Materials Science and Engineering C 76 (2017) 1354–1368

Contents lists available at ScienceDirect

Materials Science and Engineering C

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

Review

Degradation mechanisms and future challenges of titanium and its alloys

for dental implant applications in oral environment
Revathi A a,d, Alba Dalmau Borrás b,c, Anna Igual Muñoz b, Caroline Richard c, Geetha Manivasagam d,⁎
a
School of Biosciences and Technology, VIT University, Vellore, India
b
Institute for Industrial, Radiophysical and Environmental Safety, Universidad Politécnicade Valencia, Spain
c
Laboratoire de Mécanique et Rhéologie (LMR) EA 2640, Université François Rabelais de Tours, France
d
Centre for Biomaterials Cellular and Molecular Theranostics, VIT University, Vellore, India

a r t i c l e i n f o a b s t r a c t

Article history: Objective: For many decades the failure of titanium implants due to corrosion and wear were approached individ-
Received 3 November 2016 ually and their synergic effect was not considered. In recent past, developments and understanding of the
Received in revised form 26 February 2017 tribocorrosion aspects have thrown deeper understanding on the failure of implants and this has been reviewed
Accepted 27 February 2017 in this article extensively.
Available online 2 March 2017
Methods: Medline, google scholar and Embase search was conducted to identify studies published between 1993
and 2016 which were related to the analysis of degradation mechanism which the dental implants undergo after
Keywords:
Dental implants
implantation.
Corrosion Results: In-vitro tests has been extensively carried out to evaluate the tribocorrosion behavior of titanium based
Wear dental implants. However, there is still a lack of knowledge about the tangible behavior of materials under in-vivo
Tribocorrosion condition, because the in-vitro experiments are conducted using different testing protocols and conditions (solu-
Surface treatment tions, pH, time, equipment, and testing parameters). Hence, there is an urgent need to perform round-robin test
Debris in different laboratories which will help to overcome the gap between in-vitro and in-vivo conditions.
Implant loosening Conclusion: Tribocorrosion has been identified as the major degradation mechanisms that result in the failure of
dental implants. Hence, it is of utmost importance to improve the service period of dental implants by reducing
the tribocorrosion effects through developing new dental implant materials using nobler alloying elements or
through modifying the surface of the implants. In order to have a thorough understanding of tribocorrosion
behavior and failure mechanisms, round robin test are to be conducted and new protocols/standards are to be
developed for the testing of implants.
© 2017 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1355
2. Materials and methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1355
3. Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1355
3.1. Clinical aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1355
4. Degradation mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1356
4.1. Corrosion of titanium and titanium alloy dental implants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1357
4.2. Wear of titanium and titanium alloys dental implants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1358
4.3. Tribocorrosion of titanium and titanium alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1358
4.3.1. Tribocorrosion under sliding conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1358
4.3.2. Tribocorrosion under fretting conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1358
5. Strategies to prevent wear and corrosion of dental implants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1360
5.1. Surface treatments by physical or chemical subtraction (surface roughening). . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1362
5.1.1. Acid etching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1363
5.1.2. Sandblasting or grit-blasting. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1363

⁎ Corresponding author.
E-mail address: geethamanivasagam@vit.ac.in (G. Manivasagam).

http://dx.doi.org/10.1016/j.msec.2017.02.159
0928-4931/© 2017 Elsevier B.V. All rights reserved.
 A. Revathi et al. / Materials Science and Engineering C 76 (2017) 1354–1368 1355

5.1.3. Duplex treatment: sandblasting and acid-etching (SLA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1363

5.1.4. Oxidized surfaces: anodizing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1364
5.1.5. Nitriding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1364
5.1.6. Cryogenic treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1364
5.1.7. Surface treatments by addition (coatings on titanium substrate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1365
5.2. Titanium plasma spraying (TPS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1365
5.3. Other treatments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1365
6. New implant dental materials/addition of alloying elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1365
7. Conclusion/summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1366
8. Future directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1366
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1366

