Materials and Design 135 (2017) 397–410

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Materials and Design

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Coatings on implants: Study on similarities and differences between the

PCL coatings for Mg based lab coupons and final components
Deepa B. Prabhu a, P. Gopalakrishnan b, K.R. Ravi a,b,⁎
a
Structural Nanomaterials Lab, PSG Institute of Advanced Studies, Coimbatore 641004, Tamil Nadu, India
b
Department of Metallurgical Engineering, PSG College of Technology, Coimbatore 641004, Tamil Nadu, India

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

• Corrosion resistance of pure Mg, uncoat-

ed and PCL coated Mg-4Zn-0.2Ca alloy
screws are investigated.
• Corrosion of coated Mg alloys proceeds
via penetration of medium through
pores in the polymer and degradation
of substrate.
• PCL layer peels off faster in CP Mg than
in Mg-4Zn-0.2Ca due to the faster corro-
sion rate of CP Mg.
• PCL coating adheres stronger to
threaded portion of fabricated screws
than smooth regions upon immersion
in SBF.
• Corrosion resistance of a coated fully
threaded screw is better than that of a
partially threaded screw.

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

Article history: Corrosion behaviour of polymer coated Mg alloy screw is compared with a laboratory coupon with emphasis on
Received 23 May 2017 the adhesion of coating to surface features such as threads. The corrosion behaviour of poly (ε-caprolactone)
Received in revised form 7 September 2017 (PCL) coated commercial pure Mg (CP Mg) and Mg-4Zn-0.2Ca alloy in simulated body fluid (SBF) is investigated.
Accepted 18 September 2017
CP Mg with a high corrosion rate (8.426 mmyr−1) formed large amount of corrosion products on the surface
Available online 21 September 2017
which pushed out the PCL layer. In contrast the Mg-4Zn-0.2Ca alloy with a corrosion rate of 2.481 mmyr−1
Keywords:
held the PCL coating intact for up to 72 h. Fully and partially threaded screws of the Mg-4Zn-0.2Ca alloy were fab-
Biodegradable implant ricated and coated with PCL. It was found that pH variation of the medium depends on PCL adhesion to screw,
Magnesium alloys which was better in the threaded regions than in smoother areas. As a result, the fully threaded screws showed
Corrosion slower pH rise than partial threaded ones. The crests and troughs of the threads act as anchoring points for the
Poly (epsilon-caprolactone) polymer. It was found in the current study that the increased adhesion of PCL coating to threaded Mg alloy sub-
Simulated body fluid strate dominates over the increased corrosion rates of threaded surface.
Threaded screw © 2017 Elsevier Ltd. All rights reserved.

1. Introduction

Magnesium and its alloys degrade in the human body via an electro-
chemical reaction [1–3] and are good candidates for temporary ortho-
⁎ Corresponding author. paedic fixture devices [4]. Alloying with essential elements such as Ca,
E-mail address: krr@psgias.ac.in (K.R. Ravi). Zn and Mn increases biocompatibility, corrosion resistance and reduces

