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Comparative investigation on the adhesion of hydroxyapatite coating on Ti–

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 International Journal of Adhesion & Adhesives 48 (2014) 238–257

Contents lists available at ScienceDirect

International Journal of Adhesion & Adhesives

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

Comparative investigation on the adhesion of hydroxyapatite

coating on Ti–6Al–4V implant: A review paper
E. Mohseni, E. Zalnezhad, A.R. Bushroa n
Center of Advanced Manufacturing and Material Processing, Department of Engineering Design and Manufacture, Faculty of Engineering,
University of Malaya, Kuala Lumpur 50603, Malaysia

art ic l e i nf o a b s t r a c t

Article history: Hydroxyapatite (HA) has been used in clinical bone graft procedures for the past 25 years. Although a
Accepted 17 July 2013 biocompatible material, its poor adhesion strength to substrate makes it unsuitable for major load-
Available online 7 October 2013 bearing devices. Investigations on various deposition techniques of HA coating on Ti–6Al–4V implants
Keywords: have been made over the years, in particular to improve its adhesion strength to the metal alloy and its
Adhesion long-term reliability. This review comprehensively analyzes nine techniques mostly used for deposition
Hydroxyapatite of HA onto Ti–6Al–4V alloys. The techniques reviewed are Plasma sprayed deposition, Hot Isostatic
Coating Pressing, Thermal Spray, Dip coating, Pulsed Laser deposition (PLD), Electrophoretic deposition (EPD),
Ti–6Al–4V implant Sol–Gel, Ion Beam Assisted deposition (IBAD), and Sputtering. The advantages and disadvantages of each
method over other techniques are discussed. The adhesion strength and the factors affecting the
adhesion of HA coating on Ti–6Al–4V implants are also compared.
& 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Biological fixation is defined as the process where prosthetic
components become firmly bonded to the host bone by ongrowth
or ingrowth without the use of bone cements [1–3]. In the late
1960s, the concept of biological fixation of load-bearing implants
using bioactive hydroxyapatite (HA) coatings was proposed as an
alternative to cemented fixation. Hydroxyapatite (HA: Ca10(PO4)6
(OH)2), a pure calcium phosphate phase, is a preferred biomaterial
for both dental and orthopedics use due to its favorable osteo-
conductive and bioactive properties [4,5]. HA has a similar
chemical composition and crystal structure as the apatite in the
human skeletal system, and is therefore suitable for bone sub-
stitution and reconstruction [6]. Furthermore, HA has shown
significant success in implants due to its favorable in vivo behavior
[7,8] and the presence of HA films prolongs the lifetime of
prostheses [9]. However, HA coatings are susceptible to fatigue
failure, making it unsuitable for load bearing implants [10,11].
Nevertheless, there is a large demand for implants with
excellent mechanical properties. These implants should possess
similar properties to the human bones, such as in the value of its
Young's modulus, which result in less stress shielding effect [12]
and extends its service life. The implants can be made into
n
Corresponding author. Tel.: þ +603 7967 5239; fax: þ60379675330.
E-mail addresses: ehsanmohseni2008@gmail.com (E. Mohseni),
e.zalnezhad@gmail.com (E. Zalnezhad), bushroa@um.edu.my (A.R. Bushroa).
different shapes such as plates, rods, screws and pins [13].
Historically, titanium-based alloys are the most common material
for this purpose since it is known to be a tolerable metal in the
human body [14].
Titanium (Ti) and its alloys are the most commonly used
metallic materials for medical implants in orthopedic and dental
applications, due to their low density, high strength, non-toxicity
and excellent corrosion resistance [15]. However, there have been
reports on inflammatory reaction around these implants as a
result from the creation of an avascular fibrous tissue that
encapsulated the implants [16,17]. A coating of hydroxyapatite
layer can be deposited on the metal alloy to assist the osseointe-
gration of these implants with surrounding tissues [16].
The bond strength between the coating layer and the metal
substrate is a very critical factor. Separation of the coating layer
from the implant during service in the human body results in
adverse effects on the implants and the surrounding tissue caused
by detached particles [18]. The main reason of using HA coating on
metallic substrates is to keep the mechanical properties of the
metal such as load-bearing ability and, at the same time, to take
advantage of the coating's chemical similarity and biocompatibil-
ity with the bone [19].
