Materials Science & Engineering C 102 (2019) 844–862

Contents lists available at ScienceDirect

Materials Science & Engineering C

journal homepage: www.elsevier.com/locate/msec

Review

Review on titanium and titanium based alloys as biomaterials for T

orthopaedic applications
⁎
Manmeet Kaur, K. Singh
School of Physics and Materials Science, Thapar Institute of Engineering and Technology, Patiala, Punjab 147004, India

A R T I C LE I N FO A B S T R A C T

Keywords: Variety of implant materials have been employed in various disciplines of medical science depending on the
Biocompatibility requirement of a particular application. Metals, alloys, ceramics, and polymers are the commonly used bio-
Orthopaedic implants materials. The main focus of this study is to review the various structural and microstructural properties of
Titanium based alloys titanium and titanium based alloys used as orthopaedic implants. Orthopaedic implants need to possess certain
Mechanical properties
important qualities to ensure their safe and effective use. These properties like the biocompatibility, relevant
Surface modification
mechanical properties, high corrosion and wear resistance and osseointegration are summarized in this review.
Additive manufacturing techniques
Various attempts to improve upon these properties like different processing routes, surface modifications have
also been inculcated in the paper to provide an insight into the extent of research and effort that has been put
into developing a highly superior titanium orthopaedic implant.

1. Introduction taking place are summarized in Table 1.

Biomaterials play a very vital role in the modern day and age. In the
last few decades with the advancements in medicine and material
processing, a large number of biomaterials have been developed with
properties suitable for various applications [1]. Biomaterials mainly
find use in orthopaedics, dental care, drug delivery, tissue engineering
of skin and cardiovascular devices [2]. Before recognising any material
as an implant it is imperative to know that the said material is not
causing any damaging effect i.e. it should be biocompatible to the
human body. Williams defined biocompatibility as “the ability of a
biomaterial to perform its desired function with respect to a medical
therapy, without eliciting any undesirable local or systemic effects in
the recipient or beneficiary of that therapy, but generating the most
appropriate beneficial cellular or tissue response to that specific situa-
tion, and optimizing the clinically relevant performance of that
therapy” [3]. This means that the implant should not release toxic
substances in the body as these can cause systemic damage to the pa-
tient [4–7]. Any material upon implantation in the human body triggers
some kind of response. This response is more pronounced at the tissue-
implant interface since the interface is more reactive than the core of
the material. Basically, the interface is considered as a two-dimensional
imperfection where the atoms are not linked to the highest number of
neighbours. As a result, they possess higher energy than core atoms of
the materials [8]. The four general types of tissue-implant responses
Biomaterials can be divided into four major classes: metals and their
alloys, polymers, ceramics and natural materials. These are extensively
being used in different medical fields: as cardiovascular biomaterials,
for generation of skin substitutes, in drug delivery systems and in the
treatment of cancer by hyperthermia [10–17]. Extensive research is
going on to improve upon their performance [18–33]. A number of
reviews provide an insight into the properties and applications of
bioactive glasses and glass-ceramics [34–37], metallic implants [38–40]
and polymers [41].
Musculoskeletal disorders include injuries that hamper the body's
movement by causing pain in joints, muscles or tendons and result in
tissue deterioration. Persistent pain and physical disabilities caused by
musculoskeletal disorders have affected millions of lives all across the
globe. It is expected that due to the changes in lifestyle the number of
people affected by the disorders of joints and bone will increase in the
coming years. A study by Kurtz et al. [42] has indicated that by the year
2030 it is expected that the number of total hip replacements would rise
to 572,000 procedures. Also, the number of total knee replacement
procedures is expected to rise to 3.48 million. Hence, it is expected that
there will be a rise in the demand for new and improved implants and
as a result improvement in the quality of implant materials and treat-
ment procedures is a must. Musculoskeletal problems often require
surgery like in the case of total joint replacement. This is where bio-
materials play a key role in bone repair and regeneration. Surgical

⁎
Corresponding author.
E-mail address: kusingh@thapar.edu (K. Singh).

https://doi.org/10.1016/j.msec.2019.04.064
Received 12 December 2018; Received in revised form 20 February 2019; Accepted 20 April 2019
Available online 23 April 2019
0928-4931/ © 2019 Elsevier B.V. All rights reserved.
M. Kaur and K. Singh Materials Science & Engineering C 102 (2019) 844–862

Table 1
A comparison between different types of implant–tissue interactions and their subsequent consequences [9].
Implant-tissue response Consequences

Toxic Kills cells in the tissue surrounding the implant. Also can cause systematic damage to the patient.
Nearly inert Non-adherent fibrous capsule develops to isolate the host from the implant
Bioactive Tissue- implant bond at the interface.
Dissolution of implant Implant dissolves and is superseded by the tissue

Table 2
Comparison of tensile strength, yield strength and elastic modulus of various
implants with bone.
Material Tensile Yield strength Elastic References
strength (MPa) modulus
(MPa) (GPa)

Bone (cortical) 70–150 30–70 15–30 [43]

Stainless steel 490–1350 190–690 200–210 [44,45]
Co based alloys 655–1793 310–1586 210–253 [44,45]
Titanium based 690–1100 585–1060 55–110 [45]
alloys
Dense 40–100 – 70–120 [43]
HA ceramics
Bioglass 45S5 42 – 35 [46] Fig. 2. While selecting a material for a particular application it is important to
know that the mechanical properties, physiological factors and microstructure
will affect the performance of the implant.

in various orthopaedic applications like fracture fixation, hip joint re-

Fig. 1. A comparison of Young's modulus of various implants. It is evident that
the Young's modulus of all the commonly used metallic implant is quite higher
than that of the bone [45,51–53].
implants made from biomaterials are used in restoring the function of
an otherwise damaged part. Various types of implant materials are
currently in use, these have varying properties. Table 2 provides a
comparison between the mechanical properties of commonly used or-
thopaedic implant materials and compares them with the corre-
sponding values of cortical bone. Amongst metals, 316L stainless steel,
cobalt chromium alloys, and titanium based alloys are the frontrunners
placement and dentistry [47–50] and Fig. 1 gives a comparison of their
Young's modulus, an important property for orthopaedic implants.
Depending on the requirement each of these implants finds use in dif-
ferent orthopaedic applications. Table 3 gives a comparison of the ad-
vantages and disadvantages of different metallic orthopaedic implant
materials. The advancement in orthopaedic surgery has seen tre-
mendous growth in the last few years as new and improved techniques
for bone repair have been developed but still, there are some areas
where work needs to be done. Sometimes the alloys fail in the long run
owing to various reasons like corrosion, wear, mismatch of Young's
modulus with the body parts and low strength. As a result, a second
surgery becomes necessary. These revision surgeries are expensive,
painful and at times are not even successful. New metallic alloys are
being developed to overcome the issues of present implant materials. It
is important to develop materials which are tough, corrosion and wear
resistant, biocompatible, bioactive and can survive long periods of time
without failure. Hence proper knowledge about the factors affecting the
performance of implant materials is essential [56] (Fig. 2).
Titanium and titanium based alloys have emerged as the number
one choice for orthopaedic implant materials. In the present review, the
focus is mainly on titanium and titanium based alloys as orthopaedic
implants, explaining their structure, microstructure, thermomechanical
processing, mechanical properties, influence of processing parameters
on mechanical properties, biocompatibility, bone bonding, corrosion
and wear resistance. In the last section, causes of implant failures and

Table 3
Main characteristics of metallic orthopaedic implants.
Materials Advantages Disadvantages Application References

Stainless steel
Cobalt based alloys
Ti and Ti based alloys
Magnesium based
alloys
Low cost, easily available, acceptable High modulus, Temporary devices-plates and screws [45]
biocompatibility Low corrosion resistance,
Allergic reaction
Better wear and corrosion resistance, fatigue High modulus, Total hip replacement, bone plates and [45]
strength Expensive, wires
Biologically toxic
Biocompatible, corrosion resistance, fatigue Low wear resistance Total joint replacement, fracture [54]
strength, low modulus, light weight fixation elements
Biocompatible, biodegradable, low Young's Low corrosion resistance, hydrogen Biodegradable orthopaedic devices, [55]
modulus evolution during degradation bone pins and plates