1. Introduction a variety of chemical attack thereby making Ti-based implants highly

Dental implants are surgically fixed substitutes for roots of lost or
non-functional teeth. Restorative dental materials help to repair dam-
age to teeth caused by gum disease, poor bone density or trauma. The
restoration of teeth is very important because tooth damage, loss or dys-
function may cause speech disorders and may even lead to deterioration
of the temporomandibular joint with severe pain [1]. Although bridge-
work and dentures address the cosmetic problem of missing teeth,
they fail to restore proper chewing functions. Permanent implants, on
the other hand, exert appropriate force on the jawbone and keep
them functional and healthy [2]. Due to further developments in dental
care technologies, a tremendous growth in dental implants and pros-
thetics market has been observed during the past few years. Hence,
there is an extensive need of better quality dental materials, which
not only helps to restore the functions of teeth but also causes less
harm to the human body.
The choice of the dental implant materials, their manufacturing pro-
cesses, biocompatibility and long-term stability in line with medical
ethics and professional codes of practice are therefore crucial. Materials
such as ceramics and metal alloys are extensively used for the fabrica-
tion of dental implants. Ceramics either make up the entire implants
or can be applied in the form of a coating onto the metallic core. An
ideal implant should be biocompatible, possess higher strength, fatigue
and fracture toughness behavior and should be able to withstand the re-
active environment it is exposed to inside the human body [4]. In addi-
tion, the stiffness/modulus of elasticity should be as close to that of bone
to prevent stress-shielding effect. Stress-shielding effect arises when
there is a mismatch between the strength of two materials [3]. Among
the different metallic materials employed as implants, the use of stain-
less steel has been restricted as an internal fixation device because of
its poor fatigue strength and high susceptibility to pitting and galvanic
corrosion. Similarly, cobalt–based alloys suffer from poor fatigue
strength and possess comparatively high modulus of elasticity than
other implant materials used. In addition, the ion release from these ma-
terials has been found to have carcinogenic effect [4]. Thus, the above
mentioned reasons make titanium and its alloys the ultimate choice as
dental implants because in addition to exhibiting superior biocompati-
bility and high strength to weight ratio, Ti-alloys also exhibit low mod-
ulus of elasticity and enhanced mechanical properties such as high
fatigue strength (140–1160 MPa) and fracture toughness. Various tita-
nium dental implants are available commercially and are classified
into groups based on their shape (cylindrical, conical, hybrid) and the
type of connection to the prosthetic component such as Morse taper, in-
ternal hexagon, external hexagon and dodecagon [5]. Remarkably, their
corrosion resistance stems from the high affinity of Ti towards oxygen
which results in the formation of a thin and stable passive oxide layer
that protects the bulk material from reactive species [6]. The oxide
layer formed on Ti alloys typically consists of TiO2 but may coexist
along with other titanium oxides such as TiO and Ti2O3 [7]. The thick-
ness of the oxide film formed are b10 nm and offer high resistance to
corrosion resistant in the oral environment.
The main aim of this review is to focus on the degradation mecha-
nism of titanium dental implants along with the various surface treat-
ments utilized to improve the performance and service life of dental
implants. Based on an extensive review performed, the future chal-
lenges in the field of implant dentistry are also identified and presented.
2. Materials and methods
The electronic search was performed using Medline (PubMed),
Embase, Google scholar, book chapters and Prorequest dissertations
and theses database. Grey literature such as reports were also used to
analyze the current status and future scope of dental implant market.
The MESH term used were: dental implants AND market, wear and den-
tal implants, corrosion and oral environment, tribocorrosion and artifi-
cial saliva, toxicity and debris, surface modification and alloying, new
dental alloys and corrosion resistance, anodization AND titanium plas-
ma spray (TPS), nitriding, cryogenic treatment, coating AND titanium.
Languages were limited to French and English. The time period of the
literature search was between March – September 2016 and there
were no exclusions made based on the year of published paper.
Mendeley V.1.15 was used to manage the references. Important
criteria's for inclusion of articles were: Fig. 1 shows the flowchart
illustrating the inclusion and exclusion criteria and study flow for the
systematic review according to the Preferred Reporting Items for
Systematic Reviews and Meta-Analysis (PRISMA) guidelines.
3. Discussion
3.1. Clinical aspects
Osseointegration is a term that refers to the formation of a direct
functional and structural connection between living bone and an artifi-
cial implant and is governed by a variety of surface properties such as
composition, roughness, wettability, surface energy, surface tension,
orientation and texture [8]. In particular, the important factor that de-
termines osteogenesis is the adsorption of specific proteins onto the
metal surface. The adsorption of surface proteins should be such that
the bioactive peptides which helps cell-binding is available for the in-
coming proteins. The initial process involving the complex interplay of
various signaling molecules and inflammatory mediators which leads
to osteoconduction and osteoinduction takes place a period of about
21 days [9]. It has been found that there exists a critical level of
micromotion (50 and 150 μm) above which fibrous encapsulation pre-
vails over osseointegration [10].
Widely accepted protocol for the successful placement of endosteal
implants involves a traumatic surgical technique and healing period of
at least 3 months with no-load to promote regeneration and prevent fi-
brous encapsulation. In contrast, another method which ensures
quicker recovery is by adopting for immediate loading involving a
1356 A. Revathi et al. / Materials Science and Engineering C 76 (2017) 1354–1368
Fig. 1. Inclusion and exclusion criteria and study flow for the systematic review.
single-stage treatment method where the crown and abutment are
placed on the implant right after surgery. Advantages of this method
are quicker recovery and less post-surgical care. However, the chances
of implant failure are high due to overloading [8,10–13].
This paper aims to focus on the degradation mechanism of titanium
dental implants along with the various surface treatments to improve
the performance and service life of dental implants and the future
challenges in the field of implant dentistry.
4. Degradation mechanisms
The reasons for implant failure can be categorized according to
patient-related, biological and mechanical factors which are given in
Fig. 2. Patient-related factors such as smoking, metabolic diseases (dia-
betes mellitus) and disorders (anorexia nervosa) increases the risk of
implant failure when compared to healthy individuals. Other factors
that lead to implant failure include infection/peri-implantitis, aseptic
loosening, osteomyelitis and improper bone-bonding due to over-
load. In addition, there are certain electrochemical and tribological
factors such as corrosion and wear that accelerates the aforementioned
reasons thereby, leading to implant-failure [14–16].
As described earlier, the presence of protective oxide layer keeps the
current flow and the release of corrosion products at very low level.
However, no metallic material is completely resistant to corrosion or
ionization within living tissues. Mechanical disruption of the oxide
layer leads to deterioration of metal surface by processes such corrosion
and wear. Many types of electrochemical corrosion are possible in the
oral environment because saliva contains aggressive anions such as
chlorides which causes dissolution of the oxide layer and leads to re-
lease of metal ions into the surrounding tissues. The electrochemical be-
havior of Ti-based implants is dependent on various factors such as
composition, concentration of anions, pH, buffering capacity and
surface-related properties of the implant (Fig. 3) [17].
Wear, another degradation mechanism, refers to the deformation of
the surface of materials as a result of mechanical interaction between
two opposite surfaces [18]. The wear resistance of artificial dental mate-
rials is essential for long-term stability of the implant. Generally, wear
resistance is dependent upon the hardness, roughness, fracture tough-
ness and the Young's modulus of the interacting materials. As wear
 A. Revathi et al. / Materials Science and Engineering C 76 (2017) 1354–1368
Fig. 2. Factors affecting implant stability.
measurements in vivo is highly complex and time-consuming, wear
analysis is usually performed in simulators in the presence of artificial
saliva.
Similarly, fretting corrosion is another degradation mechanism
which refers to the small oscillating movements between two
interacting materials (bone-implant, plates-screws) in presence of cor-
rosive oral environment. Simultaneous action of electrochemical and
mechanical interaction occurring on materials subjected to relative
movement, i.e. wear and corrosion occurring simultaneously is referred
to as tribocorrosion. Above mentioned degradation mechanism (wear,
corrosion, tribocorrosion) causes the release of metal ions/debris into
the peri-implant region. As illustrated in Fig. 4, metal debris activates
a cascade of signaling molecules that result in the activation and differ-
entiation of osteoclast cells and leads to bone resorption/osteolysis of
the peri-implant region. As a result, the bonding between the bone
and implant is lost and results in implant loosening. Occurrence of im-
plant loosening in the absence of bacterial infection is referred to as
aseptic loosening. Smaller sized wear debris combine with biomolecules
and elicit Type IV immunogenic response and causes ezhema, prolongs
bone healing and is also accompanied with pain. Also, it has been found
that the titanium implanted region turns black. This is because the sur-
face of titanium undergoes repassivation when the oxide layer is
disrupted. In certain conditions, the repassivation process forms so
Fig. 3. Factors influencing the failure of dental implant.
1357
much TiO2 oxide layer that the region turns blacker. This process is re-
ferred to as metallosis and has been considered to be harmful [19]. It
is therefore important to study the dental implants in-vitro under phys-
iological condition to understand their behavior in the oral environment
