Materials and Design 117 (2017) 84–94

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Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Design and characterizations of novel biodegradable Zn-Cu-Mg alloys for

potential biodegradable implants
Zibo Tang a, Hua Huang a,⁎, Jialin Niu a, Lei Zhang a, Hua Zhang a, Jia Pei a, Jinyun Tan b, Guangyin Yuan a,⁎
a
National Engineering Research Center of Light Alloy Net Forming and State Key Laboratory of Metal Matrix Composite, Shanghai Jiao Tong University, 200240 Shanghai, China
b
Department of Surgery, Huashan Hospital, Fudan University, Shanghai 200040, China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Mg2Zn11 phase newly forms and pre-

cipitates by adding Mg into Zn-Cu alloy.
• Yield strength increases by 99.7% with
1 Mg addition, indicating obvious
strengthening effect of Mg for Zn-3Cu
alloy.
• Ranging from 11.4 to 43.2 μm year-1,
the degradation rates of Zn-3Cu-xMg
alloys are more suitable for clinic appli-
cation.
• The cytocompatibility of Zn-3Cu is en-
hanced apparently by Mg addition.

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

Article history: Zn-3Cu-xMg (x = 0, 0.1, 0.5 and 1.0 wt.%) alloys were developed as potential biodegradable metallic materials in
Received 23 October 2016 this study. The mechanical properties, corrosion behavior and in vitro cytocompatibility of Zn-3Cu-xMg alloys
Received in revised form 22 December 2016 were studied systematically to evaluate the feasibility as biodegradable implant materials. The secondary
Accepted 23 December 2016
phase in as-cast and as-extruded Zn-3Cu alloy was CuZn5 phase. Mg2Zn11 phase newly formed and precipitated
Available online 26 December 2016
by Mg addition. The volume fraction of Mg2Zn11 phase increased gradually with increasing Mg concentration. As
Keywords:
a result, yield strength was improved from 213.7 to 426.7 MPa and increased by 99.7% while elongation de-
Biodegradable creased from 47.1% to 0.9%. Besides, biocompatibility was improved apparently and in vitro corrosion rates in-
Zn-based alloy creased from 11.4 to 43.2 μm year−1, which is more suitable for clinic application. The present research
Mechanical properties indicated that the newly developed alloys could be promising candidates for biomedical use due to the proper
Corrosion behavior mechanical properties, degradation rate and acceptable biocompatibility.
Cytocompatibility © 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Nowadays, Zn and Zn-based alloys have drawn increasing attention
as biodegradable metallic materials due to their superior mechanical
properties, moderate in vitro degradation rate and acceptable
⁎ Corresponding authors.
E-mail addresses: huangh@sjtu.edu.cn (H. Huang), gyyuan@sjtu.edu.cn (G. Yuan).
cytocompatibility [1–9]. Bowen et al. [3] implanted pure Zn wire into
rat abdominal aorta, finding that pure Zn exhibited ideal corrosion be-
havior with gradual degradation of the implant. Moreover, as well
known, Zn has crucial roles involving functions of over 300 enzymes,
which therefore is essential to different catalysis and co-catalysis per-
formed by these enzymes, including membrane stability, wound
healing, and brain development [10]. Thus, Zn might be feasible to be
a biodegradable material candidate. However, both strength and