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M. Kaur and K. Singh
the surface treatments used to prevent the failure have been discussed.
2. Titanium and titanium based alloys
Metallic implants have been used for biomedical applications since
the 19th century. In the 1860's Lister [44] developed an aseptic surgical
technique which was a success. Lane developed a fracture plate using
steel in the early 1900's which was later modified by Sherman by re-
ducing the stress concentration [44]. Since then metallic implants have
become an integral part of orthopaedic surgery. They are used as
temporary as well as permanent implants in the body. Metals possess
many properties which make them highly acceptable for bone repair.
Tensile strength in case of metals is quite high better than polymers and
noticeably higher than most bioceramics (the exception being zirconia).
Metals are highly tough, 20 times higher than ceramics and possess a
reasonable fatigue life. Metals have Young's modulus values quite close
to those of ceramics. However, metallic corrosion can be a problem but
if carefully selected, metals can show reasonable corrosion resistance.
Metals show the ability to alloy which means their corrosion, wear, and
mechanical properties can be altered and they can be made suitable for
the required applications. Also, biocompatibility can be improved by
using those elements which show no adverse effects in the body. Hence
metals have proven to be quite useful for implantable device applica-
tions and this trend is not expected to change any time soon [56].
Titanium is the ninth most abundant element on earth. Rutile,
brookite, and anatase are the oxides bearing mineral sources of tita-
nium. Crystal structure of rutile and anatase is tetragonal and brookite
has an orthorhombic crystal structure with space group P42/mnm, I41/
amd and Pbca respectively [57], as shown in Fig. 3. In the 1950's ti-
tanium was developed for aerospace applications but after the 1960's it
has been used in surgical implants. These days, 2% of titanium is used
in medical applications. Titanium has become so popular because of its
excellent combination of strength, Young's modulus and biocompat-
ibility as compared to other metallic implant materials [56]. Com-
mercially pure (CP)-Ti (F 67) and Ti-6Al-4V extra low interstitial (ELI)
(F 136) are the most commonly used implants in biomedical applica-
tions. Table 4 gives the ASTM standards of different titanium and ti-
tanium based alloys that are used in orthopaedic devices. These are
being used in different fields in orthopaedics: fracture repair, total hip
and knee arthroplasty (Table 5). CP-Ti is being used for the acetabular,
femoral and tibial component in case hip and knee arthroplasty and in
fracture fixation. These implants reduce the risk of loosening, provide
stable fixation, and good biocompatibility. In the following sections
important properties of titanium and titanium based alloys used for
orthopaedic applications have been summarized.
Fig. 3. Crystal structure of TiO2 a) rutile b) anatase c) brookite [58].
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Materials Science & Engineering C 102 (2019) 844–862
Table 4
ASTM standards of titanium and titanium based alloys used as sur-
gical implants in orthopaedic devices [59].
Alloy ASTM specification
CP-Ti (Grade 1,2,3,4) F 67
Ti-6Al-4V (ELI) Wrought F 136
Ti-6Al-4V Wrought F 1472
Ti-6Al-7Nb Wrought F 1295
2.1. Structural properties of titanium
Titanium is widely used in various applications because of the
possibility of modifying its properties by varying the alloying element
composition. Titanium undergoes an allotropic transformation i.e. it
changes from one crystallographic form to another. At room tempera-
ture, it exists in hexagonal close-packed (HCP) structure and this is
called alpha (α) phase. At 883 °C it changes to body centered-cubic
structure (BCC) called the β phase. The temperature at which α or
α + β changes to all β is called β transus temperature. The two forms of
unalloyed titanium are shown in Fig. 4.
Titanium alloys are categorised into five crystalline categories: α,
near α, α + β, near β and β. Near alpha is very much similar to alpha
phase at low temperature. On heating, it forms some beta phase
(5–10%). Alpha-beta has alpha and transformed beta phase (10–30%
beta). On initial cooling near beta retains beta phase but upon heating,
it precipitates secondary phases. Alloying elements are categorised into
three groups according to the phase stabilised. Different stabilisers like
Zr, O, Al, N, C have been used to stabilise various crystalline phases.
These stabilisers can alter the stabilising temperatures: α stabilisers (O,
Al, N, C) increase the temperature at which α phase remains stable and
β stabilisers (V, Nb, Mo, Ta), decrease the temperature at which β phase
stabilises. β transus temperature is important because heat treatments
are carried out at some incremental temperature close to this tem-
perature. Below this temperature titanium contains α + β phase in the
presence of β stabilisers, if not then there is only α phase present [68].
The selection of processing temperature plays an important role as it
controls stabilisation of different phases and their volume fractions
decide the mechanical and other properties of titanium alloys as im-
plants. Unalloyed CP-Ti has HCP crystal structure. It is available in four
grades (Table 6).
2.2. Thermomechanical processing and microstructure of titanium alloys
Microstructure plays a crucial role when talking about the me-
chanical properties of the implants like strength, ductility, and fracture
toughness. Factors like heat treatment, chemical composition, produc-
tion history affect the microstructure to a great extent. The α to β
M. Kaur and K. Singh Materials Science & Engineering C 102 (2019) 844–862

Table 5
Some applications of titanium, as an orthopaedic implant and its benefits.
Application Component Specification Advantages

Total Hip Arthroplasty
(THA)
Total Knee Arthroplasty
(TKA)
Fracture fixation
Acetabular Tritanium primary cup (Stryker Orthopaedics,)- is a highly
porous, 3-D titanium (commercially pure) metal interface [60]
Femoral ACCOLADE II Femoral Hip System (Stryker Orthopaedics)-
proximal region of stem is coated with PureFix HA over
commercially pure titanium plasma spray substrate [62].
Tibial and Partial porous-coated metal metaphyseal-filling sleeves (Depuy,
femoral Warsaw, IN)- Used in revision TKA. Femoral part is made of
titanium and tibial part is made from titanium alloy. Porosity is
around 50–80% [64].
Humeral PHILOS plate system (Synthes, Switzerland)- Includes titanium,
preformed, angular stable locking compression plate (LCP),
designed for internal fixation of proximal humeral fractures
[65].
Modulus of elasticity close to bone, high friction co-efficient,
design improves osseointegration and reduces stress shielding
[61].
Decreases risk of aseptic loosening [63].
Provides stable fixation and structural support in patients with
notable metaphyseal bone loss [64].
Provides good biocompatibility, negligible interference with
blood supply of the humeral head [65], yield good to excellent
longer term results in 75% of the patients [66].

like alpha structure is formed whereas an intermediate cooling rate

results in basketweave morphology. High cooling rates result in
widmanstӓtten pattern and martensite pattern is observed upon water
quenching [69–72]. When the alloys are processed in the α + β phase
field below the β transus temperature the microstructure consists of
globular equiaxed α (primary) phase which has been retained to room
temperature in the transformed β matrix, the resulting structure is
called equiaxed [68]. A comparison of the properties of acicular and
equiaxed microstructures is shown in Fig. 6. Grain refinement is one of
the commonly used approaches to enhance strength of the alloys. Ding
et al. [73] studied the effect of different hot working conditions on the
microstructure of Ti-6Al-4V during thermomechanical processing. The
samples were exposed to temperatures in the range 850–1050 °C and
strain rate: 0–1.0 s−1 in order to understand the relationship between
processing, structure, and properties of the alloys. It was found that
Fig. 4. Titanium exists in two crystallographic forms. At room temperature it lamellar morphology of α phase can be divided into the following ca-
exists in HCP (α) and as the temperature increases to 883o C it changes to BCC tegories: retained prior α lamella zone, the distorted α lamella zone,
(β) form [67]. segmented α lamella zone, the diffused α lamella zone, and the sec-
ondary α lamella zone (transformed α phase) for the samples processed
in the α + β phase field. During processing in the α + β phase field, the
Table 6
mechanical deformation resulted in some degree of α → β phase
Various grades of unalloyed titanium (wt%) [68].
transformation. Fine equiaxed grain structures are considered im-
Material N C H Fe O portant because they improve the formability of titanium implants at
ASTM Grade1 0.03 0.1 0.015 0.2 0.18
low temperatures [74]. Chao et al. [75] used a novel grain refinement
ASTM Grade2 0.03 0.1 0.015 0.3 0.25 mechanism involving warm deformation of martensitic structure to
ASTM Grade3 0.05 0.1 0.015 0.3 0.35 produce ultrafine equiaxed grains. In order to produce ultrafine-grained
ASTM Grade4 0.05 0.1 0.015 0.5 0.40 titanium implants, severe plastic deformation (SPD) technique has been
used by many researchers. Equal channel angular pressing (ECAP) has
come out as a promising SPD technique. It not only improves the me-
transus temperature affects the transformation of the microstructure in
chanical properties but also the biocompatibility [76–78]. The strength
case of titanium alloys. This temperature also becomes a key factor in
of α + β and β alloys can be altered by solution treatment and aging.
deciding the kind of heat treatment required. Depending upon the
The tensile strength of Ti-6Al-4V can be increased to ~1100 MPa upon
different types of thermomechanical processing (TMP) conditions dif-
solution treating [68]. Vanadium has been found to be toxic when re-
ferent microstructures can be seen in the case of titanium alloys.
leased in the body hence vanadium free alloys like Ti-6Al-7Nb have
Titanium has to undergo the following steps during its processing:
been developed for biomedical applications. Ti-6Al-7Nb finds applica-
titanium ore is reduced to a porous form called sponge, the sponge is
tion in total hip prostheses. Fellah et al. [79] found that wear resistance
melted to form ingot, ingots are converted to mill products and sec-
of Ti-6Al-7Nb alloys with two-phase microstructure was lower than that
ondary fabrication of finished products is done by die forging, extru-
of the Ti-6Al-4V under the same testing conditions.
sion, hot and cold forming, machining, chemical milling, and joining.
Since it is possible to control the mechanical properties of an alloy
Forging and subsequent heat treatments are used to alter the micro-
by grain boundary engineering Polyakova et al. [70] studied the de-
structure and the properties of the alloys. Control over the micro-
formation mechanism of phase boundaries and the variation of me-
structure is important in order to ensure successful production of tita-
chanical properties of Ti-6Al-7Nb with the changing microstructure.
nium alloys for the specific applications. Fig. 5 shows how the working
The alloy was processed using the ECAP technique. As the strain in-
temperature affects the microstructure of different categories of tita-
creased during ECAP there was a non-monotonic variation in the den-
nium alloys.
sity of low and high angle grain boundaries of α grains. It was found
Based on various studies, it has been found that the TMP of the
that the UFG resulted in UTS value of 1210 MPa which is 20% higher
α + β alloys above the β transus temperature results in lamellar mor-
than that of hot-rolled alloy.
phology. Also, different cooling rates result in a variety of lamellar
Today the focus has shifted to β titanium alloys as they possess
structures. It has been found that for low cooling rates colonized plate-