According to Blind et al. the HA coating allows rapid osteointe-
gration as a result of bone tissue bonding properties [20]. The first
clinical results from HA coatings on titanium dental implants were
promising, showing excellent results, even with poor bone quality.
However, after a long period, mechanical failure would occur at
the interface of HA and metallic substrate [21]. The HA coating

0143-7496/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijadhadh.2013.09.030
 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257
dissolves as a result of poor crystallized structure [22,23], decrease
of adherence with the titanium surface and dramatic late implant
failure [23,24]. Moreover, HA itself has poor mechanical proper-
ties, with a bending strength of less than 100 MPa [25]. Thus, it can
be concluded that the stability of the HA coating is the most
critical factor to ensure the success of this type of implant.
Furthermore, the method used to deposit HA powder onto the
substrate could influence the coating characteristics such as its
adhesion strength and reliability.
Several techniques have been used to create the HA coating on
metallic implants, such as plasma spraying process [26], thermal
spraying [27], sputter coating [28], pulsed laser ablation [29],
dynamic mixing [30], dip coating [31], sol–gel [32], electrophoretic
deposition [33], biomimetic coating [34], ion-beam-assisted-
deposition [35], and hot isostatic pressing [36]. Amongst the
techniques listed, plasma spraying is the only process which is
approved by the Food and Drug Administration (FDA), USA for
biomedical coatings due to its excellent coating properties as
compared to other coating processes [37]. However, plasma
sprayed hydroxyapatite coatings suffer from poor mechanical
properties on tensile strength, wear resistance, hardness, tough-
ness and fatigue. Improvements in plasma spraying techniques
over the years have addressed many of these limitations. However,
other coating methods are available which can be used as an
alternative to conventional techniques.
Limitations such as high porosity, poor uniformity in thickness,
phase impurity, limited crystallinity, and poor adhesion are com-
mon in HA coating. However, low coating adhesion seems to be
the major issue, limiting its extensive use for implants at a
commercial scale [38–40]. Hence, improvement of bonding
strength between the metallic substrate and ceramic coating is a
general requirement regardless of the techniques used.
This review focuses on adhesion strengths between HA coating
and Ti–6Al–4V substrate, fabricated using various techniques such
as plasma sprayed deposition, hot isostatic pressing, thermal
spray, dip coating, pulsed laser deposition (PLD), electrophoretic
deposition (EPD), sol–gel, and ion beam assisted deposition (IBAD).
Parameters affecting the adhesion of coating and other factors
influencing the enhancement of bonding strength of coating sur-
face and the substrate are also discussed in detail.
2. Coating techniques
2.1. Plasma sprayed coating technique
Plasma spraying process involves melting of ceramics or metal
powders using the heat of ionized inert gas (plasma). The molten
powders are then sprayed onto the surface to be coated, forming
the protective layer which provides a barrier against corrosion,
wear or high temperatures. The technique offers advantages such
as low cost and rapid deposition rate [41,42]. In addition, the risk
of thermal degradation of the coating and substrate is much less
than other high-temperature processes since the gas in the plasma
flame is chemically inert and the target can be kept relatively cool
[43]. However, plasma sprayed coatings suffers from poor adhe-
sion between the coatings and substrates [44], and the process
may induce structural changes in the microstructure of the coating
material [45,46].
2.1.1. Plasma sprayed hydroxyapatite (HA) coatings
Plasma spray was the first method used for the production of
calcium phosphate coatings, such as HA coating, due to its ease of
application [26]. Plasma sprayed hydroxyapatite (HA) coatings are
biocompatible and able to bond directly to the bone [38], thus making
plasma spraying a favorable choice amongst the many techniques
239
available for coating HA layers onto metallic substrates [47]. Recent
studies on plasma sprayed HA coatings (HACs) on titanium have
shown encouraging results in orthopedic implant applications. These
studies reported that the new bone could appose directly onto the HA
coatings and very good adhesion between the HACs and the new bone
can be obtained [48–51]. The plasma sprayed HA coatings have also
assisted in overall quick bone recovery [52].
