Trends Biomater. Artif.
Organs, VolMetallic
24(1), pp Biomaterials
69-82 (2010) of Knee and Hip - A Review
Metallic Biomaterials of Knee and Hip - A Review
Marjan Bahrami Nasab, Mohd Roshdi Hassan
Department of Mechanical and Manufacturing Engineering,
Engineering Faculty University Putra Malaysia
Received 1July 2009, Accepted 5 September 2009, Published online 27 January 2010.
Introduction
One of the most significant current discussions
in orthopedic is the total joint replacements
especially hip and knee and the increasing
trend to replace degraded and destroyed
biological materials by artificial organs. It is
estimated that approximately 1 million hip
replacements and 250,000 knee replacements
are carried out per year [1]. This number is
expected to double between 1999 and 2025 as
a result of aging populations worldwide and
growing demand for a higher quality of life [2].
Another statistical data estimated that by the
end of 2030, the number of total hip
replacements will increase by 174% and total
knee arthoplasties is predicted to grow by 673%
from the present rate [3]. An increasing trend of
the number of knee replacements in different
countries over the last 10–15 years is shown in
fig 1.
Yet-increasing demand for implants makes it
crucial to accelerate efforts on biomaterials.
Unfortunately, the currently used materials have
been found to have tendencies to fail after long-
term usage due to not fulfilling some vital
requirements such as modulus close to that of
bone, high wear and corrosion resistance and
good biocompatibility. Rimnac et al.[4]
investigated the failure of orthopedic implants
in three case studies (hip and knee) and
illustrated that both material and design
deficiencies contribute to failure of total joint
replacements. Failure of current biomaterials
imposes pain for patient and after some time
revision surgery should be performed.
1
http://www.sbaoi.org
The purpose of this paper is to review some
recent researches about presently used
metallic biomaterials and discuss on great
potential of NiTi and porous NiTi shape memory
alloys (SMA) for orthopedic implant. Meanwhile
this study seeks to address the following
questions:
1) When a material is going to be used in the
human body, what kinds of requirements should
be fulfilled by that material to be considered as
a successful biomaterial?
2) What kind of problems can occur if these
requirements are not satisfied by the material?
3) Which of the requirements present in the
currently used materials and which cannot be
fulfilled?
4) What solutions are available for improving
the properties which are not completely
satisfied by the biomaterials?
5) Do the NiTi and porous NiTi shape memory
alloys have necessary requirements to be
utilized as a metallic biomaterial for orthopedic
implants especially hip and knee?
The reminder of this paper is organized as
follows; section 2 describes the requirements
and general issue about biomaterials. So the
two first research questions will be answered
in this section. Section 3 will address questions
3-5. Superior properties of these materials will
be discussed in section 4. Final section
concludes and purposes further works.
 70 M.B. Nasab, M.R. Hassan

[5] pointed out in his paper that fatigue fracture

leads some of major problems associated with
implant loosening, stress-shielding and
ultimate implant failure and it is frequently
reported for hip prostheses. Fatigue
characteristics are strongly depends on the
microstructures. The microstructures of
metallic biomaterials alter according to the
processing and heat treatment employed [6].

Adequate Strength

Strength of materials from which the implants

Figure 1: Estimated number of knee replace-
ments in different countries [4]
Requirements of Biomaterials: general issues
and concerns
An implant should possess some important
properties in order to long-term usage in the
body without rejection. The design and selection
of biomaterials depend on their mechanical and
non- mechanical characteristics.
Mechanical properties
The mechanical properties such as hardness,
tensile strength, modulus, elongation (strain),
fracture resistance and fatigue strength or life
play an important role in material selection for
application in the human body.
Long fatigue life
The fatigue strength is related to the response
of the material to the repeated cyclic loads. Teoh
are fabricated has influence the fracture of
artificial organ. Alvarado et al. [7] and Geetha et
al.[8] explained that inadequate strength can
cause to fracture the implant. When the bone-
implant interface starts to fail, developing a soft
fibrous tissue at the interface can make more
relative motion between the implant and the
bone under loading. This fact causes pain to
the patient and after a certain period, the pain
becomes unbearable and the implant must be
replaced, by a revision procedure.
Modulus equivalent to that of bone
For major applications such as total joint
replacement, higher yield strength is basically
coupled with the requirement of a lower
modulus close to that of human bones [9, 10] .