847
M. Kaur and K. Singh
Fig. 5. Different categories of titanium alloys and the effect of hot working on the microstructure [69].
Fig. 6. Comparison of equiaxed and acicular microstructure [68].
better biocompatibility and a lower value of Young's modulus. Attempts
have been made to produce equiaxed grain structures using the ap-
propriate heat treatment because of the excellent mechanical proper-
ties. Geetha et al. [80] subjected three alloys: Ti-13Nb-13Zr, Ti-20Nb-
13Zr and Ti-20Nb-20Zr to appropriate hot rolling conditions in order to
describe the effect of TMP on their microstructure. Fine equiaxed
structure was observed in the micrographs of Ti-20Nb-13Zr and Ti-
20Nb-20Zr whereas the micrographs of Ti-13Nb-13Zr revealed a mix-
ture of equiaxed and elongated α phase. Various types of strategies have
been used in order to study the effect of TMP on microstructure and
mechanical properties. A flash thermal treatment technique was used
by Sun et al. [81] on the Ti-20Nb-6Zr alloys. In this technique heavily
cold rolled samples were subjected to very short thermal treatment
based on the flash recrystallisation. This treatment produced ultra-fine
β grains along with the nano-sized α and ω phases in the β matrix.
Recently (2018), Ozan et al. [82] applied thermomechanical treatment
on the newly developed Ti-28Nb-35.4Zr alloys. The samples were
subjected to solution treatment at 890 °C for one hour and afterwards
thickness was reduced by cold rolling. The treatment resulted in the
formation of a uniform single β phase with a tensile strength of
633 MPa and Young's modulus of 63 GPa. It has also been proposed that
the presence of α′phase can reduce the value of elastic modulus as they
are able to dissolve higher content of β stabilisers. Liu et al. [83] were
able to prepare α′phase based Ti-Nb-Zr alloys with a small amount of
α′′phase. The value of modulus was very low ~39 GPa and strength was
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Materials Science & Engineering C 102 (2019) 844–862
850 MPa. The presence of Nb, Zr and the α′′ phase could be responsible
for the small value of the modulus. Precipitation of ω phase is also
believed to be crucial in improving the mechanical properties of tita-
nium alloys. Li et al. [84] found that superelasticity in the Ti-Nb-Zr
alloys improved because of the presence of the ω phase. This can be
because ω is a hard and brittle phase which can improve the strength of
the β phase. The reason that these β alloys have received immense
attention in the recent times is because these employ non-toxic ele-
ments with superior biocompatibility. So, a possible new approach can
be to develop a coating of these elements on the more commonly used
implants made of pure titanium and titanium alloys. In order to design a
suitable coating on pure titanium or titanium alloys, sputtering tech-
nique can be a good option. Frustos et al. [85] developed Ti-22Nb-10Zr
coatings with different β/α′′ratios using the sputtering technique. The
balance between the α, β and α′′ phase can be altered by changing the
bias voltage. Sputtering at a bias voltage of −63 V resulted in a low
value of Young's moduls (47 GPa), high Berkovich hardness of 5.6 GPa
and bioactivity was double as compared to Ti-6Al-4V.
Ti-Nb-Ta-Zr (TNTZ) is another promising system which can be used
as a biomedical implant. Málek et al. [86] studied the effect of TMP and
chemical composition on these alloys. The prepared alloys were sub-
jected to solution treatment (850 °C/0.5 h/water quenched) and cold
swaging. Depending on the Ta and Zr content different mechanisms of
dynamical recovery and dynamical recrystallization during hot forging
were observed. After the solution treatment, post dynamic re-
crystallization or dynamic recrystallization during the previous hot
forging resulted in recrystallized grains. Deformed microstructure was
observed after cold swaging with grains elongated in the rod axis di-
rection. After aging treatment, the value of Young's modulus was in the
range 75–90 GPa and 50–65 GPa in the cold swaged state. SPD tech-
niques like ECAP can be used to modify the microstructure and hence
the mechanical properties of titanium alloys. Li et al. [87] used ultra
fine grained (UFG) 59Ti–36Nb–2Ta–3Zr alloy to study the influence of
SPD on its properties. The alloy was prepared by ECAP of the as-hot-
extruded TNZT alloy. The ultimate strength and yield strength in-
creased in the ECAP processed alloys. The formation of α′′martensite
phase during the initial stages of ECAP which subsequently changed to
β phase through recovery during continued deformation played an
important role in influencing the behavior of the alloys. There is an-
other type of TNTZ alloy composition namely Ti-Nb-Ta-Zr-O called the
gum metal because of very high strength, low Young's modulus, super
elasticity and super plasticity. Super plasticity is observed due to the
dislocation free plastic deformation mechanism [88]. Currently,
M. Kaur and K. Singh
attempts are being made to replace the more expensive Ta with Fe and
Sn. Nocivin et al. [89] subjected Ti–Nb–Zr–Fe–O to TMP to determine
whether it can be used in biomedical applications. The alloy was sub-
jected to homogenization treatment followed by cold rolling and re-
crystalisation treatment. The high yield and ultimate tensile strength
and low modulus of elasticity proved its worth as a biomedical implant.
Mohammad et al. [90] tried to understand the influence of TMP
parameters on the mechanical and electrochemical properties of Ti-
20.6Nb-13.6Zr-0.5V. The samples were subjected to plastic deformation
in the β phase field followed by solution heat treatment below β transus
temperature and then cooled at various rates. Depending upon the heat
treatment conditions the microstructure consisted of equiaxed/elon-
gated α,β phases with different morphologies. It was suggested that
since the mechanical and electrochemical properties were better than
most alloys this can be a potential biomedical implant material. Helth
et al. [91] studied the effects of different hardening techniques to im-
prove the mechanical bio-functionality of Tie40Nb. Hot and cold
rolling and various annealing treatments were used to study the var-
iation in microstructure. Recrystallization treatment was used as a grain
refinement technique which resulted in a decrease of grain size and
increase in UTS. Cold rolling after recrystallization again lead to an
increase in the UTS value. Further aging at 723 K resulted in pre-
cipitation of some α phase and increase in the UTS. Addition of certain
alloying elements results in a decrease of the elastic modulus. These
alloys are considered new generation alloys because of their superior
mechanical and corrosion properties. In an attempt to design low
modulus implant Cai et al. [92] investigated the influence of indium on
the structural properties and elastic modulus of Tie40Nb. Addition of
In resulted in a decrease of elastic modulus to 49GPa. In order to test
the effect of In on the corrosion behavior of Tie40Nb, Gebert et al. [93]
studied its behavior in the Ringer's solution. It was reported that In does
not reduce the corrosion stability of Tie40Nb alloys hence this alloy
can be considered suitable for implant applications. Pilz et al. [94]
studied the effect of TMP on the microstructure of Ti-40Nb-3.5In and
Ti-36Nb-3.5In. TMP included solution annealing, hot rolling, cold
rolling and recrystallization annealing of the substance. These alloys
showed enhanced stability of the β phase due to the addition of In. A
single phase β microstructure was observed for solution treated Ti-
40Nb-3.5In and there was no phase transformation during thermal
processing. Zirconium is a biocompatible element which results in solid
solution strengthening because of its higher atomic radius as compared
to other commonly used alloying elements. Málek et al. [95] alloyed
Tie35Nb with different amounts of Zr and studied the influence of TMP
on its microstructure and other properties. Addition of Zr stabilised the
β phase and enhanced recrystallisation. The value of tensile strength,
0.2 proof strength, Young's modulus, and hardness varied in accordance
with the type of TMP technique (hot forging, solution treatment, water
quenching or cold swagging) used. Ti-Nb-Mo-Zr is another promising
alloy which can be used for biomedical applications. Nunes et al. [96]
used Ti-29Nb-2Mo-6Zr and Ti-24Nb-4Mo-3Zr alloys to study the in-
fluence of the degree of deformation by cold rolling after homo-
genization heat treatment. Solution treatment at 1000 °C for 24 h and
subsequent water quenching resulted in β microstructure in both the
alloys, whereas cold rolling induced precipitation of α′′ phase. The de-
gree of deformation affected the mechanical properties to a significant
extent.
So, from the above discussion, it becomes clear that the choice of
alloying elements and the type of treatment plays an important role in
the microstructure evolution and mechanical properties of titanium
alloys. The next section presents a comparison between the mechanical
properties of titanium implants and human bone which is very essential
for the selection of any material as a biomedical implant.
2.3. Mechanical properties of natural bone
Human bone is a connective tissue made up of fibres and cells. Bone
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Materials Science & Engineering C 102 (2019) 844–862
provides internal support, protects vital organs and presents an an-
chorage site for muscles. Also, the bone has to maintain calcium
homeostasis and hematopoiesis. In order to serve these functions, bone
has to be stiff to avoid bending. On the other hand, it should be able to
absorb energy hence needs to be flexible. Human skeleton can be di-
vided into two kinds of bone tissue, namely cortical and trabecular.
Cortical bone shows high compressive strength because of its high mass
per unit volume and low porosity (10%). It provides the strength and
rigidity to the bone. Trabecular bone, on the other hand, displays high
porosity. Out of the total trabecular bone volume around 50–90% is
made up of pores [97]. Hence, it has a lower value of Young's modulus
and ultimate compressive strength. It allows red bone marrow and bone
vessels to come in contact with bone by providing increased surface
area.
To use titanium as an implant one needs to ensure that the me-
chanical properties are similar to those of the human bone i.e. there is
no mechanical mismatch between the bone and the implant. The elastic
modulus of human cortical and trabecular bone are 4–30 GPa and
0.2–2 GPa, respectively. Compressive strength values of cortical and
trabecular bone are 20–193 MPa and 2–80 MPa whereas yield strength
of femoral bone and tibial bone are 104–121 MPa and 120–140 MPa
[98].
2.4. Influence of various processing parameters on the mechanical
properties
Mismatch of Young's modulus between the bone and implant has
been identified as one of the major issues associated with the current
implant materials. This phenomenon is called stress shielding. Under
normal circumstances, bone carries the load by itself. When an implant
is introduced in the bone, the load is shared between the bone and the
