Corrosion and Microstructural Aspects of Titanium and Its Alloys As Orthopaedic Devices

Geetha Manivasagam et al.
Corrosion Reviews
CORROSION AND MICROSTRUCTURAL ASPECTS OF

TITANIUM AND ITS ALLOYS AS ORTHOPAEDIC
DEVICES
G e e t h a Manivasagam 3 , U. Kamachi Mudali b , R.Asokamani 0

and Baldev R a j b
a
Sathyabama Institute of Science and Technology, Chennai-600 119,
India.
b
Metallurgy and Materials Group, Indira Gandhi Centre for Atomic
Research, Kalpakkam-603 102, India.
c
Tamil Nadu Academy of Sciences, Nuclear Physics Department,
Chennai-600 025, India.
ABSTRACT
T i t a n i u m is a w o n d e r metal, generally considered as one o f the m o s t

biocompatible and corrosion resistant metals available for clinical
applications. Since 1951, w h e n Leventhal /1 / first published an article on the
orthopaedic application of this metal, research activity and clinical
e x p e r i e n c e resulted in new d e v e l o p m e n t s in the m a n u f a c t u r i n g and use o f this
metal and its varieties o f alloys. Beginning with c o m m e r c i a l l y p u r e titanium,
and then to Ti-6A1-4V alloy, today the state o f the art -titanium alloys h a v e
been a d d e d to the list; there is a range o f materials and d e v i c e s based on
titanium, which are available for a variety o f medical applications. In this
review article an attempt is m a d e to bring out the various features of titanium
as o r t h o p a e d i c material, mainly f o c u s i n g on the physical metallurgy, alloy
d e v e l o p m e n t , microstructural aspects, and corrosion and w e a r resistances. An
attempt is also m a d e to highlight the role o f s u r f a c e m o d i f i c a t i o n in
e n h a n c i n g the corrosion resistance o f titanium and its alloys.
1. INTRODUCTION
T h e n e w century has d a w n e d with m a n - m a d e materials and devices

d e v e l o p e d to the extent that they can be used successfully to artificially
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Vol. 21, os. 2-3, 2003 Corrosion and Microstructural Aspects
of Titanium and its Alloys
rebuild almost all parts of the human b o d y . In recent years there is great
concern for health conditions, and a s h a r p increase in life expectancy has
resulted due to a d v a n c e m e n t s in medicare practices. Prosthetic devices and
implants have improved the quality of life of the aged, by restoring the
otherwise c o m p r o m i s e d functions of the human body. Natural synovial
j o i n t s , e.g., hip, knee or shoulder joints, are c o m p l e x and delicate structures
c a p a b l e o f f u n c t i o n i n g under critical conditions. Their p e r f o r m a n c e is due to
the optimized combination of articular cartilage, a load-bearing connective
tissue c o v e r i n g the bones involved in the j o i n t and synovial fluid, a nutrient
fluid secreted within the joint area /2,3/. Unfortunately, human j o i n t s are
p r o n e to degenerative and inflammatory diseases that result in pain and j o i n t
stiffness. Osteoarthritis, rheumatoid arthritis and c h o n d r o m a l a c i a are the most
c o m m o n degenerative processes affecting the synovial joints 74/ apart f r o m
n o r m a l a g e i n g of articular cartilage. In, fact 9 0 % of the population o v e r the
age o f 4 0 s u f f e r f r o m some degree o f degenerative j o i n t disease 151.
Degeneration of load-bearing joints often requires surgery to relieve pain and
to increase mobility. Replacement o f diseased joint surfaces by metal, plastic
or ceramic artificial materials is a c c o m p l i s h e d through arthoplastic surgery
when the natural joint can n o longer adequately p e r f o r m . Total joint
replacement arthoplasty is recognized as a m a j o r achievement in orthopaedic
surgery. R e p l a c e m e n t arthroplasty m a d e important a d v a n c e m e n t s during the
1950s and 1960s, with metal-on-metal hip prosthesis in which c o m p o n e n t s
were originally m a d e o f stainless steel. This was rapidly changed to a c o b a l t -
chromium-molybdenum alloy (VitalliumTM) to mitigate the excessive
friction and rapid loosening of the stainless steel pair 161.
T h e science of biomedical materials deals with the d e v e l o p m e n t of
various kinds o f materials for prosthetic devices used to replace the diseased,
fractured or missing parts of the human body. As the f u n c t i o n i n g capability
of o r g a n s such as hip, knee, tooth, heart etc. deteriorate d u e to aging and
fracture o f various parts due to trauma, the need arises for prosthesis or
implants with high biocompatibility and longevity. A biomaterial that does
not p r o d u c e any adverse reaction or inflammation and that is not rejected by
the h u m a n system is said to be biocompatible. Biocompatibility is thus
defined as the ability of a man made material to exist in an in vivo
environment for an acceptable period of time with no detrimental effect in the
host. Metals are used as biomaterials due to their excellent mechanical and
corrosion properties in addition to their biocompatibility. S o m e metals are
used as passive substitutes for hard tissue replacements such as total hip and
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knee joints, for fracture healing aids as b o n e plates and screws, spinal
fixation devices, and dental implants because of their excellent m e c h a n i c a l
properties and corrosion resistance. S o m e metallic alloys are used for m o r e
active roles in devices such as vascular stents, catheter guide wires,
orthodontic arch wires and cochlear implants. The range o f materials
available for the fabrication o f prosthetic devices and implants are vast and
the choice of these materials is based on properties such as the strength,
biocompatibility, modulus of elasticity and density. Materials such as metals,
alloys, ceramics, polymers and c o m p o s i t e s are used f o r prosthetic and
implant fabrication. T h e metallic materials can be subjected to all kinds of
loading, unlike ceramics and carbon, which can be subjected only with high
compressive load. Ceramics and polymers are applicable in the construction
of parts where high tensile stresses are absent, such as prosthesis h e a d s or
cups o f knee or hip joint. On the other hand, p o l y m e r s are suitable only for
low stress conditions as the mechanical properties of p o l y m e r s are p o o r u n d e r
both tensile and compressive stresses. In addition, c r e e p in p o l y m e r s is o n e of
the most pressing critical problems. Considering the limiting factors for
ceramics, carbon and polymers for prosthetic replacements in most cases, the
use of metallic materials is preferred. T h e metallic materials o f f e r a w i d e
range o f mechanical properties so that a suitable selection a c c o r d i n g to the
requirements is possible. Structural medical devices m a d e of metals can be
classified as low-loaded implants (e.g. plates, screws etc.) and high-loaded
implants (e.g. hip and knee prostheses). Hence, in the present article a review
of the metallic materials used in prostheses is presented with special
emphasis on titanium and its alloys.
2. M E T A L L I C B I O M A T E R I A L S
T h e use of artificial materials to repair fractured, diseased tissues and

organs dates back as early as 4 0 0 0 years ago 111. In the early ages, the G r e e k s
and Egyptians transplanted bones f r o m animals to h u m a n s and only in 1550,
a non-biological material such as gold wire was used for sutures. T h e practice
of aseptic procedures discovered by Joseph Lister in 1860, resulted in a
search for an appropriate metal f o r fabrication of specific implant and
prosthetic devices. Metals such as iron, c h r o m i u m , cobalt, nickel, titanium,
tantalum, m o l y b d e n u m and tungsten can be tolerated by the b o d y in minute
amounts and sometimes are also essential, like iron in red blood cell function
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or cobalt in the synthesis of Vitamin BI 2 , but however cannot be tolerated in