http://dx.doi.org/10.1016/j.matdes.2016.12.075
0264-1275/© 2016 Elsevier Ltd. All rights reserved.
 Z. Tang et al. / Materials and Design 117 (2017) 84–94
ductility of pure Zn are poor, which have to be improved to meet the
clinical requirements.
To improve the mechanical properties of pure Zn, alloying is a
general way. To our knowledge, Zn-based alloys for industrial appli-
cations commonly contain aluminum (Al) and copper (Cu) as the
main alloying elements [11–13], which are capable of enhancing
the mechanical properties of Zn apparently. However, Al is not suit-
able as an alloying element for biomedical materials, considering its
well-known neurotoxicity [14]. Copper is a better alloying element,
as it is one of the essential trace elements for human, with the nor-
mal level of Cu in blood serum about 1.1–1.5 μg ml− 1, and the recom-
mended dietary allowance (RDA) is 1.0–3.0 mg day− 1 for adults [20].
Besides, Cu plays a vital part in the immune system [15–17], and has
beneficial effects on endothelial cells proliferation [18,19]. More-
over, copper has been reported to enhance antibacterial property
[21,22], which can minimize the risk of infection in clinical applica-
tions. Nevertheless, intake of Cu should be controlled less than
1 mg day− 1 [23] because excessive Cu can cause neurodegenerative
diseases, including Alzheimer's, Menkes and Wilson diseases [20].
The feasibility of Cu addition into biodegradable metallic materials
has been confirmed in a previous study [24], where biodegradable
Mg-Cu alloys exhibit no cytotoxicity towards HUVECs and MC3T3-
E1 cells. In our previous study [25], as-extruded Zn-4Cu (wt.%)
alloy was characterized and evaluated. The results showed that as-
extruded Zn-4Cu alloy exhibited excellent strength and ductility,
uniform and slow degradation, good biocompatibility and significant
antibacterial effect, which made it an excellent candidate material
for biodegradable implants, especially for cardiovascular stents applica-
tion. In addition, the effect of Cu concentration on the microstructure,
mechanical properties, corrosion behavior, in vitro cytocompatibility
and antibacterial effect for Zn-Cu binary alloys has been characterized,
and the details will be published elsewhere in near future. The results
show that mechanical properties of Zn-Cu binary alloys are ideal
for potential biodegradable implants when the concentration of Cu
is no less than 3 wt.%. Nevertheless, the degradation rate (about
10 μm/year) of Zn-4Cu binary alloys in Hank's solution is relatively
slow for medical application, and meanwhile, there is still some
room to further optimize the cytocompatibility of the Zn-Cu binary
system.
On the other hand, Mg-based implants have been widely studied,
indicating that Mg has many positively biochemical features and
functions, such as stimulation of new bone formation [26,27]. Be-
sides, the degradation rate is expected to increase because of precip-
itation of Mg-Zn phase [1,4]. Hence, to fully use the advantages of
Mg, many studies try to introduce Mg into Zn-based alloys to im-
prove their properties. For example, Vojtěch et al. [1] and Gong et
al. [2] have investigated as-cast Zn-Mg alloys and as-extruded Zn-
1Mg alloy, respectively, denoting that Zn-Mg alloy system was a
promising alloy system and hot extrusion process was able to pro-
mote mechanical properties of Zn alloys effectively. Furthermore,
Murni et al. [9] and Dambatta et al. [8] researched cytotoxicity and
the influence of thermal treatment of Zn-3Mg alloy, respectively.
The results indicated that the alloy had acceptable toxicity at cellular
level and thermal treatment can significantly improve ductility of
the alloy with slight compromise in its tensile strength. All afore-
mentioned suggest that Mg as an alloying element plays a significant
role in apparently improving cytocompatibility and mechanical
properties of Zn alloys. Therefore, Mg is considered as an alloying el-
ement to further optimize the degradation rate, mechanical proper-
ties and cytocompatibility of Zn-Cu binary alloy.
In this paper, Zn-3Cu-xMg (x = 0, 0.1, 0.5 and 1.0 wt.%) alloys
were proposed considering merits of Zn-Cu alloy system and the
alloying effects of Mg element. The corresponding effects of different
Mg concentration on the mechanical properties, corrosion behavior,
and cytocompatibility of the as-extruded Zn-3Cu-xMg alloys are in-
vestigated systematically.
85
2. Experimental procedure
2.1. Materials preparation
Zn-3Cu-xMg (x = 0, 0.1, 0.5 and 1.0 wt.%) were prepared using pure
Zn (99.995 wt.%), brass (Cu-38 wt.% Zn) and pure magnesium
(99.99 wt.%). Melting was performed at about 650–680 °C in a steel cru-
cible, which was preheated at 100 °C. A mixed gas atmosphere of SF6
(1 vol.%) and CO2 (balance) was employed throughout the melting
and casting processes to prevent the oxidation of Mg element. The as-
cast ingots of alloys were homogenized at about 360 °C for 8 h, followed
by quenching in water. After homogenization, the alloys were extruded
at about 280 °C from 60 mm to 20 mm in diameter with an extrusion
ratio of 9:1 and an extrusion speed of 2 mm/s.
2.2. Microstructure characterization
The microstructures of the as-cast and as-extruded samples were
observed by optical microscopy (OM, Zeiss Axio Observer A1, Germa-
ny). After polished, all the samples were etched by a solution of 1.0 g
oxalic acid, 1.0 ml nitric acid, 1.0 ml acetic acid and 150 ml distilled
water. The volume fraction of the second phase of as-extruded samples
was measured using Image-Pro Plus 6.0 software and grain size was
measured using Nano Measurer software. An X-ray diffractometer
(XRD, Rigaku SmartLab, Japan) equipped with Cu Kα (λ = 0.154 nm)
radiation was used to analyze phase constitution of the studied alloys.
As-extruded Zn-3Cu-0.1Mg was selected to further identify the phase
constitution after extrusion using scanning electron microscopy (SEM,
FEI Quanta FEG 250, US) equipped with energy dispersive spectrometry
(EDS).
2.3. Mechanical properties
The tensile test was carried out on a universal material test machine
(Zwick/Roell Z020, Germany) according to ASTM-E8-04 [28]. Tensile
dog-bone samples (54 mm length, 10 mm gage length, 2 mm wide
and nominally 1 mm thick) were cut from the extruded rods parallel
to the extrusion direction. The tensile tests were performed with an ini-
tial strain rate of 1 × 10−3 s−1 at room temperature. For each group of
tests, three samples were tested.
2.4. Electrochemical test
The electrochemical measurements were carried out in Hank's solu-
tion [29] at 37 °C with an advanced electrochemical system (Princeton
PARSTAT 2273, USA), equipped with a three-electrode cell featuring a
graphite counter electrode and a saturated calomel reference electrode
(SCE). A surface area of 1 cm2 for each sample was exposed to the solu-
tion during the tests. After immersion at open circuit potential (OCP) for
1 h to reach a steady state, EIS tests were conducted at OCP from 0.1 Hz
up to 105 Hz, with an amplitude of ±10 mV. Potentio-dynamic polariza-
tion experiments were carried out from −0.3 V vs. OCP at a scan rate of
1 mV/s. The EIS and potentio-dynamic polarization results were fitted
and analyzed using ZsimpWin 3.10 and EClab software, respectively.
According to ASTM-G102-89 [30], corrosion rate can be calculated ac-
cording to the following equations:
icorr
CR ¼ K1   EW ð1Þ
ρ
1
EW ¼ ð2Þ
nf
∑ i i
Wi
where:
86 Z. Tang et al. / Materials and Design 117 (2017) 84–94