https://doi.org/10.1016/j.matdes.2017.09.043
0264-1275/© 2017 Elsevier Ltd. All rights reserved.
398 D.B. Prabhu et al. / Materials and Design 135 (2017) 397–410
Table 1
Chemical composition of the as cast Mg-4Zn-0.2Ca alloy.
Element Mg Zn Ca Al Si
Quantity (wt. %) 96.01 3.6 0.15 0.017 0.012
side effects of the implant [5–7]. Though corrosion resistance of magne-
sium can be increased by alloying [6,8–10] or mechanical and/or heat
treatment [11,12], the initial high electrochemical activity when in con-
tact with the body fluids has to be avoided to delay the beginning of
degradation. Surface modifications and coatings offer a barrier to the
contact between the alloy and the corrosive medium and delay the
start of deterioration [2,8,13,14]. Such biocompatible coatings are used
even in titanium based permanent implants and offer better corrosion
and wear resistance along with easier osseointegration [15–18].
Compared to coatings of metals or ceramics, biodegradable and re-
sorbable polymers offer added advantages of ease of synthesis, blend
compatibility and possibility of incorporating drug delivery to avoid in-
fection and implant rejection [19–36]. The products formed on degrada-
tion of these polymers are harmless to the human body and are
eliminated by the citric acid cycle [30]. PCL is an FDA approved, resorb-
able polymer with good solubility, blend-compatibility and body stabil-
ity for about 1 year used successfully in drug-delivery devices [37]. In
addition, degradation kinetics, mechanical properties, pore size and
stress crack resistance of PCL can be tuned by blending with other suit-
able polymers. The degradation mechanism of PCL in the human body is
not enzymatic [19] and proceeds by hydrolytic cleavage and phagocyto-
sis [30]. Use of PCL in porous composite scaffolds [38,39] show reason-
able mechanical properties and bioactivity and hence is recommended
as a candidate material for use in the repair and regeneration of non-
weight-bearing bones.
Similar to other polymers, PCL also tends to absorb large quantities
of water on immersion in body fluids and bulges and/or peels off
when applied on Mg alloys [35]. This effect is pronounced as the coating
thickness increases, and is mainly attributed to the increased defects in
the layer and subsequent corrosion of substrate with formation of mag-
nesium hydroxide and hydrogen evolution [20]. It was also found that
the corrosion resistance increases with concentration of polymer [36],
and presence of multiple coatings [23]. In vivo studies [40] of PCL coated
AZ91 alloy indicated reduced degradation rate and retention of bulk
mechanical properties, with higher bone regeneration rates compared
to bare alloy. Research on multi-layer plasma/polymer coating devel-
oped by Bakhsheshi-Rad [22] on Mg-Ca alloy showed that the bonding
strength of the PCL coating stems from the penetration of the polymer
into the nano porous plasma coating on the Mg alloy and provides sig-
nificant protection against corrosion. These studies indicate that the pa-
rameters that affect the corrosion behaviour of the base material such as
its size, shape, surface area and surface finish, also might have profound
effect on the adhesion of the coating.
To understand these parameters further, consider a commonly used
orthopaedic implant such as a compression plate with screws. The effect
of polymer coating on the plate and screws will be different due to its
different surface features. Though plate geometry can be modelled
closely by a flat coupon, there could be vast differences in
Table 2
Chemical composition of the prepared simulated body fluid.
Species Concentration (mg/l)
Magnesium, Mg 14.6
Calcium, Ca 68
Potassium, K 242
Sodium, Na 4350
Chloride, Cl− 6998
Sulphate, SO2−
4 603
Phosphate, (PO4)3− 151
Bicarbonate, HCO−
3 450
understanding the behaviour of a screw based on experiments conduct-
ed on a flat coupon. The use of polymer coatings over a threaded geom-
Mn etry adds to the complexity of the system due to the formation of
0.02
corrosion products in the interface of the two materials. The threaded
portion of the screw is responsible for its anchorage to the bone, and
fast degradation of the threads might result in loosening of the implant
before sufficient healing of the bone. Most of the in vitro tests on corro-
sion of Mg alloys are reported for laboratory coupons. Rod geometries
are typically used for biomechanical tests such as pull-out strength or
for majority of the in vivo studies. Investigations on threaded screws
are limited to in vivo studies in small animal models [41–44] where
the key focus was the integration of threaded implant to the bone and
biocompatibility of the material itself. The surface structure was found
to be critical in the mechanical properties of the alloy and the corrosion
at the threaded flanks was found to result in irregular, hole-shaped deg-
radation [41]. Recently, biomechanical properties and short to long term
fracture fixation and osseointegration studies of the MAGNESIX® screw
has been published [45]. Though there is significant difference between
the in vivo and in vitro corrosion behaviour of Mg alloys due to the com-
plex body environment that cannot be reproduced in a laboratory, it is
important to understand the corrosion of such threaded screws in sim-
ulated body environments so that a better approximation than the lab
coupons is obtained. Though these factors are addressed in corrosion
of structural materials, such studies are not commonly undertaken in
the case of biodegradable implant materials. Hence the authors have
attempted to study the corrosion behaviour of PCL coated Mg alloy in
this work on machined components in the form of partial and full
threaded screws with preliminary studies on disc shaped laboratory
corrosion coupons. Moreover the critical factor in sustaining this im-
proved corrosion resistance, namely the adhesion of PCL coating to the
Mg substrate is also addressed in this work.
2. Experimental details
2.1. Fabrication of the alloy and characterization
Commercial pure Mg (CP Mg), Zn and Mg-30% Ca master alloy were
melted in the desired proportions under protective argon atmosphere
to prepare the Mg-4Zn-0.2Ca alloy. The melt was held at 750 °C for
10 min to ensure proper mixing and then poured into stainless steel
moulds with sulphur dusting to avoid oxidation. Chemical composition
of the cast alloy was determined by inductively coupled plasma optical
emission spectroscopy (ICP-OES) in a Perkin Elmer Optima 2100 DV in-
strument and is given in Table 1. Metallographic specimens of 10 mm
thickness and 30 mm diameter were prepared from the casting as per
standard procedure. The samples were etched with acetic picral to re-
veal the microstructure and observed in a Carl Zeiss Axioscope A1 mi-
croscope. The surface was also analyzed with an Environmental
Scanning Electron Microscope (ESEM, Zeiss EVO18), equipped with an
energy-dispersive spectroscopy (EDS) attachment for identification of
various elements present. Surface roughness of the specimen is ana-
lyzed with a Mitutoyo SJ410 with a cut off λc of 0.8 μm at 0.5 mm/s
scan speed over a length of 4 mm. Average of three measurements is
presented.
Polycaprolactone (Average Mn of 80,000) (Sigma Aldrich) was dis-
solved in dichloromethane to obtain 1%, 2.5% and 5% (w/v) solutions.
Dip coating was employed since this method can be extended to final
screw shaped components also. Initial optimization of dip coating was
carried out at these three concentrations to obtain a coating of PCL on
the Mg alloy as per the following procedure: The metallic coupons
were cut from the as cast ingots with dimensions of 30 mm diameter
and 10 mm thickness. The coupons were polished with SiC sheets up
to 1200 grit followed by disc polishing with diamond paste. The cou-
pons were degreased, washed in distilled water, dried in warm air and
were dipped in the PCL solution for 10 s. The PCL solution was main-
tained in a closed glass beaker at 30 °C on a hot plate with constant
 D.B. Prabhu et al. / Materials and Design 135 (2017) 397–410
Fig. 1. Photographs of the partial and full thread screws used in the present study with dimensions.
magnetic stirring to ensure that the solution concentration and viscosity
are maintained. The coupons were removed from the solution at a con-
trolled rate of 3 mm/s with a custom made set up, and dried in a jet of
cool air for 5 min. This cycle was repeated 10 times to obtain the final
coating on the coupons. At this point there was a visible coating on
the coupon and hence the process was stopped. It was observed that
the 1% solution had a very runny nature and resulted in larger pores
on drying, due to the evaporation of large amount of solvent compared
to the solute. The 5% solution on the other hand resulted in a more com-
pact coating with less pores, at the cost of non-uniformity of the coating.
The 5% solution was highly viscous and dip coating resulted in the accu-
mulation of polymer on different parts of the Mg alloy coupon resulting
in a very uneven coating. Based on this experimental observation it was
Fig. 2. a) Coarse columnar microstructure of CP Mg and (b) finer equiaxed microstructure
of Mg-4Zn-0.2Ca alloy, revealed on etching with acetic picral.
399
decided to continue the experiment with 2.5% PCL solution. Coupons in
which the PCL layer was non uniform or had defects were stripped of
the coating and the process repeated from the disc polishing onwards.
The surface morphology of the coated specimen was observed in
ESEM. To further assess the effect of complex geometries and sharp fea-
tures on the coating adhesion and corrosion, partially and completely
threaded screws were fabricated from the Mg-4Zn-0.2Ca alloy with di-
mensions as specified in Fig. 1. The screws were degreased and protec-
tive PCL layer was applied by dip coating method.
2.2. Corrosion studies on laboratory coupons
Simulated body fluid (SBF) was prepared according to the protocol
of Kokubo [46] and the volume of SBF used for the static immersion
test was 50 times the surface area of the test specimen. The chemical
composition of the SBF was analyzed by flame spectrophotometer,
atomic absorption spectroscopy and titration method and is given in
Table 2. pH of the medium was monitored at regular intervals using a
Eutech pH 30 meter. The samples were washed in distilled water,
dried and weighed after the corrosion test. An average of three mea-
surements was taken for each group. Percentage change in mass at dif-
ferent times is calculated using the equation:
initial mass−final mass
Δm ¼  100%: ð1Þ
initial mass
Corresponding values of pH of the medium at these times was noted.
The mean and average of the three readings in each group of samples
were calculated using Origin 8.0 software and the graphs plotted in Or-
igin 8.0.
Microstructures of the specimen and surface features before and
after corrosion were studied with ESEM. X-ray diffraction (XRD) analy-
sis of the samples before and after corrosion was carried out using Cu-
Kα radiation in a PANalytical X'Pert3 Powder instrument at 45 kV, and
a scan rate of 2°/min to identify the phases formed in the material. Dif-
fraction angles were 20–80° for the metallic samples and 10–80° for the
PCL coated samples.
The corrosion rate calculation in immersion experiments is based on
the mass loss in the medium during corrosion. In this study, however,
the corrosion rate is not calculated by mass loss method. It is normal
practice to remove the corrosion products on magnesium and its alloys
by cleaning with chromic acid before weight measurement. In this case
since the attempt is not only to find the corrosion rate of the substrate,
but also to understand the various phenomenon that occur in the inter-
face of the polymer coated specimens, such attempt is not made by the
authors and the specimen preparation involves only washing in distilled
Table 3
Average surface roughness of the specimen.
Specimen Average surface roughness (Ra) (μm)
CP Mg 0.0543 ± 0.0075
Mg-4Zn-0.2Ca 0.0533 ± 0.0043
400 D.B. Prabhu et al. / Materials and Design 135 (2017) 397–410