large amounts. Based on the reactivity of a metal with the tissue, the
materials are classified as toxic, capsule and vital.
The first metal/alloy developed for implant applications in the early
1900's was "vanadium steel" /8/. Iron and steel, the most widely employed
materials, dissolve rapidly and induce erosion of adjacent bone, whereas
copper and nickel that were embedded in the bone led to discoloration of the
adjacent tissues. On the other hand gold, silver and pure aluminum, although
they did not lead to discoloration, were too soft for most applications. The
first generation metallic biomaterials were implants made of stainless steel,
chromium cobalt and + titanium alloys. Stainless steel (SS) with 18%
chromium and 8% nickel (alloying additions are given in weight percentage
throughout), which was extensively used for other applications, was first
introduced as an implant material in 1926. This was found to be more
corrosion resistant in the body fluids and much stronger than vanadium steel.
In order to have much more improved corrosion resistance, a small
percentage of Mo was added to this alloy, and the new alloy was named as
316 SS. Following this, stainless steel alloy with lower percentage of carbon
( 3 I 6 L SS) was introduced in the 1950's 191. However, 3 I 6 L SS also corroded
inside the body under certain circumstances in a highly stressed and oxygen
depleted region such as contact points under screws or fracture plates. Owing
to these reasons stainless steel was considered to be suitable for temporary
implant devices. The next alloy that was introduced in the field of
biomaterials was cobalt-chromium alloy. Two main types of cobalt-based
alloys, CoCrMo alloy in the cast form and CoNiCrMo alloy usually obtained
in wrought form by hot forging, were considered for surgical implants. The
trade designation of Vitallium is often applied for both the alloys. These
alloys were considered to be superior to stainless steels as they displayed a
balance between mechanical properties and biocompatibility. The chemical
passivation of these alloys leads to the formation of complex chromium oxide
which aids in the corrosion resistance of cobalt-based alloys. Though the
corrosion resistance of cobalt-based alloys is superior that of the stainless
steel, it is not preferred for fracture-fixation purposes owing to its increased
cost. The chemical compositions as per ASTM specifications for 316 LSS
and Co-Cr alloys are given in Table 1.
Recent studies on toxicity have shown that elements such as aluminum,
cobalt, nickel, molybdenum and chromium have long-term adverse effects.
Table 2 illustrates the reactions of various elements in human body. These
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Table 1
Chemical composition of type 316 L SS and Co-Cr alloys (in w t % )
Elements 316LSS CoCrMo CoNiCrlMo

Carbon 0.03 Max 0.0-0.35 0.0-0.025
Manganese 2.00 Max 0.0-1.0 0.0-0.15
Phosphorous 0.03 Max - 0.0-0.015
Sulfur 0.03 Max - 0.0-0.015
Silicon 0.75 Max 0.0-1.0 0.0-0.15
Chromium 17.0-20.0 27.0-30.0 19.0-20.0
Nickel 12.0-14.0 0.0-2.5 33.0-37.0
Molybdenum 2.0-4.0 5.0-7.0 9.0-10.5
Coblt - Balance Balance
Titanium - - 0.0-1.0
Iron - 0.0-0.75 0.0-1.0
Table 2
Reaction of various elements in human body environment
Element/alloy Reaction
Vanadium Potential cytotoxic effects and adverse tissue
reaction
Aluminum Potential neurological disorders
Chromium Severe tissue reactions in animals and allergic
Cobalt Severe tissue reactions in animals and allergic
Nickel Allergic
Molybdenum Adverse tissue reaction
Co-Cr-Mo Carcinogenic in animals
demerits led to the evolution of new alloys with non-toxic elements. T h e

plausible applications of titanium were considered, as it was found to be inert
and exhibited excellent corrosion resistance and biocompatibility in human
body f l u i d s / 1 0 .
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3. T I T A N I U M A N D ITS A L L O Y S
In recent times titanium and its alloys are receiving a great deal of
attention from biomedical researchers and clinicians as the biomaterial of
choice for prosthetic and implant devices. Pure titanium and its alloys such as
Ti-6AI-4V were originally developed for applications in chemical industry
and aerospace sector. The combination of high strength, superior corrosion
resistance, enhanced bioconipatibility and relatively low modulus of
elasticity has paved a path for their biomedical applications /11,12/. Titanium
and its alloys are currently used for the following applications:
1) Joint replacement parts for hip, knee, shoulder, spine, elbow and wrist.
2) Bone fixation materials such as nails, screws, nuts and plates,.
3) Dental implants and parts for orthodontic surgery and dental prosthetics.
4) Heart pacemaker housings and artificial heart valves.
5) Surgical instruments for heart and eye surgery.
6) Components in high-speed blood centrifuges.
Titanium as an element has extremely low toxicity, and is well tolerated

by both bone and soft tissue. It is found to be safe for intravascular
applications, owing to its high electronegativity and passive surface. For the
same reason titanium does not cause hypersensitivity, which makes it the best
choice for patients suspected of being sensitive to metals. For several
decades, special titanium implants have been used with outstanding success
in patients with histories of severe allergic reactions.
4. P H Y S I C A L M E T A L L U R G Y O F T I T A N I U M A N D ITS A L L O Y S
Titanium is relatively a light metal having a density of 4.54 g/cirr, which

lies between aluminum and iron. The melting point of titanium is as high as
1668C, which is higher than iron and has a modulus of elasticity between
aluminum and iron /13/. Titanium exists in two allotropic crystal forms as
phase, which has the hexagonal close-packed structure (hep), and -phase,
which has the body centered cubic (bcc) structure. The a phase, which is
very stable at room temperature, transforms to phase when heated above
883C (-transus temperature). The choice of the alloying elements to
titanium is determined by the ability of the element to stabilize either the or
the phase. Alpha-stabilizers are those elements which stabilize the hep
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structure by increasing the transformation t e m p e r a t u r e greater than 8 8 3 C ,

while stabilizers decrease the t r a n s f o r m a t i o n of the bcc structure well
b e l o w 8 8 3 C . T h e phase is stabilized by the presence o f elements like
a l u m i n u m , oxygen, nitrogen, gallium and c a r b o n , w h e r e a s transition e l e m e n t s
like v a n a d i u m , niobium, tantalum and m o l y b d e n u m stabilize the phase.
Based on the a m o u n t s of the phases present, titanium alloys can be classified
as either alloys, n e a r - alloys, + alloys, m e t a s t a b l e - alloys, n e a r -
alloys and alloys. T h e a m o u n t of and p h a s e s d e p e n d s on the a m o u n t o f
alloying elements and the thermomechanical treatment used for
m a n u f a c t u r i n g . T h e r m o m e c h a n i c a l treatments dictate the relative a m o u n t s o f
and phases and the phase m o r p h o l o g i e s , and yield a variety of
microstructures with a range of mechanical properties. T h e titanium alloys
may be treated well a b o v e or below the - t r a n s u s temperature o f the alloy.
W h e n treated a b o v e the transus temperature it is t e r m e d - h e a t treatment a n d
when annealed b e l o w the transus t e m p e r a t u r e s it is termed + heat
treatment. T h e a m o u n t o f and p h a s e s varies with the heat treatment
t e m p e r a t u r e and the rate of cooling. Microstructural variations that result d u e
to d i f f e r e n t heat treatment procedures m a y be classified d e p e n d i n g on
w h e t h e r the metal working and heat treatments were p e r f o r m e d a b o v e or
below the -transition temperature, and on the c o o l i n g rate.
The microstructures that are often o b t a i n e d in titanium alloys are
equiaxed, lamellar, martensite, duplex, solution treated and aged
microstructure. Equiaxed, lamellar, solution treated and aged microstructures
are o f interest in implantology. Of all microstructures, + titanium alloys
with e q u i a x e d structures are preferred f o r implantology /14/. T h o u g h the
d e v e l o p m e n t o f equiaxed structure is well established in + alloys, less
literature exists on the formation o f e q u i a x e d structure in the alloys. T h e
formation o f equiaxed microstructure in alloys is difficult as the - t r a n s u s
of these alloys is very low and the recrystallization process is very slow at
low temperature. T h e advantages o f various microstructures are given in
T a b l e 3.
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5. - T I T A N I U M A L L O Y S FOR B I O M E D I C A L A P P L I C A T I O N S
Although titanium and + titanium alloys possess excellent corrosion