CR is given in mm/year, icorr is the corrosion current density in μA/

cm2, EW is the alloy equivalent weight, K1 = 3.27 × 10− 3, mm g/-
μA cm year, ρ = density in g/cm3, fi = the mass fraction of the ith ele-
ment in the alloy, Wi = the atomic weight of the ith element in the
alloy, and ni = the valence of the ith element of the alloy.

2.5. Immersion test

Immersion test was also carried out in Hank's solution at 37 °C ac-

cording to ASTM G31-72 [31] with the ratio of surface area to solution
volume of 1 cm2: 25 ml. After polished with SiC paper progressively
up to 3000 grits, the Ф 12 × 3 mm specimens cut from as-extruded in-
gots were placed in Hank's solution for 480 h. Thereafter, the samples
were washed in a solution containing 200 g/l CrO3 to remove the corro-
sion products. The surface morphologies of the samples before and after
washing were observed using SEM equipped with EDS. The corrosion
rates were then calculated (μm/year) by weight loss measured on an an-
alytical balance with an accuracy of 0.1 mg according to the following
equation:
Corrosion rate ðμm=yearÞ ¼ ðK  WÞ=ðA  T  DÞ
where the coefficient K = 8.76×107, W is the weight loss (g), A is the
sample area exposed to solution (cm2), T is the exposure time (h) and
D is the density of the material (g/cm3).
2.6. Cytotoxicity evaluation
The human endothelium-derived cell line (EA.hy926) was pur-
chased from Cell Bank of Chinese Academy of Sciences, Shanghai.
EA.hy926 cells were cultured in Dulbecco modified Eagle medium
(DMEM, Gibco, USA) supplemented with 10% fetal bovine serum (FBS,
Gibco), 100 units/ml penicillin and 100 units/ml streptomycin in a cell
incubator (humidified atmosphere with 5% CO2 at 37 °C).
The cytotoxicity tests were carried out using indirect contact meth-
od. The same preparation procedure of specimens for immersion tests
is applied to cytotoxicity test. The extracts were prepared by immersing
samples in DMEM for 72 h with a ratio of 1.25 cm2 ml−1, according to
ISO 10993-5:1999 [32]. Recent study [33] reported that a minimal 6
times to a maximal 10 times dilution of extracts for in vitro cytotoxicity
test could be more close to real environment of human body. Therefore,
the extracts were diluted into 10%, 50% and 100%, and stored at 4 °C be-
fore use.
Cells were seeded in a 96-well plate with 2000 cells/well, and incu-
bated for 24 h to allow attachment. Then, the medium was replaced by
the extracts. After 1, 3 and 5 days, 10 μl CCK-8 solution was added to
each well and then it was incubated for 2 h. The optical density was
measured at the wavelength of 450 nm using a microplate reader
(iMARK, Bio-Rad, USA).
Fig. 1. Microstructures of the as-cast Zn-3Cu-xMg alloys. (a) Zn-3Cu; (b) Zn-3Cu-0.1Mg;
(c) Zn-3Cu-0.5Mg; (d) Zn-3Cu-1.0Mg. The bright and dark secondary phases are arrowed.
To further confirm the phase constitution of the studied alloys and
investigate the phase change with increasing Mg content, as-cast alloys
ð3Þ
are analyzed by XRD and the results are presented in Fig. 2. The XRD
pattern of Zn-3Cu alloy confirms that the alloy mainly consists of Zn
and CuZn5 phase. Therefore, the dendritic secondary phase (bright in
Fig. 1a) is CuZn5, whose morphology is in agreement with previous
study about Zn-Cu binary alloy [25]. The XRD patterns also show that
higher intensity of the peaks of Mg2Zn11 is detected with increasing
Mg content. Combined this with microstructure observation results in
Fig. 1, we can determine that the lamellar secondary phase (dark in
Fig. 1b, c and d) is Mg2Zn11, the morphology of which is consistent
with previous studies about Zn-Mg alloy [2].
Prior to extrusion, as-cast alloys are homogenized at 360 °C for 8 h.
The microstructures (OM images are not shown here) of the samples
after homogenization exhibit no obvious change, which implies that
the secondary phases in study alloys are thermally stable.
Fig. 3 shows the OM of the as-extruded samples. CuZn5 is crushed,
lengthened and distributes along the extrusion direction, which is in
agreement with the previous study about Zn-4Cu (wt.%) alloy [25]. Re-
ticular Mg2Zn11 is also crushed as particles distributing along the extru-
sion direction. The size of the crushed Mg2Zn11 particles is not uniform
and ranges from 2 μm to 11 μm. The volume fractions of Mg2Zn11 for Zn-
3Cu-xMg (x = 0.1, 0.5 and 1.0 wt.%) alloys are 1.25%, 8.19% and 16.63%,
respectively. Grain size of the extruded samples is much finer than that
of the as-cast and heat-homogenized ones, indicating that the micro-
structure has been refined by hot extrusion and thus the mechanical
properties should be improved correspondingly. Moreover, it is