Nevertheless, the brittle nature of the HA coating makes it
prone to crack and fracture, non-uniformity in density of coating
[53], wear of the coated layer, weak mechanical adhesion to the
substrate [44,54], and alteration of structure [55].
Overall, plasma sprayed coating did not show significant
improved long-life performance, better mechanical integrity and
reliability over uncoated implants [56,57]. An alternative to plasma
spraying is the pulsed laser deposition (PLD) which enables the
stoichiometric transfer of sintered HA yields to form a thin and
adherent bioactive coating on titanium substrate surface [58].
2.1.2. Adhesion of plasma-sprayed hydroxyapatite (HA) coatings on
Ti–6Al–4V
It is well understood that, the determination of the adhesion
between the substrate and coating is one of the main concerns
when using plasma spraying techniques [59]. It is quite compli-
cated that how coating adheres to a substrate and by today it is not
completely understood. Many theories describe the mechanism of
adhesion, although, there is no single clear interpretation for all
adhesion behaviors [60]. Many factors seem to affect the adhesion:
(1) Van der Waals physical interaction forces mechanical ancho-
rage; (2) mechanical anchorage; (3) metallurgical processes and
(4) chemical interaction [59].
Recent reports on alternative orthopedics implant fixation
utilizing plasma sprayed HA coatings (HACs) on Ti–6Al–4V have
shown that the new bone was able to appose directly onto the HA
coatings, which resulted in a very good adhesion between the
HACs and the new bone [48–51]. From the viewpoint of materials
science, characteristics of HACs are varied with the spraying
parameters such as phase composition, the microstructure, OH-
ion content, crystallinity, and the ration of calcium to phosphorus
for the HACs. Among these parameters, high bonding strength of
HACs can be achieved by high spraying power due to a denser
microstructure caused by the greatest extent of coating melting.
Yang et al. experimented on six plasma sprayed HA on Ti–
6Al–4V substrates by varying the cooling conditions and the
substrate temperatures [61]. The residual stresses and bonding
strengths were measured by XRD “sin2 φ” technique and a
standard adhesion test (ASTM C-633). Results of the bonding
strength evaluation shows that the HA coating with the lowest
residual stress exhibited a higher bonding strength (9.18 7
0.72 MPa).
The deposition stress and thermal stress are the two major
sources of residual stresses in plasma sprayed coating. Deposition
stresses are produced during the cooling of sprayed particles after
solidification. Thermal stresses are generated from differential
thermal contraction during the post-fabrication cooling phase
after coating [62,63]. The residual stresses are present near the
interface of metal substrate and coating [64–66], due to the
difference of thermal expansion coefficients between both materi-
als [62,63]. These stresses may vary with substrate cooling effects,
parameters of spraying [62,63], and coating thickness [67,68].
Generally, it is believed that the increased thickness of coating
and the temperature of the specimen during plasma spraying are
the main reasons for the rise in the residual stress.
In addition, high-powered, dense plasma sprayed HA coatings
would have stronger bonding strength than those sprayed using
low power. The result is not solely due to the difference in
240 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257
adhesive strength of HA coating. The value for bonding strength
reflects the combination of both cohesive (within the coating
layers) and adhesive (coating to substrate) strengths of a coating
[61]. In a similar study, Tsui et al. claimed that the cohesive and
adhesive integrity of the coatings influence the long term perfor-
mance of HA coated implants considerably [69]. The adhesive
strength is usually evaluated based on surface roughness, coating
properties, residual stress, and the mechanical interlocking
between the coating and the substrates, whereas the cohesive
strength is determined by coating properties, such as microstruc-
ture and crystallinity [61].
The bonding strength of HA coatings on metallic substrates can
be evaluated using several techniques such as the standard tensile
adhesion test [69], interfacial indentation test [58], tensile adhe-
sion strength (TAS) [61], and indentation method [63]. However,
there are limitations on these techniques to accurately measure
the adhesion strength, such as a probability of penetration of glue
into the coating layer, and a dependence of coating failure to the
flaw distribution at the edge of specimen [69]. However, Moham-
madi et al. have demonstrated that the tensile adhesion strength
test measured by the standard adhesion test ISO 13779-4, can be
used in conjunction with the interface indentation test to predict
the effects of different parameters on the adhesion properties of
the HA coating by plasma spraying [70]. In general, the HA
coatings with the densest structure (i.e. lowest porosity, and
predominantly amorphous phase) have a higher tensile adhesion
strength than those of lower density [61,71]. The report by
Mohammadi et al. [70] also showed that the tensile adhesion
strength was in the range of  25 MPa for HA coated on the
Ti–6Al–4V.
