Materials and Corrosion 2008, 59, No. 11
200804173 855
Corrosion aspects of metallic implants An
overview
The ability to replace or augment diseased body parts totally or
partially has improved both the quality and life span of human
population. The decline in surgical risks during recent decades
has encouraged the development of more complex procedures for
prosthetic implantation. Additionally, a variety of extracorporeal
devices, such as the heart, lung and blood dialysis machines are
used routinely, but these prosthetic elements have several limita-
1 Introduction
Many types of materials are available and used in various
biomedical devices. These materials are in conjunction with
medical intervention. The generally accepted term for such
materials is biomaterials. A biomaterial is defined as any
synthetic material that is used to replace or restore function
of a body tissue and is continuously or intermittently in
contact with body fluids. The ability to replace or augment
diseased body parts totally or partially, has improved the
quality of life for millions of people over the quarter of a
century. In the course of a single year, thousands of patients
throughout the world receive some kind of implant device.
Such devices include artificial hips, knees, elbows, pace-
makers, heart valves, intraocular lenses, etc. Figure 1
summarizes the major applications of biomaterials [1]. The
materials from which these devices are constructed range
from the sophisticated and highly specialized to the simple
and low-technology designs. Implant materials and devices
are needed for a number of reasons, such as replacing tissue
that has become damaged or destroyed by disease or trauma
[2].
Today, the field of biomaterials has evolved such that more
than 50 different materials are used in more than 40 types of
complex prosthetic devices. One of the most important
developments in clinical medicine has been the replacement
of diseased joints with artificial implants. Since the early
cemented hip replacements of the 1960s there has been a
constant flow of new materials and designs for implantable


J. M. F. Ferreira, A. Balamurugan, A. H. S. Rebelo
Department of Ceramics and Glass Engineering, University of
Aveiro, CICECO, 3810-193 Aveiro (Portugal)
E-mail: jmf@cv.ua.pt
S. Rajeswari
Department of Analytical Chemistry, University of Madras,
Chennai 600 025, Tamilnadu (India)
G. Balossier
INSERM ERM 0203, Laboratoire de Microscopie Electronique
Analytique, Universite de Reims, 21, Rue Clement Ader, 51685
Reims (France)
www.wiley-vch.de/home/wuk 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/maco.
A. Balamurugan, S. Rajeswari, G. Balossier,
A. H. S. Rebelo and J. M. F. Ferreira*
tions. Hence, research projects are currently underway to overcome
the limitations of synthetic materials by developing formula-
tions with varying properties, such as asymptomatic, long-
term function in the human physiological environment, etc., to
meet the needs of biomedical surgeons. This review focuses on
the several biomaterials corrosion and its measures to prevent
corrosion.
devices and the number is steadily increasing as technolo-
gical progress and medical practice allow for increased
functionality and safety.
2 Historical perspectives
The history of biomaterials dates back to antiquity. Many
of the initial thrusts were attempted by man to correct
deformities, since, in the years before anaesthesia and
asepsis; surgical procedures were limited to the body surface.
Earlier surgeries were those performed by Hindu surgeons
for the restoration of missing parts. Susrutha, in 600 BC,
repaired an injured nose with a patch of living flesh from the
cheek region. This technique for nose reconstruction
migrated from East to West. Around 1430, the Brancas, a
family of Sicilian Layman, perfected the method now
referred to as the Italian method for nose construction by
using skin flap taken from the arm. In 19th century, Von
Graefe and Gillies in England, Davis, Ivy and Kazanjian in
the United States and Filator in Russia were stimulated by
World War I tragedies to pioneer newer methods of wound
closure and tissue transfer [3].
The earliest written record of an application of metal in
surgical procedure is from the year 1565. However, until
Listers aseptic surgical technique was developed in the
1860s, various metal devices such as wires and pins which
were constructed of iron, gold, silver, platinum, etc., and
tissue transplantations were not largely successful mainly
due to infection after implantation. The use of alloys in
surgical implants is a relatively modern development, dating
back about a century. Early steel formulations were found to
degrade rapidly in the physiological environment and also to
produce adverse effects. Lane in England (18931912)
designed a fracture plate using steel. During the 20th century
(in mid 1920s) type 316 stainless steel (SS) was developed
and was found to be stronger than previous alloys and having
higher resistance to corrosion in body fluids. In the 1930s,
cobaltchromium (CoCr) alloys were developed for the
aerospace industry and were found to have superior
characteristics to steel for many prosthetic applications.
Around the middle of the 20th century, pure titanium (Ti)
856 Balamurugan et al. Materials and Corrosion 2008, 59, No. 11

corrosion to a certain degree, depending on the metallurgical

condition, residual or service stresses, thermal history and
final surface treatment applied prior to implantation.

3 Reconstruction materials

Tissue replacements with synthetic materials are achieved

Fig. 1. Major applications of biomaterials
implants, which have excellent biocompatibility, were used
and over the next few decades, Ti alloys with superior
mechanical characteristics to the pure metal were developed
for orthopaedic surgery. In recent years, a new material
the smart nickeltitanium (NiTi) alloy often referred to as
Nitinol (the shape-memory alloy) and the high-strength
alloy MP35N have been attracting considerable interest for
the prosthetic implants. Nowadays, CoCr and Ti alloys are
the most widely used alloys for orthopaedic surgery, with
316 and 316L (low carbon) steel and nitinol being used in
specific situations and for specific applications. A brief
summary of historical developments of biomaterials is
described in Table 1.
Other novel metals and alloys are being investigated for
possible prosthetic applications but have not yet been fully
assessed. All metallic implantable alloys are susceptible to
by selecting the material, which has physical properties most
similar to those of natural tissue. Table 2 illustrates surgical
applications of a wide range of materials namely metals and
alloys, ceramics, polymers and composites [4].
Stainless steels, titanium alloys and cobaltchromium
alloys are used universally for most of the high load bearing
applications in skeletal system. Conducting metals like
platinumiridium alloys are used for electrical stimulation of
the heart and nervous tissues. Nitinol, an alloy of nickel and
titanium finds applications in orthodontics [5].
The stable and inert nature of alumina, zirconia and titania
ceramics has their potential usage in orthopaedic joint
replacements [6]. The chemical inertness and abrasive
resistance provide improvements over the hitherto widely
used metals. The degradable ceramics, which are almost
invariably based on calcium phosphates, find applications in
hard tissue regeneration.
The resemblance of physical nature of polymers with soft
tissues of humans plays a dominant role in the replacement of
skin, tendons, cartilage, vessel walls, lens, breast and
bladder. A number of synthetic polymers find applications as
biomaterials [7].
4 Requirements for a perfect biomaterial
Materials to be implanted into the human body are
subjected to exposure in body fluids, which are hostile and
extremely sensitive that restricts the applications of a perfect
biomaterial. Additionally, there is the crucial fact that human
body tissues are extremely sensitive to foreign materials and
are very easily stimulated into showing signs of poisoning
and rejection. Hence, a biomaterial must be biocompatible
the ability of a material to perform with an appropriate
host response in a specific application (i.e. it should not elicit

Table 1. Major historical developments of biomaterials [5]

S. No. Year Author Activity

1 600 BC Sushruta Samhita Nose reconstruction

Late 18th19th century Various metal devices to fix fractures: wires and
pins made of Fe, Ag and Pt
2 18601870 Lister Aseptic surgical techniques developed
3 18931912 Lane Steel screws and plates for fracture fixation
4 1912 Sherman Vanadium steel plate, first alloy developed exclusively for
medical use; less stress concentration and corrosion
5 1926 Hey-Groves Used carpenters screw for femoral neck fracture fixation
6 1926 Large 188 s Mo(24% Mo) SS for greater corrosion
resistance than 18-8 SS
7 1931 Smith-Petersen Designed first femoral neck fracture fixation nail made
originally from SS, later changed to vitallium
8 1936 Wiles First total hip replacement
9 1946 Judet and Judet First use of biomechanically designed hip prosthesis.
First use of plastics in joint replacements
10 1958 Charnely First use of acrylic bone cement in total hip replacements
11 1958 Furman, Robinson First successful direct stimulation of heart
12 1960 Starr, Edwards Heart valves
13 1980s Kolff et al. Artificial Heart