The magnitude of bone modulus varies from 4
to 30 Gpa depending on the type of the bone
and the measurement direction [11]. Au et al.[12]
and Geetha et al.[8] emphasized about the
modulus and described that the large difference
in the Young’s modulus between implant
material and the surrounding bone can
contribute to generation of severe stress
concentration, namely load shielding from
natural bone, that may weaken the bone and

Table 1: Requirements of biomaterials and problems derived from

inadequate requirements
Significant requirements
Long fatigue life
Adequate strength
Modulus equivalent to that of bone
High wear resistance
High corrosion resistance
Biocompatibility
Osseointegration
Consequences of not fulfilling the requirements
Implant mechanical failure and revision surgery
Implant failure, pain to patient and revision surgery
Stress shielding effect, loosening, failure, revision surgery
Implant loosening, severe inflammatory response, destruction of
the healthy bone
Producing wear debris which can go to blood
Releasing non compatible metallic ions and allergic reactions
Body reaction and adverse effects in the organic system
Fibrous tissue between the bone and the implant, not well
integration of the bone and implant and finally implant loosening
 Metallic Biomaterials of Knee and Hip - A Review
Figure 2: Total knee and hip implants’ compo-
nents
deteriorate the implant/bone interface,
loosening and consequently failure of implant.
The modulus is considered as a main factor for
selection of total knee replacement (TKR)
materials.
Non-mechanical requirements
In addition to the above mentioned mechanical
properties, some non-mechanical
requirements which have significant role in
performance of the material in the human body
are describe here.
High corrosion resistance
Singh & Dahotre [13] researched on corrosion
resistance as an important issue in selection
of metallic biomaterials because the corrosion
of metallic implants due to the corrosive body
fluid is unavoidable. The implants release
undesirable metal ions which are non-
biocompatible. Corrosion can reduce the life of
implant device and consequently may impose
revision surgery. In addition the human life may
be decreased by the corrosion phenomenon.
Okazaki & Gotoh [14] expressed the fact that
dissolved metal ions (corrosion product) either
can accumulate in tissues, near the implant or
they may be transported to other parts of the
body. They revealed for example, replacement
of 20 stainless steel Charnley hip arthroplasties
in the human body after 10–13 years showed a
considerably higher metallic concentration in
body fluid in comparison with that without
implant. This included Ni concentration in blood
of ~0.51 µg/L, in plasma of ~0.26 µg/L and in
urine of ~2.24 µg/L, and Cr level in plasma of
~0.19 µg/L. Alike, the Ti concentration of ~135.57
71
µg/L was found in the serum of patients with
failed Ti–6Al–4V total knee replacements after
57 months which was greatly more than in the
control.
High wear resistance
The low wear resistance or high coefficient of
friction results in implant loosening [7, 15]. Wear
debris are found to be biologically active and
make a severe inflammatory response that lead
to the destruction of the healthy bone which
supports the actual implant. Corrosion caused
by friction is a big concern since it releases non
compatible metallic ions. It should be pointed
out that mechanical loading also can result in
corrosion fatigue and accelerated wear
processes.
Biocompatibility
One of the most important non-mechanical
requirements of orthopedic biomaterials is the
biocompatibility. Biocompatibility is the ability
to exist in contact with tissues of the human
body without causing an unacceptable degree
of harm to the body. It is not only associated to
toxicity, but to all the adverse effects of a material
in an biological system [8, 16]. Navarro et al.[16]
supported the study of Smallman and Bishop
[17] and with retrospect to the last 60 years,
categorized three generations for evolution of
biomaterials: bioinert materials, bioactive and
biodegradable materials and materials
designed to stimulate specific cellular
responses at the molecular level. Bioinert is
related to reduce the body reaction to the implant
to a minimum. Bioactivity defined as the ability
of the material to interact with the biological
environment to enhance the biological
response. The third generation refers to the
capability of the material to stimulate specific
cellular responses at the molecular level.
Williams [18] defined the biomaterial
requirements of total joint replacements in
terms of biocompatibility as, optimizing the
rate and quality of bone apposition to the
material, minimizing the release rate of
corrosion and the tissue response to the
released particles, minimizing the release rate
of wear debris and the tissue reaction to this
debris and optimizing the biomechanical
environment in order to minimize disturbance
to homeostasis in the bone and surrounding
soft tissue.
72 M.B. Nasab, M.R. Hassan
Osseointegration
Osseointegration is fundamental in orthopedic.
