Effects of extrusion ratio on microstructure,

mechanical and corrosion properties of

biodegradable Mg–Nd–Zn–Zr alloy
X. B. Zhang*1, G. Y. Yuan2 and Z. Z. Wang1
The Mg–3?08Nd–0?27Zn–0?46Zr (wt-%) alloy was hot extruded with different extrusion ratios to
refine microstructure and to optimise mechanical properties and corrosion resistance as a
biodegradable magnesium alloy. The microstructure was observed by optical microscopy, the
mechanical properties were tested at room temperature and the corrosion resistance was
evaluated in Hanks’ solution. The results show that the microstructure becomes more and more
homogeneous with increasing the extrusion ratio. The mechanical properties of the as extruded
alloy are much better than those of the as cast one. Higher strength is obtained with the extrusion
ratio of 18, and better elongation is obtained with the extrusion ratio of 25. Corrosion results show
that corrosion resistance of the as extruded alloy immersed in Hanks’ solution is better than that of
the as cast one, and higher extrusion ratio results in better corrosion resistance. Both the as cast
and the as extruded alloys exhibit uniform corrosion, which was interpreted by cyclic polarisation
test.
Keywords: Biodegradable magnesium alloy, Extrusion ratio, Mechanical properties, Corrosion resistance

Introduction alloy is a promising biodegradable magnesium alloy due

The density, elastic modulus and compressive yield
strength (YS) of magnesium are closer to those of natural
bone than other commonly used metallic implants.1
Moreover, magnesium that naturally existed in bone
tissue is essential to human metabolism and may have
stimulatory effects on the growth of new bone tissue.2,3 In
addition, magnesium has low corrosion potential, resulting
in low corrosion resistance, which makes it an intriguing
property for biodegradable material applications.1 There-
fore, magnesium alloys may potentially be applied as
biodegradable materials in orthopaedic implantations due
to their unique characterisations.4 However, rapid corro-
sion rate and local corrosion mode of magnesium alloys in
electrolytic physiological environment prevent their appli-
cations in biomedical field.5 Most of the researchers have
focused on surface modification with coatings6–11 to slow
down the corrosion rate of magnesium alloys. Never-
theless, the success of biodegradable material largely
depends on the substrate itself.12
Extrusion process is an effective way to refine the
microstructure of Mg alloys and therefore improve
the mechanical properties and corrosion resistance. The
grain refinement has a retarded cathodic kinetics, which
can stifle corrosion overall.13–15 The Mg–Nd–Zn–Zr
1
School of Materials Science and Engineering, Nanjing Institute of
Technology, Nanjing 211167, China
2
National Engineering Research Center of Light Alloy Net Forming,
Shanghai Jiao Tong University, Shanghai 200240, China
*Corresponding author, email xbxbzhang2003@163.com
to the better mechanical properties at room tempera-
ture, lower corrosion rate and better cell toxicity to
osteoblasts MC3T3-E1 than those of commercial AZ31
and WE43 alloys.16,17 Furthermore, the Mg–Nd–Zn–Zr
alloy shows a uniform corrosion behaviour in Hanks’
solution,18 and a more homogeneous microstructure
results in much more uniform corrosion,19 which is a
very favourable corrosion mode for biodegradable
materials; nevertheless, the uniform corrosion mechan-
ism was not explained clearly. In the present study, the
effects of extrusion ratio on the microstructure, mechan-
ical properties at room temperature and biocorrosion
resistance in Hanks’ solution of the Mg–Nd–Zn–Zr
alloy were studied, aiming to optimise extrusion process
and further improve the mechanical and biocorrosion
properties. Moreover, the uniform corrosion mechanism
was initially interpreted by cyclic polarisation curves.
Experimental
Mg–3?08Nd–0?27Zn–0?46Zr (wt-%) ingots (F) were
produced by conventional ingot metallurgy process, then
solution treated at 540uC for 10 h and quenched into
water at room temperature. The ingots were extruded at
280uC with extrusion speed of 2 mm s21 and extrusion
ratios of 8, 18 and 25 respectively (denoted as R8, R18
and R25). Specimens at different conditions were cut
parallel and perpendicular to the extrusion direction;
polished with 320 grit waterproof abrasive paper, 600 grit
metallographic paper and 5 and 1 mm diamond grinding
paste; cleaned in distilled water and ethanol; and then