resistance and biocompatibility, considerable controversy has been raised
over their long-term performance due to the release of large amounts of
titanium, aluminum and vanadium from Ti-6AI-4V alloy and their deposition
in tissues, organs and body fluids /15/. Vanadium and aluminum are
respectively associated with potential cytotoxic effects and potential
neurological disorders. Concern about the release of potentially harmful
vanadium ions from the alloy led to the development of V-free alloys such as
Ti-6Al-7Nb and Ti-5Al-2.5Fe to avoid the toxicity of vanadium ion /16/.
These newly developed + alloys had better corrosion resistance due to
very dense and stable passive layer. However, + titanium alloys possess
high modulus (110 G P a ) when compared to the bone (30 G P a ) and transfer
insufficient stress to the adjacent bone, resulting in bone resorption and
eventual loosening of the prosthetic devices /16/. The wear resistance of these
alloys is also inferior when compared to Co-Cr alloys and hence wear debris
of titanium and its alloys are often found in the tissues near the implants.
These wear debris cause inflammatory reaction leading to pain and loosening
of implants due to oseteolysis. Several authors have reported /17,18/ about
the presence of titanium ions near the implants in the absence of wear due to
the dissolution of the passive layer. The service period of titanium implants
are thus restricted to 10 to 15 years, whereas the implants placed in the
younger patients need to serve for more than 25 years.
Low modulus of elasticity and presence of non-toxic elements are thus the
two most important criteria that have to be considered in the selection of
materials for biomedical applications. The alloys that are presently used have
very high modulus when compared to that of the bone. Alloys with high
modulus are very rigid and hence shield the stress to the bone. This is often
referred to as 'stress shielding effect' /19/. This results in the death of the
bone cell and lead to the loosening of the implants with time. In addition to
the lack of biomechanical compatibility, the alloying elements that are
released into various parts of human system due to the wear and corrosion are
found to cause adverse effects. Hence, the current research in the field of
biomaterials is presently focused on developing titanium alloys for
manufacturing implants which possess low value of modulus and offer
superior biochemical compatibility when compared to that of the +
titanium alloys and other conventional alloys such as stainless steel and
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cobalt chromium. These new alloys fall into the category of second-
generation biomedical alloys. The cytotoxicity studies which were p e r f o r m e d
for different metallic elements revealed that only five elements viz., titanium,
zirconium, niobium, tantalum and palladium are non-toxic elements /18/. T h e
presence of zirconium and niobium in titanium is found to reduce the
modulus of the alloys to very low value that is closer to bone. In addition,
niobium and zirconium offer high corrosion resistance in body fluids o w i n g
to the formation of a stable passive layer, thereby reducing the possibility of
introducing foreign metallic ions into a stable physiological solution. A near-
beta alloy, Ti-13Nb-13Zr ( A S T M F 1713-96), exhibits higher adhesion of
osteoblasts and lower bacterial adhesion than the standard materials such as
titanium and Ti-6A1-4V 1201. This alloy is also used for designing
cardiovascular implants, as Z r 0 2 passive film is thrombogenically compatible
with blood. The low modulus of this alloy provides a more flexible and
improved contact stress levels. Further, the corrosion resistance of this alloy
is far superior due to the formation of Z r 0 2 , N b 2 0 5 that strengthens the T i 0 2
passive film formed on the surface this alloy. The room temperature
mechanical strength of the annealed alloy increases with a small increase in
the amount of zirconium. The mechanical properties and the effect of various
oxides in the human are given in Table 4. N e w titanium alloys with better
biomechanical environment and biochemical properties are presently under
investigation.
6. C O R R O S I O N O F T I T A N I U M A L L O Y S
Corrosion, the gradual degradation of materials by electrochemical attack,

is a concern particularly when a metallic implant is placed in the hostile
electrolytic environment provided by the human body /21,22/. The corrosion
behaviour of a material strongly d e p e n d s on the presence of a protective
passive film and it is a mainly a surface phenomenon. The determination of
the surface composition is of great importance as the external layers of a
biomaterial will be in direct contact with biological tissues. Though the
presently used biomedical implants are corrosion resistant, deleterious
corrosion processes have been observed in certain clinical settings /23/. T h e
presence of corrosion products will elicit inflammatory responses and
sometimes the formation of foreign body giant cells. These may have adverse
effects on the performance of an implant leading to pain, swelling and tissue
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Vol. 21, os. 2-3, 2003 Corrosion and Microstrnctural Aspects

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necrosis at the site and in some cases loosening of the implants. The
corrosion products are also found to affect the albumin present in the serum
and blood. Thus one of the deciding factors for the success of new alloys as
biomaterials is their corrosion resistance. Therefore in vitro evaluation of
their corrosion parameters is one of the first steps in the development of new
biomaterials.
Generally, it is known that commercially pure (CP) titanium and single
phase ( a or ) alloys demonstrate the best corrosion resistance properties.
From the corrosion point of view, titanium is one of the most corrosion-
resistant metals. As soon as a titanium surface is exposed to the environment
it will rapidly oxidize due to its high reactivity, and the oxide that is produced
forms as an ultra-thin, coherent, impervious layer on the surface, which
provides protection for the metal in almost all environments, including the
physiological environment. From the biological safety perspective, again the
metal is good as it has little affinity for any biological molecule and appears
to be well tolerated by the body. However, the strength of the single phase
alloys are inferior compared to the two phase alloys. Under noun-
physiological conditions, titanium and its alloys do not break down, n r . : > , .
external factor such as wear acts on them. Titanium and its alloys have also
demonstrated the absence of breakdown potential in physiologically relevant
ranges in extremely acidic medium 1241. This results in minimal release of
ionic or any other by-product residue into the periprosthetic tissue,
classifying this alloy as biologically inert or electrochemically passive in the
whole range of clinically relevant potential-pH combination. The excellent
chemical inertness, corrosion resistance and repassivation ability of titanium
and most of its alloys are due to the chemical stability and structural integrity
of the titanium oxide. Other thermodynamically highly reactive and
kinetically highly passive metals such as tantalum, niobium or zirconium
behave similarly to titanium. Therefore, these elements are the common
alloying elements added to titanium. The physico-chemical properties of
these oxides have been correlated with the observed tissue reactions of the
parent passive metals. Titanium, niobium, tantalum and zirconium exhibit a
behavior that is close to that of an inert material, without any adverse tissue
reaction under normal conditions /25/. Table 5 gives the values of standard
Gibb's free energies for the formation of the most stable oxide 1261.
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Table 5
G i b b s free energy of the most stable oxides
Metal Most stable metal A G 0 per mol of

