In vitro degradation behaviour and

fracture mechanism of Mg-0.8Ca

under a constant strain
Nur Amirah binti Shaharom
Supervised by: i) Dr. Hendra Hermawan
ii) Assoc. Prof. Ir. Dr. Mohammed Rafiq bin Abdul Kadir
Abstract
Magnesium-based alloys are currently attracted much interest owing to its
potential for biodegradable implants application. However, despite many of its
advantages which are superior to those of current implant materials, tackling the
rate of degradation of magnesium alloys is one of the grand challenges
highlighted. Mg-0.8Ca is believed to have optimum qualities to serve as implant
material, thus have been chosen as the testing materials in present work. Failure
mechanism of tested material is proposed to be evaluated to further understand
its degradation behaviour under synergistic presence of mechanical loading
along with corrosive physiological environment. It is believed that under such
condition the materials are highly susceptible to stress corrosion cracking (SCC)
which might lead to catastrophic complications and sudden failure. This study
aims to evaluate the susceptibility Mg-0.8Ca towards SCC in physiological
environment, determine the mode of SCC crack propagation and recognise the
causes of failure which will be depicted from the propose testing methods. The
understanding of failure mechanism will give contributions in the improvement of
material properties in order to be successfully applied as biodegradable implants.


Introduction
Metallic biomaterials are predominately applied for impaired bone tissue fixture and
replacement [1] due to comparable monotonic strength they exhibit for such purposes.
However, evaluation on current metallic materials used [1-5], i.e. stainless steel,
titanium and cobalt-chromium-based alloys, revealed a deleterious complications due to
debris produced from loading-related scenarios, in combination with corrosive
environment of the implantation site. Stiffness ratio of current metallic implants toward
the adjacent bones is relatively huge leading to various clinical issues due to stress
shielding effects [5, 6]. Table 1 below shows typical properties of current metallic
materials in comparison to those of human bone.

Table 1 Mechanical properties of commonly used metallic biomaterials and human bone [4]

Stainless
steel
Cobalt-chromium
alloy
Titanium
alloy
Magnesium
Human
bone
Density (g cm
-3
) 7.9 8.1 8.3 9.2 4.4 4.5 1.74 2 1.8 2.1
Youngs modulus
(GPa)
189 205 230 110 117 41 45 3 20
Compressive yield
strength (MPa)
170 310 450 1000 758 115 65 100 130 180

Development of orthopedic implants had recently shifted from classic standard of
material selection to a rather socially and economically beneficial. The selection is now
demanded the materials to be biologically active in enhancing physiological response
and implant-tissue interactions while progressively degrade during the healing period of
damaged tissue [5]. Designated to avoid secondary surgical procedure for implant
removal, biodegradable magnesium-based implants which generate mainly soluble,
non-toxic degradation products have been generally approved to serve as bone fixation
devices [2, 5, 7]. With sufficient mechanical strength and load-bearing capacity,
magnesium-based implants exceeded cotemporary polymer based implants for
orthopaedic applications. Furthermore, Youngs modulus of magnesium-based implants
is a lot closer to human bone compared to permanent metallic implants currently used
[4] which may contribute to the reduction of stress shielding effects [5]. However, the
rate of degradation of magnesium-based alloys is in biggest concern [1, 2, 4, 5, 8, 9] as
the degradation process evolves intolerant hydrogen gas accumulation and the implant
might lose its mechanical integrity before the fractured bones completely heal [4, 10].
Generally, poor corrosion resistance in magnesium alloys is believed to be influenced
by a few factors which include [11] (a) corrosion product films are too weak to inhibit the
high intrinsic dissolution tendency of magnesium, and (b) speedup of micro-galvanic
localized corrosion due to the presence of second phases serving as local cathodes. It
is believed that understanding degradation mechanism of magnesium alloys is the best
perspective in establishing a material with optimised properties most suited the implant
applications.
Alloying is one of the methods currently developed to enhance magnesium mechanical
properties and corrosion resistance [2, 4, 5, 7, 11-16]. Addition of alloying elements has
been observed analytically producing magnesium alloys with a lower corrosion rate than
that of high purity magnesium in 3% NaCl [11]. Among various alloying elements
available, calcium has been favourably chosen and considered as a unique alloying
addition owing to Mg
2
Ca phase features exhibited in low alloyed Mg-Ca systems which
further affect its microstructure, mechanical properties, electrochemical behaviour and
degradation kinetics [5, 7, 14, 15]. Addition of calcium in Mg-Ca alloys reduces grain
size and improves general and pitting corrosion resistance as well [5, 14]. Li et al. [14]
highlighted a few considerations in choosing calcium as alloying element in magnesium
for biodegradable material which include the composition of calcium in human body, its
close density to those of human bones, and the need of magnesium in calcium
incorporation into the bone have been reported [17] with potential benefit for bone
healing. Corrosion in Mg-Ca alloys with calcium content up to 0.8 wt% is well distributed
and homogenous in texture while those with higher calcium content demonstrate
uncertain, dissipated corrosion. Magnesium with 0.6 0.8 wt% calcium has been
proven exhibited slowest degradation rate [9, 15] and good biocompatibility [7].