2.2. Hot isostatic pressing technique
Hot isostatic pressing (HIP) is an enabling technology providing
an efficient method for the densification of ceramic powders
which allows production of net-shape ceramics with superior
and consistent properties [72]. HIP is an alternative method of
producing an HA coating on a Ti substrate in which pressurized
gas is used to exert the required load at the desired temperature.
This requires a gas-tight metal or glass encapsulation around the
porous HA coated implant [73]. In the HIP process, pressure and
temperature are applied to the workpiece simultaneously [74–77].
In hot isostatic pressing, high-pressure levels can be obtained
since there is no dependency on rigid tools with limited strength
(such as graphite tools in uniaxial hot pressing) to transmit the
pressure to the body. Typical operating pressure ranges are
100–320 MPa (15–50 ksi), with temperatures exceeding above
2000 1C conducted in large industrial equipment [72]. The advan-
tages of HIP are better temperature control as compared to
uniaxial hot pressing, and a resultant homogeneous material
structure and properties. The reduced sintering temperature
enables control or even avoidance of grain growth and undesirable
reactions. A very high uniformity of properties as well as freedom
from directionality can also, if desired, be obtained [72]. Some
researchers have used HIP treatments to densify plasma sprayed
coatings, and results have shown that HIP is useful in reducing the
porosity and improving the physical and mechanical properties of
ceramic coatings [78].
Thus, the most important advantage of the hot isostatic press-
ing is the ability to control the size and shape of the product to a
very high precision without costly diamond machining operations.
Under ideal conditions no change of shape (just a change of scale)
of the body occurs. It has an inherent ability to produce parts with
exceptionally accurate shape, virtually with no dimensional or
shape limitation [72].
2.2.1. Hot isostatic pressing of hydroxyapatite (HA) coatings
Reports shows that, sort of problems such as porosity and crack
appearance are conducted with existing dc plasma sprayed Ha
coating on Ti–6Al–4V [79]. In medical applications some amount
of porosity is needed for bony tissue to grow into the coating for
efficient fixation. In addition, the crack propagation needs to be
healed for the composite coating to have reasonable mechanical
strength during usage. In this sense, HIP introduces its profound
advantages by improving the adhesion and physical properties of
the plasma sprayed HA coatings as a post- treatment [79].
2.2.2. Adhesion of hot isostatic pressing of hydroxyapatite (HA)
coatings on Ti–6Al–4V
Khor et al. [79] investigated the effect of post-sprayed HIP on
plasma sprayed HA on Ti–6Al–4V. Fig. 1 shows the bond strengths
of HA coated Ti–6Al–4V for the plasma sprayed samples, and after
HIP treatment at different temperatures with respect to the coat-
ing thickness. In general, it was shown that the bonding strength
generally improves after HIP. It is also shown that the adhesion
strength decreases with increasing coating thickness. The
enhancement of the adhesion strength in the 20 wt% HA coating
after HIP is apparent for coating below 160 μm. However, the
result of adhesion strengths for coatings thicker than 160 μm
show that HIP may have adverse effects on the coating strengths.
2.3. Thermal spray coating technique
Thermal spray technology is a group of coating processes that
provide functional surfaces to protect or improve the performance
of a substrate or component. Many types and forms of materials
can be thermal sprayed to provide protection from corrosion,
wear, and heat; to restore and repair components; and for a variety
of other applications [80]. Thermal spraying of biomedical coating
is a relatively new class of applications for thermal spray coating as
compared with other industrial applications, [81]. Thermal spray
processes are grouped into three major categories: flame spray,
electrical arc spray, and plasma arc spray. These energy sources are
used to heat the coating material (in powder, wire, or rod form) to
a molten and semi-molten state. The resultant heated particles are
accelerated and propelled towards a prepared surface by either
process gases or atomization jets. A schematic diagram of thermal
spray coating is illustrated in Fig. 2.
