Surface Modification of Biomedical Titanium Alloy

coatings
Review
Surface Modification of Biomedical Titanium Alloy:
Micromorphology, Microstructure Evolution and
Biomedical Applications
Wei Liu 1 , Shifeng Liu 1 and Liqiang Wang 2, *
1 School of Metallurgical Engineering, Xi’an University of Architecture and Technology, Xi’an 710055, China;
liuwei18@xauat.edu.cn (W.L.); liushifeng66@xauat.edu.cn (S.L.)
2 State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, China
* Correspondence: wang_liqiang@sjtu.edu.cn; Tel.: +86-21-342-02641

Received: 12 March 2019; Accepted: 9 April 2019; Published: 15 April 2019
Abstract: With the increasing demand for bone implant therapy, titanium alloy has been widely
used in the biomedical field. However, various potential applications of titanium alloy implants
are easily hampered by their biological inertia. In fact, the interaction of the implant with tissue
is critical to the success of the implant. Thus, the implant surface is modified before implantation
frequently, which can not only improve the mechanical properties of the implant, but also polish
up bioactivity and osseoconductivity on a cellular level. This paper aims at reviewing titanium
surface modification techniques for biomedical applications. Additionally, several other significant
aspects are described in detail in this article, for example, micromorphology, microstructure evolution
that determines mechanical properties, as well as a number of issues concerning about practical
application of biomedical implants.
Keywords: titanium alloy; surface modification; biomedical application
1. Introduction
In the past few decades, resulting from the aging of the population and the change of people’s
lifestyle, tens of thousands of people have been plagued by orthopedic, oral and maxillofacial
diseases [1]. Thus, solving these problems enables patients to return to a high-quality life, and
the demand for medical implants increases dramatically with the growing maturity of implant
technology [2]. As scientists have predicted, more people will suffer from orthopedic diseases in the
future and the annual economic costs will be particularly huge [3].
Today, as biomaterials are developing rapidly, biomedical materials can be mainly divided into
metals, ceramics, bioactive glass, plastics and their combinations [4]. Among all biomedical materials,
metal materials are the earliest applications and the most widely used in clinical practice [5]. Titanium
alloy especially, compared with other metal alloys, has great advantages in mechanical properties,
such as elasticity modulus, tensile strength, toughness, and fatigue resistance [6,7]. At the same time,
titanium alloy has excellent corrosion resistance to physiological fluids and excellent biocompatibility,
due to its oxidation film passivation stability [8,9]. In addition, biological responses of titanium
alloy implants, such as bioactivity and osseointegration, are positive for clinical application [10].
Thus, it is not only widely used in dental implants, artificial joints and bone wounds, but also has
become an important material for human body hard tissue substitutes. Moreover, with the continuous
improvement and perfection of medical titanium alloys, the exploration of novel medical titanium
alloys and the diversification of production technology will further expand their applications [11,12].
Although titanium-based alloys have excellent mechanical properties, the exposed surface of
titanium-based implants is easily affected by the environment and may cause complications. Therefore,
Coatings 2019, 9, 249; doi:10.3390/coatings9040249 www.mdpi.com/journal/coatings