Several literatures explained about the
integration of the implant with adjacent bone
and tissue [7, 8, 19]. Osseointegration defined
as the process of formation of new bone and
bone healing. The incapability of an implant
surface to join with the adjacent bone and other
tissues due to micromotions, results in
formation of a fibrous tissue around the implant
and promote loosening of the prostheses. Thus,
materials with a proper surface are extremely
essential for the implant to integrate well with
the surrounding bone. Surface chemistry,
roughness and topography are all parameters
that influence both the osseointegration and
biocompatibility [20]. It should be considered
that in addition to properties of the implanted
biomaterial, the characteristics and
regenerative capability of the host bone affect
the osseointegration of biomaterial [21]. All the
above required properties for biomaterials are
summarized in table1.
Metallic Biomaterials
Implants are fabricated from a wide variety of
materials, including metals, polymers, ceramics
and their composites. Among these materials,
metals are an important group, for instance
knee implant has some metallic parts. Current
total knee replacement mainly has three
components: femur, tibia (includes tibial tray and
tibial insert) and patella or kneecap. The tibial
insert and the patellar components are usually
made of plastics such as ultra-high molecular
weight polyethylene (UHMWPE) or cross-
linkedpolyethylene. The femoral component
and tibial tray are metallic parts and tend to be
made of titanium alloys, stainless steel or cobalt
chromium with small amount of molybdenum
(Co-Cr-Mo) [22, 23]. Another application of
metals is in design of hip joint implant which
includes an alloy femoral stem ( Ti alloy) with a
metallic or ceramic femoral head moving in an
acetabular cup that is normally made of
UHMWPE [17]. The components of knee and
hip implants shown in fig 2. In the following,
metallic biomaterials are divided to current and
promising materials and described
respectively.
Current Metallic Biomaterials
Stainless steel, Co-Cr alloys and Ti alloys are
the current metals used in orthopedics
application such as knee and hip implant. This
section provides information about these
materials and answers research question 3 and
4.
Stainless Steel
Stainless steel is the generic name for a
number of different steels used primarily
because of their resistance to a wide range of
corrosive agents due to their high Cr content.
The Cr in the stainless steel has a great affinity
for oxygen, which allows to the formation of a
film of chromium oxide on the surface of the
steel at a molecular level which is passive,
adhesive, tenacious and self-healing [7, 16]. In
spite of this fact, Singh & Dahotre [13] indicated
that stainless steel implants are often degraded
due to pitting, crevice, corrosion fatigue, fretting
corrosion, stress corrosion cracking, and
galvanic corrosion in the body. Their corrosion
resistance can be modified by lowering the
nickel content and alloying them with Mn or N.
The wear resistance of austenitic stainless
steel is relatively poor. So rapid loosening is
generated by the large number of wear debris.
Worse corrosion resistance as well as the
danger of allergic reaction which appears in a
big number of patients [16, 24] restricts their
application in orthopedic joint prosthesis.
Moreover the modulus of stainless steel is
about 200 GPa which is much higher than that
of bone.
Stainless steel has several types and the most
mainly used for manufacturing implants is
austenitic stainless steel. Stainless steel 316L
is the type widely used in traumatological
temporary devices such as fracture plates,
screws and hip nails. Stainless steel has been
used for wide range of application due to easy
availability, lower cost, excellent fabrication
properties, accepted biocompatibility and great
strength.
Cobalt-Chrome
Cobalt chromium alloys can be basically
categorized into two types; one is the Co-Cr-Mo
alloy (which is usually used to cast a product)
and the second one is Co-Ni-Cr-Mo alloy, (which
is usually wrought by hot forging). The castable
Co-Cr-Mo alloy has been used in dentistry for
long time and recently in making artificial joints.
The wrought Co-Ni-Cr-Mo alloy is a relative
 Metallic Biomaterials of Knee and Hip - A Review
newcomer material which is now used for
making the stems of prosthesis of heavily
loaded joints such as the knee and hip [7].
Cobalt-based alloys are highly resistant to
corrosion even in chloride environment due to
spontaneous formation of passive oxide layer
within the human body environment [7, 15, 16,
25, 26]. These materials have superior
mechanical properties such as high resistance
to fatigue and cracking caused by corrosion with
a good wear resistance. Also they are not brittle
because they have a minimum of 8% elongation.
These materials have a high elastic modulus
(220–230 GPa) similar to that of stainless steel
(approx. 200 GPa) which is higher than that of
cortical bone (20–30 GPa)[7, 15]. Elements
such as Ni, Cr and Co are indicated to be
released from the stainless steel and cobalt
chromium alloys due to the corrosion in the
human body [14]. It has been found that Ni, Cr
and Co are the most toxic ions. The corrosion
products of Co-Cr-Mo are more toxic than those
of stainless steel 316L. The thermal treatments
used to Co-Cr-Mo alloys modifies the
microstructure of the alloy and alters the
electrochemical and mechanical properties of
the biomaterial [25].