oxides oxide f o r m e d
|kJ/mol |
Titanium Ti02 -888.8
Aluminum AI2o3 -1582.3
Niobium Nb205 -1766
Vanadium v2o5 -1419.5
Zirconium Zr02 -1042
7. C O R R O S I O N IN V A R I O U S M E D I A
The corrosion behavior of various titanium alloys in different

environments has been studied extensively. This is due to the fact that the pH
of the b o d y may vary f r o m 3.5 to 9.0 d e p e n d i n g upon the condition of the
area around the implant which is w o u n d e d or infected. N a k a g a w a et al. 2
studied corrosion b e h a v i o r of Ti-6A1-4V, T i - 6 A l - 7 N b , and new titanium
alloys with Pd in the wide range of pH and fluoride concentrations and found
that the Ti-0.2 Pd alloys were more resistant to corrosion in the wide range of
pH due to surface enrichment of palladium. In vitro corrosion and wear
accelerated corrosion of titanium alloys in the biological e n v i r o n m e n t using
anodic polarization m e a s u r e m e n t s in the range from 0 to 5 V were reported
by Khan et al. /28/. T h e s e studies showed that + alloys such as Ti-6AI-4V
and T i - 6 A l - 7 N b possessed the best combination of both corrosion and wear
resistances, although C P titanium and the near- titanium alloys like Ti-
13Nb-13Zr and T i - 1 5 M o alloys displayed excellent corrosion resistance. T h e
presence of protein also either inhibits or accelerates the corrosion o f a
biomaterial in the body. It has been demonstrated that the static corrosion
rates of stainless steel and C P titanium were increased by protein addition but
it did not have any e f f e c t on Ti-6A1-4V. In fretting m o d e the corrosion
resistance of stainless steel in protein decreased significantly, whereas C P
titanium and Ti-6AI-4V were not affected. Protein additions may limit the
rate at which the medium can be purged with nitrogen due to their surfactant
nature. Khan et al. 1291 have investigated the corrosion b e h a v i o r of three
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Geetha Manivasagam el al. Corrosion Reviews
titanium alloys T i - 6 A I - 4 V , T i - 6 A I - 7 N b and T i - 1 3 N b - 1 3 Z r in phosphate-

buffered saline at various p H levels and also in the presence o f the protein
solutions. Their studies revealed that T i - 1 3 N b - 1 3 Z r alloy was least affected
by the change in the p H level when compared to the other two alloys. The
reduction in hardness of the surface oxides due to corrosion in protein
solution is less in T i - 1 3 N b - l 3 Z r than in T i - 1 6 A I - 7 N b and T i - 6 A I - 4 V alloys.
Lopez et al. /30/ have explained that the high corrosion resistance o f T i -
13Nb-13Zr alloys was due to the presence of a large percentage o f zirconium
in the passive layer when compared to aluminium in the T i - 6 A I - 4 V alloy.
Moreover, the implantation of T i - 1 5 Z r - 4 N b - 4 T a alloy in rat tibia by Okazaki
et al. /12/ showed that the presence o f new bone tissue around the alloy and
the pitting corrosion was less compared to that o f T i - 6 A I - 4 V under the same
implantation conditions. Thus, T i - Z r - N b alloys seem to possess better
corrosion resistance and biocompatibility than the well studied T i - 6 A I - 4 V
alloy/12/.
Though titanium and its alloys are highly corrosion resistant, the
breakdown of the passive layer occurs owing to wear. In addition, the
presence of titanium ions near the implants was reported in the absence o f
wear, due to passive film dissolution. The failure of stressed alloy also occurs
due to repetitive deformation of the metal in a corrosive environment
resulting in acceleration of both corrosion and wear. The dissolution o f
passive film is quite significant as the metal ions released and their protein
complex cause significant tissue damage. Titanium is a reactive metal and
disruption or damage to the oxide film is repaired immediately in the
presence of air or oxidizing media, and this would also be the case in the
human body environment. Hence, it is also important to study the
repassivation behavior of titanium and its alloys in various solutions
particularly those containing protein. When the passive layer was broken
down the titanium alloy was able to release ions into solution until the
passive layer was rebuilt. The rebuilding action of this layer results from the
chemical interaction of the anions in the environment reacting with the
surface. Hence, the anions in the environment have a bearing on the chemical
composition of the repassivated layer. The properties o f this repassivated
layer may be reflected in the hardness of that surface. For all the alloys the
virgin surface is hardest due to the dense rutile titanium oxide formed. The
retention of the surface hardness of Ti-13Nb-13Zr alloy following
repassivation in the environment containing protein could point out the
enhanced performance of this alloy in comparison with the T i - 6 A 1 - 4 V and
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Ti-6Al-7Nb alloys. Similarly increase in the pH value was also found to

affect the corrosion of the biomedical alloys. When ion release occurs, the pH
of the body solution has been reduced and the medium becomes very
aggressive. The studies on corrosion resistance of the biomedical alloys Ti-
13Nb-13Zr, Ti-6Al-7Nb and Ti-6A1-4V have shown that the alloy Ti-13Nb-
13 Zr was least affected by the variation in pH as compared to the other two
alloys /30/.
8. MICROSTRUCTURAL CHANGES ON
CORROSION PROPERTIES
It has been suggested that the localized variations in stress, microstructure

and temperature are shown to promote local redistribution of ions like CI",
HC0 3 " and H + that lead to early failure of surgically implanted devices by
corrosion. Various heat treatments that are often performed to increase the
mechanical strength of the alloys generally result in the redistribution of the
alloying elements in various phases. The redistribution of alloying elements
during heat treatment has been found to influence the corrosion resistance of
an alloy. Moreover, the oxides present on the surface of the alloy
considerably change the corrosion characteristics of an alloy. In Ti-6A1-4V
alloy titanium oxide was present in the form of Ti0 2 and aluminum was
present in the most stable oxidation state 3+, corresponding to A1 2 0 3 . The
percentage of aluminum is higher on the surface when compared to the bulk
whereas the amount of vanadium in Ti-6A1-4V and Nb in Ti-6AI-7Nb is
comparatively lower in the oxide film than in the bulk. Aluminum is
distributed throughout the surface of the oxide film, while the distribution of
niobium and aluminum is not uniform on the oxide layer. Moreover,
aluminum is present on the surface of the layer, while the niobium and
vanadium are present in the interface between the bulk and the oxide layer.
The vanadium concentration is found to be higher by a factor of 2 to 3 in
areas with + phase compared to areas with pure -phase. Vanadium or Nb
and Al are not believed to form separate phases within the oxide film, and
more likely they are present as cations in substitutional or interstitial sites.
However, the main difference between the Ti-6Al-7Nb and Ti-6A1-4V is the
formation of Nb 2 0 5 which is chemically much more stable, less soluble and
more biocompatible in comparison to vanadium oxide (V 2 0 5 ) (Table 3). It
has also been suggested by Khan et al. /31 / that the alloys should have both
+ phase for better corrosion and mechanical properties in their
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microstructure, possibly more beta than alpha phase to improve corrosion