Coatings 2019, 9, x FOR PEER REVIEW 2 of 22
Coatings 2019, 9, 249titanium-based

Although alloys have excellent mechanical properties, the exposed surface 2 of of
23
titanium-based implants is easily affected by the environment and may cause complications.
Therefore, it is
it is necessary to necessary
improve thetoreliability
improve ofthe reliability
Ti-based of Ti-based
implants implants
to minimize certaintobiomechanical
minimize certain
and
biomechanical
biological function failure [13,14]. In order to overcome its harm to human body,totitanium
and biological function failure [13,14]. In order to overcome its harm human body,
alloy
titanium alloy must
must be surface be surface
modified to meetmodified to meet medical
medical application application
requirements. Thisrequirements.
review focusesThis review
on various
focuses on various surface modification methods such as plasma spray, ion implantation,
surface modification methods such as plasma spray, ion implantation, micro-arc oxidation, laser micro-arc
oxidation, laser surface
surface modification, modification,
sol-gel, sol-gel, friction
friction stir processing stirthe
(FSP) and processing (FSP) andapplications
practical biomedical the practicalof
biomedical applications
each technology. of each technology.
2.
2. Surface
Surface Modification Methods
Modification Methods
Micro-Arc Oxidation
2.1. Micro-Arc
Micro-arc oxidation
oxidation(MAO),
(MAO), forming
forminga high-quality reinforced
a high-quality ceramic
reinforced film onfilm
ceramic implant surface,
on implant
is a relatively
surface, effective effective
is a relatively technique of the surface
technique of the treatment in biomedical
surface treatment field based
in biomedical fieldonbased
anodic-
on
oxidation [15,16]. The
anodic-oxidation schematic
[15,16]. diagramdiagram
The schematic is shownisinshown
Figurein1 [17]. MAO
Figure has MAO
1 [17]. been widely studied
has been in
widely
numerous fields including
studied in numerous biomedical
fields including applications
biomedical because because
applications the advantages of low-cost,
the advantages high
of low-cost,
efficiency, highhigh
high efficiency, bonding strength
bonding between
strength betweenthethe
MAO
MAO coating
coatingand
andsubstrate,
substrate,no norestriction
restriction on
on the
surface shape of the workpiece and so on [18–20]. The microstructure and mechanical properties of
micro-arc oxide film, which are mainly controlled by electrolyte type, matrix composition and process
parameters, determine the interaction between implants and surrounding host tissues and is essential
for cell adhesion, proliferation and differentiation
differentiation [21–23].
[21–23].
Figure 1.1.Schematic
Schematicdiagram
diagram of micro-arc
of the the micro-arc oxidation
oxidation (MAO) (MAO) process
process [17]. [17]. Reprinted
Reprinted with
with permission
permission from
from reference reference
[17] [17] 2017 Elsevier.
2017 Elsevier.
haveexplored
Researchers have exploredbioactive
bioactivecoating
coatingwith
with suitable
suitable structure
structure of medical
of medical implants
implants thatthat
can
can improve the biocompatibility and shorten osseointegration time [24]. Xu et
improve the biocompatibility and shorten osseointegration time [24]. Xu et al. [25] prepared porousal. [25] prepared
porous
coatingscoatings with different
with different roughness
roughness by controlling
by controlling oxidation
oxidation durationduration
on Ti on Ti implants
implants by MAO.
by MAO. The
The porous coating surface significantly promotes adhesion and proliferation of osteoblasts.
porous coating surface significantly promotes adhesion and proliferation of osteoblasts. Similarly, in Similarly,
in order
order to to create
create functional
functional surfaceswith
surfaces withantibacterial
antibacterialand
andosteogenic
osteogenicproperties,
properties,Coquillat
Coquillat et
et al. [26]
explored the effect of processing time on coating composition and morphology in two different
electrolytes. Furthermore,
Furthermore, Li Li et
et al.
al. [27] studied the two-step micro-arc oxidation method to prepare
super-hydrophilic biomedical
super-hydrophilic biomedical coatings
coatings with macro/micro/nano three-layer structures. In In addition,
addition,
Wang
Wang etet al. [28] and Sedelnikova et al. [29] prepared coatings on Ti-based alloy with different surface
morphology, thickness and adhesion strength with MAO through controlling voltage. The SEM
micrograph is shown in Figure 2. After After MAO
MAO treatment,
treatment, the
the implant
implant has
has a promoting
promoting effect on cell
adhesion, diffusion,
diffusion, proliferation and differentiation. In addition to oxidationthe
proliferation and differentiation. In addition to oxidation duration, composition
duration, the
of electrolyteof
composition and biologicaland
electrolyte elements playelements
biological a crucialplay
role aincrucial
biocompatibility.
role in biocompatibility.
Coatings 2019, 9, 249 3 of 23
Figure 2. 2.SEM
Figure SEM micrographs
micrographs of ofthe
thewollastonite-calcium
wollastonite-calcium phosphate
phosphate (W-CaP)
(W-CaP) coatings
coatings on Tiand
on Ti (a–c) (a–c)
Figure 2. SEM micrographs of the wollastonite-calcium phosphate (W-CaP) coatings on Ti (a–c) and
and SEM
SEM micrographs
micrographs of cross-sectional
of the the cross-sectional
W-CaPW-CaP coatings
coatings on produced
on Ti (d–f) Ti (d–f) produced undervoltages
under different different
SEM micrographs of the cross-sectional W-CaP coatings on Ti (d–f) produced under different voltages
voltages
[29]. [29].
[29].
Researchers
Researchershave haveinvestigated
investigatedthethe effect
effect of
of electrolyte compositionon
electrolyte composition onthe
themicrostructure
microstructure andand
Researchers have investigated the effect of electrolyte composition on the microstructure and
properties
properties of oftitanium
titaniummatrix
matrixmicro-arc
micro-arc oxidation
oxidation coating.
coating. ItIt isis obvious
obviousthatthatthe
thecomposition
composition of of
properties of titanium matrix micro-arc oxidation coating. It is obvious that the composition of
electrolyte
electrolyte affects
affectsthe thephysical
physicaland
andchemical
chemical properties
properties of of the
the coating
coatingandandthethegrowth
growthraterate
of of
thethe
electrolyte affects the physical and chemical properties of the coating and the growth rate of the
coating
coating [30,31].
[30,31]. Recent
Recentresearch
researchhashasshown
shown thatthat biological elements,such
biological elements, suchasasCu,
Cu,Ca,Ca,Zr,Zr,
PP and
and Si Si
areare
coating [30,31]. Recent research has shown that biological elements, such as Cu, Ca, Zr, P and Si are
beneficial
beneficial forfor improving
improving thethe bioactivity
bioactivity of of materials,
materials, further
further enhancingimplant
enhancing implantosseointegration
osseointegration[32–34].
[32–
beneficial for improving the bioactivity of materials, further enhancing implant osseointegration [32–
34]. Huang
Huang et al.investigated
et al. [35] [35] investigated
bonebone regeneration
regeneration andand bactericidal
bactericidal capacity
capacity ofofMAO
MAOcoatings
coatings onon Ti
34]. Huang et al. [35] investigated bone regeneration and bactericidal capacity of MAO coatings on
Ti
in Ti in a Cu-containing
a Cu-containing electrolyte.
electrolyte. Macrophage-mediated
Macrophage-mediated osteogenesis, macrophage polarization and
in a Cu-containing electrolyte. Macrophage-mediated osteogenesis, macrophagepolarization
osteogenesis, macrophage polarization and and
macrophage
macrophage bactericidalassay
bactericidal assayexperiments
experiments showed
showed that that coating
coating with
with higher
highercontent
content ofof
CuCuis is
more
more
macrophage bactericidal assay experiments showed that coating with higher content of Cu is more
favourable for
favourable macrophage proliferation. Interaction
Interaction between macrophages and bacteria on various
favourablefor formacrophage
macrophageproliferation. betweenmacrophages
proliferation. Interaction between macrophages and
and bacteria
bacteria onon various
various
surfaces
surfaces areare shown
shown inin Figure
Figure 3.
3. The
The capture
capture behavior
behavior of bacteria
of by
bacteria macrophages
by macrophages is significant
is on theon
significant
surfaces are shown in Figure 3. The capture behavior of bacteria by macrophages is significant on the
surface with high Cu content, which indicates that the bactericidal capacity of macrophages is
thesurface
surface withhigh
with highCuCucontent,
content,which
which indicates
indicates that
that thethe bactericidal
bactericidal capacity
capacity of of macrophages
macrophages is is
promoted on the Cu-MAO surface.
promoted
promoted ononthetheCu-MAO
Cu-MAOsurface.
surface.
Figure 3. The bactericidal capacity of macrophages in response to material surfaces. The SEM images
Figure
3. 3.The
Thebactericidal
bactericidalcapacity
capacity of
of macrophages
macrophages in response totomaterial
materialsurfaces. The SEM images
Figure
showing the macrophage/bacteria interactions onindifferent
responseCu-containing surfaces.
surfaces.The SEM images
Respectively,
showing
showing thethe macrophage/bacteria
macrophage/bacteria interactions
interactions on
on different
different Cu-containing
Cu-containing surfaces.
surfaces.Respectively,
Respectively,
specimens treated with 0.2 and 2 mM CuSO4·5H2O were recorded as Cu(l)-MAO) and 2(Cu(h)-MAO).
specimens treatedwith
with0.2
0.2and
and22mM
mM CuSO
CuSO4·5H 2O were recorded as Cu(l)-MAO) and 2(Cu(h)-MAO).
specimens
The white treated
arrows indicate that bacteria 4 ·5H2 O were
are captured recorded as [35].
by macrophages Cu(l)-MAO)
Reprintedand 2(Cu(h)-MAO).
with permission
The white
Thefrom
white arrows
arrows indicate
indicate that
that bacteria
bacteria are
are captured
captured by
by macrophages
macrophages [35]. Reprinted
[35]. Reprintedwith permission
with permission
reference [35] 2018 Elsevier.
from reference [35] 2018 Elsevier.
Coatings 2019, 9, 249 4 of 23
The microstructure,
The microstructure,morphology
morphologyand andmechanical
mechanicalproperties
properties of of
thethe
micro-arc
micro-arcoxidation
oxidationcoating are
coating
affected by the alloying elements. Recently, Wang et al. [36] and Correa et al. [32]
are affected by the alloying elements. Recently, Wang et al. [36] and Correa et al. [32] have studied have studied the
effect
the of Ti-based
effect alloyalloy
of Ti-based composition
compositionon theon growth mechanism
the growth of MAO
mechanism offilms.
MAOAdditionally, in order in
films. Additionally, to
obtain bioactive surfaces, Hu et al. [37] prepared multilayer
order to obtain bioactive surfaces, Hu et al. [37] prepared multilayer TiO 2 /CaSiOTiO coating on titanium substrate
3 2/CaSiO3 coating on titanium
by MAO and
substrate electron
by MAO andbeam evaporation.
electron Surface morphologies
beam evaporation. are shown in
Surface morphologies areFigure
shown4.in The needle
Figure and
4. The
flake-like
needle andnanocrystals CaSiO3 , which
flake-like nanocrystals are 3considered
CaSiO , which areaconsidered
potential material for bone
a potential tissue
material forregeneration,
bone tissue
were deposited on TiO
regeneration, were deposited
2 coatingon TiO2 coating by electron beam evaporation. To achieve capacity
by electron beam evaporation. To achieve antibacterial and
antibacterial
cytocompatibility,
capacity an implant with
and cytocompatibility, angradient
implant structure of Ti/TiO
with gradient 2 /ZnOof
structure was developed
Ti/TiO 2/ZnO wasby MAO followed
developed by
by hydrothermal treatment, as reported by Zhang et al. [38].
MAO followed by hydrothermal treatment, as reported by Zhang et al. [38].
Figure 4. Surface
Figure 4. Surface morphologies
morphologies ofof the
the TiO
TiO22 (a,b)
(a,b) and
and TiO /CaSiO33 (c,d)
TiO22/CaSiO (c,d) coatings
coatings in
in different
different
magnifications [37]. Reprinted
Reprinted with permission from reference [37] 2013 Elsevier.
Elsevier.
From the
the above,
above,ititcan
canbebeseen thatthat
seen titanium alloyalloy
titanium micro-arc oxidation
micro-arc bioactive
oxidation coating
bioactive has highly
coating has
bondingbonding
highly strengthstrength
with thewith
matrix thedue to thedue
matrix compact
to theinterior.
compact In interior.
addition,In theaddition,
loose andtheporous
looseouter
and
layer, which
porous outerare conducive
layer, which are to protein
conducive adsorption,
to proteinosteoblast
adsorption,adhesion
osteoblastandadhesion
bone tissue
andregeneration,
bone tissue
promote bone promote
regeneration, integration andintegration
bone prevent implant-related
and prevent infections. It is theinfections.
implant-related direction ofItfurther exploration
is the direction of
to regulate
further the bioactive
exploration components
to regulate and construct
the bioactive multi-level
components micro- and
and construct nano-structure
multi-level micro- coating for
and nano-
cell adhesion
structure and proliferation.
coating for cell adhesion Additionally, in order to prevent
and proliferation. from inflammation
Additionally, in order to that would affect
prevent from
healing and further
inflammation promote
that would tissue
affect repair,
healing thefurther
and construction
promoteof multi-functional
tissue repair, thecoatings with biological
construction of multi-
activity and
functional bacteriostasis
coatings are a hotactivity
with biological researchand topic [39].
bacteriostasis are a hot research topic [39].
2.2. Plasma
2.2. Plasma Spraying
Spraying
Plasma spraying
Plasma spraying technique,
technique, asas aa practical
practical and
and reliable
reliable coating
coating method,
method, has has been
been carried
carried out
out for
for
decades. It is worthy of note that plasma-spray technique has attracted lots of attention
decades. It is worthy of note that plasma-spray technique has attracted lots of attention for biomedicalfor biomedical
field, due
field, due toto the
theadvantages
advantagesofoflow
lowcost, high
cost, highefficiency
efficiencyand ability
and to control
ability the the
to control coating thickness
coating [40].
thickness
During processing, numerous variables affect the final performance of ceramic
[40]. During processing, numerous variables affect the final performance of ceramic coating, such as coating, such as
chemical compositions, structures, and crystallinity [41,42]. The schematic diagram
chemical compositions, structures, and crystallinity [41,42]. The schematic diagram of the plasma of the plasma
spray equipment
spray equipmentisisshown
showninin Figure
Figure 5. It
5. can be seen
It can the system
be seen comprises
the system DC electrical
comprises power source,
DC electrical power
gas flow control, water-cooling system and powder feeder
source, gas flow control, water-cooling system and powder feeder [43]. [43].
Coatings 2019,9,9,249
Coatings2019, x FOR PEER REVIEW 55of
of23
22
Figure 5. Schematic diagram of plasma spraying [43]. Reprinted with permission from reference [43]
Figure
2012 5. Schematic diagram of plasma spraying [43]. Reprinted with permission from reference [43]
Elsevier.
2012 Elsevier.
Recently, with the progresses in the utilization of titanium devices coating, plasma sprayed
ceramicRecently,
coatings with
notthe onlyprogresses
achieve most in the utilization
mechanical of titanium but
requirements, devices
also coating, plasma sprayed
provide suitable growth
ceramic coatings not only achieve most mechanical requirements,
environment for bone cells and tissues [44]. It was reported that plasma sprayed ceramic but also provide suitable
coatingsgrowth
are
environment
able to increase for bone cells and
performances in tissues
bonding [44]. It was hardness,
strength, reported thatwearplasma sprayedresistance,
and corrosion ceramic coatings are
etc. There
able to increase performances in bonding strength, hardness, wear and
is no doubt that the improvements of bioceramic coating are mainly related to thermal stability, phase corrosion resistance, etc.
There
and is no doubt
chemical that the improvements
composition, of bioceramic
as well as microstructure coating
[45]. Plasma aresprayed
mainly bi-layer
related to thermal
coating stability,
containing
phase
Al and chemical composition, as well as microstructure [45]. Plasma sprayed bi-layer coating
2 O3 –13 wt.% TiO2 and ZrO2 layer was successfully deposited on Ti–13Nb–13Zr substrate, and the
containing
corrosion and Alwear
2O3–13 wt.% TiO
resistance 2 and ZrO
properties 2 layer
of the waswere
coatings successfully
significantlydeposited
increased ondueTi–13Nb–13Zr
to its lower
substrate,
porosity andand the adhesion
higher corrosionstrength
and wear resistance
[46,47]. properties
In addition of the coatings
to composition design of werebioactivesignificantly
coatings,
increased due to its lower porosity and higher adhesion
heat treatment after plasma spraying might affect the mechanical properties [48]. strength [46,47]. In addition to composition
design
Forofplasmabioactive coatings,
sprayed heat in
coatings treatment
biomedical afterimplants,
plasma spraying might affect
hydroxyapatite the mechanical
(HA)-based coatings