Ti and Ti Alloys
Manufacturing of titanium implants date back to
the late 1930s. There are three structural types
of titanium alloys: Alpha (α), Alpha-Beta (α-β) or
metastable β and Beta (β).The β phase in Ti
alloys tends to exhibit a much lower modulus
than α phase, and also it satisfies most of the
other necessities or requirements for orthopedic
application [27, 28].
Shenhar et al,. [29], Alvarado et al.[7], Budzynski
et al.[30], Geetha et al.[8] and Navarro et al.[16]
described the Titanium-based materials
properties. Ti alloys due to the combination of
its excellent characteristics such as high
strength, low density (approx. 4700 Kgm-3), high
specific strength, good resistance to corrosion
(due to the formation of an adhesive TiO2 oxide
layer at the surface), complete inertness to body
environment, enhanced biocompatibility,
moderate elastic modulus of approximately 110
GPa are a suitable choice for implantation. Ti
and its alloy also have this ability to become
tightly integrated into bone. This high capacity
to join with bone and other tissues considerably
73
Figure 3: Schematic of martensitic and reverse
transformations
improves the long-term behavior of the
implanted devices, decreasing the risks of
loosening and failure. Typically good clinical
outcome from rough surfaces of Ti and its alloy
is resulted when compared to smooth-surfaced
implants due to the good osseointegration
between the bone and the implant [31].
Commercially pure Ti (CP Ti) and Ti–6Al–4V
ELI (Ti64, Extra Low interstitial) are most
commonly used titanium materials for implant
applications. Ti-6Al-V4 is slowly replacing CP
Ti due to the greater mechanical strength [28].
According to Navarro et al. [16] and Geetha et
al.[8], long-term performance of titanium and
its alloys mainly Ti64 has raised some concerns
because of releasing aluminum and vanadium.
Both Al and V ions are associated with long-
term health problems, like Alzheimer disease
and neuropathy. Furthermore when titanium is
rubbed between itself or between other metals,
it suffers from severe wear [32]. High friction
coefficient and a rather high propensity to
seizure are attributed to this alloy [30]. Therefore
their application is limited to the locations on
the implant surface where wear resistance is
not of vital importance [27]. For example, the
poor wear resistance of titanium alloys avoids
their use for femoral head applications in typical
hip implant although the femoral stem is often
made of these alloys. Rostoker & Galante [33]
measured wear rates by in vitro methods on
UHMW-PE when rubbed by a oppose face of
the Ti-6% AI-4% V, ELI grade (ASTM F-136) with
various prepared surfaces and compared the
result with stainless steel or cast Co-Cr-Mo alloy.
74 M.B. Nasab, M.R. Hassan
Simply polished titanium alloy demonstrated an
unusual wear rate which was one order of
magnitude larger than polished AISI 316
stainless steel or cast Co-Cr-Mo alloy. Wear-
corrosion also can occur for Ti, but Ti–6Al–4V
can be modified by replacing V with Nb, Zr or Ta
in order to make it more biocompatible and
corrosion resistant [13]. . Semlitsch [34]
developed a hot forged and surface treated Ti-
6AL-7Nb and observed the same α/β structure
as Ti-6AI-4V and equally good mechanical
properties. Moreover Nb solved the problem of
releasing vanadium. The authors concluded
that the alloy is a real alternative to the wrought
Ti-6Al-4V alloy manufacturing of endoprosthetic
components. A variety of surface treatment
methods, such as ion implantation, Titanium
nitride (TiN) coating, and thermal oxidation, have
been proposed to enhance the wear resistance
[29, 30] and osseointegration [20, 31] by altering
the nature of the surface. Processing of Ti and
its alloy include of machining, forging or heat
treating is not easy [8, 16]. Two recently
developed promising biomedical alloys, Ti-
35Nb-7Zr-5Ta (TNZT) [35] and Ti-29Mo-13Ta-
4.6Zr (TNTZ) [36], show significant
improvement, in the aspect of accompanying
the high yield strength and low modules,
compared to previous generation alloys such
as Ti-6Al-4V, stainless-steel and cobalt–
chromium-based alloys [27].
The applications of Ti and its alloys include
dental implants and parts for orthodontic
surgery, joint replacement components such as
knee and hip, bone fixation devices like nails,
screws and plates, artificial heart valves and
surgical instruments.