Fig. 4. Percentage change in mass of specimens and corresponding pH of simulated body

fluid over 72 h of uncoated CP Mg and Mg-4Zn-0.2Ca alloy.

water and drying in warm air. The combined effect of mass loss due to
corrosion and mass gain due to the corrosion products is reported as a
single parameter. In addition to this, PCL when immersed in aqueous
medium tends to show an initial mass gain due to hydrolysis followed
by a reduction in mass as the polymer chain breakage occurs. These in-
dividual contributions due to the polymer, metal/alloy and corrosion
products are difficult to isolate in these experiments. The percentage
change in mass is reported as an indicator of the corrosion behaviour
which has to be understood as supplementary information to imped-
ance data. pH measurements of the simulated body fluid on progress
of corrosion are also used as an indicator of the corrosion rates in
some cases as appropriate.

2.3. Electrochemical studies

The electrochemical characterization of the specimens was carried

out with a 3 electrode system using the CH Instruments potentiostat
system with Ag-AgCl cell as the reference electrode and a Platinum
wire as the counter electrode. An exposed area of 1 cm2 of the specimen
under test served as the working electrode. The open circuit potential
(OCP) was allowed to stabilize for 30 min before carrying out further
tests. All tests were carried out at 30 °C with a volume of 300 ml simu-
lated body fluid. The electrochemical impedance was measured over a
frequency range of 0.1 Hz to 1 MHz with AC amplitude of ± 10 mV.
Three samples in each group were tested in fresh medium, and the