3. Results

3.1. Microstructure

Fig. 1 shows the optical microstructure (OM) images of the as-cast

Zn-3Cu-xMg alloys. Zn-3Cu consists of primary Zn matrix and the den-
dritic secondary phase (bright in Fig. 1a). A lamellar secondary phase
(dark in Fig. 1b, c and d) is newly formed and precipitated along the
grain boundary by the addition of Mg. It clearly shows that the volume
fraction of lamellar secondary phase increases with increasing Mg con-
tent. As a result, the dendrites are restrained and the grain size of sub-
strate decreases gradually with the addition of Mg. Besides, in
comparison with morphologies, only one type of secondary phase
forms in Zn-3Cu (wt.%) alloy and two types of secondary phase precip-
itate in Zn-3Cu-xMg (x = 0.1, 0.5 and 1.0 wt.%) alloys. Fig. 2. XRD patterns of the as-cast Zn-3Cu-xMg (x = 0, 0.1, 0.5 and 1.0 wt.%) alloys.
 Z. Tang et al. / Materials and Design 117 (2017) 84–94
Fig. 3. Microstructures of the as-extruded Zn-3Cu-xMg alloys. (a) Zn-3Cu; (b) Zn-3Cu-
0.1Mg; (c) Zn-3Cu-0.5Mg; (d) Zn-3Cu-1.0Mg.
noticeable that grain size of Zn matrix is smaller near CuZn5 phase than
that is far away from CuZn5 phase. SEM image and EDS results of as-ex-
truded Zn-3Cu-0.1Mg alloy are shown in Fig. 4. The bright secondary
phase is CuZn5 and the dark secondary phase is Mg2Zn11, which are fur-
ther confirmed by the SEM and EDS results.
3.2. Mechanical properties
Fig. 5 presents the tensile properties of as-extruded experimental
Zn-3Cu-xMg alloys. The yield strength (YS) and the ultimate tensile
strength (UTS) of as-extruded Zn-3Cu-xMg alloys are improved a lot
compared with Zn-3Cu alloy while elongation decreases obviously.
With increasing Mg content, YS values increase from 213.7 to
426.7 MPa and UTS values increase from 257 to 440.5 MPa by 99.7%.
On the contrary, elongation values of the experimental alloys decrease
from 47.1% to 0.9%. Particularly, there is a sudden change of mechanical
properties between Zn-3Cu and Zn-3Cu-0.1Mg alloys. The Young's
modulus of as-extruded Zn-3Cu-xMg alloys is about 78 to 85 GPa ac-
cording to the stress-strain curves, which is higher than that of bone
(3–20 GPa) [20].
3.3. Electrochemical test
Electrochemical measurements including potentio-dynamic polari-
zation curves and EIS have been applied to identify the corrosion mech-
anism characteristics of the samples. Fig. 6 shows the representative
potentio-dynamic polarization curves of the four as-extruded alloys.
Hydrogen evolution reaction occurs on the cathodic sides and the
Fig. 4. SEM image of as-extruded Zn-3Cu-0.1Mg alloy. Elemental composition of the marked position in panel a: (b) vs. point 1and (c) vs. point 2.
87
anodic sides of Zn-3Cu alloy are visible with passivation below the
breakdown potential. However, Zn-3Cu-xMg alloys do not exhibit this
characteristic, which might be ascribed to the Mg addition. The results
calculated from the polarization curves using Tafel fitting are summa-
rized in Table 1. According to the fitting date, corrosion rates are calcu-
lated using Eq. (1), ranging from 5.5 to 180.5 μm year−1 with increasing
Mg content.
Fig. 7 displays the EIS results. The Nyquist plots (Fig. 7a) of Zn-3Cu-
xMg are characterized by two loops, which imply the existence of the
oxide film. The diameters of capacitive loops decline with increasing
Mg content, indicating that higher Mg addition could reduce the corro-
sion resistance. Bode plots (Fig. 7b and c) show that at a low frequency
region (between 10−1 and 103 Hz), impedance values decline with in-
creasing Mg content, which are associated with phase angle from 20○
to 60○. Generally, higher impedance value indicates lower corrosion
rate.
A typical equivalent circuit, as shown in Fig. 8, is used to fit the EIS
experimental data. Herein, Rs represents the electrolyte (solution) resis-
tance; Rf and CPEf were applied to describe the properties of the film; a
CPEdl and a charge transfer resistance Rct in parallel with it are used to
describe the characterizations of the double layer existing at the inter-
face of electrolyte solution and Zn substrate. The fitted data are listed
in Table 2. Apparently, the values of Rf decrease with the increase of
Mg concentration, indicating the protection effect of oxide film decline
gradually.
3.4. Immersion test
The corrosion rates of the studied alloys calculated based on the
weight loss are shown in Fig. 9. As expected, corrosion rates increase
from 11.4 to 43.2 μm year−1 with increasing Mg content, which is con-
sistent with electrochemical test. Compared with Mg alloys [34], the
corrosion rates of the as-extruded Zn-3Cu-xMg alloys are much lower,
which are consistent with previous researches that Zn-based alloys ex-
hibit lower corrosion rates than Mg-based alloys [1,2,4]. When in com-
parison with Zn-based alloys, Zn-1Mg (about 82 μm/year) [4] for
instance, the corrosion rates of Zn-3Cu-xMg alloys are still lower though
the corrosion rates of Zn-3Cu-xMg is able to increase up to