Promising Materials
Shape memory alloys (SMA) provide new
insights for the design of biomaterials for
artificial organs and advanced surgical
instruments, since they have unique
characteristics and superior properties [37, 38].
Some unusual properties of these materials
are: one-way and two-way shape memory
effects, superelastic effect, high damping
property and rubber-like effect. Some literatures
about NiTi SMA and porous NiTi SMA are
overviewed in this section and important
aspects about these materials (RQ5) are
illustrated.
Dense NiTi shape memory alloy
Among several tens of shape memory alloys,
NiTi alloy is considered to be best due to its
excellent properties.
Phase Transformation and properties
NiTi can have three different forms; martensite
or the low-temperature phase, stress-induced
martensite or superelastic and austenite or the
high temperature phase. The reference
temperatures indicated in figure 3 show the
start and finish temperatures for the forward
transformation to martensite and the reverse
transformation to austenite, respectively. The
martensitic transformation can occur when the
alloy in the austenitic phase is cooled through
Ms--->M f, producing martensite. The reverse
transformation occurs when the alloy is heated
through A s--->A f and the material structure
returns to that of austenite. The transformation
from austenite to martensite accompanied by a
large recoverable strain. The martensitic
transformation also can be induced by stress
in a shape memory alloy at temperatures above
Ms. An increase in the applied stress provides
an effect analogous to a decrease in
temperature.
The main properties of the SMA are generally
determined by the phase transitions from
austenite to martensite and vice versa. When
the material is in its martensite form, it is soft
and ductile and can be easily deformed.
Superelastic NiTi is highly elastic (rubber-like)
while austenitic NiTi is quite strong and hard
(similar to titanium). Their specific expression
depending on the temperature in which they are
used. Alvarado et al. [7] explained the properties
of NiTi material. NiTi alloys have this ability to
combine high recovery strain, high strength as
well as a relatively low Young’s modulus. The
low elastic modulus of NiTi which is much
closer to that of bone than any other implant
metal might provide benefits in specific
applications. NiTi has unique high fatigue
resistance and ductile properties, which are
also related to its martensitic transformation.
High dampening capacity could be useful in
some cases. These properties are typically
favorable in orthopedic implantation
applications. Also, high wear resistance has
been reported compared to the Co-Cr-Mo alloy.
In addition NiTi is a non-magnetic alloy, so
magnetic resonance imaging (MRI) is possible.
 Metallic Biomaterials of Knee and Hip - A Review
Concerning Issues and Biocompatibility
Ni release from the surface of NiTi implants
which is the concerning issue of NiTi alloys have
been discussed by Kapanen et al. [39],
Mantovani [37], Machado & Savi [40] and Geetha
et al.[8]. It has been found that although, Nickel
is a necessary element for life and it is able to
stimulate the immune system [41], but it can be
severely poisonous when the high nickel
content of NiTi are generated due to the
dissolution of nickel ions or wear particles from
the alloy. Releasing of this element above
certain concentrations brings some allergic
reaction and biocompatibility problems such as
pneumonia, chronic sinusitis and rhinitis, nostril
and lung cancer for patients.
Researches on the biocompatibility of shape
memory alloy started from 1976. Castleman et
al.[42] investigated on the biocompatibility of
nitinol alloy through in vivo studies on femurs of
beagles using Cr-Co reference controls
(sham). Their results demonstrated no evidence
of either localized or general corrosion on the
surfaces of the bone plates and screws, no
signs of adverse tissue reactions resulting
from the implants and no metallic contamination
in the organs due to the implants.
Shabalovskaya [43] reviewed biocompatibility
of NiTi and performed X-ray surface
investigation. The author drew conclusions
include good biological response in vivo and
tendency of Nitinol surfaces to form TiO2 oxides
with only a minor amount of nickel. He pointed
out that a certain toxicity which usually observed
in vitro studies, probably resulted from the higher
in vitro Ni concentrations that are impossible to
attain in vivo. At the end it was concluded that
biocompatibility of Ni–Ti alloys is similar to that
of titanium, Co–Cr and stainless steel alloys.
Berger-Gorbet et al.[44] evaluated the
biocompatibility of Nitinol screws by comparison
with vitallium, CP titanium, duplex austenitic-
ferritic stainless steel and stainless steel 316L
and observed a slower osteogenesis process
with no close contact between implant and bone
in NiTi screws compared with the others.
