as-extruded
[5] Staiger M P, Pietaka A M, Huadmaia J, et al. Magnesium and its Mg-Nd-Zn-Zr alloy with different extrusion ratios. J. Mech.
alloys as orthopedic biomaterials: a review. Biomaterials, 2006, Behav. Biomed., 2012, 9: 153-162.
27: 1728–1734. [21] Ng W F, Wong M H, Cheng F T. Cerium-based coating for
[6] Cowan J A. The Biological Chemistry of Magnesium. VCH, New enhancing the corrosion resistance of bio-degradable Mg
York, 1995. implants. Material. Chem. and Phys., 2010, 119: 384–388.
[7] Nagels J, Stokdijk M, Rozing P M. Stress shielding and bone [22] Wang J, Li D D, Liu Q, et al. Fabrication of hydrophobic
resorption in shoulder arthroplasty. J. Shoulder Elbow Surg., surface with hierarchical structure on Mg alloy and its corrosion
2003, 12: 35–39. resistance. Electrochim. Acta, 2010, 55: 6897–6906.
[8] Zhu Y Y, Wu G G, Zhang Y H, et al. Growth and characterization [23] Zhang J H, Leng Z, Zhang M L, et al. Effect of Ce on
of Mg(OH)2 film on magnesium alloy AZ31. Appl. Surf. Sci., microstructure, mechanical properties and corrosion behavior
2011, 257: 6129–6137. of high-pressure die-cast Mg-4Al-based alloy. J. Alloys Compd.,
[9] Xu L, Yu G, Zhang E, et al. In vivo corrosion behavior of Mg-Mn- 2011, 509: 1069–1078.
Zn alloy for bone implant application. J. Biomed. Mater. Res., [24] Zhao X H, Yang L F, Zuo Y, et al. Hydroxyapatite Coatings on
2007, 83A: 703–711. Titanium Prepared by Electrodeposition in a Modified Simulated
[10] Kannan M B, Raman R K S. In vitro degradation and mechanical Body Fluid. Chin. J. Chem. Eng., 2009, 17: 667–671.
integrity of calcium-containing magnesium alloys in modified- [25] Miao J, Ye B, Wang Q D, et al. Mechanical properties and
simulated body fluid. Biomaterials, 2008, 29: 2306–2314. corrosion resistance of Mg-10Gd-2Y-0.5Zr alloy by hot extrusion
[11] Zhang S, Zhang X, Zhao C, et al. Research on an Mg-Zn alloy solid-state recycling. J. Alloys Compd., 2013, 561: 184–192.
as a degradable biomaterial. Acta Biomater., 2010, 6: 626–640. [26] Wang H X, Guan S K, Wang X, et al. In vitro degradation and
[12] Li Z J, Gu X N, Lou S Q, et al. The development of binary Mg- mechanical integrity of Mg-Zn-Ca alloy coated with Ca-deficient
Ca alloys for use as biodegradable materials within bone. hydroxyapatite by the pulse electrodeposition process. Acta
Biomaterials, 2008, 29: 1329–1344. Biomater., 2010, 6: 1743–1748.
[13] Song G, Atrens A. Corrosion mechanisms of magnesium alloys. [27] Chen J D, Wang Y J, Wei K, et al. Self-organization of
Adv. Eng. Mater., 1999, 1: 11–33. hydroxyapatite nanorods through oriented attachment.
[14] Song G, Atrens A. Understanding magnesium corrosion - a Biomaterials, 2007, 28: 2275–2280.
framework for improved alloy performance. Adv. Eng. Mater., [28] Pekounov Y, Petrov O E. Bone resembling apatite by
2003, 5: 837–858. amorphous-to-crystalline transition driven self-organisation. J.
[15] Gu X N, Zheng Y F, Zhong S P, et al. Corrosion of, and cellular Mater. Sci. Mater. Med., 2008, 19: 753–759.
responses to Mg-Zn-Ca bulk metallic glasses. Biomaterials, [29] Ramirez C A O, Costa A M, Bettini J, et al. Structural properties
2010, 31: 1093–1103. of nanostructured carbonate apatites. Key Eng. Mater., 2009,
396–398: 611–614.

This work was financially supported by the “100 Talents Project” of Hebei Province, China (E2012100009), the Key Research
Items in Science and Technology Support Program of Tianjin, China (12ZCZDGX46100), the Natural Science Foundation of Hebei
Province, China (E2012202017), and the National High Technology Research and Development Program (863 Program) of China
(2013AA031002).

509