Figure 1 Hydrogen evolution of Mg-Y in 0.1M NaCl. The rate of degradation can be represented by instantaneous
value from hydrogen evolution curve or by average value over a particular time period [11].
Most assessments done in vitro considered only on general practice of magnesium
alloys for orthopaedic implants, instead of simulating the implantation site condition
specifically. Improvement in corrosion resistance and mechanical properties focused on
the effect of alloying element and mechanical processes only, and despite of failure
reported experienced by current metallic biomaterial devices, no further assessment on
the mechanism of failure in corrosive environment for biodegradable implants has been
made despite of the fact that SCC in magnesium alloys would give severe effects to the
materials when in service. Thus, the present work utilizes every aspects of Mg-0.8Ca
which have been evaluated as the absolute choice of material to be applied specifically
for craniofacial fixation devices. Since the magnesium alloys corrode very fast in
chloride environment, the occurrence of SCC needs to be ascertained whether the loss
of mechanical properties is resulted from the SCC or just the reduction in specimen
cross-section due to anodic dissolution [18]. Understanding fracture mechanism
endures by Mg-0.8Ca under constant strain in simulated physiological media is
expected to contribute further improvement on its corrosion resistance and service life.

Literature Reviews
Current developments of metallic materials encompass groups of materials with fine
interaction towards biological environment and capable to progressively degrade during
the healing process of damaged tissue [5]. Instead of relying upon polymers to be
applied as implant materials, biodegradable metallic substitutes are worthier to be
established on account of better load-bearing capacity and mechanical strength they
demonstrate [5]. Magnesium and magnesium-based alloys are currently drawing much
interest as promising candidates to be applicable for such purposes. Current research
development on magnesium-based biodegradable implants is focusing mostly on Mg-Al
and Mg-RE alloy systems [14]. In vitro assessment [19] of degradation rate and
mechanism for magnesium has been summarized by Kirkland et al. detailing their
advantages and limitations.
Witte et al. [20] have conducted an investigation to compare the corrosion rates of
AZ91D and LAE442 and concluded that corrosion rates measured in vivo were orders
of magnitude lower than those measured in substitute ocean water prepared according
to ASTM-D1141-98 [21]. In vitro test has been accomplished using various solutions
which include; (i) simulated body fluid (SBF), (ii) artificial plasma (AP), (iii) phosphate
buffer saline (PBS), and (iv) minimum essential medium (MEM, Invitrogen). In vitro test
[16] conducted to evaluate the corrosion rate of various magnesium alloys reported that
high purity magnesium had the lowest corrosion rate which increased with increasing
amount and effectiveness of second phase. Song [16] concluded that Zn-containing
magnesium alloy is the most promising material to be developed into a biodegradable
material with some modifications such as anodised coating to delay the degradation and
purification to reduce the rate.
A study [22] conducted to understand failure mechanisms of commercial Kntscher
nails of type 316L stainless steel under the combined action of corrosion and stress has
been done by G. Bombara and M. Cavallini. Evaluation on damage morphology of the
device showed transgranular, branched and unblunted cracks which were first identified
as SCC behaviour rather than corrosion fatigue (CF). This was corroborated with
appearances of minor and indeterminate fretting fractographs using scanning electron
microscope (SEM). The results obtained agreed with investigation done by M.
Sivakumar and S. Rajeswari [23] which concluded SCC of failed intramedullary nail has
been worsened by high inclusion content and large grain size of the implant.
Fractography of failed commercial AISI stainless-steel 316L presented by S.