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Materials and Corrosion 2008, 59, No. 11 Corrosion aspects of metallic implants 857

Table 2. Materials used as implants

Materials Advantages Disadvantages Common applications

Metals
Stainless steels High impact strength, high Low biocompatibility, Orthopaedic load bearing
cobalt resistance to wear, ductile, corrosion in physiological and fixation devices,
chromium, absorption of high strain environment, mismatch for dental implants
titanium alloys energy mechanical properties with
soft connective tissue
Pt, PtIr alloys High conductivity Low mechanical strength Neuromuscular stimulation
Ceramics
Alumina Good biocompatibility, Undesirable surface properties, Hip and knee prostheses,
Zirconia inert, corrosion resistance, special techniques are needed dental implants, improving
high tensile strength for material fabrication biocompatibility
Calcium phosphate Biodegradable Degradation not controllable Temporary support, assists
ceramics regeneration of natural tissues
Polymers
Polyacrylates, Low density; Low mechanical strength; Cardiovascular, maxillofacial,
polyesters, easy to fabricate additives, oligomers may soft skeletal tissue such as
polyamides, cause tissue reactions tendon, ligament, space filling
polyurethanes, devices, dental implants, bone
polyether, cement, lens, intraocular and
polyolefines, middle ear prostheses
silicone rubber

an adverse response from the body, and vice versa). A perfect
biomaterial should not cause chronic inflammation, impair-
ment of cellular functions and should be non-toxic and non-
carcinogenic. Adequate physical and mechanical properties
are necessitated to meet the required demands of the body.
Figure 2 lists the requirements for a perfect biomaterial for
successful application in total joint replacement [8]. The
ideal material or material combination should exhibit the
following properties:
 A biocompatible chemical composition to avoid adverse
tissue reactions.
 Excellent resistance to degradation (e.g. corrosion
resistance for metals or resistance to biological degrada-
tion in polymers).
 Acceptable strength to sustain cyclic loading endured by
the joint.
 A low modulus to minimize bone resorption.
 High wear resistance to minimize wear debris generation.
Dependent on:
Type of material
Projected device life
Interactions with other device components
5 Nature of the physiological environment
The nature of physiological environment is extremely
hostile to all foreign materials and hence the effect of
environment on metallic implant and the effect of implant on
its host tissue are of primary concern (Fig. 3). The
concentrations of chloride ions in serum and interstitial
fluid are 113 and 117 mEq/L, respectively, which is about
one-third the concentration of brine and a seriously corrosive
environment for metallic materials [9]. The aqueous layer at
the implant site will naturally contain numerous hydrated
ionic species (Na, Ca2, etc.). The type and concentration
Requirements of Implants
Compatibility
Tissue reactions
Change in properties:
-Mechanical
-Physical
-Chemical
Degradation leads to:
-Local deleterious changes
Mechanical Properties

Elasticity
Yield stress
Mechanisms of Material Degradation: Ductility
Corrosion Toughness
Dissolution Time dependent deformation
Chemical modification Creep
Swelling Ultimate strength
Leaching Fatigue strength
Hardness
Wear
Manufacturing

Material Properties Adversely Affected: Fabrication methods

Strength Consistency and conformity to all requirements
Fracture toughness Quality of raw materials
Stiffness (elastic modulus) Superior techniques to obtain ex cellent surface finish or texture
Surface roughness Capability of material to get safe efficient sterilization
Wear resistance Cost of product
Chemical stability
Fig. 3. The effect of physiological environment on metallic
Fig. 2. Implant material requirements in orthopaedic applications implant