and develop strategies to combat the issues that lead to implant failure.
4.1. Corrosion of titanium and titanium alloy dental implants
The rate of a corrosion process depends on (i) oxide layer formed;
(ii) pH; (iii) Concentration and composition of the electrolyte; and
(iv) transport of oxygen vacancy across the film [20]. Different types
of corrosion the materials are prone to, are represented in Fig. 5.
The TiO2/Ti has an O to Ti concentration that varies gradually from
TiO2 film to a much lower ratio in the bulk [21]. Pan et al. [22] suggested
that duplex layers formed on the surface of Ti alloys comprise of an
inner barrier layer and an outer porous and less stable layer.
Fluorides are usually present in toothpastes and mouthwashes to
prevent the development of dental caries. However, exposure of higher
concentration of fluorides exerts detrimental effect on the implant as
the oxide films of dental implants react with fluoride solutions and
forms titanium-fluoride molecules such as titanium fluoride or sodium
titanium fluoride. The lattice parameters of these compounds induce
many structural defects in the oxide layer and hence, the bulk material
becomes more prone to electrochemical attack [23].
In order to determine the concentration of fluorides that causes the
disruption of the protective oxide layer of dental implants various stud-
ies have been carried out with varied concentration of fluoride ions.
Alves-Rezende et al. investigated the electrochemical behavior of
commercially-pure Ti and Ti–10% Molybdenum. The electrolyte
consisted of 0.12% chlorhexidinedigluconate, 0.03% triclosan along
with 0.05% sodium fluoride and 0.5 g/L cetylpyridinium chloride with
0.05% sodium fluoride. However, these concentrations exhibited negli-
gible effect on the stability of the oxide layer [24].
D. Mareci et al. monitored the electrochemical behavior of surface
modified Zr5Ti, Zr25Ti, Zr45Ti in artificial saliva containing sodium fluo-
ride concentration of about 0.2, 0.5 and 1 wt% simulating the fluoride
concentrations in dental rinses and showed that thermal oxidation of
ZrTi alloys in air at 500C for 2 h drastically minimized the effect of fluo-
rides on the corrosion behavior of ZrTi alloys due to the formation of a
stable passive oxide layers of TiO2 and ZrO2. The outermost layer was
found to be enriched with TiO2 which reduced the dissolution of oxide
film induced by the presence of fluoride ions [25].
1358 A. Revathi et al. / Materials Science and Engineering C 76 (2017) 1354–1368
Analogously to the fluoride effect, there are also other compounds
that affect the corrosion process of titanium alloys. L P Faverani et al. re-
ported the corrosion kinetics of Ti-6Al-4V in different mouthwash solu-
tions consisting of 0.053% cetylpyridinium chloride and 3% hydrogen
peroxide, with only artificial saliva as control. It was found that while
3% H2O2 had adverse effect, under other conditions Ti-6Al-4V was stable
and showed low susceptibility to corrosion [22].
Overall, these reports substantiate the role of oxide layer in provid-
ing corrosion resistance in most adverse oral environments which con-
sists of varying pH, acid attack and the presence of chemical compound
such as cetylpyridinium chloride, sodium fluoride and hydrogen
peroxide.
4.2. Wear of titanium and titanium alloys dental implants
The fretting behavior of cortical bone at the bone-implant interface
was investigated using commercial titanium grade 2 and TC4 alloy
against cortical bone. The wear depth and coefficient of friction were
found to be higher in case of bone-TC4 than bone-commercially pure ti-
tanium. Abrasive wear and delamination were characterized as the
wear mechanism of the cortical bone [26]. Hence, it is of utmost impor-
tance to develop highly wear resistant material or employ surface mod-
ification of titanium alloys to minimize its potential against natural
cortical bone at bone-implant interface. Cast Ti-6Al-7Nb was found to
exhibit better wear resistance than CP-Ti (grade 2 and 3) because of
higher hardness and the presence of two-phase microstructure
consisting of acicular ά phase in prior β grain [5]. Similarly, C. Ohkubo
conducted in-vitro study to evaluate the wear behavior of cast CP Ti tita-
nium along with 3 and 5 wt% copper and Ti-6Al-4V with 1 and 5 wt%
copper. The unmodified Ti and Ti6-Al-4V alloys were used as control.
Compared to other concentrations of Cu, 4 wt% Cu was found to exhibit
highest wear by introducing α-Ti/Ti2Cu eutectoid which helped to im-
prove resistance to plastic deformation and enhance wear resistance
[27].
In addition to usage of alloying elements to improve the wear char-
acteristics, coatings could also be performed on the implant surface.
Poly-ether-ether-ketone (PEEK) was coated on Ti-6Al-4V due to its
higher mechanical properties and wear resistance. The samples were
synthesized by hot-pressing the PEEK veneer onto Ti-6Al-4V cylinders.
Wear tests were carried out at 30 N load, frequency of 1 Hz with stroke
length of 3 mm in artificial saliva using Al2O3 as the counter body. As
expected, the coefficient of friction and specific wear rate was less
than the uncoated Ti-6Al-4V sample. Hence, this shows that PEEK/TI-
6Al-4V hybrid could be used to support masticatory loads, improve bio-
compatibility and wear resistance [28].
Similarly, the effect of three different surface treatments such as
plasma nitriding, TiAlN thin film deposition by closed field unbalanced
magnetron sputtering (CFUBMS) and Al2O3 coating using plasma
spray method on improving the wear resistance of Ti-6Al-4V was eval-
uated by F. Yildiz et al. Wear tests were performed using pin-on-disc
tribotester in physiological solution at 37 °C. Although, all surface treat-
ments improved the wear resistance of Ti-6Al-4V alloy, Al2O3 coating
exhibited highest wear resistance while lowest was obtained in case
of nitrided samples [29].
4.3. Tribocorrosion of titanium and titanium alloys
Tribocorrosion, which occurs under the dual action of wear and cor-
rosion, may occur under a variety of conditions such as i.e. sliding, fret-
ting, rolling, impingement in a corrosive medium. The schematic
representation of tribocorrosion mechanism is given in Fig. 6.
Fig. 4. a) Release of wear debris from the dental implant leads to the activation of immune cells. Macrophages are one of the first cells to act 48 h after exposure to debris. Debris causes both
cytotoxity and genotoxity. Macrophage takes up these debris via phagocytosis and secretes cytokines and chemokines, which enables to further activate the differentiation of osteoclast
from the precursor cells. b) Upon exposure to macrophage colony-stimulating factor (MCSF) and RANKL synthesized by the T cells and synovial fibroblasts, osteoclasts fuse to polykaryons
termed preosteoclasts, which then undergo further differentiation into mature osteoclasts leading to bone- resorption and osteolysis.
4.3.1. Tribocorrosion under sliding conditions
Tribocorrosion studies of titanium and its alloys under sliding condi-
tions with and without surface treatment are shown in Tables 1 and 3
respectively. Similarly, Tables 2 and 4 enlists the tribocorrosion study
of untreated and surface modified titanium alloys under fretting condi-
tion. In general, the tribocorrosion works are focused on the evaluation
of surface treatments, which improve the wear and corrosion perfor-
mance of bulk materials (i.e. CP-Ti and its alloys) and on the analysis
of environmental variables (pH, fluoride content in the artificial saliva,
temperature) on the tribocorrosion behavior of dental implants
[30–35].
Tribocorrosion studies are carried out under different mechanical
conditions due to the flexibility given by the experimental set-ups,
tribometers in lubricated conditions. The used average speed is between
0.1 and up to 1000 mm/s, while average contact pressure is maintained
between 23 MPa and 3.15 GPa. Vast varieties of electrolytes are used,
from very simple solutions (sodium chloride) to more complex formu-
lations. Although independent of the pH, tribocorrosion damage is
mainly due to the mechanical action in the simulated body fluids. Addi-
tion of fluorides to acidified artificial saliva accelerates the corrosion
process and increase ion release into the surrounding. Hence, pH of
the electrolyte is not the only criteria determining the tribocorrosive be-
havior of dental implants [27].
Among the 23 papers testing titanium alloys under sliding condi-
tions, 13 were carried out under electrochemical control of the system
by monitoring the OCP (open-circuit potential) or by imposing an ap-
plied passive potential [36–43]. Under OCP conditions, a potential disso-
lution of oxide layer is observed when rubbing starts due to the galvanic
coupling formed between the worn area/anode and the unworn zone/
cathode, which has been described by Vieira et al. [44]. As discussed ear-
lier, the extent of the dissolution of the protective oxide layer depends
on the surface treatment of the tested material, electrolyte and the
contact pressure, load and frequency [32,35,45].
4.3.2. Tribocorrosion under fretting conditions
In dental implants, fretting can occur at the interface between the
implant and alveolar bone during occlusal movements. In the fretting-
corrosion studies the average sliding speed used are in a narrow
range, between 0.2 and 1.8 mm/s, while the average contact pressures
vary from very low values (333 MPa), to very high ones (12 GPa). The
selected reciprocating amplitudes range between 50 and 180 μm at a
typical frequency of 1 Hz, but usually lies between 1 and 40 Hz
[36–42,46–48].
Diomidis et al. demonstrated that Ti–29Nb–13Ta–4.6Zr has the abil-
ity to repassivate both under sliding and fretting corrosion even after
depassivation. The influence of proteins and/or other inorganic com-
pounds on the passivation behavior during fretting-corrosion has also
been studied widely [49]. Viera et al. described an increase in the wear
volume and corrosion rate in the presence of cathodic or organic inhib-
itor. Hiromoto and Mischler [50] also could not find any effect of bovine
serum albumin on either on the wear rate or the wear accelerated cor-
rosion of the Ti6Al4V alloy. Similarly, Diomidis et al. [49] observed that
the presence of synovial constituents lubricated the contact making slip
easier but could not find any appreciable effect on the electrochemical
response of beta-titanium alloys.
Bao-rong Zhang et al. studied the fretting wear behavior combined
with tangential and radial fretting modes of Ti-6Al-4V ball against med-
ical pure titanium grade 2 (TA2) and Ti-6Al-7Nb disks in artificial saliva
at 37 °C and it was found that Ti-6Al-7Nb presented better dual motion
fretting wear resistance than TA2 in artificial saliva at the same test pa-
rameters. With the increase of inclined angle and decrease of imposed
A. Revathi et al. / Materials Science and Engineering C 76 (2017) 1354–1368 1359
1360 A. Revathi et al. / Materials Science and Engineering C 76 (2017) 1354–1368