43.2 μm year−1.
Fig. 10 shows the corrosion morphologies of the alloys after 480 h'
immersion in Hank's solution. During biodegradation process, large
amount of corrosion products precipitate on sample surfaces. With in-
creasing Mg content, the corrosion products become denser, which fur-
ther confirms that the corrosion rates of Zn-3Cu-xMg alloys increase
with Mg addition. The corrosion products form a layer covering the sur-
face without any severe local corrosion, which may indicate that the
corrosion mechanism of the alloys is uniform corrosion basically rather
88 Z. Tang et al. / Materials and Design 117 (2017) 84–94
Fig. 5. The mechanical properties of as-extruded Zn-3Cu-xMg (x = 0, 0.1, 0.5 and 1.0 wt.%) alloys.
than local corrosion. According to EDS analysis shown in Fig. 11, top
layer of biodegradation products of all the samples are composed of
Zn, O, C, P, Mg and Ca elements. The biodegradation products are com-
plicated and varied. Referring to current literatures [2–4,6], it is specu-
lated that the biodegradation products are mainly composed of
Zn(OH)2 and Zn3(PO4)2. With Mg addition, the ratio of different corro-
sion products might change a little while the types of them might be
the same. Further investigation is under way.
Fig. 12 shows the surface morphologies of the as-extruded alloys
after corrosion products are removed. The corrosion pits are fine, shal-
low and uniform for Zn-3Cu alloy. As for Zn-3Cu-xMg alloys, scattered
corrosion pits seems slightly larger than that on Zn-3Cu alloy, but
there are no severe localized corrosion pits, which also indicate an uni-
form corrosion mode macroscopically.
3.5. Cytotoxicity
Viability of EA.hy926 cells cultured in 100%, 50% and 10% pure Zn
and Zn-3Cu-xMg extracts is shown in Fig. 13. Based on the current ISO
standards for in vitro cytotoxicity, cell viability higher than 75% could
be considered as nontoxicity for medical devices. However, as for the vi-
ability of EA.hy926 cells cultured in 100% extracts, only Zn-3Cu-0.5Mg
and Zn-3Cu-1.0Mg meet the cytotoxicity standards. Cytocompatibility
of Zn-3Cu is similar to pure Zn. Furthermore, it is clear that the cell via-
bility is promoted while Mg concentration increases. Fig. 13b and c rep-
resents cell viability at 50% and 10% dilutions, respectively, whose
viability of all the samples were higher than 90% after 1, 3 and 5 days
of culture. Besides, there was no significant difference between pure
Fig. 6. Polarization curves of the as-extruded Zn-3Cu-xMg (x = 0, 0.1, 0.5 and 1.0 wt.%)
alloys in Hank's solution at 37 °C.
Zn and as-extruded samples by comparing cell viability shown in Fig.
13b and c.
4. Discussion
4.1. Microstructure and mechanical properties
4.1.1. Microstructure
According to the OM, XRD, SEM and EDS results, the newly formed
phase in Zn-3Cu-xMg alloys is Mg2Zn11 in comparison with Zn-3Cu
alloy. Meanwhile, without other newly formed phase can be detected,
which implies that there is no interaction between Cu and Mg elements.
Hence, the solidification behavior of Zn-Cu-Mg ternary system can be
simplified and divided into Zn-Cu and Zn-Mg binary system. According
to Zn-Cu binary phase diagram [35], a peritectic reaction
Zn + L → CuZn5 occurs at 425 °C. The CuZn5 phase with dendrite mor-
phology grows in a nonaligned way. According to Zn-Mg binary phase
diagram [35], a eutectic reaction L → Zn + Mg2Zn11 occurs at 364 °C. La-
mellar and network eutectic contains Zn and Mg2Zn11 phase. Therefore,
during solidification, CuZn5 phase precipitates from the melt first when
temperature cools down to ~425 °C, and then Mg2Zn11 appears at about
364 °C. Zn and Mg2Zn11 eutectic mixtures precipitate along the grain
boundary of Zn matrix, whose volume fraction thus increases with the
increase of Mg content. These eutectic mixtures prominently hinder
the growth of Zn matrix, which contributes to the decrease in grain
size of Zn matrix. At the same time, the growth of CuZn5 phase is also
suppressed.
The hot extrusion process effectively breaks the eutectic network
and peritectic dendritic CuZn5 phase. Dynamic recrystallization then re-
sults in the formation of new equiaxed grains of Zn. In this study, only
CuZn5 and Mg2Zn11 are found in the ternary Zn-3Cu-xMg alloys. Gener-
ally, the microstructure of as-extruded alloys becomes more uniform
and grain size is refined compared with the as-cast ones. Besides,
grain size near CuZn5 is finer than that away from CuZn5 phase. It
might be attributed to the effect of the particle stimulated nucleation
(PSN) [36], which can be simplified as a mechanism that particles pro-
mote dynamical recrystallization. Therefore, the nucleation of new
grain might occur favorably near the second phases (CuZn5) particles
because of the effect of PSN.
4.1.2. Mechanical properties
Tensile test suggests that increasing Mg content can effectively im-
prove the YS and UTS while deteriorate the elongation of the alloys. To