implant. So, the bone will experience reduced stress and hence will
experience stress shielding [99]. According to Wolff's law, the bone
tries to oppose the applied load and accordingly develop the most
suitable structure. As a result, the areas of the bone that are under high
load will have increased bone mass [100]. The areas with lesser load
would experience a decrease in bone mass. This decrease in bone mass
is called bone resorption and can cause failure of the implant. As dis-
cussed in the previous sections, CP-Ti is available in four grades. The
amount of oxygen and iron in the four grades is different. Grades having
higher interstitial content display higher strength, hardness and trans-
formation temperature than those grades which have lower interstitial
content as shown in Fig. 7. Unalloyed titanium is used because of its
superior corrosion resistance, primarily in applications where high
strength is not the priority. CP-Ti is basically all α phase titanium and
has low strength. The UTS and yield strength varies from 240 to
550 MPa and from 170 to 480 MPa as shown in Fig. 7. This is because of
the difference in the interstitial amount. Strength improves by in-
creasing the amount of oxygen and iron in the alloys. Addition of these
alloying elements significantly improves the yield strength i.e. 0.2%,
tensile strength, and hardness of titanium [101]. Young's modulus of
the four grades of CP-Ti alloy is 115 GPa [45]. CP-Ti is most commonly
used in making dental implants. Attempts are continuously being made
to improve the strength of various grades of CP-Ti. Most frequently used
technique is solid solution strengthening especially using oxygen. But
oxygen poses a problem in terms of corrosion resistance and bio-
compatibility. As a result, selective laser melting (SLM) has received a
lot of attention. SLM is a new technique using which a product is de-
veloped by melting certain regions of the powder layers when placed in
a protected environment by using a laser beam. It provides the benefit
of high material utilisation, minimal machining and results in the
production of near-fully dense components. Attar et al. [102] used SLM
to develop CP-Ti parts starting from powder and it was realised that a
suitable combination of laser power and scanning speed was important
to melt the layers. Upon increasing the applied laser scanning speed
above 100 mm/s α′ phase was formed. Due to the formation α′ phase
M. Kaur and K. Singh
Fig. 7. Comparison of (a) Tensile strength and (b) 0.2% yield strength of unalloyed titanium [68].
microhardness, UTS and compressive tensile strength increased to 261
Hv, 757 MPa and 1136 MPa which is higher than the samples formed
using conventional methods. Li et al. [103] used two different laser
powers of same energy density to fabricate CP-Ti parts using SLM
technique. Depending upon the laser power the samples displayed
different microstructure, texture and mechanical properties. It was
found that CP-Ti formed using a laser of higher power was strong tex-
tured, with isotropic mechanical properties and ultimate compressive
strength ~1.1GPa. This was due to the formation of α′ phase present in
the samples formed using laser of higher power because of higher
cooling rates. Laser engineered net shaping (LENS) is another com-
monly used additive manufacturing technique. Attar et al. [104] pre-
sented a comparative study of CP-Ti produced by SLM, LENS and
conventional methods. Based on the hardness and compression tests, it
was concluded that SLM presents superior mechanical properties than
the other two techniques. In another study by Palán and Zemko [105]
grade 2 and grade 4 titanium were passed through the continuous
forming severe plastic deformation (SPD) machine followed by cold
working. SPD is a term used for techniques that provides ultra large
plastic strain to the test material. CONFORM is one of the most com-
monly used SPD process. This increased the UTS from 480 MPa to
1050 MPa for grade 2 and from 650 to 1250 MPa for grade 4 titanium.
Apart from CP-Ti other α and near α alloys have not been widely used
in medical applications. This is mainly because of their lower strength
as compared to α + β and β titanium alloys.
α + β alloys have been the most frequently used orthopaedic im-
plants. Although they have certain limitations which have shifted the
focus to β alloys still they are quite relevant. One of the important
properties when talking about orthopaedic application is Young's
modulus. Fig. 8 gives a comparison of Young's modulus of different
titanium alloys. Ti-6Al-4V and Ti-6Al-4V ELI (extra low interstitial) are
the most commonly employed titanium alloys. The Young's modulus,
0.2% yield strength and UTS of Ti-6Al-4V is 110 GPa, 860 MPa and
930 MPa [45]. Although the strength of α + β alloys is better than that
of CP-Ti but the value of Young's modulus is quite high which causes
stress shielding. Also, aluminium and vanadium have been reported to
be harmful to the human body hence attempts are being made to find a
more biocompatible replacement of these elements. Alloys like
Ti–6Al–7Nb and Ti–5Al–2.5Fe have been developed by replacing the
toxic vanadium. Ti–6Al–7Nb has strength similar to that of Ti-6Al–4V.
It shows better ductility and better corrosion resistance [113].
Ti–5Al–2.5Fe also shows high UTS and yield strength: 1020 MPa and
895 MPa, respectively [114]. Fatigue limit is another important quan-
tity whose variation with alloying elements is shown in Table 7. In
order to improve the properties of α + β titanium alloys additive
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Materials Science & Engineering C 102 (2019) 844–862
manufacturing techniques like SLM and electron beam melting (EBM)
have been employed [121]. The Ti-6Al-4V alloy produced by SLM
consists of acicular α′ martensite and some β grains unlike the equili-
brium α and β phases present in alloys formed by conventional means
[122]. SLM has been extensively used to improve the mechanical
properties of Ti-6Al-4V like yield strength and microhardness
[123,124]. Further, EBM has been used to improve the mechanical
properties like ultimate tensile strength, micro hardness and yield
strength of Ti-6Al-4V. The microstructure of Ti-6Al-4V produced using
EBM consists of columnar β grains along with α + β grains present
within the β grains [125]. EBM and SLM can be used for improving the
fatigue performance of the Ti-6Al-4V implants [126,127].
In the last decades efforts towards developing scaffolds that can
imitate the properties of human bone have grown immensely. Porous
titanium implants possess a low value of elastic modulus and also
provide space for better ingrowth of bone. Takemotoa et al. [128]
produced porous bioactive titanium with 40% porosity. Although the
implant was found to have a relatively low value of yield strength and
fatigue strength but was strong enough to tolerate loading within the
limit. This material displayed low value of compressive modulus
(4.7 GPa) and showed better bone ingrowth. Taniguchi et al. [129]
investigated the effect of pore size on bone in-growth in rabbits. They
found that porous titanium implants with a pore size of 600 μm dis-
played better fixation ability than those with a pore size of 300 μm and
900 μm. Chang et al. [130] developed porous titanium with 70% por-
osity. The average 3D pore size was 188–390 μm. The Young's modulus
and yield stress of the three samples was close to Young's modulus and
yield stress of human trabecular bone. It was found that titanium with
relatively large pores (Ti 313 and Ti 390) displayed better bone in-
growth. Li et al. [131] developed Ti-6Al-4V reticulated meshes using
EBM method to study the effect of cell shape on mechanical properties
of the alloys. It was found that for porosities in the range 88–58% the
values of compressive strength and elastic modulus came out to be
10–300 MPa and 0.5–15 GPa, respectively. However, the porous struc-
tures suffer from certain drawbacks like lower strength. In order to
overcome these issues Fousová et al. [132] developed Ti-6Al-4V using
SLM with a gradient in their structure. When the alloys have porosity
gradient the mechanical properties can be optimised to a certain sui-
table value. This can be a promising technique since the samples pos-
sess a very low value of Young's modulus i.e. 30.5 ± 2 GPa and the
values of tensile yield strength and UTS were slightly higher than those
of hot rolled materials. A review by Wang et al. [133] presents an in-
sight into the topological design and additive manufacturing of porous
metals for scaffolds. Triply periodic minimal surfaces (TPMS) have
become appealing candidates for designing scaffolds. Yan et al. [134]
M. Kaur and K. Singh
Fig. 8. One of the prime difference between the α + β and β alloys can be seen in terms of the values Young's modulus, as is clear from the figure [45,106–112].
Table 7
A comparison of fatigue strength of different titanium alloys.
Implant type Fatigue limit MPa (in 107 cycles) Reference
CP-titanium 430 [115]
Ti-6Al–4V 500 [116]
Ti–6Al–7Nb 500–600 [117]
Ti–5Al–2.5Fe 580 [118]
Ti-13Nb-13Zr 500 [119]
Ti-12Mo-6Zr-2Fe 525 [120]
and Ataee et al. [135] have developed high porosity TPMS scaffolds
using SLM and EBM techniques, respectively. Yan et al. found that
TPMS lattices exhibited a low value of modulus in the range
0.12–1.25 GPa which is similar to the modulus of trabecular bone. Ti-
6Al-4V gyroid scaffolds developed by Ataee et al. had elastic modulus
and yield strength in the range 637–1084 MPa and 13.1–19.2 MPa,
respectively. Ataee et al. [136] also developed ultrahigh strength CP-Ti
gyroid scaffolds using SLM technique. The value of elastic modulus was
of the order of modulus of trabecular bone. SLM has also been used on
another commonly used α + β alloy Ti-6Al-7Nb [137]. Chlebus et al.
[138] tried to understand the influence of SLM technique on the mi-
crostructure and mechanical properties of Ti-6Al-7Nb. It was found that
the layered microstructure of the material results in significant aniso-
tropy in the value of Young's modulus and mild anisotropy in the other
mechanical properties.
In recent times focus has shifted to β titanium alloys which are also
called the second generation of titanium alloys. These alloys have a low
value of Young's modulus hence could solve the problem associated
with stress shielding. Another benefit is that these have better corrosion
resistance and biocompatibility because of the absence of vanadium.
The alloying elements are niobium, zirconium, molybdenum, tantalum,
and iron. These alloying elements cause an increase in the UTS and
decrease in the Young's modulus [139–141]. A new alloy Ti-25Ta-25Nb
has been developed with the value of Young's modulus calculated as
55GPa which is very small and UTS is 530 MPa [142]. The Ti–Nb–Zr–Ta
(TNZT) alloys also have very low Young's modulus (~55 GPa) [45].
Guo et al. [143] synthesized Ti-33Nb-4Sn, a metastable β-type Ti alloy.
The β phase was retained at room temperature by the higher grain
boundaries and high density of dislocations. The material was subjected
to cold rolling and annealing and displayed excellent mechanical
properties: elastic modulus (~36 GPa) and ultimate strength