Bandyopadhyay and P. Brockhurst [24] has shown evidence of SCC failure with crack
propagation both in intergranular and transgranular modes which determined the
susceptibility of austenitic stainless steel at a rather low temperature than mostly
reported.
Kannan and Raman [25] had claimed that SCC susceptibility of Mg-Al-Zn alloy is not
substantial and should not be a concern for implant applications despite of stress-
assisted failures that have been reported [2, 12, 26, 27] for current orthopaedic
implants. However, a critical review done by Atrens et al. [11] highlighted a number of
grand challenges in development of magnesium-based implants, which include
consideration of SCC due to corrosion-assisted stresses that is known existed in
implant-bone systems. This review is in agreement with investigation by Choudhary and
Raman [18] which had confirmed the SCC susceptibility of both smooth and notched
specimens of a magnesium alloy in physiological environment. In a different
investigation that has been done by Choudhary et al. [28] on AZ91D in modified SBF
and air at different strain rates revealed that the alloy is susceptible to SCC.






Materials and Methods
Sample preparation
Samples will be used are cast Mg-0.8Ca samples whose geometry and dimensions
presented in Figure 2. The sample will be ground successively to 1200 grit using SiC
paper, ultrasonically cleaned in acetone, and dried to room temperature for 24 hours
prior to testing.

Figure 1 Dimension of the proposed sample.
Microstructural characterisation
The samples which will be used for microstructure characterisation will be mechanically
ground with SiC paper up to 2500 grit and polished, follow by chemical etching in 2%
Nital solution. Surface morphology of the samples before and after the introduction of
strain will be observed using optical microscope. Furthermore, microstructure of
samples surface will be examined using SEM before and after the samples failure.
Failed samples will be first cleaned chemically using 20% CrO
3
and 10% AgNO
3

solution. The changes of microstructure morphology will be observed to further
understand the influence of strain towards failure of samples and is believed to be
closely related to the fracture mechanism. The characterisation of failed samples is
expected to have features of brittle and/or ductile fracture, and show the mode of
cracking either transgranular or intergranular.
Immersion test
The samples will be assembled to a custom-made apparatus for immersion test in
simulated body fluid (SBF) with pH value will be adjusted to 7.4 and strain variation of
0.25% and 0.5% elongation. The test will be done for 1, 2, 4, and 6 hours to evaluate
the rate of degradation under such condition from the weight loss percentage, and then
prolonged until failure. Each test will be performed in triplets in order to examine the
reproducibility. Another set of immersion test will be conducted as control experiment.
The samples for the control experiment will not be put under strain, but evaluate the
same measurement of weight loss for the same time intervals, which will then be
prolonged until failure. All samples will be taken out, left to dry at room temperature for
24 hours and be measured of the weight loss, W
a
before chemical cleaning. Then, the
samples will be cleaned with chromic acid solution to remove corrosion products and let
dry to room temperature before the final weight loss, W
b
will be recorded.
W
b
from failed samples from immersion test with introduction of strain will be compared
to W
b
of the samples from immersion test without strain at the same failure time. The
microstructure of both samples will be examined and is expected to verify the effects of
strain on the samples microstructure and their influences on degradation rate.
In situ observation
A sample from the immersion test with strain value of 0.5% will be randomly picked for
in situ observation of failure using stereo microscope. Fractography and failure
mechanism are expected to be better visualised using this method.