properties
seem to be [48].
the most widely used in surface modification, resulting from HA can lead to favorable
For plasma sprayed
biocompatibility and bone coatings in biomedical
regeneration betweenimplants,
the bonehydroxyapatite
tissue and implant (HA)-based
surface coatings seem
[49]. In order
to be the most widely used in surface modification, resulting
to improve the biological stability of HA-coated implants for long-term, Yang et al. [50] found from HA can lead to favorable
biocompatibility
industrial and bone
pure titanium canregeneration
be used as anbetween
effectivethe bone tissue
bonding and
agent to implant surface
significantly improve[49].theIninterface
order to
improve the biological stability of HA-coated implants for long-term,
bonding and stress reduction of the plasma-sprayed HA coating and Ti-alloy system. As is shown Yang et al. [50] found industrial
pure
in titanium
Figure 6, the can be used
excellent as ancan
bonding effective bonding
be observed agent commercial
between to significantly
pureimprove
titaniumthe interface
(CP-Ti) and
bonding and stress reduction of the plasma-sprayed HA coating and Ti-alloy
the substrates, and the surface roughness of CP-Ti is unaltered after application of the HA coating. system. As is shown in
Figure 6, the excellent bonding can be observed between commercial
Furthermore, the corrosion resistance and cytocompatibility were enhanced by plasma sprayed pure titanium (CP-Ti) and the
substrates,
HA and pure andTi the surface
coatings onroughness
Ti alloy matrix of CP-Ti[51]. isInunaltered after application
another study, an innovative of the HA coating.
double-layer of
Furthermore, the corrosion resistance and cytocompatibility were
HA/Al2 O3 -SiO2 nanocomposites is deposited on the surface of titanium implants by plasma sprayenhanced by plasma sprayed HA
and pure The
technique. Ti coatings on Ti alloy
results indicated matrix [51].
that bi-layer plasma In sprayed
anothercoating
study, enhanced
an innovative double-layer
roughness, of
wettability,
HA/Al
as O3improved
well 2as -SiO2 nanocomposites is deposited
the cell viability on the surface
and proliferation comparedof titanium
to singleimplants
layer of by HAplasma
coatingspray
[52].
Meanwhile, biofunctional (Mg, Sr)-HA coatings with high bonding strength were successfullyroughness,
technique. The results indicated that bi-layer plasma sprayed coating enhanced produced
wettability,
by plasma-spray as well as improved
technique [53]. In theFigure
cell viability
7, cellularandextensions
proliferationandcompared
extracellular to single
matrices layer of HA
secreted
coating
were [52]. Meanwhile,
observed, biofunctional
which demonstrated the(Mg, Sr)-HA coatings
HA composite coatingwithwithhigh
Mg andbondingSr ionsstrength were
have great
successfully produced by plasma-spray technique [53]. In Figure
biological activity. In addition to an HA coating, pure Ti coating obtained by plasma-spray technique 7, cellular extensions and
extracellular
on matrices secreted
Poly-ether-ether-ketone were seems
substrate observed,to bewhich demonstrated
an effective way for the HA modification
surface composite coating [54,55].with
Mg and Sr ions have great biological activity. In addition to an HA coating, pure Ti coating obtained
by plasma-spray technique on Poly-ether-ether-ketone substrate seems to be an effective way for
surface modification [54,55].
Coatings 2019, 9, 249 6 of 23
Figure 6. Cross-sectional electron backscatter diffraction (EBSD) images of the (a) CP-Ti and (b) HA
Figure 6. Cross-sectional electron backscatter diffraction (EBSD) images of the (a) CP-Ti and (b) HA
coating6.on
Figure the CP-Ti [50].electron
Cross-sectional Reprinted with permission
backscatter from
diffraction reference
(EBSD) [50]of
images 2013
the Elsevier.
(a) CP-Ti and (b) HA
coating on the CP-Ti [50]. Reprinted with permission from reference [50] 2013 Elsevier.
coating on the CP-Ti [50]. Reprinted with permission from reference [50] 2013 Elsevier.
Figure 7. Micrographs of (a) the surface of the control group without cells and (b–d) cell morphology
Figure 7. Micrographs of (a) the surface of the control group without cells and (b–d) cell morphology
after culture on the (Mg, Sr)-HA coatings for five days. White arrows show filopodia of cells and cellular
after culture
Figure on the (Mg,
7. Micrographs Sr)-HA
of (a) coatings
the surface forcontrol
of the five days. White
group arrows
without cellsshow filopodia
and (b–d) of cells and
cell morphology
extensions. A large magnification (d) of the white dash box in (c) shows the cellular extensions [53].
after culture on the (Mg, Sr)-HA coatings for five days. White arrows show filopodia ofextensions
cellular extensions. A large magnification (d) of the white dash box in (c) shows the cellular cells and
[53]. Reprinted
cellular with
extensions. Apermission from reference
large magnification [53]white
(d) of the 2018dash
Elsevier.
box in (c) shows the cellular extensions
[53]. Reprinted
In recent with
years, permission
several from reference
concerns have been [53]raised
2018 Elsevier.
on stress shielding, poor osseointegration,
In recent years, several concerns have been raised on stress shielding, poor osseointegration,
composition control, porosity and low adhesive strength of the coating is an immense challenge,
composition
In recentcontrol, porosity
years, several and lowhave
concerns adhesive strength
been raised on of the coating
stress shielding,is an immense
poor challenge,
osseointegration,
which influences the long-term stability of implants. To further improve the surface comprehensive
which influences the long-term stability of implants. To further improve the surface
composition control, porosity and low adhesive strength of the coating is an immense challenge, comprehensive
properties of implants, it is necessary to combine various surface modification technologies to produce
properties
which of implants,
influences it is necessary
the long-term stability oftoimplants.
combine Tovarious
furthersurface
improvemodification technologies to
the surface comprehensive
biofunctional coatings with excellent mechanical properties. In line with what Ke et al. [56] reported,
produce biofunctional
properties of implants,coatings with excellent
it is necessary mechanical
to combine properties.
various surface In line with what
modification Ke et al. [56]
technologies to
a gradient HA-based composite coating with antibacterial properties was deposited utilizing laser and
reported,biofunctional
produce a gradient coatings
HA-based composite
with excellent coating withproperties.
mechanical antibacterial properties
In line with what was
Ke deposited
et al. [56]
plasma spray technology for enhancing the mechanical properties.
utilizing laser
reported, and plasma
a gradient spray technology
HA-based composite for enhancing
coating with the mechanicalproperties
antibacterial properties.was deposited
utilizing laser and plasma spray technology for enhancing the mechanical properties.
2.3. Ion Implantation
While numerous techniques were used to modify implant material surfaces, ion implantation has
attracted wide attention for biomedical applications resulting from mechanical and electrochemical
properties of metal materials treated with ion implantation have been shown to significantly
2.3. Ion Implantation
While numerous techniques were used to modify implant material surfaces, ion implantation
has attracted wide attention for biomedical applications resulting from mechanical and
electrochemical
Coatings 2019, 9, 249 properties of metal materials treated with ion implantation have been shown 7 of to
23
significantly improve [57,58]. Particularly, it’s an effective way to enhance the anchoring strength of
coating on substrate without altering the original characteristics of the matrix material. Additionally,
improve [57,58]. is
ion implantation Particularly,
a promisingit’s an effective
strategy way infection
to prevent to enhance andthe anchoring
improve implantstrength of coating
osseointegration
on substrate without altering the original characteristics of the matrix
for biological systems [59]. In general, ion implantation technology can be divided into two material. Additionally, ion
implantation
categories: ionisbeam a promising strategy to
ion implantation prevent
(IBII) infection
and plasma and improve
immersion implant osseointegration
ion implantation (PIII). These two for
biological systems [59]. In general, ion implantation technology can be
methods are different in the way of producing high energy ions, but the physical mechanism of divided into two categories: ion
beam
surface ionmodification
implantationis(IBII) andIn
similar. plasma immersion
the ion ion implantation
implantation (PIII). These
process, energetic ions, two
whosemethods
energyare is
different in the way of producing high energy ions, but the physical mechanism
closely related to penetration depth inside the substrate, get incorporated into the substrate after of surface modification
is similar.
losing In theenergies
all their ion implantation
[60]. process, energetic ions, whose energy is closely related to penetration
depthRecently
inside the substrate,
studies haveget incorporated
found intoattracted
that PIII has the substrate
wideafter losingfor
attention all biomedical
their energies [60].
applications
Recently studies have found that PIII has attracted wide attention
due to PIII technique enables to inject various elements into the near-surface with a complex shapefor biomedical applications
due to PIII substrates
of various technique [61].enables toshown
As is inject various
in Figureelements
8, silverinto the near-surface
nanoparticles with a complex
were successfully shape
implanted
of
onvarious substrates
the hierarchical [61]. As
titanium is shown
surface in Figure
by PIII, and the 8, rough
silver nanoparticles
surface is obtained wereby successfully implanted
virtue of acid etching
on the hierarchical titanium surface by PIII, and the rough surface
[62]. Furthermore, the content and distribution of implanted ions in the matrix can be preciselyis obtained by virtue of acid
etching [62]. Furthermore, the content and distribution of implanted ions
controlled using PIII technology by adjusting the implantation parameters [63–65]. Additionally, in the matrix can be precisely
controlled using PIII technology
surface micromorphology, whichby is
adjusting the implantation
associated with the incidentparameters
current[63–65].
of PIII, Additionally,
would influence surface
the
micromorphology, which is associated with the incident current of PIII, would
corrosion resistance, Young’s modulus, nano-hardness and bioactive of cells in NiTi alloys surface, influence the corrosion
resistance,
as reported Young’s
by Li modulus,
et al. [63].nano-hardness
Previous studies and bioactive
have shown of cells
thatin the
NiTiimplantation
alloys surface,ofaszinc
reported
ions on by
Li et al. [63]. Previous studies have shown that the implantation of zinc
titanium surface by PIII technology can provide an environment with great antimicrobial and ions on titanium surface by PIII
technology
biocompatibility can provide an environment
[64]. According to Jin etwith greatZn
al. [65], antimicrobial and biocompatibility
ions were implanted [64].acid
into the oxalic According
etched
to Jin et al.
titanium [65],PIII
using Zn technology.
ions were implanted into the oxalic
The Zn-implanted acidnot
titanium etched
onlytitanium using PIII technology.
had an antibacterial effect, but
The
also Zn-implanted titanium not only
promotes osseointegration whilehad an antibacterial
without negative side effect, but also
effect promotes osseointegration
by controlling the content and
while
releasewithout negative side effect by controlling the content and release of Zn ions.
of Zn ions.
Figure 8.
Figure 8. Surface
Surface morphology
morphologyofofthe
thedesigned
designed samples
samples micro-Ti
micro-Ti (a,b),
(a,b), nano-Ti
nano-Ti (c,d)(c,d)
and and Ag-Ti
Ag-Ti (e,f) (e,f)
[62].
[62]. Reprinted with permission from reference [62] 2016 Elsevier.
There are numerous elements, such as zinc (Zn), silver (Ag), fluorine (F), tantalum (Ta), calcium
(Ca), chlorine (Cl),nitrogen (N), iodine (I), copper (Cu) and carbon (C), that might be injected into
titanium alloys surface by PIII of the corresponding ions [66–68]. Notably, these ions can divide
into metal ions and non-metal ions to achieve a variety of surface functions. Recent studies have
There are numerous elements, such as zinc (Zn), silver (Ag), fluorine (F), tantalum (Ta), calcium
(Ca), chlorine (Cl),nitrogen (N), iodine (I), copper (Cu) and carbon (C), that might be injected into
titanium alloys
Coatings 2019, 9, 249surface by PIII of the corresponding ions [66–68]. Notably, these ions can divide8 into of 23
metal ions and non-metal ions to achieve a variety of surface functions. Recent studies have pointed
that a significant enhancement of surface mechanical properties and the corrosion resistance have
pointed
been that a significant
observed enhancement
by implanting of surface
C ions with mechanical
the PIII technique properties and the corrosion
[66]. Furthermore, resistance
the nitrogen ion
have been observed by implanting C ions with the PIII technique [66]. Furthermore,
implanted the surface of Ti-35Nb-7Zr-5Ta β titanium alloy and found that the specimens have better the nitrogen ion
implantedresistance
corrosion the surface of more
and Ti-35Nb-7Zr-5Ta titanium
secure ions βrelease ratealloy
thanandthe found that the
unmodified specimens
alloy have better
[67]. Additionally,
corrosion resistance and more secure ions release rate than the unmodified alloy
ion implantation, as a promising approach, endows the surface of titanium alloys with antimicrobial [67]. Additionally, ion
implantation, as a promising approach, endows the surface of titanium alloys
effect by incorporating with ions such as Zn, Cu, Ag and F ions. There is no doubt ions’ gradual with antimicrobial effect
by incorporating
release from specimens with ions such as Zn, Cu,
into surrounding Ag and
tissues affectF the
ions. There is no
bactericidal anddoubt ions’ gradual
cell activity, which release
would
from specimens into surrounding tissues affect the bactericidal and cell activity,
elicit a favorable cells response from tissues [68]. Thus, an emerging research area is the development which would elicit
a favorable
of cells response
anti-bacterial from tissues
implant materials. For[68]. Thus, an
example, Kimemerging research
et al. [69] area isthe
indicated theconcentration
development of of
anti-bacterial implant materials. For example, Kim et al. [69] indicated the concentration
implanted silver and the topography of the surface determine the effect on the action against micro- of implanted
silver and the
organisms. As topography
is shown in of the surface
Figure determine
9, hierarchical the effect
titanium withon silver
the action against micro-organisms.
nanoparticles surface (Figure
As is shown in Figure 9, hierarchical titanium with silver nanoparticles surface (Figure
8e,f) significantly promoted cellular adhesion and proliferation while have excellent antimicrobial 8e,f) significantly
promoted
ability. cellular adhesion and proliferation while have excellent antimicrobial ability.
Figure
Figure 9.
9. Investigation
Investigation of
of the
the initial
initial adhesion
adhesion and
and spreading
spreading behaviors
behaviors of
of mesenchymal
mesenchymal stem
stem cells
cells
(MSCs) after 24 h of culture on the samples micro-Ti, nano-Ti and Ag-Ti. Note: actin, green;
(MSCs) after 24 h of culture on the samples micro-Ti, nano-Ti and Ag-Ti. Note: actin, green; nuclei,nuclei,
blue
blue [62].
[62]. Reprinted
Reprinted with
with permission
permission from
from reference
reference [62]
[62] 2016
2016 Elsevier.
Elsevier.
As
As one
one of
of the
themost
mostimportant
importantmethods
methodsfor forsurface
surfacemodification
modificationofoftitanium,
titanium,ionionimplantation
implantation is
convenient,
is convenient, controllable and
controllable flexible.
and flexible.Implantation
Implantation of ofions
ionswith
withvarious
variousfunctions
functionscan can not
not only
only
effectively
effectively improve
improve the
the physical
physical and
and chemical
chemical properties
properties oror biological
biological activities
activities of
of titanium
titanium alloys,
alloys,
but
but also
also improve the antimicrobial ability of titanium alloys. These These are
are closely
closely related
related toto the
the success
success
rate
rate of
of implants.
implants. However,
However,single
singleion
ionimplantation
implantation modification
modification only improves
only improves somesome properties of
properties
implanted materials. In recent years, with the development of composite
of implanted materials. In recent years, with the development of composite ions implantation ions implantation
technology,
technology, the development
development trend
trend of ion implantation
implantation technology
technology of of titanium
titanium materials
materials willwill be
be to
to
obtain
obtain multi-functional surface by simultaneously implanting various ions.
Coatings 2019, 9, 249 9 of 23
2.4. Laser Surface Modification