(~853 MPa). Another way to reduce Young's modulus is to make the
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Materials Science & Engineering C 102 (2019) 844–862
alloy porous and alter the level of porosity in the alloy. Porosity de-
creases the strength of the bonds as it increases the bond length. Wang
et al. [144] fabricated porous Ti-10Nb-10Zr with different porosities.
These alloys achieved higher strength than the unalloyed Ti scaffolds
with same porosity. The alloy with 59% porosity exhibited elastic
modulus and plateau stress of 5.6 GPa and 137 MPa, respectively.
Different additive manufacturing techniques are being used for de-
veloping new and improved β alloys. SLM has gained popularity be-
cause it allows meticulous control over the pores size and porosity,
hence over the mechanical performance of an implant. It has been re-
ported that addition of tantalum into titanium results in an increase in
the tensile strength and decrease in the modulus [145]. Sing et al. [146]
used selective laser melting to fabricate TiTa alloys with 50 wt% of each
element. The microstructure was made up of randomly oriented
equiaxed grains of β titanium and tantalum. The UTS and elastic
modulus of the samples came out to be 924.64 ± 9.06 and
75.77 ± 4.04 GPa, respectively. Yan et al. [147] developed TiTaZr
alloys using SLM. The microstructure was initially made up of α phase
which changed into β and finally into the α + β phase. The elastic
modulus of Ti-15Ta-10.5Zr came out to be 42.93 ± 3.28 GPa, which
was close to the modulus of human cortical bone. The interest in new β
type alloys like Ti-24Nb-4Zr-8Sn is increasing because of their low
elastic modulus and non-toxicity. Zhang et al. [148] used SLM to pro-
duce Ti-24Nb-4Zr-8Sn and found that the value of Young's modulus,
yield strength, and UTS came out to be 53 ± 1 GPa, 563 ± 38 MPa
and 665 ± 18 MPa, respectively. Yang et al. [149] also fabricated Ti-
24Nb-4Zr-8Sn using SLM and concluded that this improves the UTS and
uniform elongation. Chen et al. [150] studied the microstructure and
mechanical properties of Ti-37Nb-6Sn fabricated using SLM. The sam-
ples possessed a low value of elastic modulus (66 GPa) and high value
of UTS (891 MPa). The fine grains and limited defects resulted in the
high value of strength and the presence of α′′ martensite phase produced
a low value of elastic modulus. EBM technique is also extensively being
used to produce β implants. Liu et al. [151] used EBM to manufacture
Ti-24Nb-4Zr-8Sn alloys with 70% porosity. These implants showed very
low value of Young's modulus (0.7 ± 0.1 GPa) and compressive
strength was higher than Ti-6Al-4V with same 70% porosity. A com-
parison of the mechanical properties of titanium alloys produced by
different additive manufacturing techniques is shown in Table 8.
With the increasing porosity Young's modulus and compressive
strength both decrease [152]. This decrease in strength can be com-
pensated by adding a biodegradable polymer. Poly-L-lactic (PLLA) acid
was filled into the pores of porous titanium. The tensile Young's
M. Kaur and K. Singh
Table 8
Mechanical properties of titanium alloys produced by different additive manufacturing techniques.
Implant type Manufacturing technique Young's modulus (GPa)
Ti-6Al-4V Standard 110
SLM 131.51 ± 16.40
CP-Ti SLM 111.59 ± 2.65
TiTa SLM 75.77 ± 4.04
Ti-15Ta-10.5Zr SLM 42.9 3 ± 3.28
Ti-24Nb-4Zr-8Sn Forged - 840
SLM(101) - 950
EBM (70% porosity) 0.7 ± 0.1
Ti–37Nb–6Sn SLM 66
modulus and tensile strength remained almost constant with PLLA ad-
dition but the compressive 0.2% proof stress (the point where 0.2%
plastic deformation has occurred) improved [153]. In another attempt
to reduce Young's modulus and improve the strength, Kopova et al.
[154] developed Ti–35Nb–7Zr–6Ta–2Fe–0.5Si. It yielded above
700 MPa, UTS was above 800 MPa and Young's modulus value ~86 GPa
which is still significantly lower than that of Ti-6Al-4V. Haghighi et al.
[155] designed a Ti-Fe-Ta alloy whose microstructure was composed of
β and α′′ phases. It was reaslised that elastic modulus decreased with the
increasing Fe and Ta content. Ozan et al. [156] developed a new series
of TiTaZrNb alloys using cold-crucible levitation melting (CCLM)
method on order to improve the strength. Fatigue properties are also of
utmost importance for any implant material and they depend on the
microstructure of the material. Apart from the microstructure fatigue
properties are also dependent on the surface conditions. β titanium
alloys can be considered superior than α + β alloys in a number of ways
but their unsatisfactory fatigue strength is a drawback. One way to
enhance the fatigue strength by preserving low Young's modulus is to
add Y2O3 particles which inhibit the sliding of dislocations [157]. Liu
et al. [158] introduced oxygen into Ti-29Nb-13Ta-4.6Zr to improve its
fatigue properties. With the increase in oxygen content the fatigue limit
increased. Presence of oxygen induces strain fields which inhibits the
dislocation motion. This decreases the length of the slip line and as a
result, increases the opposition to fatigue crack initiation. TNTZ alloy
with 0.7 mass% oxygen displayed excellent fatigue limit of ~635 MPa,
high tensile strength ~1100 MPa and Young's modulus ~76 GPa.
2.5. Biocompatibility of titanium based alloys and their alloying elements
The most important alloying elements for titanium are Al, V, Nb,
Mo, Zr, Ta. This section presents a summary of the biocompatibility of
titanium and the alloying elements.
2.5.1. Titanium
Titanium has long been considered inert and safe for human use. It
produces minimal side effects in the human body. This can be seen as
one of the major reasons for using titanium as an implant. But no metal
is completely inert in-vivo as it undergoes some corrosion with respect
to time. Over the years there have been reports indicating that titanium
particles could be harmful [159]. When titanium is implanted in the
body internal exposure is increased. Titanium ions accumulate around
the dental and orthopaedic implants. Peri-implant tissues have 100–300
parts per million (ppm) of titanium concentration. This is often fol-
lowed by discoloration [160–164]. In a study on titanium implants, it
was found that increased levels of titanium were found in lungs which
were 2.2–3.8 times the mean of the animals with no failure. Also, in
regional lymph nodes the titanium concentration was 7–9.4 times
higher than mean of the levels in animals with successful implantation
[165]. Dental implant patients are susceptible to titanium allergy. Al-
though the prevalence is low but the patients showing post-operation
allergy compatible response are at higher risk [166].
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Materials Science & Engineering C 102 (2019) 844–862
UTS (MPa) Yield strength (MPa) References
930 860 [45]
1165.69 ± 107.25 1055.59 ± 63.63 [146]
703.05 ± 16.22 619.57 ± 20.25 [146]
924.64 ± 9.06 882.77 ± 19.60 [146]
805.32 ± 19.25 768.61 ± 16.09 [147]
- [149]
- [149]
35 ± 2 - [151]
891 ‐ [150]
2.5.2. Vanadium
Vanadium can have both positive and negative effects on the body.
On one hand, it has been reported that vanadium can exert anti-diabetic
effects. However, it has also been associated with gastrointestinal dis-
comfort and decreased body weight gain [167]. Animal studies have
shown that exposure to vanadium and its compounds can be carcino-
genic [168]. Vanadium is one of the most commonly used alloying
elements in titanium based alloys. These toxic effects of vanadium
cause concerns regarding the use of Ti-6Al-4V. A study has revealed a
connection between vanadium release and implant failure [169]. At-
tempts have been made to replace vanadium with a more biocompa-
tible element.
2.5.3. Aluminium
Aluminium has little function in the human body. It is toxic in high
doses. Aluminium can be linked to a number of diseases. It can cause
neurotoxicity under certain conditions. A study on mice revealed that
aluminium can cause impairment of motor functions. It can also reduce
spatial memory capacity [170]. Aluminium accumulation is also con-
sidered harmful because studies have shown possible links to Alzhei-
mer's disease [171]. Aluminium is also associated with kidney diseases.
High levels of aluminium can slow bone remodeling and eventually
cause osteomalacia [172].
2.5.4. Titanium-based alloys
These alloys display better biocompatibility than stainless steel and
cobalt based alloys. This is because of the excellent corrosion resistance
of titanium based alloys. Concerns have been raised about the use of
aluminium and vanadium as the alloying elements because of their
harmful effects upon release into the body as discussed in the above
sections [173]. In one case a patient with Ti-6Al-4V plate developed
systemic dermatitis and implant failure [174]. Although Ti-6Al-4V is
considered to be highly corrosion resistant but no material is com-
pletely bioinert. Ion release can cause allergic reactions in some cases.
Hence, extensive efforts have been put into developing titanium alloys
with relatively safer elements. Niobium, tantalum, zirconium are few
examples which are considered safer than aluminium and vanadium.
Titanium, niobium, tantalum, hafnium, and rhenium were implanted in
rats and displayed good biocompatibility [175]. β alloys were then
developed with the hope of improving the biocompatibility of the al-
ready existing titanium alloys.
2.6. Process of bone bonding
Whenever an implant is introduced into the body it will always
generate an inflammatory response from the human body. There could
be reddening or swelling post implantation in the body. This reddening
marks an increase in the blood supply. Blood brings in the cells which
are involved in the repair (Fig. 9). The cells have different shapes and
they move from blood to the tissue to handle the foreign substance like
implants. The granular cells are called polymorphs or microphages. The
neutrophils are present in large numbers to ingest bacteria. Non-
M. Kaur and K. Singh
Fig. 9. Different white blood cells involved in the repair post implantation and
the process of encapsulation of implant [9].
granular are the second type of cells and they have round nuclei.
Lymphocytes are responsible for producing antibodies. Increase in the
number of lymphocytes signifies allergy. Monocytes move from the
blood to the tissue to ingest foreign bodies. Upon reaching the affected
tissue it forms macrophages. Macrophages produce enzymes which
digest the debris when it is small in quantity. When the debris is large,
which happens in the presence of an implant the macrophages are not
successful and possibly die. The macrophages are activated and gen-
erate cytokine signals. The activated macrophages affect the fibroblasts.
Fibroblasts produce collagen molecules which form a capsule around
the implant. This capsule thickens as long as the phagocytic activity
continues [9]. An important fact to be noted is that titanium and its
alloys show minimal encapsulation whereas stainless steel and CoCr
alloys, give rise to a thicker fibrous capsule (up to about 2 μm thick)
[56]. Implants with thick fibrous encapsulation are isolated and are
unable to adhere to the bone. Owing to the lack of bioactivity these