Fig. 5. Types of corrosion taking place in an implant.

load, the extent of wear was lowered. The wear mechanisms of pure ti-
tanium TA2 and Ti-6Al-7Nb alloy under the condition of dual motion
fretting in artificial saliva were delamination, abrasive and oxidative
wear [51].
5. Strategies to prevent wear and corrosion of dental implants
The list of strategies to prevent wear and corrosion of dental implant
is represented in Fig. 7. In addition to improving biological response, by
modifying the microstructure of the implant, it is also possible the
chemical and mechanical properties as grain size and structural mor-
phology govern the friction and corrosion behavior of metallic biomate-
rial [52]. Lower production cost, higher corrosion resistance and excellent
biocompatibility make CP-Ti a suitable candidate as a dental implant.
However, the major drawback is the low wear resistance and strength
of CP-Ti than other Ti alloys. Hence, efforts are being made to improve
the mechanical properties of CP-Ti by employing different processing
techniques to obtain nanocrystalline materials, which are higher in
strength and also exhibit better biocompatibility properties [49,50,53,54].
Powder metallurgy is a new promising technique that allows
obtaining small grain and sub-grain size implant materials with similar
or better mechanical properties like hardness, tensile and fatigue
strength to those obtained by commercially used fabrication processes
[55]. Nanomaterials are classified into nanocrystalline materials and
nanoparticles. NCM are polycrystalline bulk materials with grain sizes
in the nanometer range (b 100 nm). Because of the extremely small di-
mensions, a large volume fraction of the atoms is located at the grain
boundaries atoms (20–50%) and their technologically attractive proper-
ties make them a suitable candidate as an implant material. Lucie
Ostrovska et al. evaluated the short-term metabolic behavior of
human osteoblasts and mesenchymal stem cells to ultra-fine grain tita-
nium materials which exhibited superior mechanical properties hence,
long term performance. Although, hMSC's displayed lower cell num-
bers, osteoblast cells showed better response in terms of attachment
and spreading [56].
Similarly, bulk metallic glasses (BMG's) are metallic materials with
non-crystalline structure rather than the usual micro or nano-
crystalline structures exhibited by metals. The glass-like structure of
these materials is formed as a result of rapid cooling which prevents
the formation of usual crystal nucleation in metals. Usually three or
more than three alloying elements should are employed with atomic ra-
tios b10% to achieve high glass forming ability. Many Ti-based BMG's

Fig. 6. Schematic representation of tribocorrosion mechanism.

 A. Revathi et al. / Materials Science and Engineering C 76 (2017) 1354–1368 1361

Table 1
Tribocorrosion studies under sliding conditions of Ti alloys for dental implants.

Ref. Titanium alloy Counterpart Motion Solutiona Load [N] Avg speed Electrochem. control Friction Wear
(surface treatment) (diameter) [mm] Contact (Avg [mm/s] range coefficient
geometry press) (duration) [mm3/Nm]
[MPa] [s]