resistance. In comparison to + alloys, -titanium alloys generally exhibit
superior corrosion behavior. However, their corrosion resistance is also found
to depend on several factors such as composition, environment and
microstructure 1321. The effect of the composition can be understood from the
fact that the corrosion resistance of alloy such as Ti-5Mo-5Zr-3AI is higher
when compared to pure titanium /33/. Further, niobium is considered to be a
better alternative for vanadium as it is highly beneficial with respect to
corrosion and toxicity. The presence of higher concentrations of aluminum in
the phase is found to deteriorate the corrosion resistance of this phase in Ti-
6A1-4V alloy. However, the corrosion resistance of this phase is enriched
when it consists of the beneficial alloying elements like Nb and Zr. Extensive
studies carried out on the Ti-6AI-7Nb alloy by Thair et al. /34,35/ clearly
revealed that out of as well as + heat treatments, the alloy heat treated at
950C/air cooled and aged at 550C exhibited the best corrosion performance
in Ringer's solution. The superior corrosion resistance of this heat treated
sample is attributed to the formation of duplex microstructure that led to even
distribution of the alloying elements. The heat-treated sample exhibited low
corrosion resistance when compared to sample with + heat treatment.
Elemental profiles of the passivated Ti-6AI-7Nb alloy /36/ showed that
aluminum enriched in the oxide layer in comparison to the bulk metal
composition, while the concentration of niobium in the oxide film is close to the
value in the bulk alloy. Outermost nitride layers followed by oxynitride layers
were observed from the nitrogen and oxygen profiles for the implanted-
passivated specimens of the alloy. On the other hand, corrosion studies
performed by Yu et al. /37/ on + titanium alloys revealed that solution
treated samples possess higher corrosion resistance than the solution treated
and aged alloys. Their studies further revealed that in contrast to + alloys,
alloys did not reveal any variations in the corrosion behavior of solution
treated and, solution treated and aged specimens. The presence of
beneficial alloying elements like zirconium in the phase and niobium in the
phase resulted in the high corrosion resistance of both phases of the near-
Ti-13Nb-13Zr alloy. Further, the Ti-13Nb-13Zr alloy also showed high
corrosion resistance in low pH due to the modification of T i 0 2 layer by the
formation of N b 2 0 5 and Z r 0 2 . These oxides reduced the CI" ingress into the
oxide layer. Though elemental redistribution had little effect on corrosion
behavior of the near-beta alloys, studies performed by Geetha et al. /38,39/
clearly revealed that the Ti-13Nb-13Zr alloy heat treated below transus
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Authenticated
temperature (680C and water quenched) possessed superior corrosion

resistance to that of the solution treated samples. Moreover, the
repassivation behavior of this alloy with equiaxed structure was much
superior to the other microstructures. In addition, the oxide layer formed
under this condition was very stable, while the other microstructures resulted
in an oxide layer that underwent frequent dissolution and repassivation in the
Ringer's solution. The enhanced performance of this microstructure is due to
even distribution of oxides of the alloying elements in the T i 0 2 matrix. It is
evident that an appropriate heat treatment temperature (below transus) and
the rate of cooling that will lead to even distribution of the alloying elements
in various phases will result in better corrosion performance /40/. From the
above discussions it is apparent that + heat treatment that results in two-
phase equiaxed structure is the best microstructure for both + and near-
alloys.
9. M E C H A N I C A L P R O P E R T I E S
Appropriate selection of the alloying elements and thermomechanical

treatment of titanium alloys have led to the development of implant materials
with required mechanical properties. The mechanical properties of various
biomedical implants are given in Table 6. The strength levels of titanium
alloys used for orthopedic applications generally lie within the acceptable
range and their ductility values are well retained at room temperature. The
yield strength of biomedical titanium alloys varies from 500 to 1200 MPa. A
microstructure obtained on a particular thermomechanical treatment may be
advantageous with respect to certain properties, whereas the same
microstructure may be detrimental to other mechanical properties. The
correlation between mechanical properties and various microstructures is
given in Table 6. The Widmanstatten microstructure that possesses maximum
toughness and fatigue crack growth resistance is found to have low high-
cycle fatigue lifetime (HCF). Enhancement of H C F time can be achieved
either by obtaining bimodal primary plus transformed microstructure or
by shot peening. The fatigue resistance of titanium is less compared to the
+ alloys. An increase in the fatigue strength of these alloys by solution
treatment and aging will lead to an increase in the modulus. Further, increase
in the fatigue properties is also achieved by adding controlled amounts of the
interstitial elements such as oxygen, carbon, nitrogen and hydrogen. The
fatigue properties of titanium alloys have been extensively investigated in
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different physiological environments. In general, a coarse m i c r o s t r u c t u r e is

resistant to crack propagation, w h e r e a s a finer microstructure tends to be
beneficial in delaying crack initiation. T h e initiation site in / titanium with
an equiaxed structure occurs in the primary , / or a / a interface
w h e r e a s in the Widmanstatten structure crack occurs in c o l o n i e s or prior
grains. Akhahori et al. /41/ have reported that the fatigue strength of Ti-6AI-
7 N b alloy with Widmanstatten structure w a s the s a m e as that o f T i - 6 A I - 4 V
alloy. T h e fatigue strength increases remarkably with the d e c r e a s e d primary
grain size, and the fatigue strength of T i - 6 A I - 7 N b alloy a p p r o a c h e s that o f
Ti-6A1-4V with the volume fraction o f the p h a s e obtained by fast c o o l i n g
/42/. Fatigue strength o f the biomedical alloys that are often m e a s u r e d in the
simulated b o d y solution ( R i n g e r ' s solution) w a s higher w h e n c o m p a r e d to the
typical b o d y solution that has less oxygen content. T h e p r e s e n c e of lower
oxygen concentration in R i n g e r ' s solution reduces the fatigue strength of the
Ti-5Al-2.5Fe, w h e r e a s the fatigue strength o f Ti-6A1 - 4 V is the s a m e in the
Ringer's solution as well as when implanted in a living rabbit. This
d i f f e r e n c e in the b e h a v i o r is attributed to the d i f f e r e n c e s in stress c o n d i t i o n s
of the fatigue testing m e t h o d s .
9.1 Modulus of elasticity
T h e failure of biomedical implants d u e to their high m o d u l u s has been

reported by several workers /43,44/. T h e high stiffness of the alloys with high
m o d u l u s of elasticity shields the required stress to the b o n e near the implant
system. This stress shielding effect results in the death of the b o n e cells and
leads to the loosening of the implants. Thus, the reduction o f the m o d u l u s of
elasticity of implants has been a big challenge f o r biomedical e n g i n e e r s f o r
many years. The + titanium alloys, which are extensively used in
designing biomedical implants, possess low m o d u l u s of elasticity c o m p a r e d
to that o f the conventional biomedical implants that are m a d e o f stainless
steel and c o b a l t - c h r o m i u m alloys. H o w e v e r , their m o d u l u s o f elasticity has
been greater when c o m p a r e d to the b o n e m o d u l u s . T h e term low m o d u l u s
used in the specification for orthopaedic implants refers to the Young's
m o d u l u s b e l o w 90 G P a . Near-beta alloys with n i o b i u m and zirconium have
been f o u n d to possess m o d u l u s of elasticity c o m p a r a b l e to that of the b o n e .
T h e m o d u l u s of elasticity of newly d e v e l o p e d beta alloys c o m p a r e d with
+ alloys is given in T a b l e 7. It is evident that the p r e s e n c e o f niobium and
silicon greatly reduced the modulus, while zirconium also slightly reduced
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145
Corrosion Reviews