Ryhaenen et al.[45] studied soft tissue
response and biocompatibility of Nitinol in vivo
and performed a comparison between Nitinol,
stainless steel and Ti-6Al-4V. The authors
observed clearly nontoxic response of muscular
tissues to NiTi regardless of the time period,
similarity of overall inflammatory response to
75
Nitinol, stainless steel and Ti-6Al-4V alloy, no
necroses, granulomas, or signs of dystrophic
soft tissue calcification, low response of
immune cell to Nitinol and no qualitative
differences in histology between the different
tested materials. In addition the encapsulated
thickness was equal to all the materials
examined. Based on the results of their study,
Nitinol has good potential for clinical use.
Ryhanen [46] reviewed researches on
biocompatibility of Nitinol and considered
fundamental aspects of biological responses
to Nitinol. It was indicated that most studies
supported the good biocompatibility of Nitinol
but it was not well demonstrated the long-term
in vivo performance of Nitinol and the host-
Nitinol interactions at cell and molecular level.
Finally it was concluded that Nitinol is a safe
biomaterial, at least as good as stainless steel
or titanium alloys. Kapanen et al.[39] determined
the biocompatibility of NiTi alloy on bone
formation in vivo study. They compared NiTi with
stainless steel and Ti-6Al-4V. The researchers
concluded good biocompatibility as its effects
on ectopic bone formation are similar to those
of stainless steel and the amount of nickel
released from NiTi implants was lower than the
concentration required inducing toxic reactions.
Balakrishnan et al. [47] tested the
biocompatibility of Nitinol, a nickel titanium alloy,
and stainless steel as bladder implant
materials. Similar tissue effects in all groups
with small or no inflammation was observed
and it was designated that Nitinol may be more
inert than stainless steel. Es-Souni [48]
reviewed papers published on the
biocompatibility of NiTi alloys and indicated that
NiTi SMA are usually characterized by good
corrosion properties, in most cases better than
those of conventional stainless steel or Co–
Cr–Mo based biomaterials. The majority of
biocompatibility studies demonstrated good
biocompatibility. It is also obtained that smooth
surfaces with well controlled structures and
chemistries of the outermost protective TiO2
layer results in to negligible amount of Ni
leaching, with concentrations below the normal
human daily intake.
It is obvious that although, there are few reports
on release of Ni from NiTi implants, but most of
in vivo studies and in vitro experiments
demonstrate excellent biocompatibility of this
material.
76 M.B. Nasab, M.R. Hassan
Figure 4: Failure of different metallic biomaterials for long term use in body
Surface Modification (enhanced
biocompatibility)
In addition to the above studies which
expressed good biocompatibility of NiTi, other
scholars investigated on surface modification
and coating to achieve high connection between
bones and implant, high corrosion resistance
and good biocompatibility. Firstov et al.[49]
performed surface oxidation in air on
mechanically polished NiTi alloy in temperature
range 300–800 °C and observed that oxidation
treatment at temperatures close to 500 °C
generates a smooth protective nickel-free oxide
layer that is in favour of good biocompatibility of
NiTi implants. Chen et al.[50] produced a thin
apatite layer on NiTi alloy implants in situ. The
results illustrated that large amount of new bone
was directly in contact with the host bone but
the uncoated implant/bone interface has gaps
and fibrous layer was generated. Chan et al.[51]
worked on oxygen and sodium plasma on NiTi
SMA. The method enhanced the bioactivity and
corrosion resistance of NiTi but the treatment
changed the bulk mechanical property and
phase transformation temperature. Chu et
al.[52] described the recent applications of
plasma immersion ion implantation (PIII) to the
surface modification of NiTi orthopedic
materials. It was found that the method
produced an effective surface barrier to diminish
Ni out-diffusion and the PIII treated NiTi rods
maintained the shape recovery properties by
using the proper conditions. Michiardi et al. [53]
compared the electrochemical behavior of NiTi
surfaces oxidized by a new oxidation treatment
with untreated NiTi surfaces and concluded that
the new oxidation treatment was capable of
protecting NiTi surfaces from electrochemical
degradation and, thus, NiTi can be a superb
candidate for biomedical applications. Ng et
al.[54] modified surface of NiTi by laser surface
modification methods. It was demonstrated that
the modified layers which were free from micro-
cracks and porosity acted as barrier to Ni
 Metallic Biomaterials of Knee and Hip - A Review
Figure 5: A schematic superelastic stress-
strain curve
release and improved bulk properties, such as
hardness, wear and corrosion resistance.