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858 Balamurugan et al.
of ions in solution is likely to change over a period of time as
the cells surrounding the implant react and adapt to the
presence of foreign material. Other electrolytes present in the
body fluid include Ca2, Mg2, PO3 2
4 , SO4 and organic
acid anions. Some complex compounds present in smaller
amounts are phospholipids, cholesterols, natural fats,
proteins, glucose and amino acids [10]. In addition, the
concentration of dissolved oxygen is one-fourth of that in
venous blood and 1/81/4 of that in intercellular spaces,
which accelerates the corrosion of metallic materials.
Changes in the pH of body fluids are small because the
fluids are buffered solutions and the pH usually remains
between 7.0 and 7.35 [11]. The change in the pH leads to the
inflammation around the implant [12], producing highly
reactive oxygen species [13]. These oxidizing species
(e.g. H2O2) will interact with the implant surface. The pH
of the hard tissue into which a material is implanted
decreases to approximately 5.2 and then recovers to 7.4
within 2 weeks [14]. The cells are also a kind of charging
body that may influence the corrosion of metallic materials.
Metallic materials themselves do not show any toxicity, but
some dissolved metal ions, corrosion products and wear
debris may show toxicity when they combine with
biomolecules and cells. Corrosion and electrochemical
properties of metallic materials in biological environments
was reviewed by Hanawa [15].
6 Interactions of implant material and living
tissue host response inflammation
Fixation of an implant in the human body is a dynamic
process that remodels the interface zone between the implant
and living tissue at all dimensional levels from the molecular
up to the cell and tissue morphology level and at all time
scales from the first year up to several years after
implantation [16]. This is represented in Fig. 4, in which
the logarithmic length and time scales indicate this complex
dynamic process. After implantation, a space filled with
biofluid exists next to the implant surface and as the time
progresses the proteins will be adsorbed (Fig. 5) at the oxide
Fig. 4. Dynamic behaviour of the interface between implant (left) and bony tissue
(right)
Materials and Corrosion 2008, 59, No. 11
Fig. 5. Schematic picture of cells close to material surface illus-
trating the cells with the dynamic hydration (water and ions) and
protein layers, which cover the material surface in the biological
environment
surface (nm thickness) on the implants surface that will give
rise to osteoinduction by proliferation of cells and their
differentiation towards bone cells, revascularization and
eventual gap closing. Ideally, a strong bond will be formed
between implant and tissue. However, sometimes connective
tissue is being formed at the interface resulting in a fibrous
tissue capsule that prevents osteointegration (see inset) and
will cause implant loosening [17].
There are various adverse reactions that may occur at the
implantation of medical device:
 Adsorption of proteins,
 allergic foreign body response and hypersensitivity,
 coagulation and haemolysis,
 cytotoxicity,
 mutagenicity and carcinogenesis.
Implant designs and biomaterials must be
easily accepted by the body. All implants
cause some sort of response in the surround-
ing no material can be considered to be
completely inert. Any surgical procedure
results in a disruption of blood supply and
damage to tissue. The difference between
successful tissue integration and a failure
may lie in how the biomaterial surface inter-
acts with different mechanisms of the normal
wound healing process. Complications of
medical devices are largely based on both
the effects of the implant on the host tissue
and the effects of the host on the implant.
Placing a biomaterial in the in vivo environ-
ment involves injection, insertion or surgical
implantation, all of which injure the tissues or
organs involved. This initiates a response by
the body and mechanisms are activated to
maintain homeostasis and to heal the wound.
The degree to which this condition is created
and resolved is a measure of the host reaction
to the biomaterial and may ultimately deter-
mine its biocompatibility [18].
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Materials and Corrosion 2008, 59, No. 11
Inflammation and repair are part of the normal wound
healing process. Inflammation is the bodys method of
removing foreign materials and dead cells by destruction,
dilution or isolation. Inflammation is generally defined as the
reaction of vascularized living tissue to local injury, and
serves to contain, neutralize, dilute or wall off the injurious
agent or process. In addition it sets into motion a series of
events that may heal and reconstitute the implant site through
replacement of the injured tissue by regeneration of native
parenchymal cells, formation of fibroblastic scar tissue or
combination of the two [19].
Implantation may lead to acute inflammation which is of
relatively short duration, lasting from minutes to days
depending on the extent of the injury. The main character-
istics are exudation of fluid and plasma proteins (edema) and
the recruitment of white blood cells (leukocytes), such as
polymorphonuclear granulocytes (PMS) (more commonly
called neutrophils), monocytes and platelets. If the response
persists, recruited monocytes differentiate into macrophages
that can fuse to form foreign body giant cells (FBG) and a
prolonged chronic inflammation takes place. In general a
chronic inflammation is due to the continued presence of
white cells in that area. Chemical and physical properties of
the biomaterial may lead to chronic inflammation. However,
motion at the implant site, extensive surgical injury, bacterial
infection or host factors such as poor blood supply or
nutrition can also contribute to this prolonged inflammatory
state [20].
7 Biomaterials employed in orthopaedics
Many synthetic biomaterials used for implants are
common materials familiar to the average materials engineer
or scientist. In general these materials can be divided into the
following categories: animal or human material, metals,
polymers, ceramics and composites. A short section of each
of these groups is presented below with emphasis on hard
tissue materials.
7.1 Animal or human bone material
The materials of choice for bone repair are usually fresh
autografts, due to their osteogenic capacity and biocompat-
ibility. However, drawbacks such as the need for a secondary
site surgery to harvest the autograft (adding to the degree of
morbidity) and its scarcity have directed the research towards
other bone-derived alternatives. These include allogenic and
xenogeneic bone grafts. However, a higher immunogenic
response and less revascularization of these bone grafts in
addition to the risk of viral transmission have led to a wide
use of man-made materials [21].
7.2 Metals
The high elastic modulus and yield point coupled with the
ductility of metals make them suitable for bearing high loads.
Metallic implants are therefore mostly used to replace hard
tissue. A number of authors have reviewed the use of metals
in implants. Metallic implants are used for two primary
purposes: (i) implant devices used as prostheses serve to
replace a portion of the body and include devices such as
total joint replacements and skull plates and (ii) as fixation
devices that are used to stabilize broken bones and other
tissues while normal healing. Three of the most commonly
used metals are: titanium, SS and cobaltchromium alloys.
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Corrosion aspects of metallic implants 859
During the initial days, SS and cobaltchrome alloys were
preferred for bone replacement applications. They were
primarily used for their good mechanical properties.
However, the high mechanical strength of such metallic
implants resulted in stress shielding and bone resorption due
to the elastic modulus mismatch with the surrounding bone.
This drawback combined with findings such as corrosion
leading to a reduced mechanical strength and toxic by-
products, directed the attention to titanium and its alloys.
Titanium and titanium alloys have the advantage of
possessing relatively lower modulus of elasticity and a
higher resistance against corrosion. The oxide layer of
titanium has also been proposed by some authors to have
significant influence on the integration of this metal with
bone tissue [2225].
7.3 Polymers
Polymers are long-chain high molecular weight materials
consisting of repeating monomer units. Besides the chemical
composition, other variables such as molecular weight
distribution and extent of cross-linking influence their
physiochemical properties. The physical properties of
polymers have close resemblance with soft tissue and are
hence useful in replacing skin, tendon, cartilage, vessel
walls, etc. The enormous variation in production possibilities
has contributed to a huge number of polymers available for
implantation purposes, e.g. ultra high molecular weight
polyethylene (UHMWPE) is used for one of the articulating
surface components in joint prosthesis, and polycaprolactone
has been used as resorbable sutures or resorbable screws and
plates for fracture fixation. Polymeric materials also possess
several advantages over metals. For example, the isotonic
saline solution that comprises the extracellular fluid has little
or no effect on polymeric components whereas it is
extremely hostile towards metals. Elastic modulus mismatch
between the polymers and bone is reduced, which decreases
stress shielding and bone resorption. In addition most
polymers can be made degradable which means that through
the degradation process they are gradually replaced by the
host tissue, thus eliminating the need for additional surgery.
This approach can however in some cases lead to the