Table 7. Modulus of elasticity of titanium and its alloys
Alloy Young's Modulus Young's Modulus

(GPa) (GPa)
Solution treated Solution treated
and aged and quenched
Ti-13Nb-13Zr 74.7 62
Ti-18Zr-6Nb 86.8 112
Ti-6A1-4V 112 112
Ti-6AI-7Nb 110 110
T i - 2 9 N b - 1 3 T a 4.6Zr 84 65
Ti-29Nb-13Ta 103 76
Ti-29Nb-13Ta-4Mo 73 74
Ti-29Nb-13Ta-4.6Sn 66 69
Ti-35.2Nb-5.1Ta-7.1Zr 55 -
Ti-24Nb-13Ta-4.6Zr 85 -
Ti-5AI-2.5Fe 110 -
C p Niobium 120 -
C p Tantalum 200 -
C p titanium 100 -
Co-Cr-Mo 230 -
Stainless steel 220 -
Bone 10-30 -
the modulus when present along with niobium. Tantalum on the other hand
does not affect the modulus of elasticity to any great extent although it is a
beta stabilizer. Though niobium influences the reduction of the modulus, the
weight percentage of niobium that has to be added should be carefully
selected for alloying. Niobium, when added either in the range of 10 to 20
wt%, or 30 to 50 wt%, has been found to reduce the modulus of elasticity
/45,46/. Increase in the niobium concentration may also lead to increase in
the density of the material and may lead to inhomogeneous casting due to
high melting point of this element when compared to titanium and other
alloying elements. It is also apparent from Table 7 that the quenched alloys
possess lower modulus of elasticity than that of the aged alloys, and this
could be attributed to the high strength of the aged alloys.
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9.2 W e a r of titanium and its alloys
Wear is a surface phenomenon that occurs by displacement and

detachment o f the material. When friction coefficient o f the material mating
with the bone or other materials is very high, wear of the material occurs and
it is initiated on the surface. The wear of prosthetic components generates
debris, which play a major role in the implant loosening and triggering the
release o f the particles, which further accelerates wear /47/.
One o f the major reasons for the failure o f the total joint replacements
made o f titanium alloys is aseptic loosening. This occurs due to the poor
tribological property (wear) of the implants. The interaction between
macrophage and implant derived from biomaterial wear particles that are
present in fibrous membrane surrounding aseptically loose implants results in
the implant loosening. A series of biological reactions occur due to the loose
wear debris, which eventually lead to inflammation and pain in the patients.
The accumulation of the wear debris may jeopardize the long term stability o f
the implant and various sizes of the wear particles highly influence these
reactions /46/.
Though titanium alloys possess fairly good modulus match with that o f
the bone, they do not possess good tribological properties /48/. The low wear
resistance of titanium is attributed to its hep crystal structure with low c/a
ratio. Adhesive wear is found to be dominant in T i - Z r - N b alloys, while the
mechanical wear groves are observed in conventional biomedical titanium
alloy such as T i - 6 A I - 4 V . The various oxide films formed on the alloy may
change the wear morphology in different alloys. The affinity between the
mating material and the parent material leads to the adhesive wear. The
weight loss and width of the groove of beta-titanium alloys with zirconium,
niobium, tantalum and tin are found to be highly dependent on the mating
materials. Niinomi et al. /31 / have shown that the wear resistance o f beta
titanium alloys was high when compared to T i - 6 A I - 4 V and T i - 6 A l - 7 N b
alloys. Corrosion is an accelerating factor on the wear behavior. However,
the influence o f corrosion on wear varies with different materials. The
corrosion wear as opposed to non-corrosive wear is more detrimental to the
mixed phase alpha-beta alloys (Ti-6Al-7Nb, T i - 6 A I - 4 V ) than other alloys.
However, wear resistance of these two alloys is better than other titanium
alloys in the absence o f corrosion. O n the other hand, when the influence o f
wear on the corrosion of materials was concerned (wear accelerated
corrosion), it has been shown that T i - 1 3 N b - 1 3 Z r was least affected when
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compared to the Ti-6A1-4V alloy. Though the Ti-13Nb-13Zr alloy possesses

the best corrosion resistance, it undergoes considerable loss in its hardness
following corrosion, which is of paramount importance from the tribological
point of view /28/.
10. S U R F A C E M O D I F I C A T I O N O F T I T A N I U M A L L O Y S
Long-term performance of surgical implants is often restricted by their

surface properties. Wear of prosthetic components generates debris of
polymer in the case of metal- polymer joints and it plays an important role in
the implant loosening and triggering the emission of particles that accelerate
wear. Mechanical factors lead to failure of an implant subjected to a high
stress level and a specific corrosive environment. In the case of orthopaedic
prostheses, the most frequent causes of failure are due to the wear of the load-
bearing surfaces and to the loosening of the implant in the bone. A j o i n t
prosthesis is composed of a couple of materials. Metallurgists and engineers
often treat the surfaces of metal parts to make them stronger, harder and more
resistant to corrosion.
Surface engineering can play a significant role in extending the
performance of orthopaedic devices m a d e of titanium several times beyond
its natural capability. The poor tribological properties of the titanium and its
alloys, such as low wear resistance, have reduced the service life of the
implants drastically. The presence of high titanium and vanadium in the
tissues and aluminum in surrounding muscle is often reported. Agins et al.
/49/ suggested that the metals have been found in the form of particulate wear
debris. The wear debris that has been produced during the process of wear
results in inflammatory reaction, loosening of implants and severe pain to the
patient. T h e wear resistance of any material can be improved many fold by
forming c o m p o u n d s of high hardness on the surface such as titanium nitride
(TiN), titanium diboride (TiB 2 ), titanium dioxide ( T i 0 2 ) and titanium carbide
(TiC). All of the above compounds can be formed on the surface of titanium
alloy by the application of appropriate processes such as nitriding, oxidizing,
carburizing and boranizing. Of all the methods, nitriding and oxidizing are
highly preferred as they possess better biocompatibility. Titanium nitride
c o m p o u n d s can be formed by surface modification techniques such as ion
implantation, plasma nitriding, plasma vapour deposition, chemical vapour
deposition and laser nitriding. Ion implantation is considered as a versatile
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technique to m o d i f y the surface to improve the corrosion and w e a r resistance