Fig. 1. Tensile bond strength result of plasma sprayed Ti–6Al–4V/20 wt% hydro-
xyapatite coating (as sprayed and HIPed) [79].
 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257
2.3.1. Thermal spray deposition of hydroxyapatite (HA) coatings
Thermal spraying of HAP on implant devices can be compared
with plasma spray coating technique, having the advantage of high
deposition rate and low cost [82,83]. Thermal spray technique has
the ability to produce HA layer with thickness from 30 to 200 mm
depending on the coating condition However films deposited by
thermal spraying suffers from poor coating–substrate adherence
and non-uniform crystallinity which reduces the lifetime of
implants [84,85]. In addition, thermal spray requires high sintering
temperature which may result in crack propagation on the surface
of the coating [86–90].
2.3.2. Adhesion of thermal spray deposition of hydroxyapatite (HA)
coatings on Ti–6Al–4V
Hsiung et al. [91] have evaluated the applications and char-
acterizations of biological coating such as hydroxyapatite on
titanium alloy, particularly Ti–6Al–4V, in artificial knee joint by
thermal spray coating technology. The process involves melting of
HA powder and guiding the molten mass via a jet stream of air to
form a coating on the substrate, as shown in Fig. 3. The thermal
spray process conditions of the three coating materials are shown
in Table 1, highlighting the important parameters affecting the
quality of the coating, such as inert gas compositions, currents,
voltage levels, powder feeding rates, and spraying distances.
Fig. 2. A schematic diagram of thermal spray coating [82].
Fig. 3. Fundamental stages of dip coating (the finer arrows indicate the flow of air) [94].
Table 1
Thermal spray condition of HA powders [92].
Parameters Argon (l/min) Helium (l/min) Current Voltage Powder rate (g/min) Spray distance (mm) Surface speed (m/min) Travers speed (mm) Cooling
Setting 41 60 700 52
241
The tensile test is commonly used to evaluate the bond
strength in accordance to ASTM C-633 standard method [92].
A bonding strength of 33.2 MPa was obtained by Hsiung et al. [91]
for the HA coating on Ti–6Al–4V by thermal spraying technique. In
comparison, this result is not satisfactory when compared to other
coatings for the same application such as Al2O3, ZrO2. In addition,
results of microstructure analysis shows that the HA coatings
suffers from spalling, interface separation and high levels of
porosity.
Several pre and post-treatments of HA coating were also
investigated by Hsiung et al. [91]. Treatment conditions include
high pressure cleaning, ultrasonic cleaning and cryogenic treat-
ments [92]. Table 2 shows the result of the bond strength test
using ASTM C-633 [93], indicating the bond strengths of samples
cleaned with high pressure air are lower as compared with those
ultrasonically cleaned, and the bond strengths with cryogenic
treatments are better than those without cryogenic treatments.
The result shows that the inclusion of ultrasonic cleaning
and cryogenic treatments can effectively improve the coating
properties.
2.4. Dip coating technique
Dip coating involves the deposition of a wet liquid film by
withdrawal of a substrate from a liquid coating medium. The
complete process of film formation involves several stages, as
shown in Fig. 3. The process starts by immersion of the substrate
in the solution of the coating material. When the substrate is
withdrawn from the coating fluid, a coherent liquid film is
entrained on the surface of the substrate. A thin layer of coating
is formed upon evaporations of solvents and any accompanying
chemical reactions in the liquid film. Normally an additional post-
treatment such as curing or sintering is required to obtain the final
coating. Dip coating technique is similar to sol–gel coating tech-
nique, although the process is significantly faster in which a
complete transition can be achieved within a few seconds if
volatile solvents are used [94]. Dip coating is fairly popular in
the industry and in laboratory applications due to its low cost,
simple processing steps and high coating quality.
2.4.1. Dip coating of hydroxyapatite (HA) coatings
HA can be homogenously coated onto metal substrates to
obtain coating thickness in the range of 0.05–0.5 mm. The surface
uniformity of HA can be controlled well using this technique, as
can be seen in Fig. 4. In addition, the processing time for dip
coating can be very short, even for substrate with complex shapes.