Fig. 3. SEM image of (a) CP Mg, (b) Mg-4Zn-0.2Ca alloy, c) EDS analysis of different phases
in Mg-4Zn-0.2Ca alloy and (d) PCL coated Mg-4Zn-0.2Ca alloy before corrosion. Fig. 5. Percentage change in mass of specimens and corresponding pH of simulated body
fluid over 72 h of coated CP Mg and Mg-4Zn-0.2Ca alloy.
 D.B. Prabhu et al. / Materials and Design 135 (2017) 397–410
Fig. 6. SEM image of surface of (a) CP Mg (b) bare Mg-4Zn-0.2Ca alloy and (c) PCL coated
Mg-4Zn-0.2Ca alloy after 72 h immersion in simulated body fluid.
impedance data was fitted with equivalent circuit parameters to model
the corrosion behaviour. Potentiodynamic polarization scans were car-
ried out over a range of ± 500 mV with respect to the OCP at a scan
rate of 10 mV s−1. The data for three specimens of each sample group
were fitted with the Tafel approximation to the Butler-Volmer equation,
and the corrosion parameters calculated. The results are tabulated and
average values calculated. One set of curves alone is shown for clarity
in the results, and the data for the other two in each set is presented
in tabular format.
2.4. Adhesion tests
Adhesion tests of polymer on the metallic sample were carried out
with a Universal Testing Machine (Instron 3366, USA) at a cross head
401
Fig. 7. XRD plots of (a) CP Mg and (b) Mg-4Zn-0.2Ca alloy, before and after corrosion in
simulated body fluid for 72 h.
velocity of 0.01 mm/min on both flat and corrugated samples held to-
gether with the polymer layer in between. The flat specimens of CP
Mg and alloy of 4 mm × 8 mm area and length of 40 mm were tested.
The corrugated samples of Mg-4Zn-0.2Ca alloy of width 30 mm and
thickness of 6 mm had 8 matching teeth of 3.5 mm height each. The sur-
faces were polished and cleaned, and a layer of PCL was added to hold
the mating pieces in a C-clamp tightly and left to dry for 8 h. The force
required to peel off the polymer and pull the two metallic pieces apart
is estimated from the stress-elongation curve as the point where the
stress curve starts descend. An average of two readings is presented
for CP Mg and Mg-4Zn-0.2Ca alloy.
2.5. Corrosion studies on screw specimen
The static immersion studies were conducted for the coated and un-
coated Mg-4Zn-0.2Ca alloy screws in simulated body fluid for 336 h and
the variation in pH was monitored as an indicator of the corrosion rate
of the specimens. A corrosion rate calculation based on mass loss of
the specimen was not possible in these experiments since it is difficult
to isolate the individual contributions due to the degradation of the
polymer and alloy and deposition of corrosion products on the surface
402 D.B. Prabhu et al. / Materials and Design 135 (2017) 397–410
Fig. 8. XRD plots of PCL coated Mg-4Zn-0.2Ca alloy (a) before and (b) after immersion in
simulated body fluid for 72 h.
without damage to the coating. The cross section of the threaded por-
tion in the PCL coated screw is observed under SEM before and after cor-
rosion to assess the corrosion morphology and attachment of the
coating on the alloy.
3. Results
3.1. Characterization of as cast and coated alloy
The microstructure of the as cast CP Mg and Mg-4Zn-0.2Ca alloy are
shown in Fig.2 (a–b). The CP Mg shows columnar grains whereas the
Mg-4Zn-0.2Ca alloy shows more equiaxed and finer grains with a uni-
form distribution of secondary phase particles. The average grain size
of Mg-4Zn-0.2Ca specimen is 134 ± 33 μm.
Surface roughness of the disc polished specimen before dip coating
is listed in the Table 3.
SEM micrograph of the as cast CP Mg is shown in Fig. 3(a), and
shows a single phase with no visible impurities or segregations. The
SEM image of Mg-4Zn-0.2Ca alloy presented in Fig. 3(b) reveals two dis-
tinct secondary phases of spherical and band like morphology. Semi
quantitative analysis by EDS (Fig. 3(c)) shows that they could be binary
and ternary phases respectively. The EDS analyses of these phases show
the presence of Mg and Zn in the spherical phases and Mg, Zn and Ca in
the elongated phase. The percentage of individual elements in these
phases is shown in the table adjacent to the EDS spectrum, these are
only indicative of the presence of these elements and not a measure of
the exact composition of these phases. These phases are possibly
MgZn and Ca2Mg6Zn3.
The SEM micrograph of the polymer coating formed on the Mg-4Zn-
0.2Ca alloy before corrosion is shown in Fig. 3(d) and it shows porous
surface. Analysis using ImageJ software shows that the surface has a po-
rosity of approximately 25.6% with an average pore size of 5.23 ± 0.8
μm for the smaller pores. The average pore size considering the larger
pores in the boundaries of each polymer grain is 7.24 ± 7.4 μm, which
is due to the fact that the size difference between the two types of
pores is very large. The pores on the surface of the polymer coated spec-
imens are due to the evaporation of solvent from the polymer during
dip coating and drying. The larger pores are possibly due to the shrink-
age of the polymer layer over the substrate upon drying that pulls in the
polymer chains to minimize surface area. The SEM image indicates that
there is polymer layer beneath the larger pores possibly from the earlier
layers of dip coated PCL.
3.2. Corrosion studies on laboratory coupons
The results of the static immersion tests of the uncoated CP Mg and
Mg-4Zn-0.2Ca alloy in simulated body fluid over a period of 72 h are
shown in Fig. 4 wherein the percentage change in mass of the speci-
mens with the course of the corrosion and the corresponding pH of
the simulated body fluid are plotted. It can be seen that the mass of CP
Mg and Mg-4Zn-0.2Ca show rapid decline along with an increase in
pH of the medium. The mass change of the coated CP Mg specimen
varies less than 0.25% beyond 20 h whereas that of the coated Mg-
4Zn-0.2Ca alloy is found to increase with immersion time (Fig. 5). The
pH of the coated CP Mg increases with time whereas that of the Mg-
4Zn-0.2Ca alloy is constant within 72 h of immersion time in simulated
body fluid. The average corrosion rates calculated based on mass loss for
the CP Mg and Mg-4Zn-0.2Ca alloy in the uncoated state are 8.426 and
2.481 mmpy respectively. Similar corrosion rate calculation is not
made for the coated specimen since it is difficult to remove the corro-
sion products without removing the PCL layer itself.
The SEM images in Fig. 6(a–b) for CP Mg and Mg-4Zn-0.2Ca alloy re-
spectively indicate uniform corrosion with no visible pitting. The surface
of the corroded specimen is cracked and corrosion products are not dis-
tinctly visible on the surface. The SEM image of polymer coating after
corrosion (Fig. 6(c)) reveals change in pore morphology, with more
swelled appearance of the pores. Also the grain boundaries of the poly-
mer which were initially large diameter pores are now seen tearing
away as a result of exposure to simulated body fluid leading to infiltra-
tion of more liquid into the inner layers. This degradation of the polymer
layer results in corrosion of the underlying alloy specimen, precipitation
of corrosion products and eventually peeling off of the coating itself.
A comparison of the XRD plots of the specimen before and after cor-
rosion is shown in Fig. 7(a–b). It can be seen that the samples before cor-
rosion in both cases showed only peaks that correspond to α-Mg
diffraction (JCPDS # 35-0821). The amount of secondary phases in the
Mg-4Zn-0.2Ca alloy is probably lesser than the detection limit of XRD.
The corrosion product formed on the surface of the CP Mg specimen is
identified as Mg(OH)2 (JCPDS # 44-1482) based on the plots in
Fig. 7(a). Peaks of Mg(OH)2 are also found on the surface of Mg-4Zn-
0.2Ca alloy after corrosion (Fig. 7(b)).
The PCL coated specimen before corrosion (Fig. 8(a)) show charac-
teristic peaks of PCL at 2θ values of 21.3° and 23.6° [47]. The specimen
after immersion in simulated body fluid for 72 h (Fig. 8 (b)) shows
peaks of Mg(OH)2 and calcium phosphate hydrate (β-
Ca2(P4O12)·4H2O) (JCPDS # 50-0582) that indicates their formation as
corrosion products. The formation of phosphates of Ca signifies
 D.B. Prabhu et al. / Materials and Design 135 (2017) 397–410 403

Fig. 9. (a) Electrochemical impedance with (b) equivalent circuit representation of corrosion phenomenon and (c) potentiodynamic polarization plots of CP Mg, Mg-4Zn-0.2Ca alloy and
PCL coated Mg-4Zn-0.2Ca specimens in simulated body fluid.

bioactivity of the material. The absence of such phosphate layer in case
of CP Mg and uncoated Mg-4Zn-0.2Ca alloy could be due to the flaking
off of the products in these samples and/or due to the amount of such
products on the surface being less than the detectable limit of XRD.
These products are held in tact by the polymer layer and are easily de-
tectable in case of the PCL coated specimen.
3.3. Electrochemical studies
The representative Nyquist curves (Fig. 9(a)) of the CP Mg, Mg-4Zn-
0.2Ca alloy and PCL coated Mg-4Zn-0.2Ca alloy indicate the presence of
capacitive loops at high and mid frequencies for all three specimens. In
addition there is an inductive loop at low frequency for the polymer

Table 4
Equivalent circuit analysis for electrochemical impedance.