deterioration of mechanical properties and in addition
adverse tissue reactions might occur due to released
degradation products, thus restricting the use of these
materials [2225].
7.4 Ceramics
Ceramics used for the repair and reconstruction of
diseased or damaged parts of the body are known as
bioceramics. Of the large number of ceramics known, only a
few are suitably biocompatible. These ceramics can be
grouped according to their relative reactivity in physiological
environment. They include a broad range of inorganic/non-
metallic compositions, which may be bioinert (alumina,
zirconia), resorbable [tricalcium phosphate (TCP)], bioactive
[hydroxyapatite (HAP), bioactive glasses and glass cera-
mics] or porous for tissue ingrowth (HAP coated metals,
alumina). Ceramics are stiff, hard and chemically stable and
are often used in situations where wear resistance is vital.
Applications include replacements for hips, knees, teeth,
tendons, repair for periodontal disease, maxiofacial recon-
struction, etc. Implants of bioceramic origin have in the
last couple of years played an increasingly important role.
These materials provide an interface of such biological
860 Balamurugan et al.
compatibility with bone forming cells that these lay down
bone in direct apposition to the material via some sort of
chemo-physical bonding [2227].
7.5 Composites
Composite materials are a mixture of two of more phases
bonded together so that stress transfer occurs across the
phase boundary. Consequently, because stress is not
transferred to voids, porous materials are not usually
considered composites even though they contain two phases,
solid and void. Typically, composite materials are designed
to provide a combination of properties that cannot be
achieved with a single-phase material. It is clear when
comparing human tissue with the various metals, polymers
and ceramics that there is a considerable mismatch among
their individual properties. Hence, much attention has been
paid to the development of composites, thus trying to
combine the good properties of different types of materials
while avoiding some of their drawbacks. An example of this
is the coating of a bioinert material such as alumina with a
bioactive material such as HAP or bioglass to promote direct
bone attachment in, e.g. hip replacements. From an
engineering point of view, bone is considered a composite
material since it is a mineralized form of connective tissue
composed of collagen fibres dispersed in a matrix of bone
mineral with other constituents such as mucopolysacchar-
ides, blood vessels and bone cells dispersed throughout
[13,24,25].
7.6 Alloys employed in prosthetic applications
For an implant material to be suitable for prostheses,
applications must have the appropriate functional properties
mainly mechanical for utilization, and it must be
biocompatible. Metal ions will be released from alloys into
the surrounding tissue and may be concentrated locally or
distributed systemically. It is of great importance that the
material released does not represent a danger to the patient.
This depends not only on the amount, but also on the type of
ionic species released. The host response to an implant can
be highly complex and is often linked to the material
response. It is also dependent on the anatomical position of
the implant. For a material to be biocompatible, it should not
elicit any adverse host reactions to its presence. The
applications of metallic implants in the modern era are
usually classified into three types: SS, cobaltchromium
alloy and titanium alloys [2830].
7.6.1 Stainless steels
Stainless steel is surprisingly biocompatible and has been
used for many decades as a permanent surgical implant
material. The type of SS that is normally used for implants is
316L. It achieves its biocompatibility by being highly
corrosion resistant due to the formation of a thin protective
chromium oxide layer on its surface. The environment that
SS must deal within the body is, however, rather complex
and, if corrosion occurs, release of potentially harmful
material could ensue. Due to the fact that stronger and more
corrosion-resistant materials are available and also that a
growing number of people are displaying Ni sensitivity
(apparently due to the increasing practice of body piercing),
other alloys are now usually preferred for permanent
prosthetic devices. SS are more suitable for non-permanent
implants and are still employed for permanent implantation
in certain circumstances.
Materials and Corrosion 2008, 59, No. 11
7.6.2 Cobaltchromium alloys
CoCr alloys, developed several decades ago for the
aerospace industry, also achieve their inertia through the
formation of a chromium oxide surface layer. They have
excellent mechanical properties and are widely used in
orthopaedic implants. The alloys are generally CoCrMo or
CoNiCrMo, and may also include other elements such as
tungsten or iron (Fe). Apart from the fact that Ni can be
avoided in the formulation, CoCr alloys have advantages
over SS in terms of better corrosion resistance and
somewhat better mechanical properties for certain applica-
tions. Both wrought and cast CoCr alloys are used in
prosthetic devices, each version having distinct properties.
They are often used as components in modular prosthetic
devices such as hip or knee joints, being the most suitable
for bearing surfaces (often against UHMWPE). They may
also be used for joint stems and in various other prosthetic
devices. Recently, there has been renewed interest in metal-
on-metal bearing surface for hip joints (in both total hip
replacements and surface replacements) since it appears
that strict manufacturing tolerances and the use of
appropriate CoCr alloys can lead to very low wear rates
similar to ceramic-on-ceramic surfaces. This may offer the
advantage of avoiding the production of polyethylene wear
particles associated with polyethylene acetabular cup
systems, these being implicated with tissue reactions and
eventual loosening of the hip stems.
7.6.3 Titanium and titanium alloys
In the second half of the 20th century, titanium began to
find widespread application in many industrial sectors. Its
high inertia, due to the formation of a thin surface titanium
oxide layer, light weight and excellent biocompatibility,
seemed to make it the ideal material for surgical implants.
Problems with poor mechanical strength were overcome
through the development of two-phase alloys, the most
important of which is Ti-6Al-4V (titanium, aluminium,
vanadium), though the absolute mechanical strength of this
alloy is still not as good as that of SS or CoCr alloys. Its
strength-to-weight ratio, however, is better than any other
surgical implant material. Both pure Ti and Ti-6Al-4V are
widely used in prosthetic devices, the choice depending on
the functional requirements of material. An additional
advantage of these materials is their compatibility with
imaging techniques such as computed tomography (CT)
scanning and magnetic resonance imaging (MRI). Due to
their poor tribological properties, Ti and Ti alloys are not
normally used for the bearing surfaces of articulating joints.
The good strength-to-weight ratio, fatigue resistance and low
modulus of elasticity of Ti-6Al-4V make it one of the best
alloys for implanting into bone and it is often used for the
bone stems of modular artificial joints, as well as for other
prosthetic devices. Recently, Mareci et al. [31] has expressed
some concern over the use of Ti-6Al-4V since it appears that
small amounts of both Al and V can be dissolved out of the
alloy, and both of these elements may have negative effects
on the human body. For this reason, related alloys where V is
substituted by niobium (Nb) or tantalum (Ta), and Al is
substituted by zirconium (Zr), are under investigation.
Studies on substitution with other alloying elements are also
underway. It should be noted that the amounts of Al and V
released from Ti-6Al-4V may be so small that the alloy is
perfectly acceptable as an implant material. It is generally
regarded as one of the most biocompatible of all the available
prosthetic alloys.
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Materials and Corrosion 2008, 59, No. 11
Other Ti alloys that are under consideration are the so-
called b or near-b phase alloys, having advantages in terms
of better formability, toughness and lower modulus. The
latter property is important for bone implants and is an
advantage that Ti alloys have over SS or CoCr alloys, since a
low modulus can reduce stress shielding of the surrounding
bone. Stress shielding is a well-known phenomenon caused
by the large difference in elastic modulus between bone and
implant materials, which can lead to bone loss and eventual
implant failure. b or near-b phase alloys include binary
TiMo alloys and various, more complex systems with Nb, Zr,
Fe, Ta, palladium and/or tin as alloying components.
7.6.4 Nickeltitanium alloys
In recent years, a novel material has stimulated consider-
able interest for its potential biomedical applications. NiTi or
nitinol, is a so-called smart material, with shape memory
and superelastic properties. It also has an elastic modulus
closer to that of bone than other metal implant materials.
These may be used to great advantage in orthodontics, in the
treatment of bone fractures and as bone suture anchors for
attaching soft tissues such as tendons and ligaments to bone.
A further important application of NiTi is for stents for
reinforcement of blood vessels. Due to their shape memory
property, they can be introduced into a patient through a thin
catheter before expanding into their functional form. Such
minimally invasive procedures are very much in line with the
development of modern surgical techniques. NiTi displays
excellent biocompatibility due to the formation of a thin
titanium oxide surface. It does, however, contain Ni, and its