2.4. Laser Surface
Laser Modification
surface modification technology, which uses laser as a heat source to modify the surface
of metal
Lasermaterials, has gained traction
surface modification technology, in recent
whichyears.
uses The
lasermain advantages
as a heat source to aremodify
that it the
cansurface
control
accuracy
of and features
metal materials, has of implant
gained surface
traction while years.
in recent being highly
The main efficient, pollution-free
advantages are that andit canhave low
control
material consumption [70,71]. Laser can not only be used to prepare periodic
accuracy and features of implant surface while being highly efficient, pollution-free and have low micro/nano structures
on most consumption
material material surfaces withLaser
[70,71]. various
can surface
not onlygeometries, such as dimple,
be used to prepare periodiclinear, rippled
micro/nano patterns
structures
and
on so on,
most but also
material change
surfaces phase
with structure
various surfaceand chemical composition
geometries, such as dimple, of the surface
linear, rippled by patterns
cladding
bioactive
and so on,materials
but also on substrate
change phase [72–74]. Researchers
structure have attempted
and chemical composition to find a biocompatible
of the surface by cladding surface
morphology
bioactive to improve
materials osteointegration
on substrate and tissue
[72–74]. Researchers have regeneration,
attempted towhichfind a is critical for the
biocompatible life,
surface
durability and
morphology uninterrupted
to improve functionality
osteointegration of implants
and tissue in vivo
regeneration, intheis early
which criticalphase
for theoflife,
implantation
durability
[75,76].
and uninterrupted functionality of implants in vivo inthe early phase of implantation [75,76].
Depending on
Depending on the
the feature
feature totobebemanufactured
manufacturedand andmaterial
materialtypes,
types, various
various lasers
lasers with
with unique
unique
functions
functions are used, such as femtosecond lasers, excimer laser (Nd:YAG),
used, such as femtosecond lasers, excimer laser (Nd:YAG), etc. [71]. Previous etc. [71]. Previous studies
have revealed
studies that using
have revealed femtosecond
that lasers to form
using femtosecond lasersa periodic
to form structure
a periodiccan control the
structure canproliferation
control the
of cells [77]. Laser-induced
proliferation periodic surface
of cells [77]. Laser-induced structures
periodic (LIPSSs),
surface nanopillar-(NPs)
structures and microcolumn-
(LIPSSs), nanopillar-(NPs) and
(F) textured surfaces were produced by femtosecond laser treatment on
microcolumn-(F) textured surfaces were produced by femtosecond laser treatment on Ti-6Al-4V alloy Ti-6Al-4V alloy substrate
(Figure 10)
substrate [78,79].
(Figure LIPSSs LIPSSs
10) [78,79]. and NPs andcanNPsimprove
can improveosteoblastic differentiation
osteoblastic differentiationof stem
of stemcells, as
cells,
demonstrated
as demonstrated bybyCunha
Cunha et al. [78].
et al. Recently,
[78]. it was
Recently, significantly
it was significantlyobserved
observedby Bryane
by Bryane et al.et[79] that
al. [79]
submicron
that submicron surface structures
surface with
structures various
with periodic
various ripples
periodic were
ripples wereproduced
produced on on
titanium
titanium substrate
substrate by
pulsed
by pulsedfemtosecond
femtosecond lasers, andand
lasers, cell metabolism
cell metabolism of laser ablation
of laser surface
ablation was higher
surface than the
was higher control
than the
surfaces.
control surfaces.
Figure10.
Figure 10. SEM
SEM micrographs
micrographs ofoflaser-induced
laser-induced periodic
periodic ripples
ripples surface
surface structures
structures (A–D),
(A–D),nanopillar
nanopillar
(E) and microcolumn (F) textured surfaces [78,79]. Reprinted with permission from reference
(E) and microcolumn (F) textured surfaces [78,79]. Reprinted with permission from reference [78] 2015
[78]
Elsevier.
2015 Elsevier.
In
In addition
addition to to femtosecond
femtosecond lasers,
lasers, researchers
researchers have
have also
also explored
explored the
the surface
surface modification
modification
behavior
behavior of of other
otherlasers
lasersbybycontrolling
controllingmachining
machiningparameters.
parameters. Marticorena
Marticorena etet al.
al. [80]
[80] showed
showed that
that
laser
laserirradiation
irradiation ofof pure
puretitanium
titanium films
filmswith
withdifferent
differentpulse
pulsefrequencies
frequenciesproduces
producessurface
surfacestructures
structures
with
withdifferent
differentmorphologies.
morphologies.Experimental
Experimentalresults
resultsshow
showthat
thatthe
thesurface
surfacemicrostructure,
microstructure,texture
textureand
and
roughness
roughnessofof implant
implantsurfaces are important
surfaces for the biocompatibility
are important of implantsofin vivo.
for the biocompatibility implantsAdditionally,
in vivo.
Trtica et al. [81]Trtica
Additionally, foundet that
al.liquid (water)that
[81] found is the preferred
liquid medium
(water) is the for the surface
preferred structure
medium for of
thetitanium
surface
alloy implants.
structure At the
of titanium same
alloy time, water
implants. At thealso
same showed high oxidation
time, water also showed capacity, which promotes
high oxidation capacity,
the surface
which biological
promotes activity.biological
the surface Hsiao et activity.
al. [82] developed
Hsiao et al.an[82]
efficient method
developed an to increase
efficient surface
method to
roughness in titanium
increase surface alloy in
roughness (Ti-6Al-4V) with a(Ti-6Al-4V)
titanium alloy low energywith
pulsed ultraviolet
a low (UV) laser,
energy pulsed which (UV)
ultraviolet was
laser, which was similar to laser modified surfaces. Renu et al. [83] presented laser surface texturing
Coatings 2019, 9, 249 10 of 23