Specimen R1 (Ω) R2 (Ω) L2 (H) C2 (F) R3 (Ω) C3 (F) R4 (Ω) C4 (F) L4 (H) W4 (Ω−1/2)
−6 −6 −6 a a a a
Mg_1 2.99 69.4 30.37e 10.37e 51.6 14.59e
Mg_2 0.68 78.6 27.65e−6 18.96e−6 49.6 12.3e−6 a a a a

Mg_3 0.5 76.3 23.5e−6 16.5e−6 23.9 10.8e−7 a a a a

Mg-4Zn-0.2Ca_1 0.5 73.81 57.32e−6 14.03e−9 93.88 8.81e−6 65.59 0.41e−3 a a

Mg-4Zn-0.2Ca_2 0.15 75.1 53e−6 10.1e−9 115.2 5.0e−9 45 0.5e−3 a a

Mg-4Zn-0.2Ca_2 2.3 85.6 61.6e−6 34e−9 129 1.6e−6 32 0.89e−3 a a

PCL_1 0.05 82.06 67.0e−6 13.8e−9 164.7 3.97e−6 624.8 2.077 38.98e−6 4193
PCL_2 1.3 89 56.7e−6 12.98e−9 162 3.58e−6 589 1.05 15.6e−6 5100
PCL_3 0.5 95.6 53.62e−6 11.8e−9 159 4.99e−6 593.8 2.45 36.54e−6 3856
a
Indicates that the parameter was not used in the equivalent circuit model.
404 D.B. Prabhu et al. / Materials and Design 135 (2017) 397–410

Table 5
Corrosion parameters calculated from polarization plots.

Specimen Ecorr (V, Vs Ag/AgCl) Icorr (μAcm−2) βc (mV decade−1) βa (mVdecade−1) Corrosion rate (mmpy) Rp (Ω cm2) (fitted value) R⁎p ( Ω cm2) (calculated)

CP Mg_1 −1.569 385.59 −299.8 365.8 8.701 185.5 185.78

CP Mg_2 −1.644 231.26 −264.9 217.50 5.218 224.3 223
CP Mg_3 −1.592 177.39 −216.4 271.5 4.003 294.7 293
Mg-4Zn-0.2Ca_1 −1.414 287.28 −302.5 300.3 6.483 227.7 227
Mg-4Zn-0.2Ca_2 −1.430 187.92 −222.6 237.3 4.24 265.4 264
Mg-4Zn-0.2Ca_3 −1.425 125.69 −223.0 236.9 2.836 396.8 394
PCL_1 −1.286 11.93 −187.5 222.2 0.269 3701.2 3671
PCL_2 −1.230 12.23 −169.9 182.6 0.276 3124.7 3091
PCL_3 −1.226 9.79 −170.2 182.5 0.221 3906.1 3864

Rp (Ω cm2) (fitted value): Fitted for default values of βa and βc of 120 mV, and E = ±25 mV using EC-Lab® software V10.44 (Bio-Logic-Science Instruments)
R⁎p (Ω cm2) (calculated): Calculated using the equation: Rp;E ¼
corr
ðβa βc Þ
Icorr ðβa þβc Þ ln 10

coated specimen. The diameter of the high and mid frequency loops are
indicative of the surface inhomogeneity and charge transfer resistance
of the porous layer on the surface. For the bare alloy this contribution
is mainly due to the surface corrosion products, and for the coated
specimen, this is due to the polymer coating itself. The polarization
resistance (Rp) of the bare alloy is calculated as the sum of the charge
transfer resistance and layer resistance, and is the x-intercept of the
Nyquist graph at low frequency (ideally at dc voltage or frequency =
0 Hz). The polarization resistance of the PCL coated Mg-4Zn-0.2Ca
specimen is calculated to be 898.74 Ω which is four times larger
than that of the bare alloy (223.36 Ω). A mechanism involving pene-
tration of the simulated body fluid through the polymer layer that
causes pitting in the underlying alloy is proposed in the discussion
section of this paper.
The equivalent circuit parameters for the samples are fitted with EC-
Lab® software V10.44 (Bio-Logic-Science Instruments) and are summa-
rized in Table 4 for the circuit given in Fig. 9(b)). R1 is the solution resis-
tance of the medium, R2 and C2 indicate the resistance and charge effect
offered by the inhomogenities in the porous layer of corrosion products
on the surface and inductance L2 is used to model the pores in the layer.
The medium frequency loop can be modelled with the parallel combina-
tion of R3 and C3, which represents the charge transfer resistance of the
material itself. For the Mg-4Zn-0.2Ca alloy, it was found that an addi-
tional time constant is involved possibly due to the relaxation of mass
transport through the layer of corrosion product and is modelled by
an additional R3 and C3 parameter. It was not possible to achieve an
exact fit for the curve especially below a frequency of 1 Hz with this
model. For the PCL coated samples, the diffusion through the porous
polymer layer and the pitting below the underlying corrosion layer is
modelled with the combination of inductance L4 and Warburg imped-
ance W4, along with the charge transfer resistance R4 and dielectric ef-
fect of the polymer, C4.
The corrosion parameters based on Tafel equation (Eq. (2)) for the
CP Mg, Mg-4Zn-0.2Ca alloy and PCL coated Mg-4Zn-0.2Ca alloy calculat-
ed from the polarization curves (Fig. 9(c)) are summarized in Table 5.
 E−Ecorr E−Ecorr
 corrosion products as a result of higher corrosion rate of CP Mg that re-
I ¼ Icorr 10 βa −10− βa
where, Ecorr is the corrosion potential, Icorr the corrosion current, βa and
βc are the anodic and cathodic Tafel coefficients for the anodic and ca-
thodic reactions respectively. The polarization resistance Rp is
calculated at E = Ecorr with the “Rp fit” feature in the software and
also with Eq. (3).
ðβa βc Þ
Rp;Ecorr ¼ ð3Þ
Icorr ðβa þ βc Þ ln 10
The results are summarized in Table 6 and Fig. 10(a–b) and clearly
shows that the corrosion potential (Ecorr) shifts to more positive poten-
tial in the order PCL coated Mg-4Zn-0.2Ca N Mg-4Zn-0.2Ca N CP Mg as
expected. At the same time, the values of the corrosion current (Icorr)
of the polymer-coated sample is less than that of the bare Mg-4Zn-
0.2Ca alloy, which in turn is less than that of CP Mg. The linear polariza-
tion resistance increases in the order of CP Mg b Mg-4Zn-0.2Ca alloy
b PCL coated Mg-4Zn-0.2Ca alloy. These results corroborate the finding
that the PCL coating enhances the corrosion resistance of magnesium
alloy in this study.
3.4. Adhesion tests
The representative stress-extension curves obtained from the uniax-
ial loading of the samples tested for adhesive strength are plotted in
Fig. 11(a) and the values of stress at polymer peel off are tabulated in
Table 7. The stress at peel off for the CP Mg and Mg-4Zn-0.2Ca alloy
are almost comparable. This is expected since the adhesion of a polymer
to a metal depends mainly on the surface roughness of the metal, its
cleanliness and surface pre-treatments. Since both the materials were
subject to the same sample preparation procedure, the adhesive
strengths are similar. Slight increase in value of adhesive strength for
the CP Mg samples could be attributed to the higher surface roughness
as presented in Table 3.
The adhesion tests further prove that the tendency of the coating on
CP Mg to peel off comes from the inherently faster corrosion rates of CP
Mg as compared to the Mg-4Zn-0.2Ca alloy in spite of similar adhesive
strengths in the dry state. The significant difference in the adhesion in
immersed state occurs due to the faster H2 evolution and formation of
ð2Þ sults in polymer layer peel off.
The stress required for polymer peel off in corrugated Mg-4Zn-0.2Ca
alloy sample is higher than that of the flat samples by approximately
17% (Fig. 11(d)) since the crests and troughs on the surface
(Fig. 11(c)) offer a better adhesion than the flat surface (Fig. 11(b))