use as implant material with high Ni content is questionable,
though most studies have shown that NiTi is highly stable in
the body with minimal Ni release. However, the long-term
stability and biocompatibility of this material in the various
environments encountered in the human body needs further
investigation. Recently, the related ternary system TiNiCu
shape-memory alloy (TiNi with a little amount of Cu in its
composition) has attracted interest for biomedical and other
applications due to better fatigue and modified shape-
memory properties. While some studies appear to indicate
that the corrosion resistance and biocompatibility of this
system are inferior to the binary material, further work needs
to be undertaken to fully assess this system.
The present review focuses biological corrosion phenom-
ena in alloys used for orthopaedic implant applications.
8 Corrosion of metallic implant materials
From an engineering stand point, in situ degradation of
metal-alloy implants is undesirable; the degradation process
may decrease the structural integrity of the implant, and the
release of degradation products may elicit an adverse
biological reaction in the host. Degradation may result from
electrochemical dissolution phenomena, wear or a synergis-
tic combination of the two. Electrochemical processes may
include generalized corrosion, uniformly affecting the entire
surface of the implant, and localized corrosion, affecting
either regions of the device that are shielded from the tissue
fluids (crevice corrosion) or seemingly random sites on the
surface (pitting corrosion). Electrochemical and mechanical
processes [e.g. stress corrosion cracking (SCC), corrosion
fatigue and fretting corrosion] may interact, causing
premature structural failure and accelerated release of metal
particles and ions.
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Corrosion aspects of metallic implants 861
The clinical importance of degradation of metal implants
is evidenced by particulate corrosion and wear products in
tissue surrounding the implant, which may ultimately result
in a cascade of events leading to periprosthetic bone loss.
Furthermore, many authors have reported increased con-
centrations of local and systemic trace metal in association
with metal implants [3235]. There is also a low but finite
prevalence of corrosion-related fracture of the implant. A
common occurrence with early implants was a chronic
inflammatory reaction to grossly corroded ferrous alloys
[36]. Mild corrosion in many cases can also produce
symptoms that necessitate the removal of the implant. The
symptoms range from a local tenderness at the site of the
corroded area to acute pain, reddening and swelling over the
whole general area around the device [37]. These symptoms
are an indication that the tissue is reacting to the implant. The
corrosion of metallic implants can affect the surrounding
tissues in three ways [38]: electrical currents may affect the
behaviour of cells, the corrosion process may alter the
chemical environment (pH, pO2) and the metallic ions may
affect cellular metabolism. Of the three, the last is usually the
most severe. Changes in the surrounding bone and fibrosis
are often the result of implant corrosion products.
The process of corrosion can be described as metallurgy in
reverse. When most pure metals are placed in solution they
tend to revert to soluble ionic species, oxides or hydroxides.
X-ray analysis of the corrosion products of a 29-year-old
low-alloy-steel bone plate indicates that FeCO3 and b-
FeOOH are the principal corrosion products [39].
8.1 General concept related to implant corrosion
Corrosion, the gradual degradation of materials by
electrochemical or chemical attack, is a concern particularly
when a metallic implant is placed in the hostile electrolytic
environment provided by the human body [40]. Even though
the freely corroding implant materials used in the past have
been replaced with modern corrosion resistant superalloys,
deleterious corrosion processes have been observed in
certain clinical settings.
Corrosion of biomaterials is a complex multifactorial
phenomenon that depends on geometric, metallurgical,
mechanical and solution-chemistry parameters, and a firm
understanding of these factors and their interactions is
required in order to comprehend how and why implant
materials corrode. Two essential features determine corro-
sion of metal at the implant site. The first characteristic
involves thermodynamic driving forces, which cause
corrosion (oxidation and reduction) reactions, and the
second involves kinetic barriers, which limit the rate of
these reactions. The thermodynamic driving forces that
cause corrosion correspond to the energy required or released
during a reaction. The kinetic barriers to corrosion are related
to factors that impede or prevent corrosion reactions from
taking place. The basic underlying reaction that occurs
during corrosion is the increase in the valence state that is, the
loss of electrons of the metal atom to form an ion, as
expressed by the following equation:
M , Mn ne (1)
This oxidation event may result in free ions in solution,
which then can migrate away from the metal surface or can
lead to the formation of metal oxides, metal chlorides,
organometallic compounds or other chemical species. These
latter forms may be soluble or may precipitate out to form
solid phases. The solid oxidation products may be subdivided
862 Balamurugan et al.
into those that form adherent compact oxide films and those
that form non-adherent oxide, chloride, phosphate or other
particles that can migrate away from the metal surface. In all
of these possible reactions there is a thermodynamic driving
force for the oxidation of metal atoms to their ionic form.
8.2 Thermodynamic force
In general, there are two sources of energy to be
considered in corrosion processes. The first is a chemical
driving force that determines whether corrosion will take
place under certain conditions. If the free energy for
oxidation is less than zero, then oxidation will occur
spontaneously, as in the metals of the alloys used for
orthopaedic implants. The second source of energy occurs
when positive and negative charges (metal ions and
electrons, respectively) are separated from one another
during corrosion. The ions are released into the solution or go
on to form an oxide or another compound, and the electrons
are left behind in the metal or undergo other electrochemical
reactions, such as reduction of oxygen or hydrolysis of water.
This separation between the charges contributes to what is
known as the electrical double layer and creates an electrical
potential across the metalsolution interface.
8.3 Kinetic barriers
The second factor that governs the corrosion process of
metal biomaterials is kinetic barriers that prevent corrosion
not by energetic mechanisms but by physical limitation of
the rate at which oxidation or reduction processes can take
place. The well-known process of passivation, or the
formation of a metal oxide passive film on a metal surface,
is an example of a kinetic limitation to corrosion. In general,
kinetic barriers to corrosion prevent the migration of metal
ions from the metal to the solution, the migration of anions
from the solution to the metal and the migration of electrons
across the metalsolution interface. Passive oxide films are
the best-known forms of kinetic barriers to corrosion, but
there are others, including polymeric coatings. Most alloys
used for orthopaedic appliances rely on the formation of a
passive film to prevent oxidation from taking place. These
films consist of metal oxides, which form spontaneously on
the surface of the metal in such a way that they prevent
transport of metal ions and electrons across the film. In order
to limit oxidation, passive films must have certain
characteristics. They must be non-porous and must fully
cover the metal surface; they must have an atomic structure
that limits the migration of ions and electrons across the
metal oxidesolution interface; and they must be able to
remain on the surface of these alloys even with mechanical
stressing or abrasion, which can be expected in association
with orthopaedic devices. In general terms, the more atomic
defects in oxide, the less able the oxide film is to prevent
migration of ionic species and the lower the kinetic barrier is
to corrosion [41].
8.4 Interactions with water
A surgically implanted surface initially comes in contact
with an environment that is dominated by water molecules.
The adsorption of water and hydrated ions is likely to be the
first event that occurs. The initial hydration layer, or
Helmholtz layer, extends a few angstroms to nanometres
from the surface. Although the detailed structure will be
dynamic, the local structure of the monolayer or bilayer
Materials and Corrosion 2008, 59, No. 11
closest to the surface is likely to be very different to that of
liquid water. A strong interaction with the surface may cause
dissociation of the water molecules, resulting in bound
hydroxyl groups. Alternatively, water may chemisorb
molecularly to the surface, remaining undissociated but
relatively strongly bound. On highly non-wetting or
hydrophobic surfaces, the interactions with the surface
may be very weak (equivalent or physisorption). At the
molecular level, the interactions may therefore be covalent,
ionic or weak van der Waals forces. The importance of the
interaction with water has been addressed in several
discussions of biological interactions [42].
Reactions of metals with aqueous environments are
electrochemical in nature, involving the movement of metal
ions and electrons. The oxidation of the metal (acting as an
anode) requires an equivalent cathodic reaction. For
implanted metals, the primary cathodic reaction is the
reduction of dissolved oxygen to hydroxyl ions:
O2 2H2 O 4e
metal ! 4OH