The coating layer is deposited on the surface of the substrate
without decomposition or reaction with the metal substrate.
Table 2
Bond strength test results with different pretreatment and cryogenic treatment
[92].
Coating Bonding strength ( MPa)
Without cryogenic treatment With cryogenic treatment
Ultrasonic High pressure air Ultrasonic High pressure air
HA 26.56 18.91 36.65 29.30
30 115 75 8 yes
242 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257
Fig. 4. SEM micrographs from cross-sectional view of HA coatings (via SOL 2) on
Ti–6Al–4Vsubstrates after heating at 840 1C [96].
However, this technique requires high sintering post-treatments
which may induce crack formations on the surface of the substrate
[95].
2.4.2. Adhesion of dip coating of hydroxyapatite (HA) coatings on
Ti–6Al–4V
Mavis et al. [96] had developed several compositions of the
liquid coating medium for the dip coating of HA on Ti–6Al–4V
substrates, using chemically precipitated hydroxyapatite precursor
powders. To evaluate the adhesion strength, two steel cylinders
5 mm in diameter were attached to both sides (coated and
uncoated after the coating layer was ground off) of the dipped
strips by a thin layer of glue. The adhesive strengths were
determined by measuring the tensile stress needed to separate
the cylinders from the strips [97]. It is reported that, the HA
coatings obtained were highly porous, with bonding strengths of
more than 30 MPa.
2.5. Pulsed laser deposited coating technique
Laser processing is a rapid and clean process which can be used
for surface modification and controlled micro-structuring of
materials. In biomedical applications, laser has been used to
modify the surface texture of materials to improve its bio-
functionality [98–102]. Pulsed laser deposition (PLD) technique
can be used to grow ceramic thin films. By using appropriate laser,
thin films such as semiconductor films [103], cuprate supercon-
ductor films [103,104], and ferroelectric films [105] can be depos-
ited onto substrates. PLD process involves using high power laser
energy to vaporize the bulk coating material from a target. The
vaporized material is ejected from the target and condenses on the
substrate. Repeated laser pulses will result in the deposition of the
thin film as a coating on the substrate [106].
The formation of thin film by PLS can be separated into the
following three stages [103,107,108]:
1. Laser radiation interaction with the target.
2. Dynamic ablation of the materials.
3. Deposition of the ablation materials with the substrate, nuclea-
tion and growth of a thin film on the substrate surface.
One of the main advantages of PLD technique is the ability to
retain the stoichiometry of the target in the deposition films [107].
This is due to the high ablation rate which causes all compounds
or elements to evaporate at the same time [106]. Conversely,
limitations of PLD include the splashing of the particulates
deposition on the film. Some methods have been developed to
decrease splashing problem since it is a major issues of the PLD
[109]. One method is to apply a mechanical particle filter that
includes a velocity selector acting as a high-velocity pass filter to
eliminate slow-moving particulate. The second method is using a
smooth, high-density target which can be obtained by polishing
the target surface before each coating run. The third method is by
applying a lower deposition rate or low energy density. Further-
more, the deposited films have only a small area of structural and
thickness uniformity, due to the angular distribution of the
ablation plume. Several methods have been proposed to scale up
the PLD process for large area thin films, such as laser beam
rasterizing across a rotating target [106].
High quality hydroxyapatite thin films deposited by the PLD
was first reported in 1992 [105,110] and since then the process
have been improved significantly to obtained well adhered and
highly crystalline HA thin films under certain conditions [29,111–
113].
2.5.1. Pulsed laser deposited hydroxyapatite (HA) coatings
Preparing hydroxyapatite thin films by pulsed laser deposition
allows accurate control of hydroxyapatite growth parameters at
low deposition temperatures and the ability to produce highly
crystalline HA coatings [16,112]. In-vitro evaluations shows that
these HA coatings are stable and osteoinductive [114,115]. Nanos-
tructured hydroxyapatite layer having unique biological properties
can be obtained by selection of suitable parameters for the
deposition process [16].