Table 6
Average values of corrosion parameters calculated from polarization plots.

Specimen Ecorr (V, Vs Ag/AgCl) Icorr (μA cm−2) Corrosion rate (mmpy) Rp (Ω cm2)

CP Mg −1.60 ± 0.03 264.75 ± 108.06 5.97 ± 2.44 234.8 ± 55.4

Mg-4Zn-0.2Ca −1.42 ± 0.01 200.29 ± 81.51 4.52 ± 1.84 296.6 ± 88.7
Mg-4Zn-0.2Ca + PCL −1.24 ± 0.03 11.32 ± 1.33 0.26 ± 0.03 3577.3 ± 405.2
 D.B. Prabhu et al. / Materials and Design 135 (2017) 397–410
Fig. 10. Summary of (a) Ecorr and Icorr and (b) Corrosion rate and linear polarization
resistance based on potentiodynamic polarization studies.
for the same surface preparation and roughness. These attachment points
may also be responsible for their better adhesion in the immersed state
and prevent peel off for longer duration than a smooth surface. On the
screw geometry the pitch is smaller than that of the corrugated surface
and the adhesion might even be better than this estimated value assum-
ing good contact between polymer and metallic surface.
3.5. Corrosion studies on screw specimen
The pH of the simulated body fluid after immersion of the fabricated
screws at various time intervals is monitored and plotted in Fig. 12(a). It
Fig. 11. (a) Uniaxial tensile stress vs. extension of polymer bonded metallic specimens, (b) photographic image of flat specimen, (c) photographic image of corrugated specimen and
(d) comparison of adhesive strengths calculated based on uniaxial loading tests.
405
Table 7
Adhesion strength of PCL to metallic surface tested by uniaxial loading.
Sample Adhesion strength, uniaxial loading (kPa)
CP Mg 92.5 ± 4.9
Mg-4Zn-0.2Ca 86.0 ± 7
Mg-4Zn-0.2Ca corrugated 105.0 ± 3.4
was observed that the pH of the medium increased in all samples, the
increase was highest in case of the uncoated screws of both partially
and fully threaded design. In case of coated screws, the partially
threaded configuration demonstrated higher corrosion rates compared
to the fully threaded one.
The cross sectional image of the PCL coated screw in the threaded re-
gion (Fig. 13) shows a layer of 126.5 ± 10.2 μm thickness over the alloy.
The SEM of the cross section of the coated screw after 336 h of immer-
sion in simulated body fluid is presented in Fig. 14 and it is interesting to
note that the PCL layer is still attached at some point, in spite of the
bulky layer of corrosion products of approximately 190 μm. The PCL
layer was too thin to get any useful information in the EDS analysis,
only peaks of Au sputtered on it for conductivity in SEM imaging was
obtained. The alloy showed peaks of Mg and O, whereas the corrosion
products consisted mainly of Mg, Ca and O.
4. Discussion
4.1. Static immersion in simulated body fluid
CP Mg undergoes severe corrosion in simulated body fluid as seen by
the rapid mass loss and pH increase in the medium during the 72 h of
immersion. The localised rise in pH associated with the fast degradation
of Mg results in the precipitation of corrosion products on the surface of
the specimen. An increase in the mass of the specimen after corrosion is
attributed to these corrosion products on the surface. In case of Mg-4Zn-
0.2Ca specimen, the corrosion proceeds much slower as evidenced by
the slower increase in pH of the medium. There is very little precipita-
tion of corrosion products and the rate of mass loss is more uniform.
This is also supported by the SEM images in Fig. 6(b).
In case of PCL coated CP Mg, the inherent high corrosion rate and the
small amount of corrosion medium trapped under the polymer layer re-
sults in rapid degradation of the underlying metal, higher pH rise and
more precipitation of the hydroxide products. The H2 gas molecules re-
leased from the surface and the growing solid corrosion products push
the polymer layer away from the surface resulting in peel off of the coat-
ing which is clearly evident in Fig. 15(a–b). Once the coating bulges and
peels off, the underlying layer corrodes at a faster rate and the effect of
406 D.B. Prabhu et al. / Materials and Design 135 (2017) 397–410