ß 2013 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 14 June 2012; accepted 13 August 2012
DOI 10.1179/1743284712Y.0000000107 Materials Science and Technology 2013 VOL 29 NO 1 111
Zhang et al. Effects of extrusion ratio on Mg–Nd–Zn–Zr alloy
a F; b–d images of R8, R18 and R25 parallel to extrusion direction; e-g images of R8, R18 and R25 perpendicular to
extrusion direction
1 Microstructure of Mg–Nd–Zn–Zr alloy under different conditions
dried in warm flowing air. The polished specimens were
etched with an acidic solution (10 mL acetic acid, 4?2 g
picric acid, 70 mL ethanol and 10 mL distilled water) and
then observed by optical microscopy. Tensile test samples
were cut parallel to the extrusion direction and then
polished with papers and diamond pastes gradually to
mirror surface. The tensile tests were carried out on a
material test machine at room temperature with an initial
strain rate of 1?761023 s21, and three specimens were
112 Materials Science and Technology 2013 VOL 29 NO 1
repeated for each group. Fracture surfaces were observed
by scanning electron microscopy (SEM).
Samples for immersion test with dimensions of
20 mm in diameter and 3 mm in thickness were cut
and then polished to mirror surface. Hanks’ solution,
composed of 8?0 g L21 NaCl, 0?4 g L21 KCl, 0?35 g L21
NaHCO3, 0?2 g L21 MgSO4.7H2O, 0?14 g L21 CaCl2,
1?0 g L21 glucose, 0?06 g L21 Na2HPO4 and 0?06 g L21
KH2PO4, was used as the test solution. The pH value was