Shabalovskaya et al. [55] reviewed different
studies on surface modifications of NiTi SMA
and discussed about bare Nitinol surfaces,
mechanical, chemical and electrochemical
techniques and heat treatments for their
modifications. Meanwhile the authors
investigated about the biological response to
bare Nitinol surfaces. Surface modifications with
ion and energy sources includes conventional
and plasma immersion ion implantation and
laser surface melting, sol–gel and hydrogen
peroxide, bioactive surfaces and Nitinol surface
under strain all are overviewed in their work.
Although most of literatures on surface
modification of NiTi have provided good results
in favor of Ni release as well as the
biocompatibility, but it should be considered that
these modifications may affect mechanical
properties. There have been a few studies which
examined the mechanical properties after
surface treatment. However Chu et al.[56]
developed an electropolishing (EP) and
photoelectrocatalytically oxidation (PEO)
surface on biomedical nickel titanium shape
memory alloy and investigated the
microstructure, nickel suppression and
mechanical characteristics. They indicated that
PEO resulted in formation of a sturdy titania film
on the EP NiTi substrate. A Ni-free layer near
the top surface and a graded interface between
the titania layer and NiTi substrate were
observed which was greatly efficient for both
biocompatibility and mechanical stability.
Moreover, Ni ion release from the NiTi substrate
was suppressed (10-week immersion test).
The modulus and hardness of the modified NiTi
surface was greater than before, with larger
77
indentation depths which were slightly higher
than those of the NiTi substrate but a lot lower
than those of a dense amorphous titania film.
The authors compared mechanical properties
of NiTi with after undergoing only EP. Their
results demonstrated that surface modification
by dual EP and PEO can remarkably decrease
Ni ion release and improve the biocompatibility
of NiTi without the degradation of the surface
mechanical properties. It makes the treated
materials suitable for hard tissue
replacements.
It can be concluded that NiTi shape memory
alloy has good biocompatibility and can be
improved to a higher level of compatibility with
biological system by the help of surface
modification. Meanwhile the recent work
emphasize that mechanical stability can also
be obtained after the treatment.
Porous NiTi
Porous NiTi has been considered as one of the
promising biomaterials in surgical implants
which have been used in medical fields in
Russia and some other countries. The porous
materials have many applications, ranging from
spinal fixation to acetabular hip prostheses,
dental implants, permanent osteosynthesis
plates, etc [57]. Porous biomaterials are divided
into two categories: solid substrate with porous
coating and integral porous body. Study of
integral porous body has attracted more
attention due to some problems such as
developing only at the interface and not easy
machining due to brittleness in the first group
[58].
Properties and privileges
Some literatures demonstrated that
interconnected open pores and large surface
area induce transport of body fluids (helps to
accelerate the healing process) and in-growth
of bone tissues in this special material. Porous
nature of NiTi biomaterial enables tissue and
bone cells to penetrate and integrate with the
implant and provides strong anchor between
surrounding bone and tissue with the implant.
This promotes long-term fixation without the
need for bone grafting and prevents the
loosening of implants [8, 57, 59-61]. Super-
elastic behavior also remains after tissue in-
growth [62]. Zhang et al,.[63] observed that the
78 M.B. Nasab, M.R. Hassan
porous Ti–50.8 at. % Ni SMA which was
fabricated by capsule free hot isostatic pressing
process had a recoverable strain as high as
4% in terms of a linear superelasticity. They
indicated that under a high-cyclic strain level,
the degradation of superelastic effect only was
in the first fatigue cycle and thereafter the good
linear superelasticity was maintained. Studies
on the superelastic behavior, different pore size
and various heat treatment conditions of NiTi
produced by gas expansion method revealed
that the NiTi with 16% porosity exhibited
excellent combination of mechanical properties
such as high strength (1000 MPa), low young
modulus (15 GPa), large compressive ductility
(>7%), large recoverable strains (>6%) and
high-energy absorption (>30 MJ/m 3 ) [8].
Bansiddhi et al,.[64] introduced some of the
important properties of porous NiTi. These
porous materials provide a combination of high
strength, high toughness and relatively low
stiffness. High strength is an important
parameter for preventing deformation or
fracture, high toughness is essential to avoid
brittle failure and low stiffness or low modulus
is useful to minimize stress shielding effects
[8, 61, 65]. Shape-recovery behavior can make
good mechanical stability within the host tissue
[64]. Meanwhile it has been obtained that an
appropriate range of pore sizes and
interconnectivity enable a morphology similar
to that of bone [57].Generally porous SMAs have
the ability to carry significant loads. These
materials offer the possibility of higher specific
damping capacity under dynamic loading
conditions in comparison with dense SMA
materials [66]. It has been demonstrated that a
considerable part of the impact energy is
absorbed [67].
