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Corrosion of nanostructured and ultrafine-grained

metallic implant materials

G. P. Chaudhari

To cite this article: G. P. Chaudhari (2016) Corrosion of nanostructured and ultrafine-

grained metallic implant materials, Materials Technology, 31:13, 812-817, DOI:
10.1080/10667857.2016.1242199

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 Corrosion of nanostructured and
ultrafine-grained metallic implant materials
G. P. Chaudhari
Nanostructured metallic materials are increasingly investigated for numerous biomedical implant
applications. They offer benefits of high strength with enough ductility and often possess superior
biocompatibility. Several materials processing routes involving severe plastic deformation of candidate
materials lead to bulk nanostructured and surface nanostructured metals. Literature is replete with
studies claiming their superior mechanical behaviour and biocompatibility in terms of wettability, cell
adhesion and proliferation. In spite of their metallic properties, permanent metallic implants with an
expected life span of 15 years or more, often break down prematurely and corrosion of some form
is a common cause or trigger. Therefore, in order to ensure reliable performance of newly developed
nanostructured metal implants in service, it is necessary to understand their electrochemical degradation
behaviour. Concerns stem from adverse reactions from corrosion products, desired longevity of long
term implants, and biodegradability of temporary implants. Present review covers the developments
in this domain.
Keywords:  Nanostructured, Metallic implant, Corrosion, Stainless steel, Titanium, Magnesium, Biodegradable, Ultrafine-grained, Severe plastic
deformation

This paper is part of a topical issue on Recent advances in nanostructured implantable biomaterials

Introduction exceeding 30 years is usually desired.6 Metallic implants are

Nanostructured (NS) metallic materials are a promising class
of biomaterials. Several severe plastic deformation (SPD) pro-
cesses provide a route for large scale synthesis of bulk NS and
ultrafine-grained (UFG) materials. In recent years, SPD pro-
cessing of several metallic implant materials including stainless
steels, and cobalt-, titanium-, magnesium- and zirconium-based
materials for prospective implant application have been reported.
NS and UFG metals are stronger due to Hall–Petch strength-
ening. This helps in decreasing the level of surgical intervention
by reducing the size of implants,1 improving the fatigue perfor-
mance of load-bearing implants,2 and improving the wear resist-
ance of moving components of implant devices. Strengthening
is one of the attributes required to improve the lifetime of long
term implantable devices. The other major benefit of nanostruc-
turing is better biocompatibility by avoiding the use of expensive
and toxic alloying and some NS metallic implant systems have
shown improved biological reactions on their surfaces.1 The
UFG titanium prepared by SPD route showed better biocompat-
ibility evidenced by higher cell proliferation than conventional
titanium and Ti–6Al–4 V alloy.3 The superior cellular response
to nanograined 316L material was attributed to the higher hydro-
philicity of the substrate and grain structure. Cell attachment,
proliferation and prominent proteins were strongly modulated
on NS 316 L surface.4,5
Along with these positive aspects, satisfactory long term
performance of implants necessitate good resistance to
uniform and localised corrosion. Long implant service period
Department of Metallurgical and Materials Engineering, Indian Institute of
Technology Roorkee, Roorkee 247667, Uttarakhand, India
Email: chaudfmt@iitr.ac.in.
subjected to a severe saline, ionic (Na+, Cl−, HCO3−, K+, Ca2+,
Mg2+, SO2− 7
and oxygenated environment (0.9  wt.% salts,
4
37 ± 1 °C) inside the human body. Corrosion is one of the major
contributing reasons for failure of metallic implants. Some of
the problems arising from electrochemical degradation of
metallic implants are shown in Fig. 1. Metallic implant materials
implanted inside a body may corrode over time releasing metal
ions which can have toxic effects on tissues. The order of
cytotoxicity of metal ions released from implants is: iron (less
toxic) < titanium < chromium < nickel < vanadium < cobalt
(most toxic).8 Load-bearing orthopaedic implants often fail from
pitting initiated corrosion fatigue.9 When fretting wear-promoting
conditions exist inside the body, even highly corrosion-resistant
metallic implants corrode. Table 1 lists the examples of the
metallic implants affected by specific forms of corrosion. Thus,
resistance of implants to corrosion in body fluids plays a very
important role in the in the maintenance of implant in the human
tissues and for its biocompatibility.10
Corrosion of bulk NS materials
Stainless steels
Stainless steel implants are relatively inexpensive and are
most widely used. Several studies exist on nanostructuring
of implant grade stainless steels suggesting improvements
in mechanical properties13,14 and biocompatibity.15,16 In 316L
stainless steel ECAP for 8 passes, the corrosion rate decreased
from 3.12 to 0.42 μA/cm2 for NS steel in Ringer’s solution.17
Better biological behaviour of NS steel in terms of enhanced
fibroblast cell proliferation at the NS surface was attributed
to the decrease in corrosion rate and presence of more chrome