[36] Ti6Al4V Al2O3 ball (10) Reciprocating NaCl 1 (264) 6 (1800) OCP 0.4 2.0 · 10−4
Ball on plate 5.0 · 10−4
[37] Ti6Al4V Al2O3 ball (6) Unidirectional AS, AS + fluorides 5 (960) 19 (3600) OCP, applied potential 2.5 · 10−4
Ball on plate 5.8 · 10−4
[38] Ti6Al4V Al2O3 ball (6) Unidirectional AS, AS + pHs 5 (960) 19 (3600) OCP, applied potential 1.3 · 10−4
Ball on plate 1.7 · 10−6
[39] Ti-G2, Ti-G5, Ti6Al4V, Al2O3 ball (6) Unidirectional PBS, PBS + BSA 5 (960) 19 (3600) Applied potential 2.9 · 10−4
Ti6Al4V ELI Ball on plate 7.3 · 10−4
[40] Ti29Nb13Ta4.6Zr UHMWPE (12) Reciprocating HBSS 6.5 (23) 10 (3600) OCP, Applied potential 0.15–0.3 6.8 · 10−7
Ball on plate 1.7 · 10−6
[41] Cp Ti, Ti6Al4V Al2O3 ball (28) Ball on disc AS, AS + 20 (372) (2400) OCP, Applied potential 0.4
lipopolysaccharide
[46] Cp Ti Al2O3 ball (28) Ball on disc AS, AS + pHs 20 (372) (2400) Applied potential
[45] Cp Ti Al2O3 ball (10) Reciprocating MF, MF + fluorides 3 (370) 4 (1200) OCP 0.35–0.5
Ball on plate
[89] Ti6Al4V ELI, 30CrNiMo8 (35) Block on disc SBF 40 260, 500,
Ti13Nb13Zr 1000 (600)
[35] Ti35Nb7.2Zr5.7Ta, Chromium steel Pin on disc Hank's, BS 50 (1) 1000 (2) 0.4–0.65
Ti35Nb7.2Zr5.7Ta0.5b
[42] Ti12.5Mo, Ti13Nb13Zr, UHMWPE ball Reciprocating HBSS + HA, HBSS + 6.5 10 (3600) OCP, applied potential 0.15–0.39 Ball
Ti29Nb13Ta4.6Zr (12) Ball on plate BSA, HBSS + DPPC (34–35) 2.1 · 10−7
7.7 · 10−6
[48] Ti13Nb13Zr0.5B Chromium steel Pin on disc Hank's, BS 50 (1) 1000 (2) 0.4–0.5
[90] Ti13Nb13Zr Chromium steel Pin on disc Hank's, BS 50 (1) 1000 (2) 0.22–0.5
[43] Ti6Al4V Al2O3 ball (2) Reciprocating SBF 0.098 0.1, 1, 10, 20 OCP, applied potential,
Ball on plate (356) (3600) potential sweep
a
AS: artificial saliva, BS: bovine serum, BSA: bovine serum albumin, DPPC: dipalmitoylphospatidylcholine, HBSS: Hank's balance salt solution, MF: modified Fusayama, PBS: phosphate
buffered solution, SBF: simulated body fluid.

have been fabricated with higher compressive strength, superior hard- Qin et al. evaluated the corrosion behavior of Ti45Zr10Pd10Cu31Sn4
ness and lower Young's modulus than the commercially used Ti alloys BMG using weight loss method after immersing in 1 N HCl solution and
[57,58]. found that the corrosion rate of the BMG was six times lower than that

Table 2
Tribocorrosion studies under fretting conditions of Ti alloys for dental implants.

Ref. Titanium alloy Counterpart (diameter) Motion Solutiona Load [N] Avg speed Electroch. Friction Wear
(surface treatment) [mm] Contact (Avg press) [mm/s] Control range coefficient
geometry [MPa] (duration) [mm3/Nm]
(frequency, [s]
amplitude)
[Hz, m]