analyze the underlying mechanism, grain size distribution map (Fig.
14) and image of tensile samples after tensile test (Fig. 15) of as-extrud-
ed Zn-3Cu and Zn-3Cu-0.1Mg are given. Comparing cross-section mi-
crostructure of Zn-3Cu with Zn-3Cu-0.1Mg, one can observe that there
is an apparent difference with regards to the Mg2Zn11 particles. The av-
erage grain sizes of the two studied alloys are 3.27 μm and 4.46 μm, re-
spectively. The excellent elongation of as-extruded Zn-3Cu can be
attributed to two main factors. One could be that microstructure with
 Z. Tang et al. / Materials and Design 117 (2017) 84–94
Table 1
Fitting results of the polarization curves.
Alloys Ecorr (mV vs. SCE) icorr (μA/cm2)
Zn-3Cu −1101.761 0.372
Zn-3Cu-0.1Mg −1000.497 1.177
Zn-3Cu-0.5Mg −956.774 1.563
Zn-3Cu-1.0Mg −945.170 12.413
grain size gradient is capable of contributing to both strength and plas-
ticity. Similar phenomenon has been reported that gradient nano-grain
and coarse grain architecture might enhance strength-plasticity synergy
[37]. The other is the compatible deformation effect of CuZn5 phase,
which can be proved by the elongated CuZn5 phase after extrusion.
However, after adding trace Mg, elongation of as-extruded Zn-3Cu is de-
teriorated so much.
Fig. 15a shows the image of tensile samples after tensile test. As one
can see, there is an obvious necking phenomenon for the as-extruded
Zn-3Cu alloy. On the contrary, as-extruded Zn-3Cu-0.1Mg alloy exhibits
a trait of brittle fracture. To investigate the fracture behavior of as-ex-
truded Zn-3Cu-0.1Mg alloy at length, microstructures are observed
and the OM images of marked positions from the tensile sample are
shown in Fig. 15b and c. By observing fracture morphology shown in
Fig. 15b, transgranular fracture grains are apparent on the fracture espe-
cially for coarse grains, suggesting a fracture mode of transgranular frac-
ture. In Fig. 15c, cracks appear on the Mg2Zn11 phase while substrate
grains are still intact, which indicates that Mg2Zn11 phase fractures at
the first stage of tensile tests. Hence, the effects of Mg addition on tensile
strength and elongation of Zn-3Cu can be summarized as follows. (1)
Considering the extremely low solid solution of Mg in Zn substrate, ef-
fect of solid solution strengthening can be neglected. Mg mainly exists
as Mg2Zn11 phase in as-extruded Zn-3Cu-0.1Mg alloy, which is charac-
terized as hard and brittle in nature [1,7]. In addition, the average
grain size of Zn-3Cu-0.1Mg is just a little larger than that of Zn-3Cu
(Fig. 14b and d). Thus, dispersion strengthening [38] might be the
main reason for the improvement of strength. During deformation,
Mg2Zn11 phase prevents dislocation slipping, resulting in dislocation
pile-up, which contributes a lot to the strength improvement. (2) The
Fig. 7. EIS results of as-extruded Zn-3Cu-xMg (x = 0, 0.1, 0.5 and 1.0 wt.%) alloys in Hank's solution at 37 °C: (a) Nyquist plots; (b) Impedance–frequency diagram; (c) Bode phase angle
diagram.
89
ba (mV/decade) bc (−mV/decade) Corrosion rate (μm/year)
518.0 67.2 5.54
43.6 52.8 17.57
60.4 291.3 23.62
48.8 482.0 180.48
addition of Mg strengthens Zn-3Cu so much that it also compromises
the plasticity significantly at the same time. When dislocations pile, brit-
tle Mg2Zn11 probably plays a role as initiation source of crack at the very
beginning of fracture. The cracks in Mg2Zn11 are perpendicular to the
tensile direction (Fig. 15c). With the crack propagating in Zn matrix,
premature fracture will occur and then result in transgranular fracture
and poor plasticity of Zn-3Cu-0.1Mg alloy. In conclusion, precipitates
of Mg2Zn11 can not only contribute to tensile strength improvement
by dispersion strengthening but can also initiate microcracking during
deformation and deteriorate the plasticity. Since the solid solution of
Mg in Zn matrix is very low in room temperature, Mg2Zn11 would
form even with a small amount of Mg addition and then results in
strength improvement and plasticity reduction obviously.
The mechanical property results suggest that as-extruded Zn-3Cu
alloy with YS of 213.7 MPa and elongation of 47.1% might be considered
as candidate for biodegradable cardiovascular stent application due to
its proper strength and excellent plasticity. However, the higher Young's
modulus (78–85 GPa) of Zn-3Cu-xMg alloys than that of natural bone
(3–20 GPa) may result in “stress shielding effect”, which could be con-
sidered to be fabricated into the porous scaffold to avoid the disadvan-
tage of higher modulus.
4.2. Corrosion behaviors
Corrosion rates, measured by weight loss as well as electrochemical
tests, evidence that in vitro degradation rates increase with increasing
Mg content. Firstly, this might be explained by the difference of stan-
dard potential between Zn matrix and Mg2Zn11 eutectic. The standard
potential of Mg2Zn11 is reported to be lower than Zn matrix [39]. With
90 Z. Tang et al. / Materials and Design 117 (2017) 84–94