© 2016 Informa UK Limited, trading as Taylor & Francis Group

Received 19 September 2016; accepted 22 September 2016
812 DOI 10.1080/10667857.2016.1242199 Materials Technology: Advanced Bio Materials   2016  VOL. 31  NO. 13
 Chaudhari  Ultrafine-grained metallic implant materials

1 Schematic illustrating the forms of corrosion and associated problems observed with metallic implants

Table 1 Examples of implants affected from specific corrosion forms:11,12

Type of corrosion Affected implants/locations

Crevice corrosion Screw/plate interface under the screw head, under washers, hip nails, intersection of two piece components,
head–neck taper connection of modular prosthesis
Pitting corrosion Dental implants, hip prosthesis
Corrosion fatigue Cyclic load bearing implants e.g. hip implant, knee implant
Fretting corrosion Load bearing metallic orthopaedic implants including bone/stems interface, the stem–cement interface and on
the interface of modular connection between implant components
Galvanic corrosion Dental implants
Uniform corrosion Release of ions which may be carcinogens, allergens and toxic at the implant location

oxide on the surface. In another work, NS 316L stainless
steel obtained by phase reversion concept using deforma-
tion–annealing sequence was tested in phosphate-buffered
saline (PBS) solution of pH 7.2 at 37  °C.5 It showed that
nanograin-structured steel developed a more stable passive
chromium oxide film and exhibited a higher corrosion resist-
ance as compared to coarse-grained counterpart. Enhanced
pitting resistance of NS 316L stainless steel in chloride envi-
ronment was ascribed to passive film properties influenced by
an increase in the grain boundary volume, and homogenisa-
tion of pit inducing impurities and non-metallic phases.9 NS
304 stainless steel produced by severe rolling tested in arti-
ficial saliva showed higher polarisation resistance and lower
amount of potentially toxic Ni, Cr ions release as compared to
its coarse-grained counterpart.18 Cytotoxicity test showed no
toxic effect with murine fibroblast cells and human cell lines.
Titanium and titanium alloys
Titanium and Ti-based alloys have superior biocompatibility
because of spontaneous formation of about 3 nm thick stable
passive film of titanium oxide.19 One of the drawbacks in the
use of Ti as an implant material is its low strength, insufficient
hardness and low wear resistance. Other than alloying, one
approach to improve the hardness and strength of titanium
implants is microstructural modification to produce UFG or
nanocrystalline microstructure.20 How this approach influ-
ences the corrosion behaviour, however, is relatively less
studied.21,22 It is important because decreased viability of
bone cells is attributed to a consequence of high corrosion of
titanium.23,24 Nearly equiatomic nickel–titanium alloy, Nitinol,
has less corrosion resistance and nickel dissolution makes it
less biocompatible.25,26
However, as seen in Table 2 many studies point to
improved corrosion resistance of NS titanium-based materi-
als. Zheng et al. produced a hierarchical porous surface layer
on ECAP Ti by combined grit blasting, acid etching and alka-
line treatment. This porous surface with increased surface
roughness and wettability showed lower corrosion rate in SBF
with no evidence of pitting corrosion.27 An interesting point
defect model based on in situ AFM studies is propounded to
describe the growth of passive film on Ti–24Nb–4Zr–8Sn
alloy.28 Corrosion of this < 50 nm grain size NS alloy resulted
in rapid formation of an amorphous passive film that was less
defective, more homogeneous and thicker as compared to the
coarse-grained alloy. The two-layered passive film was found
to be rich in Ti and Nb and lean in oxygen. The suboxide layer
showed a strong grain size dependence and was 50% thicker
as compared to the coarse-grained alloy.
UFG CP Ti produced by cryomilling followed by spark
plasma sintering, exhibited enhanced corrosion resistance
in Ringers solution due to formation of thicker inner
passive oxide layer as compared to CG Ti.29 It reduced
inflammatory response and showed enhanced cell adhe-
sion compared to coarse-grained Ti. A study on ECAP-
processed biocompatible Nb–2Zr UFG alloy discusses
the corrosion fatigue behaviour in Hank’s solution.30 The
electrochemical parameters were similar to coarse-grained