[40] Ti29Nb13Ta4.6Zr Al2O3 ball (10) Reciprocating HBSS 10 (400) 0.2 (1800) OCP, 0.2–0.6 5.9 · 10−5
Ball on plate applied 1.4 · 10−4
(1, 100) potential
[91] Ti6Al4V Ti6Al4V, CoCrMo Reciprocating PBS 0.5–50 0.125 (125) Applied 0.3–0.7
cone-shaped flat Pin on plate
bottom pin (0.35–0.8) (1.25, 50)
[92] Ti6Al4Fe, Ti12.5Mo, Al2O3 ball (10) Reciprocating HBSS, HBSS + BSA, HBSS + HA, 10 (400) 0.2 (3600) OCP, 0.4–1 1.7 · 10−4
Ti13Nb13Zr, Ball on plate HBSS + DPPC applied 4.9 · 10−3
Ti29Nb13Ta4.6Zr (1, 100) potential
[93] Ti6Al4V Al2O3 ball (8) Reciprocating AS, AS + fluorides 3 (440) 1.8 (3600) OCP 1.0 · 10−8
Ball on plate 1.5 · 10−8
(5, 180)
[94] Cp Ti Al2O3 ball (8) Reciprocating HBSS 3, 5, 7, 10 1.8 OCP
Ball on plate (500–1200) (150–7200)
(5–10, 180)
[95] Ti6Al4V Si3N4 ball (4) Reciprocating BS 49.6 (2680) 8 (90000) – 0.05–0.08 8.4 · 10−10
Ball on plate 1.6 · 10−9
(40, 100)
[50] Ti6Al4V Al2O3 ball (10) Reciprocating PBS, PBS + collagen, PBS + BSA, 10–30 0.2 (3600) Applied 0.5–0.8
Ball on plate HEPES, HEPES + BSA (607–876) potential
(1, 100)
[54] Ti G2 Al2O3 ball (10) Reciprocating AS, AS + citric acid, AS + cathodic 2 (333) 0.4 (5000, OCP, 0.7–0.9 1.0 · 10−5
Ball on plate inhibitor, AS + anodic inhibitor, AS + 10,000) applied 1.5 · 10−5
(1, 200) organic inhibitor potential
a
AS: artificial saliva, BS: bovine serum, BSA: bovine serum albumin, DPPC: dipalmitoylphospatidylcholine, HBSS: Hank's balance salt solution, MF: modified Fusayama, PBS: phosphate
buffered solution, SBF: simulated body fluid.
1362 A. Revathi et al. / Materials Science and Engineering C 76 (2017) 1354–1368
Table 3
Tribocorrosion studies of surface treated Ti alloys under fretting condition.
Ref. Titanium alloy Counterpart Motion Contact geometry
(surface treatment) (diameter) [mm] (frequency, amplitude)
[Hz, m]
[96] Ti6Al7Nb (N implantation) Zr2O (25.2) Torsional
Ball on plate
[51] Cp Ti (anodized) Al2O3 ball (8) Reciprocating
Ball on plate
(5, 180)
a
AS: artificial saliva, BS: bovine serum, BSA: bovine serum albumin, DPPC: dipalmitoylphospatidylcholine, HBSS: Hank's balance salt solution, HEPES: 2-[4-(2-hydroxyethyl)-1-
piperazinyl]-ethanesulfonic acid, PBS: phosphate buffered solution.
of stainless steel [57]. Furthermore, by developing coatings on TiN and
(Ti, Al) N on Ti40Zr10Cu36Pd14 BMG using magnetron sputtering
(PVD) resulted in porosities in the range of 6.4% and 2.7% for TiN and
(Ti, Al) N respectively. The coated BMG's exhibited four and ten times
decrease in the corrosion resistance (3.5 × 10− 4 A/m2,
8.8 × 10−4 A/m2) than the unmodified BMG substrate
(3.5 × 10− 3 A/m2) [66]. Additionally, the biocompatibility of the
BMG's were also evaluated by Wang et al., who studied and compared
the in vitro and in vivo biocompatibility of Ti-based BMG
(Ti41.5Zr2.5Hf5Cu37.5Ni7.5S1Sn5) by performing direct and in-direct
toxicity tests using murine fibroblast cultures (1929 cells and NIH3
cells) with CP-Ti as control. Proliferations rates were found to be 60%
and between 55 and 65% for 1929 and NIH3 cells respectively. Though
low cell viability was observed in vitro, it was not the case with the re-
sults obtained by in vivo test conducted after one month of implantation
in dogs as they revealed proper osseointegration. This difference was
attributed to the fact that the metabolism in the living organism did
not allow the accumulation of Cu ions as they are considered to be the
reason behind the toxicity of this BMG material [59].
One of the major problems with the use of metallic implants is the
mismatch between the Young's modulus or in other term the stiffness
of the metallic implant and the cortical bone. The much stiffer implant
shields the bone from the pressure that is usually necessary for normal
bone functioning and the maintenance of normal bone structure. When
the pressure is not evenly distributed throughout the skeleton, the
stress-shielded bone eventually gets resorbed into the body in a process
termed as disuse atrophy. This problem could be overcome by
employing metallic foams (metal air composites) as their modulus of
elasticity (ductility) can be adjusted according to the need (patient's
bone density). However, the reduction in ductility is accompanied
with decrease in strength. Metallic glass foams (MGF), however, exhibit
higher strength than the conventional foam and hence, it is possible to
fabricate MGF with open, closed or intermediate porosity by using ther-
moplastic foam method with reduced ductility while still maintaining
the required strength [60].
Similarly, by inducing porosity it is possible to reduce the elastic
modulus of the implant materials. In addition, the porous structure pro-
motes bone in-growth. Xue et al. fabricated porous implant with 27%
porosity and the pore sizes varied between 100 and 800 μm using
laser engineered net shaping (LENS) technique [61]. Similarly, by
employing LENS method, Amit Bandyopadhyay et al. were able
Table 4
Efficiency of the common surface treatments for the Bone-to-Implant Contact (BIC)
[97,98].
Surfaces % BIC
Electro-polished 20 to 25
Acid-etched (unmeasured roughness) 20 to 25
Sandblasted (with low roughness Sa b 1 μm) 20 to 25
Sandblasted (with high roughness Sa: 1 to 3 μm) 30 to 40
SLA 50 to 60
TPS 30 to 40
Solutiona Load [N] Avg speed [mm/s] Electroch. control
(Avg press) [MPa] (duration) [s]
20% BS 100 – –
Ringers 3 (500) 1.8 (3600) OCP
to achieve Young's modulus closer to that of bone (10–20 GPa) by
inducing porosities between 35% and 42%.
Ostuki et al. studied the 3D bone in-growth on four sintered porous
Ti-samples with 48%–70% porosity with pore size ranging from 233 and
333 mm respectively. The porous samples were implanted into femoral
condyles of male rabbits till 12 weeks. It was found through matching
analysis that narrow pores inhibited bone in-growth while the wider
ones exhibited higher distribution of bone cells [62].
In order to prevent the dental alloys from the aggressive oral envi-
ronment, surface modification of dental implants are employed to ren-
der them protection from both wear and corrosion. In addition to the
surface treatments, new dental implants are also being fabricated with
non-toxic or less toxic alloying elements to improve their biocompati-
bility. The surface treatment processes for dental implants are varied
and can be classified into two categories: surface treatments by subtrac-
tion/alterations or modifications of the titanium surface, surface rough-
ening and surface treatments by addition/coatings on the titanium
substrate [63,64].
5.1. Surface treatments by physical or chemical subtraction (surface
roughening)
Laser polishing or electropolishing helps produce smooth surfaces
with an average surface roughness (Sa) of 0.5 to 0.8 μm. Surface rough-
ness can take three different scales:
• Macro-roughness defined by a roughness ≥ 10 μm: this roughness
scale depends on the implant geometry with its machined threads
or depends on the surface treatment used to carry out this surface
state. Some authors showed that this high roughness increased the
risks of peri-implantitis (in fine loss of crestal bone) and the ionic re-
lease. It is therefore more appropriate to use a lower roughness,
• Micro-roughness defined by a roughness between 1 and 10 μm.
This roughness may promote the procurement of bone cells and
their mineralization,
• Nano-roughness defined by a roughness between 0.01 and 1 μm can
make a significant contribution to the adsorption of proteins, migra-
tion and differentiation of osteoblasts and hence, the osteointegration
velocity [65]
Similarly, Wennerberg and Albrektsson [66] categorized the
roughness of implants into several levels:
• Slightly rough implants with a roughness between 0.5 and 1 μm,
• Moderately rough implants with a roughness between 1 and 2 μm,
• Strongly rough implants with a roughness higher than 2 μm.
They reported that the optimal surface roughness (golden point)
was around Sa = 1.5 μm; higher or lower Sa give a weaker bone re-
sponse. Various studies have investigated and proved that rough surface
of implants achieves stronger anchorage in jawbone than the smooth
surfaces. The cellular differentiation is fundamental for the Bone-to-
 A. Revathi et al. / Materials Science and Engineering C 76 (2017) 1354–1368