Expected results and discussion
The degradation rate will be computed from experiments conducted in different
conditions; (i) sample will be put under strain in SBF, (ii) sample will be put under strain
in air, and (iii) sample will be immersed in SBF for 24 hours then be put under strain in
air. Each of the experiments however, will be repeated thrice. The variation in testing
condition is to recognise the causes of failure [18]; either it is indeed a result of the
synergistic effect of stress and corrosive environment (i.e. SCC) or simply attributed to
the continuously reducing cross-sectional area of the sample due to high corrosion rate
of magnesium alloys.
Table 2 Design of experiment that is expected to be achieved with some data obtained from current conducted
experiments.
Media Displacement Time to failure Weight Loss pH Degradation Rate
SBF
EXPERIMENT 1 - Degradation Rate of MgCa Under Tension Stress
0.50%
Time (min) W W W - W W
b
W - W
b
pH pH
i
(W - W
b
)/t
60 1.87 1.869 0.001 1.838 0.032 7.2 7.9 0.000533333
120 1.89 1.886 0.004 1.852 0.038 7.2 7.9 0.000316667
240 1.929 1.927 0.002 1.835 0.094 7.2 8.2 0.000391667
360 1.803 1.804 -0.001 1.656 0.147 7.4 8.4 0.000408333
t
f
- 960 1.94 1.86 0.08 1.654 0.286 7.3 9.2 0.000297917
EXPERIMENT 2 - Degradation Rate of MgCa Under Tension Stress
0.25%
Time (s) W W W - W W
b
W - W
b
pH pH
i
(W - Wb)/t
60 1.75 1.78 -0.03 1.655 0.095 7.1 7.6 0.001583333
120 1.78 1.82 -0.04 1.727 0.053 7.1 7.6 0.000441667
240 1.88 1.9 -0.02 1.788 0.092 7.1 7.8 0.000383333
360 1.75 1.73 0.02 1.64 0.11 7.1 7.9 0.000305556
T2 W20

EXPERIMENT 3 - Degradation Rate of MgCa Under Tension Stress
0%

W W W - W W
b
W - W
b
pH pH
i


1h W21

2h W22

4h W23

6h W24

T5 W25

Results obtained in Table 3 are from the first round of experiments. From the data,
some graphical evaluation could be made as shows in Table 3. Computing stress vs.
time curves will show changes in mechanical properties of the sample tested for each
assessed conditions. It is expected that maximum reduction in mechanical properties
which might fail the fastest among the samples tested is the one under strain in SBF. It
is expected that stress-time curve for the samples that will be pulled in air indicate some
similar behaviours in comparison to those pre-immersed samples.
Table 3 Degradation rate evaluated for current conducted experiments.

Fractograph of the sample that will be tested under strain in SBF is expected to show
common mode for SCC crack propagation of magnesium alloys, i.e. localised attack at
the sample circumference which in higher magnification, will reveal transgranular
cracking and localized cracks (Figure 3).
60 120 240 360 tf - 960
0.50% 0.00053333 0.00031667 0.00039167 0.00040833 0.00029792
0.25% 0.00158333 0.00044167 0.00038333 0.00030556
0
0.0002
0.0004
0.0006
0.0008
0.001
0.0012
0.0014
0.0016
0.0018
W
e
i
g
h
t

L
o
s
s

(
g
)

Rate of Degradation (gm-1)
Degradation rates of Mg-0.8Ca under various strain
values in SBF