Fig. 12. (a) pH variation of medium during corrosion of coated and uncoated screw specimens in simulated body fluid (b) threaded portion of uncoated screws are corroded more after
336 h (c) comparison of uncoated and coated partially threaded screws and (d) comparison of uncoated and coated fully threaded screws on immersion in simulated body fluid for 336 h.

polymer is no longer there. This effect manifests initially at sharp cor- not only on the absence of porosity in the coating but also on the adhe-
ners and edges of the coated specimen, and hence the layer peels off sion of polymer to the alloy surface. This is further demonstrated in the
from the edges. From this event forth, there is an increase in pH of the current work on threaded screws undergoing corrosion in simulated
coated CP Mg specimen. The mass change is slower since it is the com- body fluid for a period of 336 h.
bined effect of polymer swelling/degradation, corrosion mass loss of the The corrosion of polymer coated specimen is a complex combination
metal and deposition of corrosion products (Fig. 5). of one or more of these processes: Polymers such as PCL undergo both
In case of coated Mg-4Zn-0.2Ca alloy, the corrosion rate is slower, and surface and bulk degradation in simulated body conditions [37]. A sche-
hence the underlying metallic layer does not degrade at a much faster matic representation of the mechanism of corrosion of PCL coated Mg
rate. The slower corrosion, sluggish pH change, lesser precipitates and re- alloy shown in Fig. 16(a) clearly indicates these different aspects. If
duced H2 evolution from the surface enables the polymer layer to cling on the rate of hydrolytic cleavage of surface bonds occurs faster than the
longer to the alloy. There is also mass gain in case of the polymer coated penetration of liquid into the polymer bulk, surface degradation or ero-
alloy that can be a combined effect of swelling of the polymer and the cor- sion occurs, and the coating material becomes thinner. The reverse is
rosion products. Photograph of the specimen after exposure to simulated true in bulk degradation, where the rapid penetration of water into
body fluid for 72 h are seen in Fig. 15(c) which supports this proposition.
Surface analysis of the coated specimen after corrosion using SEM
shows swelling in the polymer due to hydrolysis and the pores have be-
come more rounded with visibly thinner edges and opened up as seen
in Fig. 6(c) and inset of Fig. 14. This will further increase the exposure
of the alloy surface to the simulated body fluid. It has to be considered
that the volume of the medium seen by the alloy surface is small and
there is also a lesser chance of the ions released as part of the corrosion
to diffuse into the bulk of the medium due to the barrier offered by the
polymer layer. Hence there is a stagnation zone between the polymer
and the alloy with a higher pH medium due to the corrosion of the mag-
nesium alloy. This high alkalinity can result in the precipitation of the
corrosion products, mainly hydroxides and phosphates of Mg and Ca.
It is posited that these products along with hydrogen gas evolved
from the magnesium corrosion result in the bulging of the PCL layer
[20,29,35] away from the surface of the Mg-4Zn-0.2Ca alloy eventually
peeling off the layer. Park et al. [35], proposed the use of molten poly-
mer as an alternative to the solvent based method to avoid the forma-
tion of pores in the coating. It can be safely assumed that the long Fig. 13. Cross sectional SEM of the PCL coating on Mg-4Zn-0.2ca alloy screw before
term presence of polymer coating on the alloy surface is dependent corrosion.
 D.B. Prabhu et al. / Materials and Design 135 (2017) 397–410
Fig. 14. Cross sectional SEM of coated Mg-4Zn-0.2ca alloy screw after 336 h corrosion with EDS analysis.
the entire bulk of the polymer results in random cleavage of ester bonds
within the bulk. The increase in the number of carboxyl end groups
(\\COOH) [48] formed as a product of the ester bond cleavage in the
polymer bulk increases the acidic content within (Fig. 16(b)). Diffusion
of surface carboxyl groups (\\COOH) into the surrounding medium, re-
sults in the degradation of the material from inside out. It is difficult to
isolate these two modes of degradation occurring in the PCL coating
on Mg specimen in our study. The degradation of the polymer layer re-
sults in the penetration of the simulated body fluid to the metallic sur-
face and its subsequent corrosion. The acidic pH resulting from the
polymer degradation itself may affect the corrosion rate of the substrate.
The pH variation of the medium is the effect of the degradation of poly-
mer and that of the alloy. It is difficult to isolate these two parameters in
a coated sample. Due to the thin layer of PCL and higher corrosion rate of
the Mg alloy itself, the effect of metal corrosion will be dominant. The
pH of uncoated alloy varies from 7.4 to 9 whereas that of the coated
alloy is below 8. This stable value of pH indicates that the coating is in-
tact. However, the presence of corrosion products within the layer indi-
cates that corrosion has occurred in the interface.
4.2. Electrochemical studies
Electrochemical impedance spectroscopy analysis is a steady state
technique that provides valuable insight into the mechanism of corro-
sion of coated Mg-4Zn-0.2Ca alloy. The two capacitive time constants
indicate that there are two rate controlling processes that occur in this
case due to the material and a partially protective layer on the surface.
The high frequency loop could be indicative of the surface non homoge-
neity of the alloy and is almost similar for the CP Mg and coated/uncoat-
ed Mg-4Zn-0.2Ca alloy. This loop includes no contribution from the
polymer layer and it means that the corrosion mechanism is almost
Fig. 15. Photographic image of (a) coated specimen, (b) Mg specimen with coating peeled off with dense layer of corrosion products on its surface and (c) Mg-4Zn-0.2Ca coated specimen is
intact after 72 h of immersion test, localised corrosion products visible in the substrate.
407
similar in the underling alloy material and the bare alloy. The mid fre-
quency time constant is associated with the charge transfer resistance
Rct of the material and the double-layer capacitance, Cdl, at the interface
of the coating and base alloy and is maximum for the PCL coated speci-
men, since the contribution is mainly from the polymer layer itself. In
the CP Mg and Mg-4Zn-0.2Ca alloy, the partially protective surface corro-
sion layer offers only a small resistance to the corrosion process. The size
of the capacitive loops at mid frequency can be taken as a representation
of the corrosion resistance of the uncoated and coated specimen in simu-
lated body fluid. There appears to be a third capacitive loop in the low fre-
quency region which could be indicative of the relaxation of mass
transport through the corrosion product layer or polymer layer for the
coated specimen, a supporting evidence for the partially protective nature
of the coating or product layer. These multiple mass and charge transfer
processes occur simultaneously and interdependently in the material.
The low frequency inductive loop in the coated Mg-4Zn-0.2Ca alloy
specimen indicates that there is possible pitting corrosion that occurred
below the polymer layer. This is possible due to the penetration of the
simulated body fluid through the pores in the PCL layer, and subsequent
corrosion of the alloy in a highly concentrated medium confined to a
small space. Though pitting corrosion is not seen in the uncoated Mg-
4Zn-0.2Ca alloy, the chances of its occurrence in the coated specimen
is higher due to the localised exposure of the specimen surface to the
simulated body fluid that penetrates the pores of the polymer coating.
The low volume of chloride ion rich SBF medium trapped in the inter-
face of the polymer and alloy surfaces cause pitting in coated specimen.
4.3. Corrosion of screw specimen
An observation from the photographs in Fig. 12(c–d) is that the ad-
hesion of the coating is better in the fully threaded specimen (specimen
408 D.B. Prabhu et al. / Materials and Design 135 (2017) 397–410