remain as foreign materials [9]. In the case of biomaterials, the thick-
ness of fibrous tissue has a direct relation to its biocompatibility as well
[176]. It is difficult to avoid fibrous capsule around metallic implants,
no matter how thin it might be. A combination of thick fibrous capsule,
high amount of macrophages, osteoclasts and lymphocytes is linked
with bio-incompatibility of the implant material. This thickness is a
function of the chemical and topographical nature of the surface of the
implant [177]. Most metals have this layer around them, which even-
tually leads to loosening of the implant. To the surprise of many, tita-
nium implants display strong integration with the host bone. To un-
derstand the bonding mechanism, it is required to be aware of the
chemistry of the bone. Bone has both organic and inorganic compo-
nents. Two third of the bone weight is made up of hydroxylapatite (HA)
crystals Ca10(PO4)6(OH)2 (HA). HA is responsible for providing the
bone with strength. HA is carbonated in the bone i.e. PO43− is replaced
by CO32−.The other one-third of the weight is because of collagen fi-
bres. These are flexible in nature hence are able to tolerate bending.
Studies to understand the bonding between implant and bone began
with the bioglass. Strength of the bond is such that fracture does not
occur at the interface between the implant and the bone but in either
the implant or the bone. The interface in general acts as a buffer to
prevent the crack movement. There have been varying explanations
about the type of bond between the implant and the bone. In the1970's,
a biological bonding theory was developed. According to this theory as
shown in Fig. 10 the collagen fibres enter the bioactive implant and are
responsible for strengthening of the implant. Bioactive glass was found
to develop a carbonated hyrdoxylapatite (CHA) layer on the surface
[178]. This step is critical to bone bonding. This bone bonding is known
as the bioactivity of the material. Biologically active CHA layer is
853
Materials Science & Engineering C 102 (2019) 844–862
Fig. 10. After the implantation a CHA layer is formed on the surface of the
implant, followed by collagen fibres entering this layer and forming a bond.
formed as a result of the ion exchange reaction that occurs between the
bioactive implant and the body. This CHA layer is very similar to the
mineral phase of the bone. There is a natural affinity between the
collagen and the CHA. They have such a strong desire to blend together
that upon formation of activated carbonate apatite layer the collagen
fibres of the bone enter this layer forming a biological bond [179].
Titanium implants unlike other metal implants bond with the bone
and are not encapsulated by a fibrous tissue which is a major difference
between the titanium based implants and other metallic implants.
Biological processes produce hydrogen peroxide and its interaction
with surface oxide can form a titanium-peroxy gel on the surface. This
can be a possible reason behind the bioactivity of titanium [180]. To
speed up the process titanium implants are sometimes pre-treated. The
key question still remains how does a CHA layer develop on the surface
of titanium implants. In order to get answers, an experiment was done
in which CP-Ti plates were soaked in 4 M NaOH for 24 h and then he-
ated at 600 °C. The chemical treatment resulted in the formation of
apatite layer on the implant, both in-vivo and in-vitro tests [181]. It is
believed that chemical treatment accelerates the formation of TiO2
hydrogel on the surface of titanium implant [182]. This titania hydrogel
allows apatite nucleation [183]. It then immediately grows by ab-
sorbing calcium and phosphate ion from the surroundings and forms
the apatite layer to which the collagen bonds.
One can say that in order to avoid encapsulation and to ensure
strong bonding between the bone and the implant, the synthetic nature
of the implant needs to be masked. It should be able to imitate the
constituents of the body. To improve the bone anchorage and bioac-
tivity a number of surface modification techniques have been used. HA
layer can be formed on titanium substrate to improve bioactivity. A
titania buffer layer could be used to improve bonding between HA and
titanium substrate [184]. Another technique is to use bioactive glass
coatings on titanium alloys to improve biofixation [185]. Titanium
implants subjected to alkali based treatment displayed calcium uptake
and mineralization on the implant surface [186]. It has been realised
that surface modification by magnesium can improve bone bonding
[187–189]. Magnesium is widely being used to improve the properties
of titanium implants because even the release of Mg2+ improves me-
tabolic reaction and bone bonding. Recently (2018), Jiang et al. [190]
developed TieMg composites to synthesize a load bearing implant with
low Young's modulus, sufficient strength, and excellent biocompat-
ibility. Tao et al. [191] studied the effects of Mg, Sr and Zn substituted
HA coatings on the osseointegration in case of titanium implants. Based
on a comparative study on the female Sprague-Dawley rats it was
concluded that these coating can improve the osseointegration with Sr
coating giving the best results. A number of techniques have been
employed to create HAP coatings on metallic implants: sol-gel dip
M. Kaur and K. Singh
coatings, electrochemical deposition, plasma spraying and sputter
coating [192–194]. Liu et al. [195] prepared calcium carbonate coat-
ings on sandblasted and acid-etched titanium implants. It was con-
cluded that the early bone ingrowth and osseointegration improve with
calcium carbonate coatings. This could be because calcium ions cause
osteoblast response mediated by the integrin. Li et al. [196] used gra-
phene coatings to improve the osseointegration of titanium alloys. It
was found that graphene not only improved osseointegration but also
enhanced the biocompatibility of titanium alloy, hence could be a
promising material for nano-coatings for bone defect repair. Yu et al.
[197] found that Zn-doped calcium silicate coatings result in better
bone contact and improved regeneration and can be helpful in treating
osteoporotic bone tissue. It has also been found by Ma et al. [198] that
in order to obtain osseointegration in implants, 3,4-dihydroxy-L-phe-
nylalanine (Dopa) coatings can be used in osteoporotic patients. The
reason can be related to Dopa's ability to inhibit the expression of os-
teoclastogenesis related genes. Jiang et al. [199] used a different ap-
proach when they wrapped a porous Ti layer over a dense TieMg
composite. Since the sample exhibited high compressive strength
(110 MPa) and low Young's modulus (5 GPa) it can find application in
load-bearing applications. The fate of an implant also depends on the
inflammatory response produced in the body. It is beneficial if an im-
plant has inflammation regulatory effect. Li et al. [200] incorporated
magnesium into porous TiO2 coating titanium substrate. It was con-
cluded that magnesium can be used as an anti-inflammatory agent and
can help in mediating osteogenesis. Incorporating a strontium layer
over the titanium implant is believed to improve osseointegration as
strontium can decrease bone resorption and improve bone formation.
Porous titanium implants have received a lot of attention because they
are able to improve the mechanical mismatch and also allow a me-
chanical interlock but they are still unable to provide sufficient os-
seointegration comparable to that of the natural bone. Pulsed electro-
magnetic fields (PEMF) therapy improves bone growth on titanium
surface [201]. Jing et al. [202] have found that PEMF stimulation can
improve bone ingrowth and osseointegration in case of porous titanium
implants. PEMF is able to promote activation of canonical Wnt sig-
naling which helps with the new bone formation. It was also found that
a hard nanostructured TiC layer provides a better bone-implant contact
than uncoated implant [203].
Since implant surface makes the first contact with the tissue upon
implantation it plays an important role in deciding the success of the
implantation. It has been found that rough surface results in better
osseointegration [204]. Ren et al. [205] used sandblasting, acid etching
and anodic oxidation to fabricate a hierarchical morphology with mi-
croscale valleys and nanoscale tubes on the titanium substrates. The
surface was completely covered with HA after being dipped in simu-
lated body fluid (SBF) for 14 days which shows that the modified sur-
face shows commendable bioactivity. Nanostructured surfaces are also
believed to enhance osseointegration by improving the bone-implant
contact [206]. Salou et al. [207] showed that nanostructured surfaces
improve osseointegration in titanium implants as proved by the en-
hanced bone-to-implant contact and bone growth values as compared
to other implant surfaces. It has also been noticed that the surface oxide
layer can play an important role in improving the biocompatibility of
the titanium implants [208–210]. Hence various oxidation techniques
such as thermal oxidation, alkali treatment have been employed to
improve osseointegration in case of titanium implants [211,212].
2.7. Corrosion and wear in implants
Metallic implants undergo corrosion in the body as the body's en-
vironment is highly reactive. A report by Egusa et al. [213] suggested
that an allergic reaction could by caused by titanium dental implants in
some patients. Blood and other constituents of the body fluid include
several components like water, sodium, chlorine, and proteins that
make the body's environment highly reactive for metals [214].
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Materials Science & Engineering C 102 (2019) 844–862
Fig. 11. A comparison of repassivation time of various metallic alloys [215].
Corrosion of implants is undesirable primarily because of two reasons,
it affects the strength of the material and it releases products which are
potentially dangerous for the human body. Every metal has different
corrosion resistance. Corrosion is not always problematic: some metals
upon exposure to air develop an oxide layer on the surface which
prevents the transfer of ions from the implant to the body fluids.
Titanium is very reactive and develops an oxide layer on the surface.
The corrosion characteristics of titanium depend strongly on the sta-
bility of the oxide film. The oxide layer is stable if passivation holding
current density is low. Once the surface oxide film is damaged corrosion
process starts again and metal ions are continuously released. Hence
repassivation is important to stop this release of ions into the body.
Repassivation time is different for different materials as shown in
Fig. 11. It is clear from the figure that repassivation time for stainless
steel is more than that for titanium alloys, implying that more ions
would be released from steel than from titanium alloy. This is one of the
superior qualities of titanium alloys over stainless steel. Titanium oxide
bonds strongly to the implant surface. Titanium alloys are able to tol-
erate the corrosive environment of the body to a great extent [216].