Fig. 8. The equivalent circuit for fitting Nyquist plots.

increasing Mg content, the volume fraction of Mg2Zn11 increases, as a

result of which the alloys corrode more rapidly. In addition, the values
of Rf decline gradually, suggesting that Mg addition contributes to
weakening oxide film of alloys. Thus, Zn-3Cu-xMg alloys corrode faster
than Zn-3Cu alloy.
One can observe that the corrosion rates of as-extruded Zn-3Cu-xMg
alloys in Hank's solution are much lower than Mg-based alloys [34]. On Fig. 9. The corrosion rate of the Zn-3Cu-xMg (x = 0, 0.1, 0.5 and 1.0 wt.%) alloys immersed
in Hank's solution for 480 h at 37 °C.
the one hand, Zn itself is nobler in nature than magnesium because of
higher standard potential [40]. The corrosion rates of the experimental
alloys range from 11.4 to 43.2 μm year−1, which are in the same order for pure Zn, both the rate of penetration and the immediate effects of
of magnitude with other literatures [2,4]. Besides, the degradation prod- generated products meet the requirements for sent application [3]. In
ucts can also provide certain protection against corrosion. The degrada- present study, the in vitro degradation rates of the studied alloys
tion behavior of Zn alloys could be described as the following reaction range from 11.4 to 43.2 μm year−1, which are close to the degradation
[1]: rate of pure Zn in vivo during different period of implanting. Therefore,
Zn-3Cu-xMg alloys are promising biodegradable material with respect
Zn þ 2H2 O ¼ Zn2þ þ H2 ↑ þ 2OH− ð4Þ to the biodegradation rates.

The Nyquist plots imply the existence of oxide films on the surface of
the alloys, which may be mainly composed of Zn(OH)2 and Zn3(PO4)2
[2–4,6]. As a result, the degradation products play a role in preventing
Zn substrates from degrading too fast.
The in vitro biodegradation uniformity can be ascribed to the follow-
ing two reasons: Firstly, CuZn5 and Mg2Zn11 are crushed and distributed
uniformly on the metal matrix during hot extrusion process. Homogeni-
zation treatment and hot extrusion together contribute to the homoge-
nous microstructure and grain refinement. Secondly, there are no
significant difference of the standard potential between CuZn5 and Zn
matrix. As one can see, Zn-3Cu, with a low corrosion rate, shows finer
corrosion pits than Zn-3Cu-xMg alloys. Meanwhile, as reported, the cor-
rosion potential of Zn was −1.043 V and Mg2Zn11 was −1.083 V in 3.5%
NaCl solution [39], which means severe microgalvanic would not form
between Mg2Zn11 and Zn matrix either. Thus, the acceleration effect of
corrosion because of Mg addition might be not so obvious, when Mg
content is lower than 1 wt.%. Consequently, it is reasonable that the se-
vere microgalvanic corrosion would not occur. Fine and uniform corro-
sion pits as well as slow corrosion rate prove such inference.
An appropriate degradation rate is essential to biodegradable im-
plants. The degradation rate should not be too high, so that the implants
could keep their mechanical integrity during the process of healing,
which takes about 6–12 months [41,42]. For example, A general design
constraint for biodegradable cardiovascular stents is that the corrosion
rate should be less than 20 μm·year−1 [3]. Bowen et al. suggests that,
4.3. Cytocompatibility
In present study, for 100% extracts (Fig. 13a), biocompatibility in-
creases with Mg addition, which means the cytotoxicity of the studied
alloys can be improved by the addition of Mg. As we know, nutrient el-
ement Mg element is essential to cellular reactions and is regulator of
over 300 proteins. Normal blood serum level of Mg is about 0.73–
1.06 mmol L−1 [43]. Therefore, the cytocompatibility of Zn-3Cu-xMg al-
loys is enhanced because more Mg ions are released through more rapid
degradation.
On the other hand, as for 100% extracts (Fig. 13a), only Zn-3Cu-
0.5Mg and Zn-3Cu-1.0Mg meet the cytotoxicity standards. However,
pure Zn and many Zn-based alloys have been proved with eligible bio-
compatibility [3,4]. In vitro cytotoxicity of Zn-3Cu-xMg is better than
that of the pure Zn, which seems safe in vivo [3]. Hence, the four studied
alloys may all meet the cytocompatibility requirements actually. Sec-
ondly, according to literature [33], a minimal 6 times to maximal 10
times dilution of extracts is recommended for in vitro cytotoxicity of
magnesium-based materials. It might be also suitable for Zn-based ma-
terials too. The EA.hy926 cells cultured in 50% (Fig. 13b) and 10% (Fig.
13c) extracts for 1, 3 and 5 days exhibit good cell viability. Therefore,
the cytotoxicity results exhibited in Fig. 13b and c, whose extracts
were diluted, might be more convincing, which means that all the
four studied alloys might be biocompatible. Thirdly, there is no signifi-
cant difference of cell viability in 10% and 50% extracts. It might be

Table 2
Fitting results of the EIS.