similar to laser modified surfaces. Renu et al. [83] presented laser surface texturing of titanium alloy
(Ti-6Al-4V)
of titaniumwith
alloyline and dimple
(Ti-6Al-4V) geometry
with line and using ArF geometry
dimple excimer laser.
usingAfter
ArFlaser modification,
excimer Young’s
laser. After laser
modulus, corrosion resistance and nano-hardness increase as compared with the as-received
modification, Young's modulus, corrosion resistance and nano-hardness increase as compared with titanium.
The fluorescencetitanium.
the as-received micrographTheshowed that the
fluorescence surface morphology
micrograph controls
showed that cell adsorption
the surface morphology andcontrols
growth
direction, as shown in the Figure 11.
cell adsorption and growth direction, as shown in the Figure 11.
Figure 11.
Figure 11. Micrographs
Micrographsofof(a)
(a)asasreceived
receivedand
andlaser
lasersurface textured
surface texturedwith (b)(b)
with lineline
geometry
geometryandand
(c)
dimple
(c) geometry
dimple showing
geometry showing thetheattachment
attachment ofof
MC3T3-E1
MC3T3-E1mousemousefibroblast
fibroblastcell
cellon
onthe
the surface
surface [83].
permission from
Reprinted with permission from reference
reference [83]
[83] 2015
2015 Elsevier.
Elsevier.
In order
order to to overcome
overcomethe theproblem
problemofofthe theconstituent
constituent metals
metalsleach
leachfrom
from thethe
implant,
implant,which
whichmay be
may
at risk of biotoxicity, and further improve biocompatibility and bioactivity,
be at risk of biotoxicity, and further improve biocompatibility and bioactivity, researchers have researchers have proposed
laser coating
proposed bioactive
laser coatingcoating
bioactive on coating
the surface of implants
on the surface of [84,85]. Figure
implants 12 shows
[84,85]. Figure the12principle
shows the of
laser cladding
principle (LC)
of laser that the (LC)
cladding high-energy
that the laser beam melts
high-energy laserthe material
beam meltsand
thethen directly
material andcoats
thenitdirectly
on the
target
coats itsurface
on theand merges
target surfacewith andit. merges
Furthermore,
with it.asFurthermore,
a flexible technology, we can
as a flexible obtain multifunctional
technology, we can obtain
coatings by changing
multifunctional coatingsthe bycomposition
changing the of power.
composition of power.
A great
greatamount
amount of researchers
of researchers have have
focused on exploring
focused the effectthe
on exploring of morphology and composition
effect of morphology and
of bioceramicsofsurface
composition on implants.
bioceramics surfaceThe mechanical
on implants. The properties
mechanical andproperties
biological and
responses of theresponses
biological coatings
can
of thebe coatings
controlled canaccurately
be controlled by biomimetic
accurately design of the roughness
by biomimetic design ofand the graded
roughness porosity of the
and graded
coatings without affecting the chemical structure of the matrix [86,87]. In this
porosity of the coatings without affecting the chemical structure of the matrix [86,87]. In this case, case, calcium phosphate
coatings
calcium with different
phosphate morphologies
coatings by changing
with different the pulse by
morphologies frequency
changingwere theobtained, as reported
pulse frequency by
were
Paital et al.as[88].
obtained, After treatment,
reported by Paital the hydrophilicity
et al. of the samples
[88]. After treatment, the is enhanced, which
hydrophilicity of theimproved
samplesthe is
proliferation
enhanced, which and diffusion
improvedability of the cell. According
the proliferation and diffusion to Zheng
ability et
ofal.
the[89],
cell.the bioceramic
According coatings
to Zheng et
were prepared
al. [89], on Ti-6Al-4V
the bioceramic by LC.
coatings Simulated
were prepared body
on fluids (SBF)by
Ti-6Al-4V results show that the
LC. Simulated body appearance
fluids (SBF)of
flake-like
results show and cotton-like morphology
that the appearance of of apatite provides
flake-like favorable
and cotton-like conditions for
morphology of osseoconnection.
apatite provides
In addition,
favorable the multifunctional
conditions design of implants
for osseoconnection. In addition,is closely related to the composite
the multifunctional design ofcoating,
implants andis
coupled with appropriate
closely related to the composite post-treatment,
coating, and which can further
coupled affects the post-treatment,
with appropriate biomedical applicationwhich can of
implants. Rasmithe
further affects et al. [90] used LC
biomedical to prepareoffunctionally
application implants. Rasmi graded et material
al. [90] (FGM)
usedHA-TiO , which
LC to 2prepare
comprises
functionally ofgraded
five different
material preplaced
(FGM) HA-TiOlayers on Ti-6Al-4V
2, which alloy. Figure
comprises of five13 indicates
different that the layers
preplaced interface
on
thickness
Ti-6Al-4Vbetween the composite
alloy. Figure 13 indicatescoatingthatand
thethe substrate
interface is higher,between
thickness and cellular structure was
the composite observed
coating and
in
thethe upper part
substrate of CL. and
is higher, Apparently,
cellular the FGM with
structure multiphase,
was observed in micro-textured
the upper part coating provides better
of CL. Apparently, the
metallurgical bonding atmicro-textured
FGM with multiphase, the interface, and the wettability
coating and the
provides better protein adsorption
metallurgical bondingcapacity of FGM
at the interface,
are
andsignificantly
the wettability improved.
and the protein adsorption capacity of FGM are significantly improved.
Figure 12. Laser cladding (LC) schematic diagram [90]. Reprinted with permission from reference [90]
2018 Elsevier.
further affects the biomedical application of implants. Rasmi et al. [90] used LC to prepare
functionally graded material (FGM) HA-TiO2, which comprises of five different preplaced layers on
Ti-6Al-4V alloy. Figure 13 indicates that the interface thickness between the composite coating and
the substrate is higher, and cellular structure was observed in the upper part of CL. Apparently, the
FGM with
Coatings 2019,multiphase,
9, 249 micro-textured coating provides better metallurgical bonding at the interface,
11 of 23
and the wettability and the protein adsorption capacity of FGM are significantly improved.
Figure 12. Laser cladding (LC) schematic diagram [90]. Reprinted