Corrosion potential and corrosion current densities are important
quantities while comparing corrosion properties. Fig. 12 compares the
average values of corrosion potential Ecorr and current densities icorr of
Ti-6Al-4V, Ti-6Al-7Nb and Ti-13Nb-13Zr. In order to further improve
the corrosion resistance, titanium is alloyed with other elements.
Adding niobium in place of vanadium improves the corrosion resistance
of titanium alloy as it stabilises the oxide layer and improves passiva-
tion [218]. According to a study by Zhou et al. [219], TieTa showed
better corrosion resistance than Ti-6Al-4V. This is because the Ta2O5
film is able to strengthen the TiO2 layer. Titanium alloys are widely
used in dental applications. These days fluoride therapy is widely used
to prevent dental caries. It has been found that corrosion in titanium
alloys is dependent on the fluoride concentration and pH levels [220].
Ti–13Nb-13Zr displays better corrosion resistance in comparison to Ti-
6Al-4V because the corrosion products of niobium and zirconium are
less soluble in human plasma than those of aluminium and vanadium.
Also, the oxide layer that forms on Ti–13Nb-13Zr is much more inert.
The oxide layer is responsible for corrosion resistance of the material
but it can break down leaving the implant vulnerable to corrosion. So,
the repassivating capacity of the alloys is of utmost interest. An in-
vestigation was performed on Ti-6Al-4V, Ti-6Al-7Nb and Ti-13Nb-13Zr
by Khan et al. [221] to study their ability to repassivate in phosphate
buffered saline (PBS) solution. It was found that an increase in pH af-
fected the corrosion of Ti-6Al-4V, Ti-6Al-7Nb more than that of Ti-
13Nb-13Zr. With the increase in pH corrosion resistance of Ti-6Al-4V,
Ti-6Al-7Nb decreased implying that the repassivation became difficult.
Increase in pH had the opposite effect on Ti-13Nb-13Zr. This could be
because of the lower solubility of niobium and zirconium ion in the
presence of increased hydroxyl concentrations as compared to that of
M. Kaur and K. Singh
Fig. 12. Gives a comparison of the average values of corrosion potential (mV(SCE) Ecorr and current densities (nA/cm2) icorr of different titanium alloys [217].
aluminium and vanadium ions. The influence of pH on corrosion de-
creased upon the inclusion of protein to phosphate-buffered saline
(PBS) solution. Another point to be noted is that upon corrosion,
hardness of the surface decreased. One can say that the original rutile
titanium oxide surface is the hardest in all cases.
Surface coatings play a key role in improving the corrosion char-
acteristics of titanium alloys. Oliveira et al. [222] used plasma assisted
physical vapour deposition (PVD) technique to deposit TiN and TiAlN/
TiAlCrN on the Ti–6Al–4V alloy. It was found that as a result of the TiN
and TiAlN/TiAlCrN coatings the corrosion resistance of Ti–6Al–4V alloy
improved. The TiN monolayer coating displayed better corrosion re-
sistance than the TiAlN/TiAlCrN multilayer coating. The corrosion re-
sistance of TiN is associated with its chemical inertia. Also, TiN showed
better corrosion resistance than TiAlN/TiAlCrN, which can be attrib-
uted to the presence of aluminium as it increases the reactivity of the
samples. The higher thickness of TiAlN/TiAlCrN coating and a small
number of interfaces are also responsible for reducing corrosion re-
sistance in comparison to TiN coating. In another study by Lu et al.
[223], a nanograined (NG) layer was developed on CP-Ti (grade 2) by
the means of sliding friction and this was compared to the conventional
coarse-grained titanium. Studies have claimed that nanocrystalline
structure can quickly form a passive layer improving corrosion re-
sistance. NG titanium displays a great combination of high corrosion
resistance with improved biocompatibility. This can be ascribed to the
formation of a thicker passive layer that hindered the electron migra-
tion. Thermal oxidation (TO) method is used to improve the corrosion
resistance of an alloy. Coating by rutile phase of TiO2 has gained a lot of
attention as it is believed that it has higher bonding strength and
thickness as compared to naturally forming oxide. Wang et al. [224]
formed hardened rutile TiO2 coatings on Ti-6Al-4V alloys using (TO). It
was found to improve the corrosion resistance and wear of the alloys.
Xu et al. [225] deposited tantalum oxide layers on titanium substrates
using polymer-assisted deposition (PAD) technique. As a result, the
corrosion resistance of titanium substrates improved. Surface mor-
phology also affects the corrosion resistance of an implant. To study this
effect four groups of samples (smooth surface (P), microstructure sur-
face (M), micro/nanostructure surface (MN) and functionalized micro/
nanostructure surface (Ag-PDA)) were prepared. Their corrosion be-
havior was studied in Ringer's solution. Corrosion resistance was dif-
ferent for the four samples: Ag-PDA > MN > P > M; Ag-PDA dis-
played the highest corrosion resistance [226]. Mokgalaka et al. [227]
formed NiTi intermetallic coatings on the surface of Ti-6Al-4V using
laser metal deposition (LMD) process in order to improve the corrosion
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Materials Science & Engineering C 102 (2019) 844–862
resistance. This improves corrosion resistance possibly because NiTi is
nobler than Ti-6Al-4V.
Titanium alloys have a high coefficient of friction, low surface
hardness, as a result have low wear resistance. Wear in implants be-
comes a problem due to the fact that the wear debris results in loos-
ening of the implant and eventually causes failure. Total joint re-
placements (TJR) made from metal head and polymer cup are
susceptible to loosening of the implant. As a result, these implants have
to be replaced after some years via revision surgery. Studies have
proven that wear is a principal mode of failure for these implants. TJR
surgeries make use of a metallic femoral head coupled with an ultra-
high-molecular-weight polyethylene (UHMWPE) acetabular cup. The
problem in applying UHMWPE and Ti-6Al-4V combination for TJR lies
in the fact that wear rates for this combination have been reported to be
35% more than that for Co-Cr-Mo alloys. Higher wear rates can be
caused by the mechanical instability of oxide film on the implant sur-
face. External stresses can break the passive oxide layer on the surface
of titanium alloys. The exposed surface is not able to repassivate im-
mediately resulting in consumption of the alloy. This poses a big pro-
blem in terms of application of titanium alloys in TJR. Titanium alloys
are preferred because of their lower Young's modulus, higher corrosion
resistance and better biocompatibility in comparison to their counter-
parts (stainless steel and cobalt alloys) but they lack in terms of wear
properties [51].
Some surface modifications are used to improve the wear resistance
of the titanium implants. Methods like thermal treatment, ion im-
plantation, physical vapour deposition coatings have been tested.
Thermal treatment has been used to improve the wear resistance of
titanium implants. TO treated Ti-6Al-4V resulted in significantly en-
hanced wear resistance. This is because of the tough rutile phase oxide
film that forms on the surface. It improves boundary lubrication, hence
decreasing the wear rate [228]. Molybdenum is used to improve the
wear resistance of titanium alloys. Guo et al. [229] produced modified
Mo layers on the surface of Ti-5Zr-3Sn-5Mo-15N. This resulted in a
lower coefficient of friction and enhanced corrosion resistance. A study
by McKellop and Rostlund [230] showed that abrasive wear resistance
of Ti-6Al-4V can be improved by nitrogen ion implantation. Processing
routes also influence hardness, wear friction of an implant. It was re-
ported by Bartolomeu et al. [231] that Ti-6Al-4V produced by SLM
displayed higher wear resistance. In order to study the effect of nitrogen
ions on the wear behavior, Li et al. [232] implanted nitrogen ions on
the surface of pure titanium, Ti-6Al-4V and Ti-6Al-7Nb. Plasma im-
mersion ion implantation technique was used. This increased the
M. Kaur and K. Singh
hardness as well as the resistance against the torsional fretting wear.
With the increase in ion implantation dose wear resistance further
improved. Ti-Nb-Zr-Ta alloys have received a lot of attention because of
their lower Young's modulus and better corrosion resistance than Ti-
6Al-4V but they possess poor wear resistance. Chan et al. [233] used
laser treatment to improve the wear resistance of Ti-35.3Nb-7.3Zr-
5.7Ta alloy. Wear and corrosion resistance were tested for the sample
placed in Hank's solution. The laser treated samples showed higher
open-circuit potential and lower current density hence, better corrosion
resistance.
2.8. Implant failures and their surface treatments
Studies on dental implants and hip joint replacements have found
that the probability of implant failure is around 5–20% [234,235]. Poor
early bone healing at the implant-bone interface is considered to be one
of the prime reasons for implant failure post-surgery [236,237]. Post
surgery factors like bacterial infection and excessive reactive oxygen
species (ROS) production can result in this improper bone healing.
Attempts have been made to minimise these complications by surface
modification of the implants. Chen et al. [238] formed a multilayered
structure made up of chitosan-catechol (ChieC), gelatin (Gel) and HA
nanofibers on Ti substrates. The multilayered system resulted in pro-
tection of the cells against oxidative stress damage caused by ROS. It
was found Chi-C multilayered implant can result in enhanced bone
healing. Ueno et al. [239] studied the influence of UV-pretreatment on
the ROS production in case of CP-Ti implants. It was found that ROS
production was reduced by 40–50% by UV pre-treatment of the im-
plant. This could be because UV treatment enhances the hydrophilicity
and removes hydrocarbons deposited on the implant surface.
A number of techniques have been used to prevent bacterial at-
tachment with the implant. Bhadra et al. [240] used chemical hydro-
thermal treatment and high temperature for fabrication of titanium
nanopatterned arrays on titanium surfaces. It was found that this ap-
proach improved adherence of human cells to the substrate and in-
creased the bactericidal properties of the surface. Zhao et al. [241]
synthesized and immobilized chitosan –lauric acid conjugate on a ti-
tanium substrate. Polydopamine was used as an intermediate layer. It
was concluded that these enhance osteoblast growth and hinder bac-
terial adhesion. Fielding et al. [242] coated titanium substrates with
silver and strontium doped HA. This was done to enhance the anti-
bacterial activity and bone formation. In another work by Yamaguchi
et al. [243] gallium ions were incorporated on the surface of titanium
by chemical and heat treatment. This serves a dual purpose: inhibits
bone resorption by forming apatite layer on the surface and displays
antimicrobial activity by the release of gallium ions. Ordikhani and
Simchi [244] fabricated a chitosan-bioactive glass coating on a titanium
substrate. Chitosan is known for its antibacterial and antimicrobial