 Materials Technology: Advanced Bio Materials  2016  VOL. 31  NO. 13 813

Chaudhari  Ultrafine-grained metallic implant materials

Table 2 Effect of nanostructuring of titanium-based implant alloys on their corrosion rate

Nanostructuring As a result of nanostructur-

Alloy process route Test solution Grain size ing the corrosion rate Reference
Ti/nano-Ti5S3–TiCx Ball Milling + SPS Ringer’s 40 nm–1 μm Insignificantly increased com- 31

pared to c.p. Ti.

CP Ti Cryo-milling + SPS Ringer’s 250 nm–1 μm Decreased 29

Ti Hydrostatic extrusion 0.9% NaCl 90 nm Slightly decreased 32

CP Ti ECAP SBF (Kokubo) 280 nm Decreased 27

CP Ti ECAP SBF (Kokubo) 238 nm Decreased by an order of 33

magnitude
CP Ti ECAP SBF (Kokubo) 183 nm Decreased, pitting tendency 34

also decreased
CP Ti HPT PBS 5–10 nm Increased 35

Ti–13Nb–13Zr alloy ECAP Hank’s ~600 nm Decreased 36

Ti–24Nb–4Zr–8Sn Hot forging + cold 0.9% NaCl <50 nm Decreased 28

alloys rolling
Ti–Zr–Ta–Nb alloy ARB Ringer’s UFG to nano- Decreased 37

crystalline
Ni50.2Ti49.8 alloy HPT Hank’s solution and Not provided Decreased, pitting tendency 38

artificial saliva also decreased

Notes: CP = commercial purity, SPS = spark plasma sintering, ECAP = equal channel angular pressing, HPT = high pressure torsion,
ARB = accumulative roll bonding, PBS = phosphate-buffered solution.

alloy demonstrating its excellent corrosion resistance. In Corrosion of biodegradable implants