Reprinted with permission from reference [90]
Coatings 2019, 9, x Laser cladding
FOR PEER REVIEW 11 of 22
Elsevier.
2018 Elsevier.
Figure 13. Cross-sectional morphology of 100% HA and functionally graded material (FGM) laser
Figure 13. Cross-sectional morphology of 100% HA and functionally graded material (FGM) laser
2 (a,c)
cladding at laser energy density (LED) 21.6 J/mm interface between the crust layer (CL) and
cladding at laser energy density (LED) 21.6 J/mm (a,c) interface between the crust layer (CL) and the
2
the transition layer (TL) (low magnification) and (b,d) CL (high magnification) [90]. The top layer of
transition layer (TL) (low magnification) and (b,d) CL (high magnification) [90]. The top layer of
cladding is identified as CL. Beneath the CL, the TL is present, where transition of elements between
cladding is identified as CL. Beneath the CL, the TL is present, where transition of elements between
cladding and substrate occurs. Reprinted with permission from reference [90] 2018 Elsevier.
cladding and substrate occurs. Reprinted with permission from reference [90] 2018 Elsevier.
The composite material composed of bioceramics and metal can not only improve the mechanical
The composite
properties of implant material composed
surface, but also affectofthe
bioceramics and metal
chemical properties such can not only improve
as biocompatibility the
[91,92].
mechanical properties of implant surface, but also affect the chemical properties
MgO doped Ta coatings are successfully created by high power lasers on CP-Ti substrate. With the such as
biocompatibility [91,92]. MgO doped Ta coatings are successfully created by high power
addition of MgO, the hardness of the coating is four times higher compared to CP-Ti. Additionally, lasers on
CP-Ti
the substrate. Withand
biocompatibility the addition of MgO, the
cells proliferation hardness
was further of the coating
improved by is four times higher
incorporating MgOcompared
in the Ta
to CP-Ti. Additionally, the biocompatibility and cells proliferation was further
coatings [91]. In studies by Deng et al. [92], LC was used to create a compositional gradient improved
NiTi/HA by
incorporating
coatings MgO
on NiTi in the Ta
substrate, ascoatings [91]. In studies
well as sintered by Deng et al. coating
NiTi (sNiTi)/HA-acid [92], LCwhich
was used to createbya
is obtained
compositional gradient NiTi/HA coatings on NiTi substrate, as well as sintered NiTi (sNiTi)/HA-acid
acid-etching post-treatment. Figure 14 shows that by coating NiTi with HA the biocompatibility of NiTi
coating which
implants is obtained
was further by acid-etching
enhanced. An increasepost-treatment.
in extracellularFigure
matrix14 shows that
generation andbymineral
coatingdeposition
NiTi with
HA
of the biocompatibility
osteoblasts was seen onofsNiTi,
NiTi sNiTi/HA
implants wasand further enhanced.
sNiTi/HA-acid An increase
coatings. in extracellular
In particular, matrix
the presence of
generation and mineral deposition of osteoblasts was
HA significantly promoted the proliferation of osteoblasts. seen on sNiTi, sNiTi/HA and sNiTi/HA-acid
coatings. In particular, the presence of HA significantly promoted the proliferation of osteoblasts.
During the implantation process, the applied stress may exceed the coating-substrate adhesion
strength, which causes the separation of the coating from the metal surface, thereby impairing its
function of promoting bone integration [93]. Therefore, Miranda et al. [94] proposed a novel
integrated approach to avoid the detachment of HA coatings during implantation and affecting
Coatings 2019, 9, 249 12 of 23
Figure 14. Osteoblast morphology on different sNiTi plates [92].After three days of osteoblast culture,
Figure 14. Osteoblast morphology on different sNiTi plates [92].After three days of osteoblast culture,
the top view of the cell monolayers was imaged by SEM: (A) sNiTi; (B) and (D) sNiTi/HA-acid;
the top view of the cell monolayers was imaged by SEM: (A) sNiTi; (B) and (D) sNiTi/HA-acid; (C)
(C) and (E) sNiTi/HA. Representative areas in (A–C) showing mineral deposits (yellow arrows),
and (E) sNiTi/HA. Representative areas in (A–C) showing mineral deposits (yellow arrows), cell
cell nuclei (blue arrows), and lamellipodia (red arrows). Some cells displayed a dome shape on
nuclei (blue arrows),
sNiTi/HA-acid, and lamellipodia
as in (D); and sNiTi/HA, (red
as arrows).
in (E); noSome cells
similar displayed
cells were founda dome shape Cross
for sNiTi. on sNiTi/HA-
sections
acid, as in (D); and sNiTi/HA, as in (E); no similar cells were found for sNiTi. Cross
of the osteoblast monolayer were also imaged: (F) sNiTi; (G) sNiTi/ HA-acid; (H) sNiTi/HA. A fibrous sections of the
osteoblast monolayer were also imaged: (F) sNiTi; (G) sNiTi/ HA-acid; (H) sNiTi/HA.
structure which is highlighted by yellow rectangles was observed in (G,H) and possibly represents A fibrous
Figure 14.which
structure Osteoblast morphology
is highlighted by on different
yellow sNiTi plates
rectangles was [92].After
observed inthree
(G,H)days
andofpossibly
osteoblast culture,
represents
extracellular matrix. The red rectangle in (H) indicates possible mineralized microspheres attached to
the top view matrix.
extracellular of the cell
Themonolayers
red was imaged by SEM: (A) sNiTi; (B) andmicrospheres
(D) sNiTi/HA-acid;
attached(C)
the cell monolayer. Scale bar:rectangle in (H)
10 µm. Reprinted indicates possible
with permission mineralized
from reference [92] 2018 Elsevier. to
andcell
the (E)monolayer.
sNiTi/HA. Scale
Representative
bar: 10 µm.areas in (A–C)
Reprinted withshowing
permissionmineral deposits (yellow
from reference [92] 2018arrows),
Elsevier.cell
nuclei (blue arrows), and lamellipodia (red arrows). Some cells displayed
During the implantation process, the applied stress may exceed the coating-substrate a dome shape on sNiTi/HA-
adhesion
acid, as in (D); and sNiTi/HA, as in (E); no similar cells were found for sNiTi.
strength, which causes the separation of the coating from the metal surface, thereby impairing Cross sections of the its
osteoblast
function monolayer
of promoting bonewere also imaged:
integration [93]. (F) sNiTi; (G)
Therefore, sNiTi/ HA-acid;
Miranda et al. [94] (H) sNiTi/HA.
proposed A fibrous
a novel integrated
structure which is highlighted by yellow rectangles was observed in (G,H) and possibly represents
approach to avoid the detachment of HA coatings during implantation and affecting biological activity.
extracellular matrix. The red rectangle in (H) indicates possible mineralized microspheres attached to
As explained by the schematic diagram as seen in Figure 15, the holes on the surface of Ti6-Al-4V are
the cell monolayer. Scale bar: 10 µm. Reprinted with permission from reference [92] 2018 Elsevier.
processed by Nd:YAG laser, and then filled with HA by laser sintering.
Figure 15. Schematic representation of the experimental procedure used to produce laser sintered
Ti6Al4V doped HA structures [94]. Reprinted with permission from reference [94] 2019 Elsevier.
2.5. Sol-Gel
Sol-gel technology is a versatile chemical synthesis technology that has been developed recently
Figure 15. Schematic representation of the experimental procedure used to produce laser sintered
relates to hybrid
Figure 15. materials
Schematic which can of
representation bethe
used to achieveprocedure
experimental unusual used
composite propertiessintered
to produce [95,96]. To
Ti6Al4V doped HA structures [94]. Reprinted with permission from reference [94] 2019 laser
Elsevier.
someTi6Al4V
extent, doped
the application of sol-gel method can produce excellent coating owing to
HA structures [94]. Reprinted with permission from reference [94] 2019 Elsevier. its advantages
properties such
It can be as from
seen low process
the above temperature, facile
that the energy and inexpensive
density, wavelengthpreparation [97]. speed,
width, scanning The process
pulse
illustrated
2.5. in Figure
Sol-Geland
frequency surface16 texture
is not really complete.
design In fact,
of the laser will altering the
affect the initial precursors,
biomechanical time allowed
properties for
of the final
gelation,
surface. catalysts,
Laser degree of solvation,
claddingisisa versatile gelation
a flexiblechemical conditions
and effective method,or physical
by mixing processing
different of the gel itself
powder materials, can
Sol-gel technology synthesis technology that has been developed recently
control the coating performance [96].
relates to hybrid materials which can be used to achieve unusual composite properties [95,96]. To
some extent, the application of sol-gel method can produce excellent coating owing to its advantages
properties such as low process temperature, facile and inexpensive preparation [97]. The process
illustrated in Figure 16 is not really complete. In fact, altering the initial precursors, time allowed for
gelation, catalysts, degree of solvation, gelation conditions or physical processing of the gel itself can
Coatings 2019, 9, 249 13 of 23
forming a special biological coating on the surface of parts, so as to obtain the desired properties.
However, due to the inconsistency between the thermal expansion coefficient of the cladding layer and
the matrix, surface quality problems, such as cracks and pores that maybe difficult to control precisely
in the cladding layer.
2.5. Sol-Gel
Sol-gel technology is a versatile chemical synthesis technology that has been developed recently
relates to hybrid materials which can be used to achieve unusual composite properties [95,96]. To some
extent, the application of sol-gel method can produce excellent coating owing to its advantages
properties such as low process temperature, facile and inexpensive preparation [97]. The process
illustrated in Figure 16 is not really complete. In fact, altering the initial precursors, time allowed for
gelation, catalysts, degree of solvation, gelation conditions or physical processing of the gel itself can
control2019,
Coatings the 9,
coating performance
x FOR PEER REVIEW [96]. 13 of 22
Figure 16.
Figure Gel synthesis
16. Gel synthesis routes.
routes. Processes
Processes are
are defined
definedasassol–gel
sol–gelby
bythe
thetransition
transitionofof
colloidal
colloidalsolution to
solution
an interconnected gel network (gelation). The further processing stages illustrated are non-redundant
to an interconnected gel network (gelation). The further processing stages illustrated are non-
and may beand
redundant combined
may bedepending on the specific
combined depending needs
on the of theneeds
specific application
of the [96]. 3D: three-dimensional.
application [96]. 3D: three-
Reprinted with
dimensional. permission
Reprinted withfrom referencefrom
permission [96]reference
2016 Elsevier.
[96] 2016 Elsevier.
Recently, Çomakl
Recently, Çomakletetal. al.[98]
[98]indicted
indictedthat
that a titanium
a titanium dioxide
dioxide thinthin
filmfilm structure
structure prepared
prepared by
by the
the sol-gel
sol-gel on CP-Ti
on CP-Ti substrate
substrate is more
is more stable
stable andand thickerinincomparison
thicker comparisontotothe thecontinuous
continuous ionion layer
layer
adsorption and reaction (SILAR) method, and the wear properties and corrosion
adsorption and reaction (SILAR) method, and the wear properties and corrosion resistance is resistance is enhanced.
The surfaceThe
enhanced. morphology of sol-gel and
surface morphology ofSILAR
sol-gelsamples
and SILARis shown
samplesin Figure 17. Moreover,
is shown in Figure sol-gel method
17. Moreover,
can also be combined with a variety of coating technologies and can produce
sol-gel method can also be combined with a variety of coating technologies and can produce ideal biological coating
ideal
by selecting the appropriate conditions [99,100]. Anjaneyulu et al. [101] prepared
biological coating by selecting the appropriate conditions [99,100]. Anjaneyulu et al. [101] prepared sol–gel-derived HA
coatings via spinHA
sol–gel-derived coating on Ti-6Al-4V
coatings alloy substrates.
via spin coating on Ti-6Al-4V Thealloy
sol–gel-derived
substrates. HA The surface has excellent
sol–gel-derived HA
corrosion resistance and great cellular response in terms of cell attachment, growth
surface has excellent corrosion resistance and great cellular response in terms of cell attachment, and proliferation.
Since theand
growth loose particles on Since
proliferation. the medical implant
the loose may cause
particles on thecancer
medicaland implant
inflammation, the coating
may cause cancerneeds
and
to be firmly bonded
inflammation, to theneeds
the coating implant.to be firmly bonded to the implant.
sol-gel method can also be combined with a variety of coating technologies and can produce ideal
biological coating by selecting the appropriate conditions [99,100]. Anjaneyulu et al. [101] prepared
sol–gel-derived HA coatings via spin coating on Ti-6Al-4V alloy substrates. The sol–gel-derived HA
surface has excellent corrosion resistance and great cellular response in terms of cell attachment,
growth2019,
Coatings and9, proliferation.
249 Since the loose particles on the medical implant may cause cancer and
14 of 23
inflammation, the coating needs to be firmly bonded to the implant.
Figure 17. Cross-section SEM micrographs of (a) sol-gel and (b) SILAR
SILAR samples
samples [98].
[98]. Reprinted with
reference [98]
permission from reference [98] 2018
2018 Elsevier.
Elsevier.
Andrew et al. [102] improved the bonding strength and optimized the mechanical properties of
the sol-gel coating by controlling the annealing temperature. In addition, researchers have found that
the pretreatment of the precursor had a significant effect on the adsorption strength and mechanical
properties of the coating [103]. Roest et al. [104] found that anodizing treatments could improve the
adhesive bonding of HA on Ti substrates, especially for titanium alloys. Analogously, a dense and
stable SiO2 coating was deposited on the surface of pre-oxidized TiNi alloy by sol-gel method. This way
improves the bonding strength between the substrate and film and corrosion resistance. Additionally,
the release of Ni ions can be effectively prevented to ensure the biocompatibility of the implant, as
reported by Yang et al. [105].
Sol-gel coating can not only act as a barrier layer to isolate the metallic substrates from the human
body environment, but also achieve multi-functional coating by adding different components, such
as corrosion inhibitors, growth factor and antibacterial factor [106]. Michelina et al. [107] prepared
organic-inorganic composite coatings on the surface of CP Ti grade 4 substrates by sol-gel method,
and successfully improved the elastic-plastic coating without cracks by adding poly (ε-caprolactide).
Furthermore, on a cellular level, the implants had excellent bioactive and biocompatibility.
Sol-gel technology is an interesting way to modify the surface of the implants. The sol-gel
technology is essentially the use of various materials that are controlled at processing media level,
instead of raw materials in traditional processes that are neither geometrically controlled and chemically
controlled or only geometrically controlled. With no doubt, combined with the change of coating
preparation process and adding other functional components, different functional coatings can be
obtained. In addition, how to shorten the processing time and improve the binding energy between the
surface and the matrix by changing the processing parameters seems to be the main research direction
at present.
2.6. Friction Stir Processing

Friction stir processing (FSP), heat source of processing is friction heat and plastic deformation
heat, is a new method applied to surface repair. For the biomedical field, it is mainly used to
modify surface microstructure or fabricate a composite layer on the surface of substrate. In particular,
composite coatings produced by FSP not only can improve surface properties such as hardness,
abrasion resistance, ductility, corrosion resistance, fatigue life and frictional properties, but also obtain
Coatings 2019, 9, 249 15 of 23
desired multifunctional biomedical coating without or less affecting the matrix properties of the
material [108–110].
FSP is one of the prospective surface modification technologies that allows to control mechanical
properties by changing localized microstructure in a surface layer while retaining properties of the
base material. In general, the final microstructure of FSP surface is dependent on several independent
factors, such as processing parameters, chemical composition of modified material and consequent
heat treatment [111]. As a fairly environmentally friendly process, FSP is used for uniform distribution
of composition and microstructure, fabrication of ultra-fine grained materials and elimination of
casting defects [112]. As reported in recently work, FSP was employed to obtain defect-free and
homogenous fine-grained surface layer of the Ti-6Al-4V alloy by the applied processing parameters.
The ultra-refined α phase or Martensite-α’ phase produced by phase transformation provides
Coatings 2019, 9, x FOR PEER REVIEW
a
15 of 22
beneficial condition for the enhancement in hardness and dry sliding wear performance [113]. In order
to further
tool optimize
with probe mechanical
is applied properties
to pack the holesforcompletely.
biomedicalItapplications, Wangthat
should be noted et al. [114] systematically
dimension, shape and
studied the microstructure evolution of Ti-35Nb-2Ta-3Zr alloy surface by FSP.
number of holes and distance between each other can be varied to achieve required volume As is shown in Figure 18,
fraction
the size of equiaxed grains is considerably refined by the severe shear deformation
of the second phases. In general, when a reinforcing phase is incorporated into a matrix, surface in stir zone.
Moreover,
compositesit showis apparent that the occurrence
the synergistic of dynamic
effect of grain recrystallization
refinement by FSP and is accompanied
reinforcementbyparticle
phase
transition
[118,119]. due to severe plastic deformation during three-pass FSP.
Figure 18.
18. EBSD
EBSD maps
maps of equiaxed grains for three-pass friction stir stir processing
processing (FSP)-processed
(FSP)-processed
sample at a rotational
rotational speed
speed of
of300
300r/min:
r/min:(a)(a)orientation
orientationmap,
map,(b)(b)
distribution
distributionof of
grain sizesize
grain andand
(c)
misorientation
(c) angle
misorientation distribution
angle distributioninin
stir
stirzone
zone(SZ),
(SZ),and
and(d)
(d)orientation
orientationmap,
map,(e)
(e) distribution
distribution of grain
misorientation angle
size and (f) misorientation angle distribution
distribution inin transition
transition zone
zone (TZ)
(TZ) [114].
[114]. Reprinted with permission
reference [114]
from reference [114] 2017
2017 Elsevier.
Elsevier.
Numerous studies have demonstrated that FSP is an effective method of fabricating surface
composites [115,116]. The common method with reinforcement particles in the fabrication of surface
composites by holes is explained in Figure 19 [117]. In the first step, the holes with proper dimensions
are machined on the modified plat and the reinforcement particles are filled in the holes. Then, the tool
with probe is applied to pack the holes completely. It should be noted that dimension, shape and
number of holes and distance between each other can be varied to achieve required volume fraction
of the second phases. In general, when a reinforcing phase is incorporated into a matrix, surface
composites show the synergistic effect of grain refinement by FSP and reinforcement particle [118,119].
Figure 18. EBSD maps of equiaxed grains for three-pass friction stir processing (FSP)-processed
sample at a rotational speed of 300 r/min: (a) orientation map, (b) distribution of grain size and (c)
misorientation angle distribution in stir zone (SZ), and (d) orientation map, (e) distribution of grain
size and (f) misorientation angle distribution in transition zone (TZ) [114]. Reprinted with permission
Coatings 2019, 9, 249 16 of 23
Figure 19. Schematic