Figure 2 Factograph of failed sample with common mode of SCC cracks propagation for magnesium alloys: (a)
overall fracture surface, and (b) evidence of trransgranular cracking [18].
The experiment will use weight loss method in evaluation of degradation rate of Mg-
0.8Ca sample. At least two from three types of measurement, i.e. weight loss rate,
hydrogen evolution rate and rate of Mg
2+
leaving the metal surface, are recommended
by Atrens et al. [11] to be implemented to better clarify the rate of corrosion on
magnesium alloy in service. However, since this study is not focus on the rate of
corrosion, only weight loss rate will be measured to give a framework of service and
learn the impact of such simulated condition on the specimen towards fracture. It is
believed that the rate of corrosion is closely related to the failure mechanism of
implants.
There are two types of apparatus for transgranular SCC evaluation, the Linearly
Increasing Stress Test (LIST) and the Constant Extension Rate Test (CERT). Review
done by Atrens et al. [11] described that both of these methods are useful to identify the
occurrences of SCC and have capabilities to measure the threshold stress and crack
velocity from the final crack size divided by the time of cracking when coupled in
identification of crack initiation. The increased crack propagation time under CERT
conditions may be important in determining the mechanism for SCC in magnesium
alloys. However, the experimental setup presented in this study will be custom-made,
an apparatus that simulate the condition which initiate conventional SCC. There may be
a room for improvement by applying either LIST or CERT, or both to better evaluate
failure mechanism of proposed material.
Choudhary and Raman [18] had done SSRT under different testing conditions which
included continuous cathodic charging and simultaneous strain in SBF for indication of
possible combined effect of hydrogen-induced cracking and anodic dissolution.
Furthermore, circumferential notch tensile (CNT) testing was used in their work to
determine the threshold stress intensity factor for SCC (K
ISCC
) of the tested samples in
SBF. SEM fractographs (Figure 4) of the failed samples from CNT test had provided
better description on the failure mechanism.

Figure 3 SEM fractographs obtained from CNT: (a) the overall fracture surface showing machined notch, fatigue pre-
crack, SCC and mechanical failure zones, (b) fatigue pre-cracked and SCC zones (arrow indicate crack propagation
direction), and (c) mechanical failure zone showing dimples [18].
Intergranular in magnesium alloys occurs typically by micro-galvanic corrosion, when
there is a presence of continuous or nearly continuous second phase along the grain
boundaries, a microstructure typical of many cast creep-resistant magnesium alloys. In
contrast, transgranular SCC occurs through the -phase magnesium matrix. From the
review done by Atrens et al. [11], they concluded that SCC is associated with
environmental conditions leading to the local breakdown of a partially protective surface
film which is usually caused by localized corrosion by chloride ions. However, load may
be influenced the breakdown as well since the occurrence of SCC is observed on pure
magnesium and magnesium alloys (AZ91, AM60, AS41, ZK60A-T5) in distilled water.
The influenced of hydrogen to the fracture behaviour and the effect of alloying elements
on SCC propagation are not well understood currently. In advance, the understanding of
microstructure influences on SCC is required to better understand magnesium
transgranular SCC. Furthermore, the understanding of effective hydrogen diffusion rate
to the fracture process zone needs to be included which requires an understanding of
hydrogen-trap interactions in magnesium alloys. Although Kannan and Raman [13]
found insignificant decreases of strength and ductility for AZ91 in simulated body fluid
using CERT which indicate SCC, such failure is still largely unexplored.







Conclusion
Current studies on the possibilities to implement magnesium-based alloys as
degradable implants demanding a much deeper understanding of the degradation
behaviour, particularly involving microstructural analysis, to tackle rapid corrosion of the
material in physiological environment. SCC is one of many failures recognised among
metallic materials, thus it is demanded to have absolute evaluation on such issues to
provide crucial information on whether the materials will be tolerable for the given
service time of the device in practical. Such studies have been done on industrial
magnesium alloys, which are less likely applicable as implant materials. Thus, the
present work emphasised the SCC susceptibility assessment and the mechanism of
SCC involved, if applicable, leading to failure of the proposed implants material, Mg-
0.8Ca.











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