of the alloy /50/. It has been observed that there is 100-fold increase in w e a r
resistance in nitrogen ion implanted Ti-6A1-4V alloy than the un-implanted
Ti-6A1-4V alloy /51/. Studies by Sundararajan et al. h a v e shown that nitrogen
ion implanted T i - m o d i f i e d 3 1 6 S S exhibits three fold increase in corrosion
resistance when implanted with a dose o f 1 10 17 ions/cm 2 /52/. In addition,
in vitro studies by Sundararajan et al. /53,54/ have s h o w n the e n h a n c e d
corrosion resistance o f nitrogen ion implanted C P titanium and Ti-6AI-4V
alloy in R i n g e r ' s solution. Corrosion studies on Ti-6A1-4V alloy showed that
dose levels o f 4 10 16 and 7 10 16 ions/cm 2 lead to m a x i m u m corrosion
resistance in R i n g e r ' s solution /55,56/. T h e e n r i c h m e n t o f nitrogen in the
passive film and formation of oxynitrides in the implanted and passivated
layers have i m p r o v e d the corrosion resistance. Further, the thickness of the
passive film on the ion implanted specimen also increased after ion
implantation, thus leading to better surface property. Selection o f appropriate
d o s a g e is very important in improving the w e a r resistance o f the alloy.
Johnson et al. /57/ observed that there was n o specific i m p r o v e m e n t in the
17
wear resistance of the ion implanted specimens at the d o s e o f 5 10 N+
2
ions /cm when the sample was implanted in rabbit cortical bone and
retrieved at d i f f e r e n t time intervals. Thair et al. / 3 5 , 5 8 , 5 9 / have reported on
the corrosion resistance of Ti-6AI-7Nb s p e c i m e n s that were subjected to
nitrogen ion implantation at 100 k e V , where with a d o s e of 2.5 10 17
2
ions/cm corrosion resistance was superior in R i n g e r ' s solution as c o m p a r e d
to that o f the specimen implanted with the d o s e o f 3 10 17 ions /cm 2 . T h u s ,
selection o f an appropriate dose level is highly essential for achieving
optimum corrosion p e r f o r m a n c e . S I M S studies established the c h a n g e s in the
nature and composition of the implanted area as well as of the passive film
formed after implantation that had explained the enhanced corrosion
resistance for the nitrogen ion implanted Ti-6A1-4V and T i - 6 A l - 7 N b alloys in
simulated b o d y fluid. From these studies they o b s e r v e d a systematic increase
in N + concentration with increase in dose. T h e m a x i m u m N + concentration
reaches 2 0 a t % at a depth of approximately 0.35 with Ti-6Al-7Nb
17 2
specimen implanted with the dose of 2.5 10 ions/cm . Elemental profiles
of the passivated Ti-6AI-7Nb alloy showed that aluminum enriched in the oxide
layer in comparison to the bulk metal composition, while the concentration of
niobium in the oxide film is close to the value in the bulk alloy. O u t e r m o s t
nitride layers followed by oxynitride layers were observed f r o m the nitrogen
and oxygen profiles for the implanted-passivated s p e c i m e n s of the two
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alloys.
Though the corrosion resistance of ion implanted surface is very high, the
ion implanted layer is often found to wear off with time /60/. The techniques
such as plasma vapour deposition (PVD), plasma assisted chemical vapour
deposition (PACVD) are also being tried. However, the thickness of nitrided
zone achieved in all these methods is of only a few nanometers. In vitro
studies of Bordji et al. I6\l have shown that the cytocompatibility of PVD
and PACVD specimens is not as good as ion implanted specimens. Thair el
al. 1621 have noticed that plasma nitrided Ti-6Al-7Nb alloy showed
improvement in its corrosion behavior; however, the corrosion resistance was
lower than that for nitrogen ion implanted Ti-6Al-7Nb alloy and this was
attributed to the large size of titanium nitride precipitates formed on the surface
after plasma nitriding which increase the film dissolution. Presently laser
nitriding is being studied with great interest to modify the surface to obtain
very high hardness. The high energy of the laser beam causes the metal
surface to melt. This process takes place in a nitrogen-containing atmosphere
to produce titanium nitride coatings. The amount of nitride formed depends
on the melting time, i.e. on the scanning velocity of the laser beam. Using
this process, titanium nitride coatings of several 100 thickness can be
produced. The hardness of the surface as well as the thickness of the
modified zone was very high in the laser nitriding process owing to their high
power. The hardness levels obtainable with this process lie in the range of
1000 VHN in nitrogen-containing argon atmospheres and up to 2000 VHN in
pure nitrogen. Pure nitrogen atmosphere, however, results in the formation of
surface cracks, the number of which decreases with decreasing nitrogen
content. Crack-free surfaces were obtained in tests using pure helium and
with atmospheres containing nitrogen less than 70% /63/. Though cracking is
a major problem associated with laser nitriding, surface modification carried
out on the Ti-Zr-Nb alloys in nitrogen atmosphere by Geetha et al. /63,64/
using Nd:YAG laser has been shown to produce high hardness without crack
formation. However, the surface roughness of the laser nitrided specimens
was found to be very high. The surface melting is carried out in dilute as well
as in the pure nitrogen environment. Nitriding the alloy in pure and dilute
nitrogen environment results in a hardness of 1600 VHN, and 650 VHN,
respectively. Cracks are not observed either on the surface or in the vertical
cross section of the samples nitrided in the two different environments. XRD
analysis of the sample nitrided in pure nitrogen environment confirms the
formation of TiN, TiN 0 j, alpha and beta phases along with ZrN. Quantitative
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Authenticated
analysis by electron probe microanalysis () shows the enrichment of

zirconium and titanium in the dendrites. The corrosion resistance of the laser
nitrided samples in simulated body environment (Ringer's solution) was
found to be significantly better for the laser nitrided samples than the
untreated alloy. However, further in vitro and in vivo studies of these laser
nitrided specimens are necessary to gauge their suitability for biomedical
application.
The alternative technique used for surface modification is oxygen
diffusion treatment, which is known as oxygen diffusion hardening ( O D H )
technique. Several workers have tried various ODH treatments and proved
them to be very compatible. The abrasive wear of Ti-13Nb-13Zr is found to
be comparable to that of Co-Cr alloys when its surface is hardened by O D H
treatment. The abrasion resistance of diffusion-hardened Ti-13Nb-13Zr is
reported to be superior to that of Co-Cr alloys and TiN-coated Ti-6A1-4V.
The wear resistance of Ti-6AI-7Nb was found to be drastically improved by
ODH treatment. The corrosion rate of ODH treated titanium alloy was found
to be about 12 times less than that of the Ti-6A1-4V alloy and 20 times less
than that of the cobalt-chromium alloys I M I. The improved performance of
this technique is due to the adherent surface modification by oxygen
diffusion which does not spall or delaminate like the overlay coatings.
11. B I O C O M P A T 1 B I L I T Y
The surface characteristics and properties of a biomaterial like roughness,