Fig. 7. Strategies to prevent wear and corrosion.
Implant Contact (BIC – Table 4). It is therefore preferable to produce
rough surfaces [67].
Three techniques are commonly used in implant industry:
• Acid-etching with one or several acids,
• Sandblasting by grits which can be different origins
• Or a combination of these two treatments: sandblasting/acid-etching
(SLA).
The major advantage of these processes is the increase of the
implant surface roughness without contamination by additive micro-
particles [68].
5.1.1. Acid etching
This process involves corroding the implant surface by immersion in
strong acids baths consisting of sulfuric acid, hydrochloric acid,
hydrofluoric acid and nitric acid or their mixtures. The implant is im-
mersed in one or several acidic baths with different compositions versus
Fig. 8. OSSEOTITE® Surface obtained by a DAE process with 66.3% sulfuric acid and 10.6%
hydrochloric acid during 5 min at 70 °C. The roughness is about 500 nm. The magnification
is 20,000 [89].
1363
the grade of the implant for a given period of time. The temperature of
bath, its composition, the duration of etching, the prior roughness of
the implant before treatment are the most important parameters to be
controlled in this process. Indeed, the major drawback of acid-etching
process is the ability of hydrogen embrittlement which can cause
microcracks on the surface of the implant. The corrosion of the implant
surface by acid etching generally creates a micro-roughness of 0.5 to
3 μm and irregular pits with a depth varying from 1 to 2 μm. A dual-
acid etching (DAE) technique was also developed. This treatment re-
sults in a decontamination of the machined implant and creates surface
micro texture. By this way, the quality of the TiO2 layer is controlled
and a micro-topography is involved. Fig. 8 shows an example of a DAE
surface developed by Biomet 3I Company [69].
5.1.2. Sandblasting or grit-blasting
Sandblasting refers to the use of very fine materials bits which are
propelled at a very high-velocity to clean/etch the surface, generally
by compressed air and a blaster nozzle. Aluminum trioxide (alumina
or corundum (Al2O3)) and titanium dioxide (titania (TiO2)) are used
to be the most commonly grit material. Widely used bioceramics
as Tricalcium phosphate (TCP-mostly Ca3(PO4)2), Hydroxyapatite
(HA-Ca10(PO4)6(OH)2) or even a mixture of hydroxyapatite (HA) and
β-TCP (BCP® - Biphasic Calcium Phosphate) can be also employed
[70]. The sandblasting process depends on several parameters such as:
▪ Grain-size of the grits varies between 25 and 250 μm,
▪ The nature of the grits: alumina is hardest and increases the surface
roughness but can contaminate the surface of the implant (the inlay
of the alumina grits can represent 10 to 30% of the treated titanium
surface). Since, alumina is considered to exhibit poor biocompatibil-
ity and bioactivity in comparison with other proposed grit materials,
titania or TCP are highly preferred.
▪ Surface and the nozzle distance and air pressure [71]
5.1.3. Duplex treatment: sandblasting and acid-etching (SLA)
Sandblasting is used for modifying the titanium surface for eliminat-
ing the organic contamination (cleaning). The grit size distribution
1364 A. Revathi et al. / Materials Science and Engineering C 76 (2017) 1354–1368
Fig. 9. Surface treatments on a 3i T3® conic implant [69].
reaches the range between 250 and 500 μm. Secondly an attack with a
mild acid as hydrochloric acid is carried out for the elimination of the
embedded grits on the metallic surface due to the sandblasting. They
are rinsed and dried. Then an acid–etching with a strong acid (H2SO4
for example) is used for creating a roughness between 1 and 2 μm. By
controlling the process parameters it is possible to tailor the surface
morphology of Ti alloys [7].
Fig. 9 shows that a dental implant can successively receive different
surface treatments (here triplex treatment with a TPS coating) [69].
5.1.4. Oxidized surfaces: anodizing
Titanium anodizing is an oxidation process that is carried out either
in an alkaline or acid solution and is used to harden the implant surface
without altering the bulk property of the material [72,73]. Oxide layer
Fig. 10. (a) Thickness of TiO2 layer versus anodic voltage – (b) examples of anodized dental implants in different colors that make it easy to recognize the working diameters during
operation. They also have depth markings to guide the user safely [74].
causes the coloration of implant surface through interface phenomena
(Fig. 10) [74]. The process is usually composed by:
• A pickling and rinsing of titanium medical implant
• Titanium anodization
• Rinsing of medical implant
• Drying
The structural properties can be tailored by modifying the tempera-
ture, electrolyte composition, current and the potential applied. If the
voltage is b300 V, the anodic oxidation is qualified group I, under
400 V - group II, under 500 V - group III and 550 V - group IV. The objec-
tive is also to obtain a porous TiO2 coating [75]. Fig. 11 shows a typical
anodized surface of titanium.
5.1.5. Nitriding
Nitriding is a thermal process that creates a case hardened surface by
diffusing nitrogen into the surface of a metal. Titanium aluminum ni-
tride coatings are widely performed because of their advantageous
properties such as high hardness, wear and corrosion resistance. More-
over, varying the chemical composition, it is possible to modify the color
of Ti1 − xAlxN similar to the color of gum tissue. In an experimental
study conducted by G.T. Liu et al. Ti1 − xAlxN coating was performed
on Wiron 88 (Ni-based alloy) and Olympia (gold-based alloy).
Both the corrosion test and pin-on-disc test against cemented tungsten
carbide showed enhanced tribocorrosion behavior compared to the un-
coated samples [47].
5.1.6. Cryogenic treatment
Cryogenic treatment methods are also employed to enhance the
wear resistance of dental implants in which the material is cooled to
approximately −185 °C (−301 °F) usually using liquid nitrogen. This
process removes the residual stresses and thereby improves wear resis-
tance. The effect of cryogenic treatment on wear resistance of Ti–6Al–4V
alloy has been investigated by Kaixuan Gu et al. Improvement in wear
resistance was observed. Cryogenic treatment was found to lead to
grain refinement and reduction of β phases. Furthermore, it was hy-
pothesized that high dislocation density and the presence of twins dis-
sipated high energy produced during sliding friction and resisted the
formation of cracks on the worn surface [76].
 A. Revathi et al. / Materials Science and Engineering C 76 (2017) 1354–1368
Fig. 11. Anodized titanium surface [12].
5.1.7. Surface treatments by addition (coatings on titanium substrate)
Fig. 13 compares the reduction of wear rate and wear volume of dif-
ferent surface treated titanium alloys tested in tribological conditions.
Metallic implants have been coated with layers of calcium phosphates
mainly composed of hydroxyapatite (HA). HA constitutes the inorganic
portion of the bone and coating HA on implant surface would help to
promote osseointegration as the chance of bone of grow next to a chem-
ically similar material is high (biomimetic). The porosity can be con-
trolled in order to improve the differentiation of osteoblasts cells
(osteoconduction). Coating thickness between 20 and 50 μm is obtained
using convention plasma spray coatings where, coatings with a thick-
ness below 50 μm are considered as thin coatings [77]. The quality of
HA is very important: the ratio Ca/P and the crystallinity need to be
carefully chosen to promote bone-bonding. Different other coating
methods have also been developed other than plasma spray such as
sputter-deposition (radio frequency sputtering (RF) and magnetron
sputtering), sol–gel coating, electrophoretic deposition, biomimetic
precipitation, Pulse Laser Deposition (PLD) and Micro-Arc Oxidation
(MAO). These processes are the other non-exhaustive techniques
which can deposit HA, TCP or even brushite (CaHPO4, 2H2O) coatings
[78]. However, only the plasma-spray coating method has been used
for titanium dental implants in clinical practice.