(2)
For all metals, there is a potential difference between the
metal and a solution that contains only metallic ions [43,44].
8.5 Various types of implant corrosion
8.5.1 Uniform attack
Uniform attack refers to the inevitable corrosion to which
all metals immersed in electrolytic solutions are encoun-
tered.
Titanium-base alloys have lower overall corrosion rates
compared to SS and cobaltchromium alloys. However,
serum proteins can complex with chromium and nickel,
increasing uniform attack by 2- to 10-fold [45].
8.5.2 Galvanic corrosion
Dissolution of metals driven by macroscopic differences
in electrochemical potentials, usually as a result of dissimilar
metals in proximity is termed as galvanic corrosion.
Inappropriate use of metals, e.g. an SS cerclage wire in
contact with a cobalt or titanium-alloy femoral stem, a
cobalt-alloy femoral head in contact with a titanium-alloy
femoral stem and a titanium-alloy screw in contact with an
SS plate [46].
Using radioactive tracer techniques, Bowden et al. [47]
have shown that significant amounts of metal were
transferred from screwdrivers to screw heads and from drill
bits to plates.
Work hardening and surface-finishing processes that
produce plastic deformation generally make the deformed
metal basic with respect to undeformed material of the same
composition. Compositional differences, either between
parts because of manufacture from different master ingots
within the same specification limits or because of deliberate
mixing of metals, are the most likely causes of such effects.
8.5.3 Fretting corrosion
Whenever two metal surfaces are in contact, micromotion
of the surfaces disrupts the passivation film and permits the
area of contact to corrode rapidly. This type of damage is
called fretting corrosion [48]. The corrosion occurring at
contact areas between materials under load subjected to
vibration and slip tears out small particles of metal from the
surfaces.
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Materials and Corrosion 2008, 59, No. 11
Fretting may occur in metal-on-metal joint prostheses,
producing particles of metal from 0.1 to 1 mm in diameter.
Repeated oscillatory motion is required, such as when
multicomponent implanted devices are placed in weight
bearing limbs or when the fixation achieved by a screw and
plate construct is unstable. Cohen [49] subjected plate and
screw assemblies to cyclic stresses in saline solutions and
found the greatest corrosions in the screw assemblies where
the heads rubbed on the plate and where the nuts and washers
were in contact. This is due to disruption of the passivation
layer. Similar assemblies, which were not subjected to the
cyclical stresses, did not show this marked effect. Weinstein
et al. [50] examined multiple component implants, such as
plate with screws, and found that 2728 SS implants
demonstrated fretting corrosion.
8.5.4 Crevice corrosion
Crevice corrosion is undoubtedly the most prominent form
of corrosion. This is a form of local corrosion due to
differences in oxygen tension or concentration of electrolytes
or changes in pH in a confined space, such as in the crevices
between a screw and a plate [51]. Crevice corrosion is
commonly associated with SS multicomponent devices; it is
often accompanied by severe tissue reaction to the corrosion
products, making removal of the device necessary. The
narrower and deeper the crack, more likely is the crevice
corrosion to start [45]. The principal cause of crevice
corrosion is differential aeration of the stagnant solution
[48]. The oxygen-deficient regions within the crevice
become anodic in relation to the material as a whole, and
corrosion proceeds more rapidly. The low oxygen tension in
wounds probably accelerates this effect in vivo.
Recent retrieval studies have shown that 1635% of
modular total hip implants demonstrated moderate to
severe corrosion in the conical head neck taper connections
[52]. Studies of retrieved SS multipart internal fixation
devices show visible corrosion at the junction between screw
head and the plate in 5075% of all devices [45]. Other
typical crevices are scratches on the surface of an implant,
the interface between bone and an implant, the cementmetal
interface and any other sharp interface likely to be depleted
of oxygen relative to another oxygenated area [53].
8.5.5 Pitting corrosion
Another common form of corrosion that occurs with
metallic implants is pitting. It is a form of localized,
symmetric corrosion in which pits form on the metal surface.
Metals are particularly susceptible to pitting in environments
containing chloride ions, as in tissues, and it is also enhanced
when the oxygen content of the solution is low. Pitting is
probably associated also with the stability of the passivation
film and with crevice corrosion. Once the passivation film
is broken, the crevice, with its low oxygen content and the
presence of chloride ions greatly hinders the self-healing of
the passivation film. A high current density at the pit resulted
in the creation of pinholes into the metal surface while most
of the surface remains unaffected [23].
Stainless steel is particularly predisposed to pitting
corrosion due to inclusions of a dissimilar material trapped
in the metal during a manufacturing process. These
impurities may initiate pitting corrosion in relation to a
grain boundary and thus can lead to component failure [53].
It can also be initiated by scratches or handling damage.
Pitting was frequently observed in older SS fracture fixation
hardware, e.g. on the underside of screw heads. It also occurs
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Corrosion aspects of metallic implants 863
Fig. 6. Scanning electron micrograph view of the (a) crack origin
and (b) pit on the failed implant surface
infrequently on the neck or the underside of the flange of
proximal femoral endoprostheses [45]. Sivakumar et al. [55]
have investigated failures of SS orthopaedic implant devices.
Their diagnostic studies described that the failure of the
implant is typically due to pit-induced fatigue corrosion.
They reported that the pitting attack on the prosthesis has
been initiated owing to the low molybdenum content and
excess of sulphide inclusion. Figure 6 shows that the edges
were severely pitted and most cracks were associated with
pits. A typical crack origin from the pit on the implant
surface was exhibited and severe damage was also observed
at the proximal end of the prosthesis.
8.5.6 Intergranular corrosion
Another form of corrosion sometimes encountered with
implanted metallic devices is intergranular corrosion [56].
This is a form of galvanic corrosion due to impurities and
inclusions in an alloy. Intergranular corrosion is associated
with the sensitization of austenitic SS. SS, if improperly
heat-treated after fabrication, may corrode by this mechan-
ism owing to a relative depletion of chromium from the
regions near the grain boundaries. This phenomenon is called
sensitization. Welding of metals, which produce local
melting and solidification, can also lead to a variant of this
process, called knife-edge attack [45].
8.5.7 Leaching
This form of corrosion results from chemical differences
not within grain boundaries but within the grains themselves
[45]. Leaching occurs in alloy, which contains more than one
phase (multiphasic), e.g. 35% Ni containing cobalt-base
alloy, F582.
8.5.8 Stress corrosion cracking
SCC is another corrosion-related cause of failure for some
implants. It is due to residual tensile stresses resulting from
deformation (bending) of an implant. It is a phenomenon in
which a metal in a certain environment, especially those rich
in chlorides, is subjected to stress and fails at a much lower
level than usual as a result of corrosion [57].
SCC is not frequent, but it has been reported [58]. Lisagor
[59] described a clinical case in which an intramedullary nail
had undergone sufficient loading to cause permanent
deformation of the nail. This resulted in high residual
surface tensile stresses, making the nail sensitive to stress
corrosion. A straight fracture plate, when flexed, will
experience a tensile stress on its convex surface and a
compressive stress on its concave surface. This produces a
difference in electrochemical potential, which renders, the
convex surface anodic with respect to the rest of the plate.
Corrosion, as an acceleration of uniform attack, or perhaps
secondary tensile rupture of the passive film, will then attack
the convex surface preferentially [45].
864 Balamurugan et al.
Fig. 7. Scanning electron micrograph view of (a) the crack
associated with pits and (b) the crack morphology was transgranular
and branched
The same process will occur at stress risers in loaded
devices, such as screw holes in fracture fixation plates or
kinks in cerclage wire. In this case, the regions of higher
stress, in the immediate vicinity of the stress risers, will
corrode at the expense of the surrounding less stressed
material [45].
Sivakumar and Rajeswari [60] have reported that failure
of SS orthopaedic implant devices was a result of SCC due to
propagation of cracks radiating from a pit. The crack was
aggravated by the high inclusion content and large grain size
of the implant (Fig. 7).
8.6 Survey of failed implant devices
Orthopaedic implants have improved the quality of life for
millions of people over the last quarter of a century. Over
450 000 total knee and total hip replacement operations were
performed in the United States in 1994, with an anticipated
increase of 10% per year [61]. The typical useful life for a
replaced joint is between 10 and 15 years [62]. The problems
are due to loosening of the implant because of its bioinertness
and/or stress concentration related to higher stiffness of the
implant than the natural bone. It is important to understand
that the corrosion of orthopaedic biomaterials is not just an
exercise in physics and chemistry. There are real problems
related to the corrosion of implants that are in current clinical
use.
8.6.1 Corrosion at modular interfaces of joint-replacement
components
A current problem related to orthopaedic alloys is
corrosion at the taper connections of modular joint
replacement components. With the large and growing
number of total joint designs that include metal-on-metal
conical taper connections, the effects of crevices, stress and
motion take on increasing importance. Recent retrieval
studies have shown that a severe corrosive attack can occur in
the crevices formed by these tapers in vivo [6365]. This
attack was observed in components consisting of a Ti-6Al-
4V-alloy femoral stem and a cobalt-alloy femoral head as