adjusted to 7?4 with NaOH or HCl solution, and the
temperature was kept at 37¡0?5uC during experiments.
The ratio of immersion solution volume to specimen
surface’s area is 30 mL cm22 according to ASTM G31-
72. The immersion test lasted for 120 h, and the im-
mersion solution was renewed every 24 h in order to keep
a relatively stable pH value. Hydrogen volume was
recorded before renewing the immersion solution. After
the immersion test, the corrosion products were removed
in a chromic acid solution (200 g L21 Cr2O3z10 g L21
AgNO3). Then, the samples were rinsed with distilled
water and ethanol and then dried in warm flowing air.
The dried samples were weighed, and the corrosion rate
was calculated. Mean results were obtained by five
samples at each state.
Cyclic polarisation curves of the alloys were measured
in Hanks’ solution at 37¡0?5uC using a PARSTAT
2273 instrument. A three-electrode electrochemical cell
was used, with a saturated calomel electrode as a
reference electrode and a high density graphite electrode
as the counter. The specimens were prepared as those for
the immersion test. The cyclic polarisation measurement
began after the sample was immersed for 1 h. The
forward scan started from a cathodic potential of
20?2 V relative to the open circuit potential. The reverse
scan began at an anodic potential of 21?3 V where the
anodic current increased dramatically. The scan rate was
1 mV s21, and the step height was 1 mV.
Results and discussion
Effect of extrusion ratio on microstructure of
Mg–Nd–Zn–Zr alloy
Figure 1 shows the microstructure of the alloy under
different conditions. The microstructure of F (Fig. 1a)
consisted of a-Mg matrix and nearly continuously
distributed Mg12Nd, which was reported by Fu et al.20
After extrusion, the microstructure is refined signifi-
cantly, as shown in Fig. 1b–d, observed parallel to the
extrusion direction, and in Fig. 1e–g, observed perpen-
dicular to the extrusion direction. The inhomogeneous
microstructure of R8 and R18 mainly composes of fine
grains and long elongated grains, as shown in Fig. 1b
and c. The fine grain size of R18 is even smaller than
that of R8. The microstructure of R25 composes of tiny
and relative coarse grains, as shown in Fig. 1d. The
precipitated Mg12Nd after extrusion is so fine that it can
hardly be observed by an optical microscope. It can be
seen that the amount of the long elongated grains
decreases with increasing the extrusion ratio from
Fig. 1e–g, observed perpendicular to the extrusion
direction.
The fine grains are the results of dynamic recrystallisa-
tion, while the long elongated grains may occur from
previous unextruded structures that have survived the
dynamic recrystallisation.21 No long elongated grain was
observed in R25, while the relative coarse grains can be
observed. The extrusion temperature of the alloy in the
present study is 280uC, and the alloy can hardly be
extruded at even lower temperatures, if the other
extrusion parameters are the same. Since the plastic
stored energy of the alloy during extrusion is not uniform,
some areas undergo dynamic recrystallisation, while the
other areas survive and form long elongated grains. A
larger extrusion ratio leads to larger total strain, and a
Zhang et al. Effects of extrusion ratio on Mg–Nd–Zn–Zr alloy
2 Tensile curves of Mg–Nd–Zn–Zr alloy tested at room
temperature
higher strain rate leads to higher deformation stress
and higher deformation energy. With the increase in the
extrusion ratio, the recrystallisation temperature de-
creases and the grains have large enough plastic stored
energy to trigger recrystallisation. Therefore, not the long
elongated grains but some relative coarse grains are
observed in R25, indicating that the alloy undergoes
complete dynamic recrystallisation and grain growth.
Effect of extrusion ratio on mechanical
properties of Mg–Nd–Zn–Zr alloy
Tensile curves of the alloy tested at room temperature
are plotted in Fig. 2, and the values are listed in Table 1.
Both the YS and the ultimate tensile strength (UTS)
increase first and then decrease with increasing the
extrusion ratio. R18 shows the highest YS and UTS,
which is increased by 253 and 88% compared with F. In
addition, the tensile curve of F shows obvious work-
hardening, while that of R8 and R18 shows no apparent
workhardening. The tensile curve of R25 shows an
obvious yield drop, a plateau and then a slight work-
hardening. The elongation of the as extruded alloy is
improved; particularly, that of R25 is improved by 139%
compared with that of the as cast one (F).
As described above, the microstructure of the as
extruded Mg–Nd–Zn–Zr alloy becomes finer and more
homogeneous with increasing the extrusion ratio. There-
fore, the extrusion ratio plays a significant role in the
strength improvement due to the microstructure refine-
ment, homogeneity and the precipitation of Mg12Nd.
The dislocation density of F increases during plastic
deformation stage, and hence, an obvious workharden-
ing was observed in the tensile curve. Zhang et al.22 have
reported that larger grain size and lower dislocation
density in grains are beneficial to the dislocation
accumulation, which generates workhardening during
tensile deformation. After hot extrusion, the micro-
structure of R8 and R18 was not homogeneous; even
Table 1 Mechanical properties of Mg–Nd–Zn–Zr alloy
Alloy YS/MPa UTS/MPa Elongation/%
F 102¡1.2 194¡0.8 11.1¡0.01
R8 306¡2.8 307¡3.5 15.3¡0.14
R18 360¡8.6 365¡10.1 14.6¡2.92
R25 246¡10.8 269¡2.4 26.5¡0.67
Materials Science and Technology 2013 VOL 29 NO 1 113
Zhang et al. Effects of extrusion ratio on Mg–Nd–Zn–Zr alloy