In addition to HA, zirconia-based ceramics have also gained impor-
tance because of its high strength and toughness properties. In an at-
tempt to obtain wear and corrosion resistant coating, C. Richard et al.
[79] investigated the tribocorrosion behavior of new nano-ZrO2 and
Al2O3-13 wt% TiO2 thermal sprayed coatings on commercially pure
(cp)-Ti (grade 4) and titanium alloy substrates. 13 wt% Al2O3 along
with TiO2 was found to reduce coefficient of friction and wear rate.
5.2. Titanium plasma spraying (TPS)
The plasma spray process is basically the spraying of molten or heat
softened material (feedstock) onto a surface to modify surface related
properties. This process involves the latent heat of ionized inert gas
(plasma) being used to create the heat source. Material in the form of
powder is injected into a very high temperature plasma flame, where
it is thus rapidly heated and accelerated to a high velocity. The hot ma-
terial impacts on the substrate surface and rapidly cools forming a coat-
ing. The TPS process commonly develops 30 μm thick coatings [80,81]
Used since 1974, TPS modified surfaces have been found to accelerate
bone healing than the uncoated implants. TPS creates a
macrotopography on titanium implant surface and provides higher
roughness than sandblasted, acid-etched or HA-coated titanium im-
plants. The roughness of TPS implant is between 2.1 and 3.1 μm. Never-
theless, the risk of pre-implantitis is high and the adhesion of the
coating on the titanium substrate can be weak (problem of residual
1365
stresses at the interface if the parameters of the process (around one
hundred as grain size distribution of the powders, distance between
the nozzle and the surface, temperature, mixture of gas for the plasma
generation, preparation of the surface before spraying, etc.) are not
well controlled. The TPS process highly employed as the HA plasma
spray process [82,83].
5.3. Other treatments
Numerous surface treatments and multiple combinations are possi-
ble for the dental implants. Fig. 12 shows an example of some of them
with the use of the Gold-Tite® abutment screw coated with at least 40
microinches of 99.99% pure gold as solid lubricant. This layer reduces
the friction between the thread of the screw and the implant. The
screw can expand and the clamping force can be more important [84].
The major objective is the control and formation of better surface rough-
ness for the maximum osteointegration and avoids friction (fretting,
tribocorrosion), loosening, and ion leakages. Table 4 summarizes the
different efficiencies for the BIC versus the common surface treatments.
6. New implant dental materials/addition of alloying elements
Various efforts have been made for the development of new Ti-
alloys which consists of non-toxic elements such as niobium, zirconium,
silver, gallium, tin, gold etc. Hence, β-type Ti alloys are gaining impor-
tance in biomedical application. Ti-Mo and Ti-Nb alloys have gained in-
terest because of their favorable properties such as low modulus and
non-toxicity. Hence, they can be used as an alternate to the commercial
dental implants.
One recently developed biomedical alloy composed of Ti-Nb-Sn
showed improved mechanical properties and corrosion resistance for
dental implants requirements. Previous studies on Ti-Nb-Sn alloys
Fig. 12. Gold-Tite® abutment screw [84].
1366 A. Revathi et al. / Materials Science and Engineering C 76 (2017) 1354–1368
Fig. 13. Tribocorrosion studies of surface treated Ti alloys under sliding conditions. Alloys - Ti64: Ti-6Al-4V, Ti1313: Ti-13Nb-13Zr. Surface treatments - A: Anodizaton, HA:
Hydroxyapatite, HT: Hydrothermally treated, MAO: Microarc oxidized, N-Nitriding, NCD: Nano-crystalline diamond, TSC: thermal sprayed coatings.
have showed that addition of 2 wt% of Sn decreases the porosity, elastic
modulus and the corrosion rate of the alloy. In addition, Ti–Nb–Sn alloys
have been found to exhibit appropriate cellular response without
causing cell toxicity [85,86].
Similarly, the electrochemical behavior of few β-stabilizing elements
such as Ta, Zr, Mo and Sn was studied by Daniel Mareci et al. for dental
application. Obtained values of barrier layer indicated that the β alloying
elements improved the electrochemical corrosion behavior of Ti alloys
in both artificial saliva and fluoridated artificial saliva (0.1% fluoride
ions, F-) at 37 °C, compared to the Cp-Ti, and are influenced by the
type of β alloying elements; the corrosion resistance were in the
order: Ti60Ta alloy N Ti12Mo alloy N Cp-Ti alloy [87].
Similarly, use of Gallium (Ga) has a long history and hence, the study
of Ti-Ga alloys for dental application is quite promising. Experimental
investigation of Ti-Ga alloys with varying concentration of Ga (2, 5
and 10 wt%) in presence of NaF, showed that presence of 2 and 5 wt%
Ga resulted in solid-solution strengthening and therefore, improved
both corrosion and wear resistance [88].
7. Conclusion/summary
The degradation mechanisms of titanium and titanium alloys in sim-
ulated body fluids have been reviewed together with the present strat-
egies to prevent their corrosion and wear damage. From the published
literature the following conclusions can be extracted:
1. Titanium and its alloys spontaneously form an oxide layer on its sur-
face under typical physiological conditions. The physico-chemical
property of this layer depends on the chemical composition of the
bulk material but also on the solution chemistry.
2. The presence of fluorides in toothpastes and mouthwashes causes
active dissolution of the protective oxide layer thus exposing the
bare metal layer resulting in corrosion.
3. The release of wear debris during tribocorrosion results in the activa-
tion of a cascade of immune response and finally may result in
aseptic loosening. These problems could be overcome by either
employing surface treatment methods to obtain hard coatings or
developing new wear resistant implant materials.
4. β-Titanium alloys composed of non-toxic alloying elements such as
Nb, Zr, Ga, Mo, Pd, Se, Sn, Ta, Ge are considered to be safest alloying
elements. In addition to improving the biocompatibility, these
alloying elements also improve the mechanical properties, wear
and corrosion resistance
5. Bulk metallic glasses, nanocrystalline materials and samples fabricat-
ed by techniques such as powder metallurgy, rapid manufacturing
techniques - laser engineered net shaping (LENS) have been exten-
sively studied due to their desired mechanical and biocompatible
properties.
6. Similarly, surface modification techniques such as acid etching,
sandblasting, anodizing, nitriding and coating methods such as
plasma spraying, pulsed laser deposition, pulsed vapor deposition,
electrophoretic deposition, sputter deposition are being widely
used to obtain wear and corrosion resistance coatings.
8. Future directions
After reviewing the present understanding of the degradation
mechanisms of titanium and its alloys in the oral environment together
with the description of the potential improvements in the dental mate-
rial development (i.e. alloying elements, coatings), three main research
directions have been identified:
- A round robin test which involves the use of same method, same
conditions by different laboratories will enable a fundamental un-
derstanding of the degradation mechanisms, which is necessary to
translate the laboratory knowledge to medical practice.
- From the experimental point of view, there is a need to translate the
complexity of the in-vivo environment to the in in-vitro testing by
considering all involved phenomena (biomechanics, electrochemis-
try, biochemistry, materials and tribology). The design of in-vivo
testing is also needed for a system approach with clinical relevance.
- For new material development, specific theoretical models for
tribocorrosion applications are needed. The theoretical models and
significant understanding of the involved phenomena in a
tribocorrosion system should be the basis for the development of
new smart materials (i.e. materials with functionalized surfaces
which allows for incorporating active compounds for drug delivery
or rapid bone bonding and healing).
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