properties, whereas bioglass enhances osteointegration and bioactivity.
Chitosan was loaded with vancomycin which is an antibiotic. It was
found that almost no bacteria survived on the coatings proving that
these coating significantly reduced the risk of infection. Kalaivani et al.
[245] fabricated a coating of Cu2+ doped CaSiO3 on Ti metal through
electrophoretic deposition technique and found that these display
bioactivity and anti-bacterial properties. Janson et al. [246] used CP-Ti
(grade 2) discs to produce an anti-bacterial surface by soaking in 30 wt
% hydrogen peroxide held at 80 °C. The samples were then subjected to
subsequent alkaline treatments in sodium hydroxide and calcium hy-
droxide, and a final autoclaving step to achieve enhanced bioactivity
and biocompatibility. Xu et al. [247] used octenidine dihydrochloride
(OCT) to enhance the antibacterial property of CP-Ti substrates. OCT
was loaded on the mesoporous silica nanoparticles (MSNs)-in-
corporated titania coatings formed on the titanium substrates. It was
concluded that loading with OCT enhances the antibacterial efficiency
of titanium substrates (with composite coating) to a great extent
without compromising their cytocompatibility. Many other methods of
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Materials Science & Engineering C 102 (2019) 844–862
avoiding bacterial adhesion have also been used: creating a polymer
layer (e.g. dextran [248] and poly(methacrylic acid) (PMAA)-silk co-
polymer [249]), introducing tantalum oxide coatings [250] and fabri-
cating titanium dioxide nanotube arrays [251] on a titanium substrate.
Laser treatment can also be used to improve the antibacterial properties
of the implants. Chan et al. [252] studied the influence of laser surface
treatment on enhancing the antibacterial activity of titanium implants.
This treatment resulted in a notable decrease in the bacterial adhesion.
Reduced hydrophobicity, thicker and stable oxide films and the nano-
features can be considered responsible for this type of behavior. A re-
cent (2018) review by Spriano et al. covers various strategies used to
make the Ti surfaces bioactive and anti-bacterial at the same time
[253].
Osseointegration is also important to minimise the chances of im-
plant failure. Different techniques have been employed to ensure the
formation of a secure contact between the bone and implant.
Covarrubias et al. [254] fabricated a nanoporous silica coating loaded
with bioactive glass nanoparticles on titanium surface and found that
this accelerates apatite formation. This speeds up the formation of bone
tissue close to the implant after 3 weeks of exposure. Also in order to
improve upon osseointegration and stress shielding, porous titanium
alloys are being coated with bioactive materials. Domínguez-Trujillo
et al. [255,256] have used porous titanium substrates and applied
bioglass and HAP coatings on its surface. As a result of the pores, it
becomes easy for the HAP to infiltrate and result in good bone in-
growth. It has also been reported that nano-HAP coated Ti–13Nb–11Zr
alloy result in increased osteoblast adhesion [257]. Surface wettability
is another property that can influence the rate of osseointegration
[258]. In the case of biomaterials, surface wettability is mostly assessed
by measuring the contact angles (CA). A high value of CA indicates low
wettability or hydrophobic nature and a low CA signifies high wett-
ability or hydrophilic surface [259]. It has been reported that hydro-
philic implant surfaces result in accelerated early osseointegration as
compared to hydrophobic surfaces [260,261]. Oshida et al. [262] did a
comparative study to study the effect of surface texture on the wett-
ability of CP-Ti, titanium‑aluminium‑vanadium alloy (Ti-6Al-4V), tita-
nium‑nickel alloy (TiNi), pure Ni, 316 L stainless steel, and co-
balt‑chromium alloy (CoeCr). These materials were subjected to
mechanical polishing and oxidation at 300 °C for 30 min in pure
oxygen. It was found that the titanium materials were covered with a
tetragonal type TiO2 film. 316 L stainless steel, CoeCr alloy, and pure
Ni were covered by a cubic structured spinel oxide film. The tetragonal
rutile film formed on Ti-6Al-4V could be responsible for the low initial
CA and low rate of change of CA. Whereas, the spinel oxide film on
316 L stainless steel, CoeCr alloy could be the cause of high initial CA
and low rate of change in CA. Different modification techniques like
incorporation of nanoscale TiO2 nanotube topography on the surface
[263], chemical modification of conventional sand-blasted large grit
and acid-etched titanium implants [264], surface adsorption of poly-
electrolytes like chitosan (CHI), poly(L-glutamic acid) (PGA), and poly
(L-lysine) (PLL) [265] enhance the hydrophilic nature of titanium im-
plants and hence improve osseointegration.
Surface modifications are performed to increase the surface rough-
ness using techniques like blasting and abrading. Laser is a compara-
tively new technique which is used to modify the structure at micro-
meter and nanometre level. Branemark et al. [266] tried to study the
effect of site-specific surface modification of the implants using laser to
improve bone formation. The implants with micro and nanoscale to-
pography were implanted in rabbit tibia and femur. It was concluded
that the laser treatment improved bone-implant interface anchorage.
Shah et al. [267] selectively laser ablated CP-Ti implants. It resulted in
microtopography, along with a superimposed nanotexture and a thick
oxide layer on the surface. It was concluded that laser modified surfaces
improve bone bonding. It has also been found that surface roughness at
micro- and nanoscale can also improve osseointegration. Gittens et al.
[268] developed a surface modification method to produce nanoscale
M. Kaur and K. Singh
features on the titanium substrates. It was concluded that this resulted
in enhanced osteoblast differentiation which could enhance osseointe-
gration. One can say that nanophase materials are the next generation
of biomaterials. These materials possess distinctive surface and me-
chanical properties. Due to the presence of collagen and hydro-
xylapatite, bones possess a highly nanostructured surface [269]. Also,
bone formation around implants depends on the surface topography. It
is expected that by mimicking the surface nanoroughness of bones it is
possible to improve properties of the implants [270,271]. A number of
groups are working on producing a biologically inspired nanostructured
surface to replicate the environment to which the bone-forming cells
are mostly accustomed in the body. This approach, known as the bio-
mimetic approach presents a number of benefits: increased osteoblast
adhesion [269,272], excellent osteogenic properties [273], better os-
seointegration [274] and reduced bacterial adhesion [275] in com-
parison to the conventional titanium surfaces. Further, by blending
nanocomponents and engineering nanocomposite-materials the me-
chanical properties can be enhanced to a greater extent as compared to
the microscopic and macroscopic materials [276].
Further, biocompatibility is another property that material must
possess to ensure successful implantation. Different coatings on the
implant surface have been used to improve the biocompatibility and
bioactivity. Biocompatibility can be improved by coating with ceramics
like SiO2, B2O3, and other alkali metal oxides as these are biocompa-
tible. Urbanski et al. [277] coated stainless steel 316 L (SS) and tita-
nium alloy (Ti6Al4V) with titanium dioxide (TiO2) and silica (SiO2)
coatings which were prepared by sol-gel method. These materials were
implanted into rat femur. They found that this resulted in lower in-
flammatory response in both the biomaterials which directly suggests
improvement in biocompatibility. It has become a common practice to
coat titanium implants with plasma-sprayed HA as this combines ex-
cellent mechanical properties of titanium and biocompatibility of HA.
Ke et al. [278] mixed MgO and SiO2 to HA coatings which resulted in
increased osteogenesis, osseointegration, and bone mineralization. A
new approach could be to coat these materials with agriculture waste
like rice husk ash, sugarcane leave ash, peanut and corn husk etc. as
these contain high amount of silica and other related oxides in the
nanoparticle or microparticle range [279,280]. This approach has al-
ready been used for bioglass and ceramics where rice husk is used in
place of silica as a coating on the bioglass [281,282].
3. Conclusion
This review was an attempt at exploring the basic properties of ti-
tanium and its alloys. Since the 1960's titanium alloys have been used
as implant materials. They have stood the test of time and even today
are extensively used in various orthopaedic and dental applications.
Perpetual research has since been going on to alter the alloy composi-
tion and the surface characteristics to develop a material which pos-
sesses the best combination of mechanical and chemical properties.
CP- Ti and Ti-6Al-4V (ELI) are the most widely applied implants but
both of these have certain drawbacks. The Young's modulus of these
implants is certainly less than that of stainless steel and cobalt based
alloys but it is still greater than that of bone. Today β titanium implants
have been developed with the aim of decreasing the Young's modulus
and improving the fatigue strength. Although the value of Young's
modulus for β alloy is smaller than of its predecessor's still it is not close
enough to the Young's modulus of bone. Materials with very low value
of Young's modulus have been developed (~55 GPa) but they possess
low wear resistance. Different thermomechanical processing techniques
have been used to alter the microstructure and eventually the me-
chanical properties of the titanium implants. Further porous implants
have received special attention as they help reduce Young's modulus
and improve bone ingrowth. Alloying elements like aluminium and
vanadium, widely used in various titanium implants are considered
potentially dangerous. To a great extent these implants have proven
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Materials Science & Engineering C 102 (2019) 844–862
their biocompatibility but still there have been few cases where allergy
could have been caused due to the release of dangerous ions into the
blood. As a result, efforts are being put into producing implants which
display better biocompatibility. Also, different surface treatments are
being used to improve the properties like wear and corrosion resistance
and bone bonding in case of titanium implants.
Different advanced processing techniques followed by proper sur-
face coatings and modifications are being used to achieve the required
properties of titanium implants however, more resources and research
is needed to turn the dream of developing an implant material which is
tough, biocompatible, corrosion and wear resistant and has the value of
Young's modulus closer to that of bone, into reality.
Acknowledgement
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
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