a F; b R8; c R18; d R25

3 Fracture morphologies of Mg–Nd–Zn–Zr alloy under different conditions

though the strength was significantly improved by grain and homogeneous grains can be coordinated easily
refinement, no obvious workhardening was observed. during plastic deformation. Consequently, the R25 alloy
Generally, a basal slip system can be easily activated and exhibits much better elongation than the others.
accelerates the accumulation of dislocation during
plastic deformation, which is the origin of workharden- Effect of extrusion ratio on corrosion properties
ing. The highest dislocation density of the alloys of Mg–Nd–Zn–Zr alloy
extruded with extrusion ratios of 8 and 18 has almost Figure 4 shows the hydrogen evolution curves of the alloys
reached critical level, which restricts further dislocation immersed in Hanks’ solution for 120 h. The hydrogen
accumulation and workhardening. However, for the evolution volume of F is the highest and decreases with
R25 alloy with fine and homogeneous microstructure, increasing the extrusion ratio. Furthermore, the hydrogen
both basal and non-basal dislocations were activated, evolution at the first 24 h is the least, and then it shows an
and the deformation of the fine grains could be increase for the alloys at all conditions with the extension
coordinated. Shear band could run through the tensile of immersion time. Hence, there should be a protective film
specimens, and the dislocation density of the shear band on the surface of the alloy at the early stage of the
increased suddenly. Therefore, the yield drop was immersion, which slows down the corrosion rate of the
generated at the beginning of the plastic deformation. substrate material.
Local plastic deformation started subsequently. The
local plastic deformation was extended to other regions,
which could provide y6% of macroscopic plastic
deformation. When the local plastic deformation
extended to the whole marked distance, the uniform
plastic deformation occurred and slight workhardening
was observed.
The long elongated grains play a positive role on the
improvement of strength but a negative role on the
elongation. As a result, the strengths of R8 and R18 are
higher than those of R25; however, the elongations of
them are lower than those of R25. Figure 3 shows the
fracture morphologies of the alloys. The fracture pattern
of F is cleavage fracture, and those of R8 and R18 are
cleavage fracture for the long elongated grains and
intergranular fracture for the fine equiaxed grains.
Nevertheless, numerous dimples exist in the fracture
surface of R25, which suggests ductile fracture. The
significantly improved elongation of R25 is due to the 4 Hydrogen evolution volume of Mg–Nd–Zn–Zr alloy
fine and homogeneous microstructure because the fine immersed in Hanks’ solution for 120 h