fatigue crack growth tests performed in Hank’s solution,
however, there was slight acceleration of crack growth rate
values in UFG NbZr alloy.
Surface NS materials
Surface nanostructuring attained by severe plastic defor-
mation of surfaces rather than the entire bulk is explored in
order to alter the surface properties alone. This can retain
the properties (e.g. toughness) of the bulk to some extent,
and can enhance the fatigue strength,39 wear resistance and
the corrosion behaviour of the implants. However, such
processing can additionally induce residual stress in the
processed components, which may influence their corrosion
behaviour.
In 316L stainless steel, corrosion fatigue strength in
0.9% NaCl solution increased by 50% from nanocrystal-
line surface modification obtained using surface mechan-
ical attrition treatment (SMAT).40 This was attributed to
the thicker oxide layer, high strength of the surface layer,
residual compressive stresses and lower tendency for inter-
granular corrosion in the nanocrystalline layer. The pitting
corrosion resistance however remained unchanged. NS
Co–Cr coatings prepared by plasma spraying were found
to be more corrosion-resistant than coarse-grained Co–
Cr coatings in Hank’s solution.41 It showed lower passive
current densities and uniform corrosion rather than more
damaging localised intergranular corrosion. Higher grain
boundary density decreased the thermodynamic driving
force for corrosion by reduced compositional difference
between the grain interior and the grain boundary, by
equalisation of potential of strained grain interior and grain
boundaries, and from improved repassivation kinetics.
Increased corrosion resistance of shot-peened nanocrys-
talline NiTi samples tested in Ringer’s solution was ascribed
to an increased surface atomic activity, to the changes in the
passive film structure and to the enhancement of the passive
film density.42 Surface nanocrystalline NiTi alloy obtained
from SMAT and tested in 0.9% NaCl solution for corrosion
potential and electrochemical impedance spectroscopy meas-
urements showed early formation of a passive oxide layer,
which however was degraded by Cl− ions upon longer expo-
sure in immersion tests.43
As against the more corrosion-resistant implant materials
addressed so far, biodegradable metallic implants are being
vigorously researched for temporary biomedical fixation.
These are mainly magnesium and its alloys with Zn, Ca and
Mn being the principle alloying elements. They possess better
strength as compared to polymers, bone-compatible Young’s
modulus values in the range of 41–45 GPa, and exhibit good
biocompatibility. Magnesium has an active standard potential
of −2.37 V and is severely corroded in saline human body
fluids, accompanied by its absorption in the body. The net
corrosion reaction in aqueous physiological environment can
be written in a simplified form as:
Mg + 2H2 O → Mg(OH)2 + H2
Rapid corrosion of magnesium is undesirable on two accounts.
Firstly, the rate of subcutaneous hydrogen bubble generation
accompanying the corrosion is too high to be handled by the
surrounding tissue.44,45 Therefore, limiting hydrogen evolution
rate by limiting the corrosion rate of magnesium is a formi-
dable challenge. Secondly, in load-bearing applications the
implants may lose their strength and fail before the tissue
heals.46 Thus, it is necessary to lower the dissolution rate of
magnesium alloys in physiological environment.47 Although
alloying with Al, Zn, Ca, Mn, Cu, and Zr has been explored
to mitigate this problem, the success is limited due to their
restricted solid solubility.48,49
Nanostructuring of magnesium alloys is showing some
promise in both improving the mechanical properties50
and in controlling the degradation kinetics. The purpose
of nanostructuring is to provide a surface that will provide
high corrosion resistance in the initial period of exposure to
the physiological environment. This enables maintaining of
mechanical integrity until the tissue gets enough time to heal.
However, over a period of time, the surface is expected to
become less effective and thus undergo corrosion at slow to
moderate rates accompanied by bioabsoption of Mg.
It has been reported that a decrease in grain size of AZ31
decreased the corrosion rate in PBS.51 This was evidenced by
a lower initial corrosion potential and higher charge transfer
resistance, and was attributed to presence of a mixed com-
pact layer of magnesium hydroxide and P-containing com-
pounds. More homogeneous UFG (700 nm) microstructure