Fig. 16. (a) Degradation mechanism of PCL coated Mg alloy in simulated body fluid, (b) cleavage of ester bonds and formation of carboxyl end groups.

3 in Fig. 12(d)), on account of the enhanced roughness due to the ma-
chined threads that act as anchoring points for the coating. The smooth
portion of the partially threaded screw has a higher tendency of corro-
sion due to the smoother and plain geometry (specimen 3 in
Fig. 12(c)), in which the medium can penetrate easily and peel off the
coating. In contrast the coating in the threaded area stays intact longer.
For the threaded specimen, the increased number of crests and troughs
also acts as points of steadfast contact of the coating with the metal over
its entirety. Hence the exposure of the specimen at any one thread is iso-
lated from the rest of the length and the overall corrosion rate is much
slower than the coated partially threaded screw. Also since a small
portion of the corroding alloy is now exposed to a larger volume of
the medium, the effect of local rise in pH that happens usually under
the coating is absent here and therefore lesser corrosion products are
observed in this case.
There are however unresolved issues at this point not addressed in
this work. It is expected that under in vivo conditions, since there is a
steady pH maintained due to the replenishment of the tissue fluid in
the human body and diffusion of released ions into the tissue, the corro-
sion behaviour is different from the stagnant tests carried out in vitro.
However, the high pH at the interface of the alloy and polymer coating
can occur under such circumstances also, with a chance of large amount
 D.B. Prabhu et al. / Materials and Design 135 (2017) 397–410
of corrosion products precipitated between the polymer and alloy.
Wong et al. [40] demonstrated that a PCL coated AZ91 alloy showed
no toxicity in vitro and cell attachment occurred in 3 days. The specimen
implanted in rabbit model on removal after 2 months of implantation
showed signs of bone tissue formation. However no mention was
made of corrosion products on the interface of AZ91 alloy and PCL coat-
ing. Additional influencing parameters occur when the material is im-
planted in an animal model and these are considered beyond the
scope of the current work and needs further evaluation.
Based on these observations, it is the authors' opinion that the re-
sults obtained from laboratory scale experiments on coated corrosion
coupons of simple geometry cannot be extended to the final product.
In an uncoated Mg alloy screw, the sharp geometrical features such as
thread crests are stress raisers and have higher tendency to corrode.
Hence in an uncoated partially threaded geometry, the smooth surface
will corrode slower than the threaded portion. This scenario changes
when a polymer coating is applied as is demonstrated in the current
work. The polymer coating tends to peel off faster from a smooth surface
than a threaded one, and hence a reversal of scenario occurs. The
smoother area under the polymer layer now corrodes faster than the
threaded area under the polymer. Thus our experiments in this work
show that the sharp edges of the threads in spite being at higher risk
for corrosion (Fig. 12(b)) also anchored the polymer coating better
(specimen 3 of Fig. 12(d)) and served to reduce the degradation of the
coated fully threaded screw. The result is a slower rise in the pH of the
medium compared to the bare specimens. Within a component,
threaded and smooth portions corrode at dissimilar rates and affect
the polymer attachment differently as seen from the partially threaded
screw. Hence the effect of bulk and surface geometrical features of the
end use component on the attachment of the coating has to be individ-
ually investigated in each component designed for implant applications.
5. Conclusion
Corrosion rate of coated Mg-4Zn-0.2Ca alloy decreased from 4.52 to
0.269 mmpy on application of PCL coating. Infiltration of the simulated
body fluid through the pores of the polymer and its bulk degradation re-
sult in corrosion of the substrate. Uniaxial adhesion strength of PCL on
CP Mg and Mg-4Zn-0.2Ca are 92.5 ± 4.9 and 86.0 ± 7 kPa respectively
in dry state, but coating on CP Mg peels off faster in simulated body fluid
due to higher corrosion rate of substrate. Pitting corrosion is also ob-
served under the polymer layer. A fully threaded screw fabricated
from the alloy and coated with PCL shows slower pH rise in the medium
than a partially threaded screw of same major dimensions when tested
in simulated body fluid for a period of 336 h. Partial threaded configura-
tion results in peel off of PCL coating in smooth regions and rapid in-
crease in pH. It is found in the current study that increased adhesion
of PCL coating to threaded Mg alloy substrate dominates over the in-
creased corrosion rates of threaded surface.
Acknowledgements
The authors would like to acknowledge funding support for part of
this work by the Department of Science and Technology, Government
of India [Project No. SR/WOS-A/ET-79/2013(G), dated 29.5.2014].
The authors would also like to thank Mr. G. Sathish kumar (Adhesion
Tests), Ms. Anju Gupta, Dr. N. Meenakshi Sundaram, Dr. R.
Sivasubramanian and Dr. V. Udhayabanu for valuable discussion at var-
ious stages of this study.
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