well as in those consisting of a cobalt-alloy stem and a
cobalt-alloy head. It has been postulated that this corrosion
process is the result of a combination of stress and motion at
the taper connection and the crevice geometry of the taper
[66]. The stresses resulting from the use of prosthesis cause
fracture and abrasion of the oxide film and thus covering
these passive metal surfaces. This in turn causes changes in
the metal surface potential, making it more negative, and in
the chemistry of the crevice solution as the oxides
continuously fracture and repassivate. Such changes may
result in deaeration (loss of oxygen) of the crevice solution
and in a decrease in the pH in the crevice, as is expected in
Materials and Corrosion 2008, 59, No. 11
crevice corrosive attack [52,67]. The ultimate result of this
process is a loss of the oxide film and its kinetic barrier effect
and an increase in the rate of corrosive attack in the taper
region. A severe and extensive corrosive attack has been seen
primarily in cobalt-alloy systems with modular taper
connections. However, a corrosive attack in titanium-alloy
stems also has been reported [68]. The corrosion processes in
cobalt alloy have consisted of intergranular corrosion (form
of galvanic corrosion due to impurities and inclusions in an
alloy [44]), etching, selective dissolution of cobalt and
formation of chromium-rich particles including oxides,
oxychlorides and phosphates. The corrosion products
generated at the taper connections have migrated into the
periprosthetic tissue and the bearing surface of the acetabular
component [69]. There are three instances in which a
retrieved cobalt-alloy stem had such extensive intergranular
corrosion that fatigue failure had ensued at its neck [70,71].
A key factor that may contribute to relative motion (fretting)
at modular connections and ultimately to abrasive loss of the
passivating oxide layer is angular mismatch between the
taper on the male aspect of the connection and the bore on the
female aspect. Such a mismatch may result if the tolerances
are relatively large, leading to poor mechanical stability of
the connection. In this situation, the loads produced during
the normal gait cycle may dislodge the interference fit of the
modular connection, leading to disruption of the metal
surfaces and initiation of the cascade just described. These
observations point to the effect of combined stresses and
motion and to the electrochemical processes that occur at
metal oxidesolution interfaces. The mechanical integrity of
the oxide films that form on these alloys is essential for the
long-term stability and survival of the implant.
8.6.2 Corrosion at internal fixation devices
The development of corrosion resistant, biocompatible
metal alloys was one of several essential factors in the
evolution of internal fixation as a treatment for closed
fractures. The history of this process, until the precursors of
modern-day alloys were introduced, was described in detail
by Venable and Stuck [72] and, more recently, by Peltier
[73]. Two case reports in which lane plates were removed
after more than 50 years provide additional indication of the
corrosion of these devices and the deposition of large
amounts of corrosion products in the surrounding tissue
[74,75]. Hundreds of internal fixation devices and early joint-
replacement prostheses were examined in retrieval studies in
the 1960s and 1970s. Many of the SS and cobaltchromium
alloy devices that were used during this period were prone to
accelerated corrosion because of improper selection of
materials, faulty fabrication techniques and use of mixed
metals. These deficiencies have largely been eliminated in
modern implants through sound metallurgical practice and
fabrication processes. Although modern, single-part devices
used as permanent implants rarely show visible signs of
corrosion, Cook et al. [76] found some degree of interface
crevice corrosion in 89% of the plates and 88% of the screws
of 250 multiple-part SS internal fixation devices removed
between 1977 and 1985.
9 Corrosion in dentistry
Alloys that are used in dentistry are permanently exposed
to changeable conditions of the oral environment, which is
practically ideal for corrosion and chemical disintegration of
often used materials. Implant materials must be wear
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Materials and Corrosion 2008, 59, No. 11
resistant, chemically inert in many basic and acid food
components and also in the oral fluids. If the materials used
in dental practice are not resistant to dissolution in the oral
cavity, the developed products are harmful for the tissue
(ions, etc.) and can cause pathological changes. The
influence of such metal prosthesis reflects on the remaining
teeth, on the mucus of the oral cavity and even on distant
organs. Other teeth can be damaged when prosthesis creates
conditions beneficial to caries and parodontosis. For
prosthetic practice, alloys of silver, gold, chromium, cobalt,
nickel, molybdenum, iron and carbon are mostly used in
various combinations. Dental alloys should have an optimal
ratio of hardness and ductility, and consequentially a high
hardness value is not always desirable. For example, alloy of
iron and carbon, i.e. steel, is inappropriate for fixed
prostheses because its high value of hardness leads to
abrasion of the natural teeth in the opposite jaw. CoCr alloys,
because of their high strength, hardness, corrosion resistance
and biocompatibility, have wide use for various implants in
dentistry and medicine. However, their drawbacks are low
ductility and possible cancerogenic influence. Namely, there
is a possibility that the corrosion products of CoCr alloys can
cause health problems inside the body. It is known that cobalt
inhibits the absorption of iron in the blood and causes
anaemia, while chromium species lead to disturbances in the
central nervous system. As all metals corrode more or less in
the oral cavity environment, it follows that their corrosion is
almost impossible to prevent. The solution to this problem is
the reduction of corrosion by applying materials of better
quality, such as titanium which does not corrode noticeably
and does not create harmful effects in the body. It is well
known that titanium has excellent biocompatibility, elasticity
and corrosion resistance, and is therefore recommended for
dental and orthopaedic implants. A high-strength biomedical
alloy Ti-6Al-4V is mostly used. However, it was found that
vanadium, as an alloying element, is very cytotoxic. Namely,
corrosion reaction is unavoidable when the metallic material
is exposed to body fluids for longer time. As Ti-6Al-4V
contains vanadium, which irritates the mucous membrane of
respiratory organs and is also harmful for the circulatory
system, a new alloy of titanium with niobium has been
developed. Assis and Costa [77] found that Ti-6Al-7Nb alloy
is considerably less cytotoxic, more ductile and corrosion
resistant than Ti-6Al-4V alloy. Corrosion resistance of
dental materials could be evaluated according to distinct
criteria [78]. Recently Popa et al. [79] reported the relation
between electrochemical tests and in vitro evaluation of
titanium-alloy biocompatibility. Thus, a great deal of
research has been performed on the orthodontic materials
and has provided warning on the adverse effects of corrosion.
10 Suggested measures to prevent corrosion
(3) Passivation: The metals or alloys owe their good
10.1 Manufacturing process
10.1.1 Surface treatment
(1) Shot-peening or nitriding: It has been recently shown
that nitriding can reduce the magnitude of fretting
corrosion of Ti-6AI-4V devices [80].
(2) Ion implantation: Implantation of ions helps to harden
the surface and improve the resistance to wear-
accelerated corrosion phenomenon. Ion implantation,
a process that is widely used to modify the electronic
properties of semiconductor devices had become well
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Corrosion aspects of metallic implants 865
established commercially by the early to mid 1970s.
After its successful applications in the semiconductor
industry, ion implantation process has been extended for
the treatment of biomaterials to improve their corrosion
and wear resistance. The concept of using ion
implantation as a surface modification technique in
improving the wear accelerated corrosion of orthopaedic
implant materials was first introduced by Buchanan et al.
[81]. Ion implantation involves the introduction of a
small, economical amount of the atoms of any element to
the surface of the material by means of high-velocity
ions, without modifying the surface finish or the bulk
properties of the underlying material and independent of
thermodynamic constraints. In orthopaedic applications,
titanium and its alloys showed poor wear properties that
impede the use of the alloy. Ion implantation process has
been shown to be extremely effective in enhancing the
wear performance of titanium surfaces. Williams and
Buchanan [82] reported a very significant reduction in
the corrosive wear of titaniumbased alloys as a result of
nitrogen ion implantation. Spire Corporation has
implanted many different ion species (carbon, nitrogen,
oxygen, boron, argon, etc.) on Ti-6Al-4V knee, hip joints
and showed best resistance to corrosion and wear as a
function of nitrogen ion implantation in human body
environment [83]. Sundararajan et al. [84,85] have
reported that nitrogen ion implantation on titanium and
its alloys and also titanium modified 316L SS (at
different doses ranging form 1  1015 to 2.5  1017 ions/
cm2) exhibited high corrosion resistance to wear.
Nitrogen ion implantation on CoCr-based alloys had
proven to be extremely effective in enhancing the
corrosion resistance. Sioshansi [86] reported that
implantation of light ion species such as boron, carbon
and particularly nitrogen on 316L SS has been very
effective in enhancing the high fatigue of these alloys.
Significant results were obtained for nitrogen implanted
316L SS and CoCr alloys. Bordji et al. [87] have
conducted the test to improve the wear and corrosion
resistance as well as the hardness of 316L SS implant.
Three surface treatments, such as (1) glow discharge
nitrogen implantation, (2) carbon-doped SS coating
sputtering and (3) low temperature plasma nitriding,
were performed on 316L SS. Surface characterization
according to the different treatments showed that
corrosion and wear resistance were strongly improved,
especially by ion implantation or carbon doped SS
coating sputtering. The effect of such treatments on the