114 Materials Science and Technology 2013 VOL 29 NO 1


5 Corrosion rate of Mg–Nd–Zn–Zr alloy immersed in
Hanks’ solution for 120 h
Figure 5 shows the corrosion rate of the alloy
obtained from mass loss experiment. The corrosion rate
of the ingot F is the highest, and that of the as extruded
alloys reduces slightly with increasing the extrusion
ratio. The result obtained from the mass loss test has a
good agreement with that obtained from hydrogen
evolution test.
The improved corrosion resistance of the Mg–Nd–Zn–
Zr after extrusion is mainly attributed to the grain
refinement and microstructure homogeneity. Grain
boundaries have higher energies than the bulk and are
more chemically active. Thus, a high density of grain
boundaries increases the reactivity of the surface through
increased electron activity and diffusion. Increased
reactivity coupled with more sites for nucleation of an
oxide film on the surface of grain refined alloy is
a, b F; c, d R25
6 Images showing surface morphology of Mg–Nd–Zn–Zr alloy after removing corrosion products
Zhang et al. Effects of extrusion ratio on Mg–Nd–Zn–Zr alloy
considered to result in a more rapid formation of a
protective film.23 The reduction of the second phase
size has been suggested to contribute to increased
corrosion resistance. The second phase Mg12Nd in the
as extruded Mg–Nd–Zn–Zr alloy is also refined and
distributes uniformly. Thus, the improvement of the
corrosion resistance is also attributed to the second phase.
Consequently, the increased corrosion resistance of the
alloy with increasing the extrusion ratio is attributed
to the finer and more homogeneous microstructure
including a-Mg grains and the second phase Mg12Nd
grains.
The F and R25 alloys have been chosen to study the
corrosion mode and corrosion mechanism of the as cast
and the as extruded Mg–Nd–Zn–Zr alloy. The images of
F and R25 alloys taken by digital camera and SEM after
removing corrosion products from the surface are shown
in Fig. 6. The corroded surfaces are relatively uniform
and smooth, and no serious pitting corrosion is found,
indicating that both the as cast and the as extruded Mg–
Nd–Zn–Zr alloys exhibit uniform corrosion mode.
Kirkland et al.5 studied biocorrosion rates of 31 kinds
of magnesium alloys. The result showed that 29 kinds of
them underwent pitting corrosion or extreme localised
corrosion. Uniform corrosion is a crucial requirement
for biodegradable magnesium alloy because the biode-
gradable implants play a supportive role in the human
body; if the biodegradable magnesium implants such as
cardiovascular stents, scaffolds and plates exhibit severe
pitting corrosion (local corrosion) mode, the supportive
function of the implants probably lapses before the
tissue has been completely healed. However, as for the
uniformly corroded alloy, the lifetime of the implants
can be predicted and the unexpected failure caused by
local corrosion can be avoided; thus, it is suitable for
biodegradable applications.
Materials Science and Technology 2013 VOL 29 NO 1 115
Zhang et al. Effects of extrusion ratio on Mg–Nd–Zn–Zr alloy
7 Cyclic polarisation curves of Mg–Nd–Zn–Zr alloy after
immersion in Hanks’ solution for 1 h
In order to reveal the uniform corrosion mechanisms
of the as cast and the as extruded Mg–Nd–Zn–Zr alloys,
the cyclic polarisation curves of the F and R25 alloys are
shown in Fig. 7. The data obtained from the cyclic
polarisation are listed in Table 2. The current density of
F is higher than that of R25, indicating that the
corrosion rate of F is faster than that of R25. This is
also confirmed by hydrogen evolution and mass loss
experiments. The corrosion potential of the forward
scan Ecorr-fs is lower than that of the reverse scan Ecorr-rs
for the Mg–Nd–Zn–Zr alloy. The forward scan to some
extent represents the polarisation behaviour of the non-
corroded areas, while the reverse scan is associated with
the corroded areas. Owing to the galvanic effect, an area
with a more negative potential is corroded and the area
with a more positive potential is protected.24 The Ecorr-fs
of the Mg–Nd–Zn–Zr (both F and R25) alloy is lower
than Ecorr-rs, which means that the corrosion in the
corroded area is likely to be retarded by the non-
corroded surrounding area, and the non-corroded area
is easily attacked by the corrosion occurring next to it.
As a result, the corrosion of the alloy spreads across the
surface from grain to grain and results in uniform
corrosion.
Conclusions
Microstructure, mechanical properties and biocorrosion
properties of the Mg–Nd–Zn–Zr alloy extruded with
different extrusion ratios for biomedical applications
were studied in the present paper. The microstructure is
refined significantly by hot extrusion and becomes more
and more homogeneous with increasing the extrusion
ratio. The microstructure of R8 and R18 is inhomoge-
neous, which undergoes partially dynamic recrystallisa-
tion, while that of R25 is homogeneous due to
completely dynamic recrystallisation. Both YS and
UTS of the alloy at room temperature increase first
Table 2 Corrosion potential and current density of Mg–
Nd–Zn–Zr alloy obtained from cyclic polarisation
curves after immersion in Hanks’ solution for 1 h
Alloy Ecorr-fs/V Ecorr-rs/V DEcorr/V I/mA cm22
F 21.837 21.737 0.100 6.7
R25 21.747 21.640 0.107 5.1
116 Materials Science and Technology 2013 VOL 29 NO
and then decrease with increasing the extrusion ratio.
The highest YS (360 MPa) and UTS (365 MPa) were
obtained from the R18 alloy, and the best elongation
(26?5%) was obtained from the R25 alloy. The fracture
morphologies of R8 and R18 are cleavage fracture and
intergranular fracture, while that of R25 is ductile
fracture. The corrosion resistance of the alloy tested by
hydrogen evolution test and mass loss test shows the
same trend that it is improved by increasing the
extrusion ratio. A fine and homogeneous microstructure
is attributed to this improvement. Furthermore, the
corrosion potential of the forward scan is lower than
that of the reverse scan for the Mg–Nd–Zn–Zr alloy,
resulting in a uniform corrosion mode, which is a very
favourable property for biodegradable implants.
Acknowledgements
This project was supported by the China Postdoctoral
Science Foundation (grant no. 20100470030) and the
Introducing Talents Funds of Nanjing Institute of
Technology (grant no. YKJ201201). The authors thank
Dr Y. J. Wu (Shanghai Jiao Tong University) and Dr
M. Kwak and Dr D. Yu (Yale University) for their
valuable discussions and language polish.
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