814 Materials Technology: Advanced Bio Materials   2016  VOL. 31  NO. 13


of Mg–Y–RE obtained from friction stir processing exhibited
higher corrosion resistance 3.5 wt.% NaCl solution as evident
from higher charge transfer resistance and shallower pits.52 An
order of magnitude lower corrosion rate was attributed to a
higher HAGB density in the UFG magnesium microstructure
that produced a more tenacious passive layer due to decrease
in lattice mismatch between the crystalline oxide layer and
the hcp substrate.53
With the decrease in grain size especially in the UFG
regime, it is widely reported that in neutral53–55 and basic56,57
sodium chloride electrolytes the corrosion resistance of Mg is
improved. This was attributed to a better passive film as sup-
ported by observation of reduced cathodic kinetics. Although
increased defect density (twins and dislocations) in materials
processed by severe plastic deformation should increase the
cathodic reaction kinetics, it is argued that corrosion response
is influenced less by residual stress than by the grain size.58
As compared to the as-cast alloy, the icorr of the HPT-treated
Mg–Zn–Ca alloy in the immersion tests in SBF decreased by
about two orders of magnitude. HPT-treated sample exhibited
more homogeneous corrosion due to conversion of the second
phase into nanosized particles, and their uniform distribu-
tion throughout the microstructure rather than along the grain
boundaries.59 On the other hand, corrosion rates of ECAP-
processed WE43 (MgYNdZr) alloy with different micro-
structures in a physiological (1% NaCl) solution showed that
the alloy with <1 μm grain size dissolved faster.60 This was
ascribed to larger area of the grain and interphase boundaries.
There are few studies on corrosion behaviour of surface
NS magnesium alloys – e.g. cryoburnishing of AZ31B alloy
produced 263  nm grain size surface structure with signif-
icantly improved corrosion resistance based on hydrogen
evolution tests.61 In 7 h of test, the volume of hydrogen gen-
erated from the cryogenic-burnished sample was 36% less
than that of a ground sample and comparatively smaller pits
were observed from immersion tests. Whereas, NS Mg–1Ca
alloy (50–100  nm grain size) produced by SMAT showed
increased corrosion rate which is explained based on the high
density of dislocations and grain/subgrain boundaries.62 The
Mg(OH)2 films formed on the SMAT alloy did not provide
any increase in protection.
Summary and challenges
Above review of literature reveals that there are numerous
studies on metallic biomedical implant materials that mention
an improvement in either uniform or localised forms of corro-
sion in simulated body fluids. However, there are also reports
of corrosion resistance being either unaffected or affected
adversely which points toward some uncertainty. Most of the
studies are focused on uniform corrosion behaviour. The main
arguments propounded by the workers for such improvements
are summarised in brief below.
(1) With nanostructuring of metals, the surface exposed
to the body fluids consists of very high grain boundary
density and nanoscale or ultrafine grains containing
low dislocation density. High grain boundary density
represents larger fraction of high energy area in the
microstructure. It is postulated that the corrosion rates
are decreased because of improved kinetics of passive
film formation on such large-active-area microstruc-
ture. Secondly, there is a decrease in the galvanic
potential difference between the high energy active
grain boundaries and the nobler grain interior. Because
of nanostructuring, the physical separation between
 Materials Technology: Advanced Bio Materials  2016  VOL. 31  NO. 13
Chaudhari  Ultrafine-grained metallic implant materials
local nanoscale anodic and cathodic areas tends to
diminish.52 Thus, the oxidation becomes more uniform
and corrosion rates decrease.
(2) 
Most implant metals with exception of magnesi-
um-based materials rely on the formation of an inert,
compact, tenacious, continuous and adherent passive
film for their corrosion resistance. Such materials are
also therefore, susceptible to localised corrosion. The
improvement in localised forms of corrosion such as
pitting, intergranular corrosion, corrosion fatigue is
related to the passive film properties. In NS metallic
materials, the passive film properties like semicon-
ducting nature, defect density, thickness, degree of
compactness, stress condition from lattice mismatch
with metallic substrate, etc. are influenced by homog-
enisation of pit inducing non-metallic phases and oth-
erwise segregated impurities, and by an increase in
the grain boundary volume.9,29,31 These can reduce the
passive current density.
Because of diversity of processing routes employed for
nanostructuring, and variety of implant materials, there is
a lack of universal approach that can describe and predict
the behaviour of implants in biological environments. The
observed behaviour is specific to the material and the pro-
cessing method. There is a need and scope for improving
the understanding of corrosion behaviour of NS metallic
implants. There is mention of a possibility that beneficial
effect of nanostructuring accrue below certain nanostructur-
ing dimensions.52 It is a topic of investigation if there is any
threshold or critical size parameter, may be process-specific,
which can be determined to ensure the benefits of nanostruc-
turing from corrosion point of view.
The corrosion resistance and associated biocompatibility
of the metallic materials are dependent on the oxide surface
layer. Modelling studies considering the change in kinetics of
film formation and dissolution arising from change in grain
boundary density and defect (e.g. dislocation) density in sim-
ple single phase and more complex multiphase NS systems
could be explored. Experimental work involving surface film
characterisation using in situ higher resolution scanning elec-
trochemical microscopy, transmission electron microscopy, in
situ AFM and XPS could augment the understanding further.
Disclosure statement
No potential conflict of interest was reported by the author.
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