biocompatibility of 316L SS was studied with human
osteoblast and fibroblast cultures. Such surface treat-
ments may have relevance for increasing the lifetime of
316L SS biomedical devices.
corrosion resistant properties to a thin and corrosion
resistant layer of reaction products, which is formed on
the exposed surface and drastically lowers the dissolu-
tion rate of metal ions. This phenomenon is called
passivation. The primary aim of passivation is to
enhance the protective passive film by changing its
composition, structure and thickness, and or by reducing
weak points such as non-metallic inclusions. Several
authors have studied the effect of alkali [88,89] and acid
treatment on metals. Miyazaki et al. [90] have
investigated the effect of thermal treatments on
mechanical properties and apatite-forming ability of
the surface of the NaOH treated tantalum metal. SS
866 Balamurugan et al.
forms a chromium oxide, a process that can be enhanced
by chemical treatment with hot, concentrated nitric acid
(passivation), boiling in distilled water or electro-
chemically (anodization). Noh et al. [91] have reported
that both the enrichment of chromium oxide on the
surface and removal of MnS from the surface of 316L SS
take place during nitric acid passivation. The examina-
tion of H2SO4 passivation of SS by Peled and Itzhak [92]
also ensures a passive film, which resists pit initiation.
Kannan et al. [93,94] have studied the electrochemical
behaviour of HAP coatings on both nitric acid and
sulphuric acid treated SS, respectively. The results have
indicated that the HAP coatings on metal surfaces
treated with acid delay the onset of pitting and thus
promote the tendency to resist the metallic corrosion.
Thus, the literature survey regarding the surface
treatment of metals ensures the importance of surface
modification.
(4) Electropolishing and thermal methods: Various cost-
effective and simple treatments like electropolishing and
thermal methods have had a profound effect on the
corrosion properties of metals. Waisielewski and
Lindblad [95] suggested that the tensile strength of cast
CoCrMoC alloy was found to be improved by specific
treatment in oxygen atmosphere and hot isostatic
pressing. This process may heal the microvoids that
arise in castings during solidification. 316L SS and Ti-
6Al-4V samples heated to the optimal temperature at
280 8C for 20 min and 3 h, respectively resulted in the
formation of oxide layer. This oxide layer is reported to
have the maximum osseointegration of bone. Further it is
speculated that it would be possible to create a condition
where bony ingrowth to various metal implants would be
predetermined according to specific demands by altering
the heating temperature in various gaseous environ-
ments. It was also proved that the electropolishing of the
implant specimens played a major role in enhancing the
corrosion resistance of metal specimens.
(5) Bioceramic coatings on implants: At present, for all
those clinical applications where load-bearing properties
are required, most of the implants used are metallic, with
subsequent and serious problems due to: (a) the large
differences in mechanical properties between the
artificial implant and the natural bone, giving rise to
ruptures, (b) the presence of ions that, released from the
artificial plant, could be toxic or harmful and provoke
pains and (c) the impossibility to regenerate natural
bone. An alternative option, until a more similar material
to bone becomes available, is to coat the metallic
implants with bioceramics. This technique is being used
nowadays, both for dental implants and hip joint
prosthesis. There is still a long way to follow, but
several metallic implants with bioceramics coatings are
commercially available already, and the research in
problem solving is underway.
The bioceramics coating process on a metallic substrate is
quite complicated, and several methods are available in this
sense. A great deal of the clinical success depends on this
coating, since the quality and durability of the interface
attachment greatly depend on the purity, particle size,
chemical composition of the coating, layer thickness and
surface morphology of the substrate. An additional
advantage of bioceramics coating is the reduction of release
of ions from the metal alloy. The bioceramics coating
represents a truly effective barrier that hinders the metallic
Materials and Corrosion 2008, 59, No. 11
ion kinetics of release towards the living body. HAP
[Ca10(PO4)6(OH)2] is being specifically used for this
purpose, in order to improve the bone ingrowth and to
minimize the motion at the implant-bone junction. HAP
possesses excellent biological properties such as non-
toxicity and lack of inflammatory response and fibrous
and/or immunitary reactions.
HAP, TCP and their biphasic combinations are important
ceramic materials in the replacement of hard tissues, because
they can form a strong bond with the bone and favour bone
formation. However, the poor mechanical properties of
calcium phosphates limit the use of the bulk material to non-
load bearing implants. For this reason, one of the most
important uses of these calcium phosphates is to coat inert or
biotolerable implants with mechanical properties adequate
for orthopaedic substitutions. In this way, the coated implants
will not only have the good mechanical properties of the
substrate but also an enhanced osseointegration and
bioactivity due to the calcium phosphate layer [96]. Terada
et al. [97] have evaluated the significant effects of 316L SS
on the clinical success and Fathi et al. [98] studied the bone
tissue response and histopathological results of HAP coated/
uncoated metallic implants (316L SS and Ti) in animals. The
results showed that different substrates had pronounced
effects on the histopathological response to HAP coated on
different implants with beneficial corrosion resistance of the
coatings.
Plasma spray technique is currently the only method
commercially available for coating metallic substrates [99].
The significant deficiencies found in the plasma sprayed
HAP coatings have promoted the search for new deposition
methods, such as ion beam assisted deposition, magnetron
sputtering, solgel, pulsed laser deposition [100], etc.
Although different deposition methods have been applied
in the last years, solgel method offers a good alternative
since the synthesis temperature are low and it can be applied
to a great number of substrates, including those which would
oxidize at higher temperatures. Solgel technology offers a
chemically homogeneous and pure product and has been
used for HAP production since 1988 [101]. Several authors
have prepared HAP via solgel technique using different
precursors. Balamurugan et al. [102,103] have deposited
single-phase HAP coatings on Ti-6Al-4V by the solgel
dipping technique form aqueous solutions containing triethyl
phosphite and calcium nitrate. Balamurugan et al. [103106]
have reported that the coating thickness alters the shear
strength and corrosion resistance of solgel derived apatite
and reinforced apatite films of 316L SS.
10.1.2 Quality control
(1) Improved standards and quality control. The manufac-
turer should adopt the recommended metallurgical
standards, fabricate the implants with care and maintain
adequate testing facilities.
(2) Improvements in design to minimize pits, crevices, large
grain size, inclusions and porosity [54]. Improved alloy
cleanliness, especially the use of vacuum melting, and
remelting, has largely eliminated pitting in such
hardware [45].
(3) The reduction of carbon to less than 0.03% has virtually
eliminated the risk of intercrystalline corrosion, which
can occur when there is precipitation of chromium
carbide at the grain boundary in SS with carbon content
above this value [54]. Unfortunately, lowering the
carbon content resulted in lowering the ultimate tensile
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Materials and Corrosion 2008, 59, No. 11
strength of SS. Pitting corrosion inevitably occurs when
304 steel is supplied instead of 316 [107].
(4) Proper heat treatment after welding will restore the
appropriate compositional distribution and prevent
intergranular attack [45].
(5) Avoiding implantation of different types of metal in the
same region in the manufacturing process, matched
parts from the same batch of the same variant of a given
alloy must be provided. It must be ensured that
instruments are made from the same material as the
implant [107].
10.1.3 Research and development
(1) Development of alloy with good wear resistance and
ability to repassivate at a high rate (to prevent fretting).
(2) Coupling of two metals widely separated in the galvanic
series, e.g. titanium and chromium may not result in
galvanic corrosion but in enhancement of protection.
The risk, however, is a potential increase in pitting or
crevice corrosion.
(3) Using an alloy whose open circuit or rest potential lies
below the critical potential for pitting [54].
11 Future directions
Biomaterials corrosion remains a serious clinical concern.
Even though the freely corroding implant materials used in
the past have been replaced with modern corrosion-resistant
superalloys, deleterious corrosion processes have been
observed in certain clinical settings. There is a reason to
believe that attention to variables related to metallurgical
processing, tolerances of modular connections, surface-
processing modalities and appropriate selection of materials
could decrease the rate of corrosion and minimize the
potential for adverse clinical outcomes. The mechanical
electrochemical interactions of passive metal oxide surfaces
must be investigated further. The stresses and motion that are
needed to fracture passivating oxide films as well as the
effects of repeated oxide abrasion on the electrochemical
behaviour of the interface and ultimately the implant are
areas of active investigation. The role of particulate corrosion
products in adverse local tissue reactions also needs to be
investigated further. The clinical ramifications of increase in
metal content in body fluids and remote organs of patients
who have a metal implant need to be elucidated. Consider-
able work is required to discern the chemical form of the
metal, the nature of its ligands and ultimately the potential
toxicity.
Acknowledgements: The financial support from CICECO,
University of Aveiro, Portugal and Indian Council of
Medical Research (ICMR), New Delhi, India is gratefully
acknowledged.
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(Received: December 10, 2007) W4173
(Accepted: January 14, 2008)