Alloys Rs (Ω cm2) CPEdl n Rct (Ω cm2) CPEf n Rf (Ω cm2) Chi square

(μΩ−1 cm−2 s−1) (μΩ−1 cm−2 s−1)

Zn-3Cu 20.89 8.325 × E−6 0.9046 1.4 × E5 2.620 × E−6 0.5385 1533.0 2.64 × E−4
Zn-3Cu-0.1Mg 18.26 6.621 × E−5 0.9250 1770 2.730 × E−6 0.4041 908.3 3.56 × E−4
Zn-3Cu-0.5Mg 16.49 1.664 × E−5 0.9168 5181 3.340 × E−6 0.4879 629.3 4.31 × E−4
Zn-3Cu-1.0Mg 18.16 1.502 × E−3 0.9016 1154 2.839 × E−6 0.3489 464.8 3.88 × E−4
 Z. Tang et al. / Materials and Design 117 (2017) 84–94 91

Fig. 10. SEM micrographs of the as-extruded alloys after immersion in Hank's solution for 480 h at 37 °C. (a) Zn-3Cu; (b) Zn-3Cu-0.1Mg; (c) Zn-3Cu-0.5Mg; (d) Zn-3Cu-1.0Mg.

attributed to the dilution of extracts decreasing Mg ions concentration, 5. Conclusions

which makes it hard to exhibit the benefits of Mg element to cells.
With respect to Cu element, the blood serum level was about 1.1–
1.5 μg ml−1 and daily allowance is approximately 1–3 mg [20]. Consid-
ering the degradation rate of the studied alloys, the release of Cu ele-
ment can be controlled under a level of 0.034 μg ml−1 and
8.6 μg day−1, which is far below the permitted amount. Therefore, ac-
cording to all aforementioned above, the experimental alloys could be
all considered as biocompatible materials.
In present study, newly developed Zn-3Cu-xMg (x = 0, 0.1, 0.5 and
1.0 wt.%) alloys are investigated for potential biomedical application.
The following conclusions can be drawn.
1. The second phases in these as-cast and as-extruded alloys are CuZn5
and Mg2Zn11. Compared with Zn-3Cu, with increasing Mg content,
the tensile strength of the Zn-3Cu-xMg ternary alloys increases

Fig. 11. Elemental composition of corrosion products of as-extruded Zn-3Cu-xMg in Hank's solution for 480 h at 37 °C: (a) Zn-3Cu; (b) Zn-3Cu-0.1Mg; (c) Zn-3Cu-0.5Mg; (d) Zn-3Cu-
1.0Mg.
92 Z. Tang et al. / Materials and Design 117 (2017) 84–94

Fig. 12. Surface morphologies of as-extruded Zn-3Cu-xMg (x = 0, 0.1, 0.5 and 1.0 wt.%) alloys after immersion in Hank's solution for 480 h at 37 °C and then acid washing.

dramatically whereas the elongation decreases due to Mg2Zn11
phase increases.
2. After homogenization treatment and hot extrusion the grain size of
the alloys is refined and microstructure becomes more uniform,
which consequently results in a relatively uniform corrosion behav-
ior. Compared with magnesium the in vitro degradation rates of
the experimental alloys are much slower. Besides, with increasing
Mg content, the in vitro degradation rates increase.
3. In vitro cytotoxicity test results indicate that Zn-3Cu-xMg alloys
are biocompatible, which means good biosafety of the alloys at
cellular level. The cell viability is enhanced with increasing Mg
content.
4. As-extruded Zn-3Cu alloy could be considered as a candidate for po-
tential cardiovascular stent applications and as-extruded Zn-3Cu-
xMg alloys might be more appropriate as a candidate for potential
porous scaffold.
Competing financial interests
The authors declare no competing financial interests.

Fig. 13. The viability of EA.hy926 cells cultured in (a) 100%, (b) 50% and (c) 10% extracts of pure Zn and as-extruded Zn-3Cu-xMg (x = 0, 0.1, 0.5 and 1.0 wt.%) alloys for 1, 3 and 5 days.
 Z. Tang et al. / Materials and Design 117 (2017) 84–94 93

Fig. 14. OM images and grain size distribution map of the studied alloys. (a) and (b) as-extruded Zn-3Cu; (c) and (d) as-extruded Zn-3Cu-0.1Mg.

a
As-extruded Zn-3Cu

As-extruded Zn-3Cu-0.1Mg

b c

250 µm

Fig. 15. (a) Image of tensile samples after tensile test; (b) and (c) OM images of marked positions from the tensile sample.

Acknowledgement
This work was supported by the National Key Research and Develop-
ment Program of China (2016YFC1102401), the Science and Technology
Commission of Shanghai Municipality (No. 14DZ1940802), the Science
and Technology Commission of Minhang District, Shanghai City (No.
2014MH124), and Shanghai Jiao Tong University Medical-engineering
Cross Fund (YG2015MS66 and YG2014MS62).
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