2.5.2. Adhesion of pulsed laser deposited hydroxyapatite (HA)
coatings on Ti–6Al–4V
Adhesion strength of HA coating on metals depends on the
microstructure of the substrate, the surface chemistry and the PLD
process parameters such as laser power density and substrate
temperature. [58,116–118]. Various surface modification techni-
ques have been used to improve the metal–ceramic interface such
as nitridation, surface oxidation and ion implantation [119–123].
Blind et al. reported that adhesion of pulsed laser deposited HA
films on titanium alloy is due to the existence of an oxide,
specifically titanium dioxide, at the interface between the sub-
strate and the coating layer [20]. Another report suggests that
there may be some effects of epitaxy between the oxide and
coating [124]. Fernández-Pradas et al. [54] commented whether
the presence of a titanium oxide interface would favor adhesion of
the HA coating to the Ti–6Al–4V substrate is still a cause for
debate. Some authors consider that such a layer favours adhesion
[125,126]. Other studies have attributed the weak adhesion in the
first calcium phosphate coatings deposited by PLD at high tem-
peratures to the formation of a titanium oxide layer during the
process of pressure stabilization [105]. A study of the adhesion
strength in coatings deposited by ion bombardment on passivated
and non-passivated substrates, suggest that this oxide layer should
be as thin as possible [127].
Koch et al. [16] investigated pulsed laser deposition of hydro-
xyapatite on Ti–6Al–4V for medical and dental applications.
A pull-off testing method was used to determine the coating-to-
substrate adhesion strength. Garcia-Sanz et al. had also examined
hydroxyapatite films prepared using pulsed laser deposition using
a pull-off test based upon a modified ASTM C-633 procedure [128].
The measured tensile strength of hydroxyapatite grown at 480 1C
was 58 MPa and failure was observed at the coating–substrate
interface. Wang et al. obtained tensile bonding strength values
within the range of 30 MPa and 40 MPa for hydroxyapatite
 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257 243

coatings grown on Ti–6Al–4V in an argon–water atmosphere at

500–600 1C [129]. Zeng et al. determined the bond strength values
for hydroxyapatite films grown using 3rd harmonic YAG:Nd lasers
(λ ¼ 355 nm), and 4th harmonic YAG:Nd lasers (λ ¼ 266 nm) on
Ti–6Al–4V substrates in an argon–water atmosphere at 500–
520 1C [116]. Films grown on unpolished titanium substrates had
tensile strength values of  30 MPa while films grown on polished
titanium possess lower tensile strength values of  20 MPa.
In a study to enhance the bonding strength of HA, Nelea et al.
[110] utilized a TiN interfacial layer between the Ti–6Al–4V
substrate and HA coating. The study reported that the adhesion
was improved due to better bonding of HA to TiN, which is a
ceramic, and then to the surface of metallic substrate. Man et al.
[40] and Chen et al. [130] described the utilization of a pre-
treatment process which included etching and laser surface
nitriding on titanium to produce a TiN dendritic scaffold network
structure. This coralline-like structure provides additional surface
area for interlocking of the coating material. Fig. 6. Average surface roughness of titanium substrates treated with different
Man et al. [119] reported the influence of pre-treatments on the laser pulses and HA coating compared with control sample [132].
adhesion of the HA coating to the substrate. Five types of pre-
treatments, shown in Fig. 5 were: (i) mirror finished specimen, (ii)
60 grit grinded SiC paper (specimen 2), (iii) 320 grit grinded SiC
paper (specimen 3), (iv) mirror finish with 1-μm diamond paste
(specimen 1), and (v) 10 s etching with Knoll solution after
polishing (specimen 4). The surface roughness of the specimens
were determined using a profilometer (Taylor Hobson Surtronic
25) and the adhesion strengths between HA coatings and the
substrates were evaluated in accordance to ASTM C-633 [131]. The
maximum adhesion strength obtained was  16 MPa for specimen
5 (nitrided þ etching).
Fig. 5 shows the adhesion strength of deposited HA on different
pre-treated specimens and surface roughness. Generally, an
increase in surface roughness increases the adhesion strength.
Based on these results, it can be concluded that significant
enhancement in the adhesion strength of pulsed laser deposited
HA on Ti–6Al–4V can be obtained by laser surface nitriding and
subsequent etching [119].