area, hydrophobicity and porosity have a significant effect on bacterial
adherence and colonization. Most artificial materials, once implanted in the
patient's body, induce a cascade of reactions with the biological environment
through interaction of the biomaterial with body fluid, proteins and various
cells. The sequence of local events often leads to the classic foreign-body
response and the formation of a fibrous tissue capsule around an implant. It is
clear that a major factor influencing the (favorable or unfavorable) reaction of
the body is the biomaterial surface, since the first contact of the body is with
the surface. The specific surface interactions determine the body's response
to the foreign material, the path and speed of the healing process and the
long-term development of the biomaterial-body interface. Both the chemical
composition and the topography (structure, morphology) of a surface are
believed to be important in bone contacting implants. They regulate the type
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Vol 21, Nos. 2-3, 2003 Corrosion and Microstructural Aspects
and degree of the interactions that take place at the interface like adsorption
of ions and biomolecules such as proteins, formation of calcium phosphate
layers, interaction with different types of cells (macrophages, bone marrow
cells, osteoblasts). Thus, the nature of the initial interface that is established
between an artificial material and the attached tissue determines the ultimate
success or failure of the implant.
Materials to be used as permanent implants in the human body must,
therefore, be biocompatible, corrosion-resistant and tissue compatible in
order to serve for a longer period. No surgical implant has ever been shown
to be completely free of adverse reactions in the human body. Titanium is
considered to be well tolerated and nearly an inert material in the human
body environment. In an optimal situation titanium is capable of
osseointegration with bone 1651. In addition, titanium forms a very stable
passive layer (Ti0 2 ) on its surface and provides superior biocompatibility.
Even if the passive layer is damaged the layer is immediately rebuilt. In the
case of titanium, the nature of the oxide film that protects the metal substrate
from corrosion is of particular importance, and its physico-chemical
properties such as crystallinity, impurity segregation, etc. have been found to
be relevant. Surface roughness is particularly important for the integration
and stability of titanium devices in bone. In vitro cytotoxicity tests are often
conducted using L929 cells and osteoblast-like MC3T3- El cells. The
relative growth of these cells was estimated to test the cytotoxicity of the
developed alloy. Titanium alloys show superior biocompatibility when
compared to the stainless steel and chromium-cobalt alloys. In spite of the
above-stated merits, the question of the biocompatibility of titanium materials
has been widely discussed and various studies have been carried out.
Reservations have been expressed about the presence of long-term implants
made of Ti-6AI-4V because elements such as vanadium are toxic in the
elemental state. These concerns have led to the development of special
titanium implant alloys such as Ti-A15-Fe2.5 (TIKRUTAN LT 35) and Ti-
6Al-7Nb. In addition, the increased use of beta titanium alloys containing
zirconium, niobium, tin and tantalum as implant materials has been observed
in recent years, -titanium alloys also exhibit better cytocompatibility than
+ titanium alloys. Studies performed by Okazaki et al. 1661 showed that
the relative growth of the L929 and MC3T3-E1 cells for the beta alloys such
as Ti-15Zr-4Nb-4Ta, Ti-15Mo-5Zr-3Al, Ti-15Sn-4Nb-2Ta is much higher
than that for the Ti-6A1-4V alloy. Similarly, Mitsuo Niinomi et al. 1611 have
shown that the cell viability of Ti-29Nb-13Ta-4.6Zr is much superior than the
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TAV alloy. Thus, it is clearly evident the new -type biomedical titanium
alloys are more promising for biomedical applications than the conventional
+ titanium alloys.
12. COST EFFECTIVENESS
The machining cost of titanium is generally high and hence the titanium
products are not cost effective. One of the major requirements for a
biomaterial is the low cost price so that it is affordable by everyone. The cost
of the titanium products is lowered by precision casting method. However,
cast titanium alloys have low fatigue strength and low elongation compared
to wrought or forged ones due to the coarse microstructure. Hence
microstructural refinement is often required to improve the mechanical
properties without conducting deformation processing that is without
changing the shape of the products. Thermomechanical process with post
heat treatment is found to increase the strength, elongation and fatigue
strength of biomedical + titanium alloys. The improvement is supposed to
be due to high plastic deformability of unstable phase introduced by post
heat treatment. The other technique that is useful in producing cost effective
titanium alloys is powder metallurgy process. This method is a near net shape
process and therefore, effective in the reduction of the machining cost of
titanium alloys. Moreover, the alloys that are difficult to fabricate through the
ingot melting process can be easily fabricated by PM process. In addition,
powder metallurgical process is very useful in producing more homogenous
biomedical alioys with high melting point alloying elements such as Nb
and Ta /68/.
13. FUTURE RESEARCH
The corrosive wear resistance of new -titanium alloys such as Ti-29Nb-

13Ta-4.6Zr and Ti-29Nb-13Ta-4.6Sn is highly dependent on the mating
material 169/. As the bonding affinity of the mating material with the
substrate increases, the greater is the wear loss. Hence, a systematic approach
and detailed study on the wear behavior of the titanium alloys with different
mating materials has to be carried out in order to have a deeper understanding
of the wear mechanism of the alloys. Further, investigation on the wear
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Vol. 21, Nos. 2-3, 2003 Corrosion and MicrostrucluraI Aspects
b e h a v i o r of the biomedical alloys in the conditions similar to that of the

human system is highly necessary to develop an appropriate surface
modification technique that will e n h a n c e the life o f the biomedical alloy. T h e
combination o f metallic alloys with other biomaterials can result in implants
with improved mechanical and physical properties. Current a t t e m p t s in
designing c o m p o s i t e implants have not yielded highly successful results;
however, the future possibilities for improvement are promising. The
concurrent d e v e l o p m e n t s in other biomaterials, such as ceramics, and n e w e r
m o d i f i e d polyethylenes, such as cross-linked polyethylene, h o p e f u l l y will
result in i m p r o v e m e n t s in longevity of total joint r e p l a c e m e n t s either with the
success o f alternate b e a r i n g surfaces or with the use o f c o m p o s i t e materials.
Further work on titanium alloys should be continued in this direction to
improve their p e r f o r m a n c e .
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Geetha Manivasagam et al.

CORROSION AND MICROSTRUCTURAL ASPECTS OF

G e e t h a Manivasagam 3 , U. Kamachi Mudali b , R.Asokamani 0

T i t a n i u m is a w o n d e r metal, generally considered as one o f the m o s t

T h e n e w century has d a w n e d with m a n - m a d e materials and devices

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T h e use of artificial materials to repair fractured, diseased tissues and

or cobalt in the synthesis of Vitamin BI 2 , but however cannot be tolerated in

Elements 316LSS CoCrMo CoNiCrlMo

demerits led to the evolution of new alloys with non-toxic elements. T h e

Titanium as an element has extremely low toxicity, and is well tolerated

Titanium is relatively a light metal having a density of 4.54 g/cirr, which

structure by increasing the transformation t e m p e r a t u r e greater than 8 8 3 C ,

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Although titanium and + titanium alloys possess excellent corrosion

Corrosion, the gradual degradation of materials by electrochemical attack,

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Metal Most stable metal A G 0 per mol of

The corrosion behavior of various titanium alloys in different

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titanium alloys T i - 6 A I - 4 V , T i - 6 A I - 7 N b and T i - 1 3 N b - 1 3 Z r in phosphate-

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Ti-6Al-7Nb alloys. Similarly increase in the pH value was also found to

It has been suggested that the localized variations in stress, microstructure

microstructure, possibly more beta than alpha phase to improve corrosion

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temperature (680C and water quenched) possessed superior corrosion

Appropriate selection of the alloying elements and thermomechanical

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different physiological environments. In general, a coarse m i c r o s t r u c t u r e is

9.1 Modulus of elasticity

T h e failure of biomedical implants d u e to their high m o d u l u s has been

(ST), aged 1060-1100 1000-1060 18-22 64-73

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Table 7. Modulus of elasticity of titanium and its alloys

Alloy Young's Modulus Young's Modulus

Stainless steel 220 -

9.2 W e a r of titanium and its alloys

Wear is a surface phenomenon that occurs by displacement and

compared to the Ti-6A1-4V alloy. Though the Ti-13Nb-13Zr alloy possesses

Long-term performance of surgical implants is often restricted by their

technique to m o d i f y the surface to improve the corrosion and w e a r resistance

analysis by electron probe microanalysis () shows the enrichment of

The surface characteristics and properties of a biomaterial like roughness,

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12. COST EFFECTIVENESS

13. FUTURE RESEARCH

The corrosive wear resistance of new -titanium alloys such as Ti-29Nb-

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b e h a v i o r of the biomedical alloys in the conditions similar to that of the

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11. Y. Okazaki, E. Nishimura, H. Nakada and K. Kobayashi. Biomaterials,

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implanted Ti-6AI-4V and Ti-6AI-7Nb alloys". Proceedings of the First

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47. H.S. D o b b e s and T. Scales. " B e h a v i o r o f commercially pure titanium

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ion implanted Ti-6A1-4V and T i - 6 A I - 7 N b alloys using S I M S , Corrosion