Figure 19. illustration of
Schematic illustration of the
the process
process of
of producing
producing the
the FSP-modified
FSP-modified Ti/SiC
Ti/SiC metal
metal matrix
matrix
nano-composite (MMNC) [117].
nano-composite (MMNC) [117].
Targeting on tissue-substrate interactions, several works has been done to explore the effects
of FSP surface composites on titanium alloys for medical implant. Recently, FSP titanium alloys
reinforced by HA, TiC, SiC and TiO2 nano-particles are suitable for biomedical application [120].
Zhu et al. [117] successfully utilized FSP to fabricate titanium/silicon carbide composite layer on the
surface of pure Ti substrate and found an increase of microhardness. Furthermore, the adhesion,
proliferation and osteogenic differentiation of the cells on the surface of the nanocomposite material
were enhanced. Then, TiO2 /TC4 composite coating, which provides a no biotoxicity environment for
cells and promotes cell adhesion and proliferation, was produced [121]. Wang et al. [122] produced a
promising biomaterial−TC4/Ag metal matrix nanocomposite, which can achieve a balance between the
antibacterial effect and biocompatibility. In Figure 20, with the increase of silver content, the number
of staphylococcus aureus (S. aureus) cells decreased significantly and dead cells with an indistinct or
deformed membrane were observed on 2 mm-Ag-FSP.
This section mainly focused on introducing all the aspects and biomedical applications of FSP that
is a novel and advanced solid-state surface modification technology, as well as reviewing the reported
short literature on this subject. On the one hand, it is effective to refine the grain structure and eliminate
surface defects during FSP because of dynamic recrystallization phenomena that occur in severe
thermal deformation [123,124]. On the other hand, recent studies pertaining to coating pointed out that
FSP has great potential to obtain functional gradient multifunctional composite coating from powder
pre-placed sheet system by using different lengths of grooves and tools. However, the inferior flexibility
of FSP limits its usage. This limitation restricts the use of the FSP technique to manufacture complex
counterparts with precise dimensional tolerance as compared to the other fusion-based technology.
were enhanced. Then, TiO2/TC4 composite coating, which provides a no biotoxicity environment for
cells and promotes cell adhesion and proliferation, was produced [121]. Wang et al. [122] produced
a promising biomaterial−TC4/Ag metal matrix nanocomposite, which can achieve a balance between
the antibacterial effect and biocompatibility. In Figure 20, with the increase of silver content, the
number
Coatings of 9,staphylococcus
2019, 249 aureus (S. aureus) cells decreased significantly and dead cells with
17 ofan
23
indistinct or deformed membrane were observed on 2 mm-Ag-FSP.
Figure 20.
Figure 20. SEM
SEM images
images of of S.
S. aureus
aureus cells
cells introduced
introducedononsample
samplesurfaces;
surfaces;(a–c)
(a–c)are
areTC4,
TC4,0 0mm-FSP,
mm-FSP, and
and 2
2 mm-Ag-FSP at low magnification, respectively, and (d–f) are highly magnified images.
mm-Ag-FSP at low magnification, respectively, and (d–f) are highly magnified images. Yellow arrows Yellow
arrows
show cellshow cellwhereas
fission, fission,black
whereas
arrowsblack
showarrows show
dead cells dead
with cells withoran
an indistinct indistinct
deformed or deformed
membrane [122].
membranewith
Reprinted [122]. Reprintedfrom
permission withreference
permission from
[122] reference
2018 Elsevier.[122] 2018 Elsevier.
3. Conclusions
This section mainly focused on introducing all the aspects and biomedical applications of FSP
that The
is a novel
surfaceand advanced of
modification solid-state surface
biomaterials hasmodification
become a vital technology, as wellinas
topic, especially reviewing the
overcoming the
reported short literature on this subject. On the one hand, it is effective to refine the grain
rejection reactions, such as inflammation and allergic reactions. When these biomaterials are implanted structure
and eliminate
into the body, surface
most ofdefects
them willduring FSP because
interact with theof dynamicenvironment,
maternal recrystallization
whichphenomena that occur
cannot achieve the
in severe thermal deformation [123,124]. On the other hand, recent studies pertaining
desired effect. Thus far, surface modification of biomaterials is believed to be the best way to improve to coating
pointed
its variousout that FSP This
properties. has paper
great summarizes
potential to the
obtain functional
methods gradient
and research multifunctional
progress composite
of biomedical surface
coating frominpowder
modification pre-placed sheet system by using different lengths of grooves and tools.
recent years.
However, the inferior
This review flexibility
provides of FSPoflimits
a summary its usage. emphasized
the commonly This limitation restricts
surface the use ofmethods,
modification the FSP
technique to manufacture complex counterparts with precise dimensional tolerance
such as plasma spraying, ion implantation, micro-arc oxidation, laser surface modification, sol-gel as compared to
the other
and fusion-based
FSP. These methodstechnology.
are of great help to the practical application of biomedical implants; however,
there are still some deficiencies. In order to improve the success rate of implants and achieve long-term
3. Conclusions
stability of implants, it is necessary to combine surface modification and biomedicine to design the
optimal
Thesurface
surfacemorphology
modificationand formulate effective
of biomaterials coating
has become immobilization
a vital strategies.
topic, especially in overcoming the
rejection reactions, such as inflammation and allergic reactions. When these biomaterials are
Funding: The authors would like to acknowledge the financial support provided by National Science Foundation
implanted
under Grant into
Nos. the body, 51831011,
51674167, most of them will51874225,
51302168, interact 51671152.
with the maternal environment, which cannot
achieve the desired effect. Thus far, surface modification of biomaterials is believed to be the best
Acknowledgments: The authors sincerely thank Qingge Wang and Haibo Wu from Xi’an University of Architecture
and Technology for data analysis of this paper.
Conflicts of Interest: The authors declare no conflict of interest.
References
1. Kurtz, S.; Mowat, F.; Ong, K. Prevalence of primary and revision total hip and knee arthroplasty in the
United States from 1990 through 2002. J. Bone Jt. Surg. Am. 2007, 89, 780–785.
2. Barrere, F.; Mahmood, T.; De Groot, K.; Van Blitterswijk, C.; Van Blitterswijk, C. Advanced biomaterials
for skeletal tissue regeneration: Instructive and smart functions. Mater. Sci. Eng. R Rep. 2008, 59, 38–71.
[CrossRef]
3. Zethraeus, N.; Borgström, F.; Ström, O. Cost-effectiveness of the treatment and prevention of osteoporosis—A
review of the literature and a reference model. Osteoporos. Int. 2007, 18, 9–23. [CrossRef]
Coatings 2019, 9, 249 18 of 23
4. Singh, R.; Singh, S.; Hashmi, M. Implant materials and their processing technologies. In Reference Module in
Materials Science and Materials Engineering; Elsevier: Amsterdam, The Netherlands, 2016.
5. Rony, L.; Lancigu, R.; Hubert, L. Intraosseous metal implants in orthopedics: A review. Morphologie 2018,
102, 231–242. [CrossRef] [PubMed]
6. Rabadia, C.D.; Liu, Y.J.; Wang, L.; Sun, H.; Zhang, L.C. Laves phase precipitation in Ti-Zr-Fe-Cr alloys with
high strength and large plasticity. Mater. Des. 2018, 154, 228–238. [CrossRef]
7. Wang, L.Q.; Lu, W.J.; Qin, J.N.; Zhang, F.; Zhang, D. Microstructure and mechanical properties of cold-rolled
TiNbTaZr biomedical β titanium alloy. Mater. Sci. Eng. A 2008, 490, 421–426. [CrossRef]
8. Niespodziana, K.; Jurczyk, K.; Jakubowicz, J.; Jurczyk, M. Fabrication and properties of titanium–
hydroxyapatite nanocomposites. Mater. Chem. Phys. 2010, 123, 160–165. [CrossRef]
9. Cao, H.; Liu, X. Activating titanium oxide coatings for orthopedic implants. Surf. Coat. Technol. 2013, 233,
57–64. [CrossRef]
10. Shariq, N.; Zohaib, K.B.D.S.; Sana, Z.B.D.S.; Muhammad, S.Z.B.D.S. Bioactivity and osseointegration of PEEK
are inferior to those of titanium: A systematic review. J. Oral Implantol. 2016, 42, 512–516.
11. Noman, H.; Liu, S.F.; Lu, E.Y.; Wang, L.Q.; Liu, R.; Lu, W.J.; Zhang, L.C. Mechanical behavior and phase
transformation of β-type Ti-35Nb-2Ta-3Zr alloy fabricated by 3D-Printing. J. Alloy. Compd. 2019, 790,
117–126.
12. Rabadia, C.D.; Liu, Y.J.; Jawed, S.F.; Wang, L.; Li, Y.H.; Zhang, X.H.; Sercombe, T.B.; Sun, H.; Zhang, L.C.
Improved deformation behavior in Ti-Zr-Fe-Mn alloys comprising the C14 type Laves and β phases.
Mater. Des. 2018, 160, 1059–1070. [CrossRef]
13. Chakraborty, R.; Shahid Raza, M.; Datta, S.; Saha, P. Synthesis and characterization of nickel free
titanium–hydroxyapatite composite coating over Nitinol surface through in-situ laser cladding and alloying.
Surf. Coat. Technol. 2019, 358, 539–550. [CrossRef]
14. Bosco, R.; Van Den Beucken, J.; Leeuwenburgh, S.; Jansen, J. Surface engineering for bone implants: A trend
from passive to active surfaces. Coatings 2012, 2, 95–119. [CrossRef]
15. Aliasghari, S.; Skeldon, P.; Thompson, G. Plasma electrolytic oxidation of titanium in a phosphate/silicate
electrolyte and tribological performance of the coatings. Appl. Surf. Sci. 2014, 316, 463–476. [CrossRef]
16. Çelik, I.; Alsaran, A.; Purcek, G. Effect of different surface oxidation treatments on structural, mechanical and
tribological properties of ultrafine-grained titanium. Surf. Coat. Technol. 2014, 258, 842–848. [CrossRef]
17. Chu, H.J.; Liang, C.J.; Chen, C.H.; He, J.L. Optical emission spectroscopic determination of the optimum
regions for micro-arc oxidation of titanium. Surf. Coat. Technol. 2017, 325, 166–173. [CrossRef]
18. Karbowniczek, J.; Muhaffel, F.; Cempura, G.; Cimenoglu, H.; Czyrska-Filemonowicz, A. Influence of
electrolyte composition on microstructure, adhesion and bioactivity of micro-arc oxidation coatings produced
on biomedical Ti6Al7Nb alloy. Surf. Coat. Technol. 2017, 321, 97–107. [CrossRef]
19. Ha, J.Y.; Tsutsumi, Y.; Doi, H.; Nomura, N.; Kim, K.H.; Hanawa, T. Enhancement of calcium phosphate
formation on zirconium by micro-arc oxidation and chemical treatments. Surf. Coat. Technol. 2011, 205,
4948–4955. [CrossRef]
20. Rao, X.; Li, J.; Feng, X.; Chu, C.L. Bone-like apatite growth on controllable macroporous titanium scaffolds
coated with microporous titania. J. Mech. Behav. Biomed. 2018, 77, 225–233. [CrossRef]
21. Yang, W.; Xu, D.; Wang, J.; Yao, X.; Chen, J. Microstructure and corrosion resistance of micro arc oxidation
plus electrostatic powder spraying composite coating on magnesium alloy. Corros. Sci. 2018, 136, 174–179.
[CrossRef]
22. Liu, S.M.; Li, B.; Liang, C.H.; Wang, H.S.; Qiao, Z.X. Formation mechanism and adhesive strength of a
hydroxyapatite/TiO2 composite coating on a titanium surface prepared by micro-arc oxidation. Appl. Surf.
Sci. 2016, 362, 109–114. [CrossRef]
23. Li, L.H.; Kong, Y.M.; Kim, H.W.; Kim, W.Y.; Kim, H.E.; Heo, S.J.; Koak, J.Y. Improved biological performance
of Ti implants due to surface modification by micro-arc oxidation. Biomaterials 2004, 25, 2867–2875. [CrossRef]
[PubMed]
24. Zafar, M.S.; Farooq, I.; Awais, M.; Najeeb, S.; Khurshid, Z.; Zohaib, S. Chapter 11-Bioactive surface coatings
for enhancing osseointegration of dental implants. In Biomedical, Therapeutic and Clinical Applications of
Bioactive Glasses; Woodhead Publishing: Cambridge, UK, 2019; pp. 313–329.
25. Xu, L.; Wu, C.; Le, X.; Zhang, K.; Liu, C.; Ding, J.; Shi, X. Effect of oxidation time on cytocompatibility of
ultrafine-grained pure Ti in micro-arc oxidation treatment. Surf. Coat. Technol. 2018, 342, 12–22. [CrossRef]
Coatings 2019, 9, 249 19 of 23
26. Santos-Coquillat, A.; Tenorio, R.G.; Mohedano, M.; Martinez-Campos, E.; Arrabal, R.; Matykina, E. Tailoring
of antibacterial and osteogenic properties of Ti6Al4V by plasma electrolytic oxidation. Appl. Surf. Sci. 2018,
454, 157–172. [CrossRef]
27. Li, Y.; Wang, W.; Duan, J.; Qi, M. A super-hydrophilic coating with a macro/micro/nano triple hierarchical
structure on titanium by two-step micro-arc oxidation treatment for biomedical applications. Surf. Coat.
Technol. 2017, 311, 1–9. [CrossRef]
28. Wang, X.; Li, B.; Zhou, L.; Ma, J.; Zhang, X.; Li, H.; Liang, C.; Liu, S.; Wang, H. Influence of surface
structures on biocompatibility of TiO2 /HA coatings prepared by MAO. Mater. Chem. Phys. 2018, 215, 339–345.
[CrossRef]
29. Sedelnikova, M.; Komarova, E.; Sharkeev, Y.; Tolkacheva, T.; Khlusov, I.; Litvinova, L.; Yurova, K.;
Shupletsova, V. Comparative investigations of structure and properties of micro-arc wollastonite-calcium
phosphate coatings on titanium and zirconium-niobium alloy. Bioact. Mater. 2017, 2, 177–184. [CrossRef]
[PubMed]
30. Wang, P.; Wu, T.; Peng, H.; Guo, X.Y. Effect of NaAlO2 concentrations on the properties of micro-arc oxidation
coatings on pure titanium. Mater. Lett. 2016, 170, 171–174.
31. Yang, W.; Xu, D.; Guo, Q.; Chen, T.; Chen, J. Influence of electrolyte composition on microstructure and
properties of coatings formed on pure Ti substrate by micro arc oxidation. Surf. Coat. Technol. 2018, 349,
522–528. [CrossRef]
32. Correa, D.R.N.; Rocha, L.A.; Ribeiro, A.R.; Gemini-Piperni, S.; Archanjo, B.S.; Achete, C.A.; Werckmann, J.;
Afonso, C.R.M.; Shimabukuro, M.; Doi, H.; et al. Growth mechanisms of Ca- and P-rich MAO films in
Ti-15Zr-xMo alloys for osseointegrative implants. Surf. Coat. Technol. 2018, 344, 373–382. [CrossRef]
33. Tsai, M.T.; Chang, Y.Y.; Huang, H.L.; Wu, Y.H.; Shieh, T.M. Micro-arc oxidation treatment enhanced
the biological performance of human osteosarcoma cell line and human skin fibroblasts cultured on
titanium–zirconium films. Surf. Coat. Technol. 2016, 303, 268–276. [CrossRef]
34. Wang, Y.; Wang, L.; Zheng, H.; Du, C.; Ning, C.; Shi, Z.; Xu, C. Effect of frequency on the structure and cell
response of Ca-and P-containing MAO films. Appl. Surf. Sci. 2010, 256, 2018–2024. [CrossRef]
35. Huang, Q.; Li, X.; Elkhooly, T.A.; Liu, X.; Zhang, R.; Wu, H.; Feng, Q.L.; Liu, Y. The Cu-containing TiO2
coatings with modulatory effects on macrophage polarization and bactericidal capacity prepared by micro-arc
oxidation on titanium substrates. Colloids Surf. B Biointerfaces 2018, 170, 242–250. [CrossRef]
36. Wang, C.H.; Ma, F.C.; Liu, P.; Chen, J.; Liu, X.K.; Zhang, K.; Li, W.; Han, Q.Y. The influence of alloy elements
in Ti6Al4V and Ti35Nb2Ta3Zr on the structure, morphology and properties of MAO coatings. Vacuum 2018,
157, 229–236. [CrossRef]
37. Hu, H.J.; Qiao, Y.Q.; Meng, F.H.; Liu, X.Y.; Ding, C.X. Enhanced apatite-forming ability and cytocompatibility
of porous and nanostructured TiO2 /CaSiO3 coating on titanium. Colloids Surf. B Biointerfaces 2013, 101, 83–90.
[CrossRef]
38. Zhang, R.R.; Liu, X.J.; Xiong, Z.Y.; Huang, Q.L.; Yang, X.; Yan, H. Novel micro/nanostructured TiO2 /ZnO
coating with antibacterial capacity and cytocompatibility. Ceram. Int. 2018, 44, 9711–9719. [CrossRef]
39. Najeeb, S.; Zafar, M.S.; Khurshid, Z.; Zohaib, S.; Hasan, S.M.; Khan, R.S. Bisphosphonate releasing dental
implant surface coatings and osseointegration: A systematic review. J. Taibah Univ. Med Sci. 2017, 12, 369–375.
[CrossRef]
40. Daroonparvar, M.; Yajid, M.A.M.; Yusof, N.M.; Bakhsheshi-Rad, H.R.; Hamzah, E. Deposition of duplex
MAO layer/nanostructured titanium dioxide composite coatings on Mg–1%Ca alloy using a combined
technique of air plasma spraying and micro arc oxidation. J. Alloy. Compd. 2015, 649, 591–605. [CrossRef]
41. Heimann, R.B. Thermal spraying of biomaterials. Surf. Coat. Technol. 2006, 201, 2012–2019. [CrossRef]
42. Lima, R.S.; Marple, B.R. Thermal spray coatings engineered from nano-structured ceramic agglomerated
powders for structural, thermal barrier and biomedical applications: A review. Therm. Spray Technol. 2007,
16, 40–63. [CrossRef]
43. Zhou, L.; Zhou, W.C.; Su, J.B. Effect of composition and annealing on the dielectric properties of ZnO/mullite
composite coating. Ceram. Int. 2012, 38, 1077–1083. [CrossRef]
44. Balani, K.; Anderson, R.; Laha, T. Plasma-sprayed carbon nanotube reinforced hydroxyapatite coatings and
their interaction with human osteoblasts in vitro. Biomaterials 2007, 28, 618–624. [CrossRef]
Coatings 2019, 9, 249 20 of 23
45. Shamray, V.; Sirotinkin, V.; Smirnov, I.; Kalita, V.; Fedotov, A.; Barinov, S.; Komlev, V.; Fedotov, A.; Komlev, V.
Structure of the hydroxyapatite plasma-sprayed coatings deposited on pre-heated titanium substrates.
Ceram. Int. 2017, 43, 9105–9109. [CrossRef]
46. Sathish, S.; Geetha, M.; Aruna, S.; Balaji, N.; Rajam, K.; Asokamani, R. Studies on plasma sprayed bi-layered
ceramic coating on bio-medical Ti–13Nb–13Zr alloy. Ceram. Int. 2011, 37, 1333–1339. [CrossRef]