Biocompatibility and surface treatment
Porous NiTi has good biocompatibility,
comparable to conventional porous stainless
steel and titanium implant materials [68]. No
adverse tissue response due to the implant
occurs and no fibrous tissue is formed at the
interface of new bone/ implants for the porous
NiTi alloy. Porous NiTi alloy shows better
osteoconductivity and osteointegration than
bulk one [61]. Porous NiTi SMA is less corrosion
resistant than the solid one [60] because the Ni
release is unavoidable due to the large exposed
surface area which directly contacts with
adjacent bone and tissue. In order to prepare
porous NiTi surfaces with minimal or negligible
Ni release and corrosion rates, several surface
treatments have been used to create uniform,
homogeneous, and thick TiO2 on NiTi surfaces.
Some surface modification can reduce Ni
release rate by a factor of 3–24 to levels below
the normal daily Ni intake [64]. The amount of
nickel that is normally present in food with the
dietary intake of nickel estimated to be in the
range of 300–600 µg per day [69]. Current
surface treatments applied on porous NiTi
consist of thermal annealing, oxygen plasma
immersion ion implantation, pre-soaking in SBF
solution, HA coatings, TiN and TiO2-PVD
coatings, chemical treatment and combinations
thereof. Jiang & Rong [70] produced
hydroxyapatite coating on porous NiTi shape
memory alloy. The results illustrated greatly
decrease in the amount of nickel release from
the porous NiTi SMA after formation of a uniform
hydroxyapatite layer. The amount of Ni release
after 50 days for untreated was 6.7 ppm and for
treated surface was 0.48 ppm. Wu et al.[71]
performed thermal annealing for porous NiTi.
The optimized annealing temperature was
found to be 450 °C. In lower temperatures (300–
450 °C) Ni leaching level of treated NiTi
decreased by a factor of two as compared to
untreated NiTi (from0.45 ppm to 0.2 ppm). Ho
et al. [59] investigated oxygen plasma
immersion ion implantation (PIII) method for
porous NiTi. Their observation showed that Ni
release was considerably reduced after oxygen
PIII and excellent durability of the layer in a
biological medium was approved. The authors
concluded that depletion of Ni from the near
surface region after oxygen PIII and the high
corrosion resistance of the oxygen rich surface
layer can provide better properties. All the
literatures confirm that the amount of Ni release
can considerably decrease after surface
modification, but in their study the effect of
surface treatment on superelasticity and other
mechanical properties is not investigated.
Practical use of porous NiTi SMA requires a
complete research on surface modification
accompanying with examining mechanical
properties and biological response to the
treated material. Figure 4 shows failure of
different metallic biomaterials for long term use
in body. Since NiTi SMAs have enough potential,
so their superelastic behavior and damping
properties are explained in the next section.
 Metallic Biomaterials of Knee and Hip - A Review
Advantages of the superior properties of dense
and porous NiTi shape memory alloy
Shape memory alloy in addition to fulfilling the
requirements have some especial
characteristic such as superelastic and
damping properties which are efficient to be
utilized in orthopedic application. So these two
important parameters are explained here.
Superelastic behavior
The superelastic behavior is similar to that of
elasticity but in a higher and complex order of
magnitude. Super-elastic materials (SEM) return
to their original shape upon unloading after a
substantial deformation [72]. Since the
mechanism is not conventional, this effect is
also termed as “pseudoelasticity” or
“transformational superelasticity”. It is caused
by stress-induced martensitic transformation
[73]. If a stress is applied above M s , the
martensite can be stress-induced. The
transformation from austenite to martensite is
accompanied by large recoverable strain and
the material returns to the original shape when
the stress is no longer applied because the
martensite is completely unstable without
stress assistance [74]. A schematic
superelastic stress-strain curve is shown in
figure 5 while ól, óu, åt and åp are the loading
stress, unloading stress, the total strain and
unrecoverable strain respectively.
Fully austenitic NiTi material usually is suitable
for surgical implantation [7]. So this property
probably can be useful for joint replacement
where the load is frequently applied and
removed during daily activities from the aspect
of unrecoverable or residual strain.
Damping capacity
The high-damping effect is the ability of a
material to transform mechanical energy which
is provided for example by an applied force into
thermal energy. This irreversible energy
transformation helps the material to resist
shocks and absorb vibrations [37]. When a
shape memory material is cyclically loaded
further than a critical value, the transformation
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79
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Biomaterial selection is one of the most
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The present study reviewed the currently used
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