47. Sathish, S.; Geetha, M.; Aruna, S.; Balaji, N.; Rajam, K.; Asokamani, R. Sliding wear behavior of plasma
sprayed nanoceramic coatings for biomedical applications. Wear 2011, 271, 934–941. [CrossRef]
48. Kumari, R.; Majumdar, J.D. Wear Behavior of plasma spray deposited and post heat-treated hydroxyapatite
(HA)-based composite coating on titanium alloy (Ti-6Al-4V) substrate. Metall. Mater. Trans. A 2018, 49,
3122–3132. [CrossRef]
49. Hung, K.Y.; Lo, S.C.; Shih, C.S.; Yang, Y.C.; Feng, H.P.; Lin, Y.C. Titanium surface modified by hydroxyapatite
coating for dental implants. Surf. Coat. Technol. 2013, 231, 337–345. [CrossRef]
50. Yang, Y.C.; Yang, C.Y. Mechanical and histological evaluation of a plasma sprayed hydroxyapatite coating on
a titanium bond coat. Ceram. Int. 2013, 39, 6509–6516. [CrossRef]
51. Rahman, Z.U.; Shabib, I.; Haider, W. Surface characterization and cytotoxicity analysis of plasma sprayed
coatings on titanium alloys. Mater. Sci. Eng. C 2016, 67, 675–683. [CrossRef]
52. Ebrahimi, N.; Hossein, Z.A.S.A.; Vaezi, M.R. A new double-layer hydroxyapatite/alumina-silica coated
titanium implants using plasma spray technique. Surf. Coat. Technol. 2018, 352, 474–482. [CrossRef]
53. Cao, L.; Ullah, I.; Li, N.; Niu, S.; Sun, R. Plasma spray of biofunctional (Mg, Sr)-substituted hydroxyapatite
coatings for titanium alloy implants. J. Mater. Sci. Technol. 2018, 35, 719–726. [CrossRef]
54. Walsh, W.R.; Bertollo, N.; Christou, C.; Schaffner, D.; Mobbs, R.J. Plasma-sprayed titanium coating to
polyetheretherketone improves the bone-implant interface. Spine J. 2015, 15, 1041–1049. [CrossRef]
55. Hickey, D.J.; Lorman, B.; Fedder, I.L. Improved response of osteoprogenitor cells to titanium plasma-sprayed
PEEK surfaces. Colloids Surf. B Biointerfaces 2019, 175, 509–516. [CrossRef]
56. Ke, D.; Vu, A.A.; Bandyopadhyay, A.; Bose, S. Compositionally graded doped hydroxyapatite coating on
titanium using laser and plasma spray deposition for bone implants. Acta Biomater. 2019, 84, 414–423.
[CrossRef] [PubMed]
57. Lin, Z.; Li, S.J.; Sun, F.; Ba, D.C.; Li, X.C. Surface characteristics of a dental implant modified by low energy
oxygen ion implantation. Surf. Coat. Technol. 2019, 365, 208–213. [CrossRef]
58. Feng, H.; Yu, Z.; Chu, P.K. Ion implantation of organisms. Mater. Sci. Eng. R 2006, 54, 49–120. [CrossRef]
59. Fang, J.; Sun, Y.; Ma, H.Y.; Yu, X.L.; Ma, Y.; Ni, Y.X.; Zheng, L.; Zhou, Y.M. Biocompatibility and antibacterial
properties of zinc-ion implantation on titanium. J. Hard Tissue Biol. 2014, 23, 35–43. [CrossRef]
60. Rautray, T.R.; Narayanan, R.; Kim, K.H. Ion implantation of titanium based biomaterials. Prog. Mater. Sci.
2011, 56, 1137–1177. [CrossRef]
61. Ming, M.; Wan, R.X.; Gong, H.H.; Lv, X.F.; Chu, S.S.; Li, D.J.; Gu, H.Q.; Cheng, P. Study on the in vitro and
in vivo antibacterial activity and biocompatibility of novel TiN/Ag multilayers immobilized onto biomedical
titanium. J. Nanosci. Nanotechnol. 2019, 19, 3777–3791.
62. Zhu, C.; Bao, N.R.; Chen, S.; Zhao, J.N. Antimicrobial design of titanium surface that kill sessile bacteria but
support stem cells adhesion. Appl. Surf. Sci. 2016, 389, 7–16. [CrossRef]
63. Li, Y.; Zhao, T.T.; Wei, S.B.; Xiang, Y.; Chen, H. Effect of Ta2 O5 /TiO2 thin film on mechanical properties,
corrosion and cell behavior of the NiTi alloy implanted with tantalum. Mater. Sci. Eng. C 2010, 30, 1227–1235.
[CrossRef]
64. Xu, J.; Ding, G.; Li, J.L.; Yang, S.H.; Fang, B.S.; Sun, H.C.; Zhou, Y.M. Zinc-ion implanted and deposited
titanium surfaces reduce adhesion of Streptococccus mutans. Appl. Surf. Sci. 2010, 256, 7540–7544. [CrossRef]
65. Jin, G.D.; Cao, H.L.; Qiao, Y.Q.; Meng, F.H.; Zhu, H.Q.; Liu, X.Y. Osteogenic activity and antibacterial effect
of zinc ion implanted titanium. Colloids Surf. B Biointerfaces 2014, 117, 158–165. [CrossRef]
66. Shanaghi, A.; Chu, P.K. Enhancement of mechanical properties and corrosion resistance of NiTi alloy by
carbon plasma immersion ion implantation. Surf. Coat. Technol. 2018, 365, 52–57. [CrossRef]
67. Vlcak, P.; Fojt, J.; Weiss, Z.; Kopeček, J.; Perina, V. The effect of nitrogen saturation on the corrosion behaviour
of Ti-35Nb-7Zr-5Ta beta titanium alloy nitrided by ion implantation. Surf. Coat. Technol. 2019, 358, 144–152.
[CrossRef]
68. Chouirfa, H.; Bouloussa, H.; Migonney, V.; Falentin-Daudré, C. Review of titanium surface modification
techniques and coatings for antibacterial applications. Acta Biomater. 2019, 83, 37–54. [CrossRef]
Coatings 2019, 9, 249 21 of 23
69. Kim, S.; Park, C.; Cheon, K.H.; Jung, H.D.; Song, J.; Kim, H.E.; Jang, T.S. Antibacterial and bioactive properties
of stabilized silver on titanium with a nanostructured surface for dental applications. Appl. Surf. Sci. 2018,
451, 232–240. [CrossRef]
70. Weng, F.; Chen, C.Z.; Yu, H.J. Research status of laser cladding on titanium and its alloys: A review. Mater. Des.
2014, 58, 412–425. [CrossRef]
71. Kurella, N.B.; Dahotre, A. Review paper: Surface modification for bioimplants: The role of laser surface
engineering. J. Biomater. Appl. 2005, 20, 5–50. [CrossRef]
72. Du Plooy, R.; Akinlabi, E.T. Analysis of laser cladding of titanium alloy. Mater. Today Proc. 2018, 5,
19594–19603. [CrossRef]
73. Long, J.; Fan, P.; Gong, D.; Jiang, D.; Zhang, H.; Li, L.; Zhong, M. Super-hydrophobic surfaces fabricated by
femtosecond laser with tunable water adhesion: From lotus leaf to rose petal. ACS Appl. Mater. Interfaces
2015, 7, 9858–9865. [CrossRef]
74. Tian, Y.; Chen, C.; Li, S. Research progress on laser surface modification of titanium alloys. Appl. Surf. Sci.
2005, 242, 177–184. [CrossRef]
75. Antalya, H.S.L.; Bolander, J.; Rustom, L.E.; Johnson, A.W.; Luyten, F.P.; Picart, C. Bone regeneration strategies:
Engineered scaffolds, bioactive molecules and stem cells current stage and future perspectives. Biomaterials
2018, 180, 143–162.
76. Das, R.K.; Zouani, O.F. A review of the effects of the cell environment physicochemical nanoarchitecture on
stem cell commitment. Biomaterials 2014, 35, 5278–5293. [CrossRef]
77. Shinonaga, T.; Tsukamoto, M.; Kawa, T. Formation of periodic nanostructures using a femtosecond laser to
control cell spreading on titanium. Appl. Phys. B. 2015, 119, 493–496. [CrossRef]
78. Cunha, A.; Zouani, O.F.; Plawinski, L. Human mesenchymal stem cell behavior on femtosecond laser-textured
Ti-6Al-4V surfaces. Nanomedicine 2015, 10, 725–739. [CrossRef] [PubMed]
79. Lee, B.E.J.; Exir, H.; Weck, A. Characterization and evaluation of femtosecond laser-induced sub-micron
periodic structures generated on titanium to improve osseointegration of implants. Appl. Surf. Sci. 2018, 441,
1034–1042. [CrossRef]
80. Marticorena, M.; Corti, G.; Olmedo, D. Laser surface modification of Ti implants to improve osseointegration.
J. Appl. Phys. 2007, 59, 662–665. [CrossRef]
81. Trtica, M.; Stasic, J.; Batani, D.; Benocci, R.; Narayanan, V.; Ciganovic, J. Laser-assisted surface modification
of Ti-implant in air and water environment. Appl. Surf. Sci. 2018, 428, 669–675. [CrossRef]
82. Hsiao, W.T.; Chang, H.C.; Nanci, A.; Durand, R. Surface microtexturing of Ti–6Al–4V using an ultraviolet
laser system. Mater. Des. 2016, 90, 891–895. [CrossRef]
83. Kumari, R.; Scharnweber, T.; Pfleging, W.; Besser, H.; Majumdar, J.D. Laser surface textured titanium alloy
(Ti–6Al–4V)–Part II–Studies on bio-compatibility. Appl. Surf. Sci. 2015, 357, 750–758. [CrossRef]
84. Paital, S.R.; Balani, K.; Agarwal, A.; Dahotre, N.B. Fabrication and evaluation of a pulse laser-induced Ca–P
coating on a Ti alloy for bioapplication. Biomed. Mater. 2009, 4, 015009. [CrossRef]
85. Kurella, A.; Dahotre, N.B. Laser induced hierarchical calcium phosphate structures. Acta Biomater. 2006, 2,
86. Bose, S.; Robertson, S.F.; Bandyopadhyay, A. Surface modification of biomaterials and biomedical devices
using additive manufacturing. Acta Biomater. 2018, 66, 6–22. [CrossRef] [PubMed]
87. Koch, C.; Johnson, S.; Kumar, D.; Jelinek, M.; Chrisey, D.; Doraiswamy, A. Pulsed laser deposition of
hydroxyapatite thin films. Mater. Sci. Eng. C 2007, 27, 484–494. [CrossRef]
88. Paital, S.R.; He, W.; Dahotre, N.B. Laser pulse dependent micro textured calcium phosphate coatings for
improved wettability and cell compatibility. J. Mater. Sci. Mater. Med. 2010, 21, 2187–2200. [CrossRef]
89. Zheng, M.; Fan, D.; Li, X.K. Microstructure and in vitro bioactivity of laser-cladded bioceramic coating on
titanium alloy in a simulated body fluid. J. Alloy. Compd. 2010, 489, 211–214. [CrossRef]
90. Ranjan, B.R.; Abshar, H.; Ravi, S.M. Laser cladding with HA and functionally graded TiO2 -HA precursors
on Ti–6Al–4V alloy for enhancing bioactivity and cyto-compatibility. Surf. Coat. Technol. 2018, 352, 420–436.
91. Bandyopadhyay, A.; Bose, S.; Roy, M. MgO-doped tantalum coating on Ti: Microstructural study and
biocompatibility evaluation. ACS Appl. Mater. Interfaces 2012, 4, 577–580.
92. Deng, B.W.; Bruzzaniti, A.; Cheng, G.J. Enhancement of osteoblast activity on nanostructured
NiTi/hydroxyapatite coatings on additive manufactured NiTi metal implants by nanosecond pulsed laser
sintering. Int. J. Nanoned. 2018, 13, 8217–8230. [CrossRef]
Coatings 2019, 9, 249 22 of 23
93. Hseni, E.; Zalnezhad, E.; Bushroa, A.R. Comparative investigation on the adhesion of hydroxyapatite coating
on Ti–6Al–4V implant: A review paper. Int. J. Adhes. Adhes. 2014, 48, 238–257.
94. Miranda, G.; Sousa, F.; Costa, M.; Bartolomeu, F.; Silva, F.; Carvalho, O. Surface design using laser technology
for Ti-6Al-4V-hydroxyapatite implants. Opt. Technol. 2019, 109, 488–495. [CrossRef]
95. Liu, W.C.; Wang, H.Y.; Chen, L.C.; Huang, S.W.; Wu, C.T.; Chung, R.J. Hydroxyapatite/tricalcium silicate
composites cement derived from novel two-step sol-gel process with good biocompatibility and applications
as bone cement and potential coating materials. Ceram. Int. 2019, 45, 5668–5679. [CrossRef]
96. Owens, G.; Singh, R.K.; Foroutan, F.; Alqaysi, M. Sol–gel based materials for biomedical applications.
Prog. Mater Sci. 2016, 77, 1–79. [CrossRef]
97. Çomakli, O.; Yazici, M.; Yetim, T.; Yetim, A.F.; Çelik, A. The Effects of aging time on the structural and
electrochemical properties of composite coatings on Cp-Ti substrate. J. Bionic Eng. 2017, 14, 532–539.
[CrossRef]
98. Çomaklı, O.; Yazıcı, M.; Kovacı, H.; Yetim, T.; Yetim, A.F.; Çelik, A. Tribological and electrochemical properties
of TiO2 films produced on Cp-Ti by sol-gel and SILAR in bio-simulated environment. Surf. Coat. Technol.
2018, 352, 513–521. [CrossRef]
99. Balaganapathi, T.; Kaniamuthan, B.; Vinoth, S.; Thilakan, P. PEG assisted synthesis of porous TiO2 using
sol-gel processing and its characterization studies. Mater. Chem. Phys. 2017, 189, 50–55. [CrossRef]
100. Catauro, M.; Bollino, F.; Veronesi, P.; Lamanna, G. Influence of PCL on mechanical properties and bioactivity
of ZrO2 -based hybrid coatings synthesized by sol–gel dip coating technique. Mater. Sci. Eng. C 2014, 39,
101. Anjaneyulu, U.; Priyadarshini, B.; Stango, S.A.X.; Chellappa, M.; Geetha, M.; Vijayalakshmi, U. Preparation
and characterisation of sol–gel-derived hydroxyapatite nanoparticles and its coatings on medical grade
Ti-6Al-4V alloy for biomedical applications. Mater. Technol. 2017, 32, 800–814. [CrossRef]
102. Greer, A.I.; Lim, T.S.; Brydone, A.S.; Gadegaard, N. Mechanical compatibility of sol–gel annealing with
titanium for orthopaedic prostheses. Mater. Sci. Mater. Med. 2016, 27, 21–27. [CrossRef]
103. Ergün, Y.; Başpınar, M.S. Effect of acid passivation and H2 sputtering pretreatments on the adhesive strength
of sol-gel derived Hydroxyapatite coating on titanium surface. Int. J. Hydrogen Energy. 2017, 42, 20420–20429.
[CrossRef]
104. Roest, R.; Latella, B.; Heness, G.; Ben-Nissan, B. Adhesion of sol–gel derived hydroxyapatite nanocoatings
on anodised pure titanium and titanium (Ti6Al4V) alloy substrates. Surf. Coat. Technol. 2011, 205, 3520–3529.
[CrossRef]
105. Yang, S.; Zhou, F.; Xiao, T.; Xu, D.B.; Li, Z.; Xiao, Z.; Xiao, Z.A. Surface modification with SiO2 coating on
biomedical TiNi shape memory alloy by sol−gel method. Trans. Nonferrous Met. Soc. 2015, 25, 3723–3728.
[CrossRef]
106. Andrea Alcantara-Garcia, A.; Garcia-Casas, A.; Jimenez-Morales, A. Electrochemical study of the synergic
effect of phosphorus and cerium additions on a sol-gel coating for Titanium manufactured by powder
metallurgy. Prog. Org. Coat. 2018, 124, 267–274. [CrossRef]
107. Catauro, M.; Bollino, F.; Papale, F. Surface modifications of titanium implants by coating with bioactive and
biocompatible poly (ε-caprolactone)/SiO2 hybrids synthesized via sol–gel. Asian J. Chem. 2018, 11, 1126–1133.
[CrossRef]
108. Sharma, V.; Prakash, U.; Kumar, B.V.M. Surface composites by friction stir processing: A review. J. Mater.
Process. Technol. 2015, 224, 117–134. [CrossRef]
109. Misra, R.; Thein-Han, W.; Pesacreta, T.; Hasenstein, K.; Somani, M.; Karjalainen, L. Cellular response of
preosteoblasts to nanograined/ultrafine-grained structures. Acta Biomater. 2009, 5, 1455–1467. [CrossRef]
[PubMed]
110. McNelley, T.R. Friction stir processing (FSP): Refining microstructures and improving properties. Rev. Met.
2010, 46, 149–156. [CrossRef]
111. Weglowski,
˛ M.S. Friction stir processing–State of the art. Arch. Civ. Mech. Eng. 2018, 18, 114–129. [CrossRef]
112. Khodabakhshi, F.; Gerlich, A. Potentials and strategies of solid-state additive friction-stir manufacturing
technology: A critical review. J. Manuf. Process. 2018, 36, 77–92. [CrossRef]
113. Li, B.; Shen, Y.; Hu, W.; Luo, L. Surface modification of Ti–6Al–4V alloy via friction-stir processing: Microstructure
evolution and dry sliding wear performance. Surf. Coat. Technol. 2014, 239, 160–170. [CrossRef]
Coatings 2019, 9, 249 23 of 23
114. Wang, L.Q.; Xie, L.E.; Liu, Y.T.; Zhang, L.C.; Chen, L.Y.; Meng, Q.; Qu, J.; Zhang, D.; Lu, W.J. Microstructure
evolution and superelastic behavior in Ti-35Nb-2Ta-3Zr alloy processed by friction stir processing. Acta Mater.
2017, 131, 499–510. [CrossRef]
115. Gu, H.; Ding, Z.H.; Yang, Z.; Yu, W.Q.; Wang, L.Q. Microstructure evolution and electrochemical properties
of TiO2 /Ti-35Nb-2Ta-3Zr micro/nano-composites fabricated by friction stir processing. Mater. Des. 2019, 169,
10768. [CrossRef]
116. Xie, L.C.; Wang, L.Q.; Wang, K.S.; Yin, G.L.; Fu, Y.F. TEM characterization on microstructure of Ti–6Al–4V/Ag
nanocomposite formed by friction stir processing. Materialia 2018, 3, 139–144. [CrossRef]
117. Zhu, C.; Lv, Y.; Qian, C. Proliferation and osteogenic differentiation of rat BMSCs on a novel Ti/SiC metal
matrix nanocomposite modified by friction stir processing. Sci. Rep. 2016, 6, 38875. [CrossRef] [PubMed]
118. Qin, D.Q.; Shen, H.R.; Shen, Z.K.; Chen, H.Y.; Li, F. Manufacture of biodegradable magnesium alloy by high
speed friction stir processing. J. Manuf. Process. 2018, 36, 22–32. [CrossRef]
119. Lv, Y.T.; Ding, Z.H.; Xue, J.; Sha, G.; Wang, L.Q. Deformation mechanisms in surface nano-crystallization
of low elastic modulus Ti-6Al-4V/Zn composite during severe plastic deformation. Scr. Mater. 2018, 157,
120. Rahmati, R.; Khodabakhshi, F. Microstructural evolution and mechanical properties of a friction-stir processed
Ti-hydroxyapatite (HA) nanocomposite. J. Mech. Behav. Biomed. Mater. 2018, 88, 127–139. [CrossRef]
121. Zhang, C.J.; Ding, Z.H.; Xie, L.H.; Zhang, L.C.; Wu, L.Z.; Fu, Y.F.; Wang, L.Q.; Lu, W.J. Electrochemical
and in vitro behavior of the nanosized composites of Ti-6Al-4V and TiO2 fabricated by friction stir process.
Appl. Surf. Sci. 2017, 423, 331–339. [CrossRef]
122. Yang, Z.; Gu, H.; Sha, G.; Lu, W.J.; Yu, W.Q.; Zhang, W.J.; Fu, Y.J.; Wang, K.S.; Wang, L.Q. TC4/Ag metal
matrix nanocomposites modified by friction stir processing: Surface characterization, antibacterial property,
and cytotoxicity in vitro. ACS Appl. Mater. Interfaces 2018, 10, 41155–41166. [CrossRef]
123. Wang, L.Q.; Qu, J.; Chen, L.Y.; Meng, Q.; Zhang, L.C.; Qin, J.N. Investigation of deformation mechanisms in
beta-type Ti-35Nb-2Ta-3Zr alloy via FSP leading to surface strengthening. Metall. Mater. Trans. A 2015, 46A,
4813–4818. [CrossRef]
124. Ding, Z.H.; Zhang, C.J.; Xie, L.C.; Zhang, L.C.; Wang, L.Q.; Lu, W.J. Effects of friction stir processing on the
phase transformation and microstructure of TiO2 -compounded Ti-6Al-4V alloy. Metall. Mater. Trans. A 2016,
47A, 5675–5679. [CrossRef]
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Surface Modification of Biomedical Titanium Alloy

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Keywords: titanium alloy; surface modification; biomedical application

Coatings 2019, 9, 249; doi:10.3390/coatings9040249 www.mdpi.com/journal/coatings

Coatings 2019, 9, 249titanium-based

2.4. Laser Surface Modification

Coatings 2019, 9, x FOR PEER REVIEW 10 of 22

Figure 12. Laser cladding (LC) schematic diagram [90]. Reprinted

Coatings 2019, 9, x FOR PEER REVIEW 12 of 22

2.6. Friction Stir Processing

Figure 19. Schematic

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