A related study has concluded that a controlled surface micro-
structure can be obtained by using few laser pulses without
affecting the bulk mechanical property of titanium substrate Fig. 7. Failure values obtained by scratch test (Lc1, Lc2 and Lc3) for the HA coatings
on different irradiated and non-irradiated titanium substrate [132].
[132]. Fig. 6 plots the average surface roughness values, measured
after laser treatment and after HA coating versus their initial
roughness. micro-scratch tester (micro-combi tester; CSM Instrument Swit-
Fig. 7 compares the adhesion strengths of HA coating on zerland) equipped with a diamond Rockwell tip of 100 μm [132].
substrates treated with 500–18,000 laser pulses with those of It was found that in all cases, the laser treated substrates would
untreated, polished titanium. The adhesion of HA to the substrate have higher bonding strengths, which imply that the surface
is examined in accordance to ISO 20502:2005(E) [133] using a roughness directly influences the adhesion strength. Varying the
laser pulses would affect the surface morphology. Fig. 6 shows that
the roughness increases with the increase in the number of laser
pulses, which starts from 0.4 μm at 500 laser pulses/min up
to  1 μm at 12,000 pulses/min. However, there is a significant
decrease in the roughness value for laser pulses in the range of
12,000–18,000 laser pulses/min. Low rate of laser pulses (500,
1000, and 3000 pulse/min) would only etch the surface and may
not be able to control the surface roughness. The surface rough-
ness is under control only after  3000 pulses/min. A surface with
controlled structure/pattern is obtained using 18,000 pulses [132].
The polished surface of specimen does not have much adhesion
strength to the coating. However, once the surface is treated with
laser, the surface roughness increases which results in increased
adhesion (from 0 to 1000 pulses/min) due to the initial material
removal from the surface. However, at this stage, certain regions
are unaffected by the laser and a control over the adhesion at this
stage is not predictable. Once the laser pulses reaches  3000
Fig. 5. Comparison of adhesion strength for HA on substrates with different pre- pulses/min, the surface attains a certain level of smoothness since
treatments [119]. the large, number of pulses would completely remove the original
244 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257
top surface to uncover a fresh coating surface. Therefore, the
morphology and adhesion can be controlled by the number of
laser pulses (3000–18,000) [132]. Fig. 7 shows the trend of
adhesion strength versus number of laser pulse, showing that
the adhesion strength would gradually increase until 1000 pulse/
min, then decreases in between 1000 and 3000 pulse/min, and
increases again past 3000 pulse/min. The highest adhesion
strength obtained was 10.87 N and 11.21 N at 2000 and 18,000
laser pulses respectively, while untreated substrate showed a
lower adhesion strength value of 4.57 N [132].
HA coatings by PLD exhibit good biocompatible and mechanical
properties making it suitable for medical implants. PLD HA coat-
ings, on titanium alloy such as Ti–6Al–4V, resulted in higher
adhesion between the coating and substrate and have only minor
undesirable phase under optimal conditions [54,106].
2.6. Electrophoretic deposition coating technique
Electrophoretic deposition (EPD) is a process in which particles
in a suspension is coated onto an electrode under the effect of an
electric field [134]. The colloidal particles suspended in a liquid
medium migrate under the influence of an electric field (electro-
phoresis) and are then deposited onto an electrode. Electrophore-
tic deposition (EPD) is particularly advantageous for ceramic film
and coatings as well as laminar ceramic composites applications
[134–137]. Furthermore, the method used low-cost equipment,
easy to set-up, and is able to coat complex shapes and patterns.
A high degree of control on the coating results can be achieved by
regulating the deposition conditions and the ceramic powder size
and shape [138]. EPD is a cheaper method than chemical vapor
deposition, sol–gel deposition, and sputtering for producing films
of a wide range of thickness, from less than 1 mm to more than
100 mm thick [139]. However, limitations of the technique includes
low adhesion strength, and cracking on the coated surface due to
post-process shrinkage.
EPD has shown its potential use in biomedical applications in
recent years [140–142]. The interest in electrophoresis for biome-
dical applications [143–147] stems from a variety of reasons such
as the possibility of stoichiometric deposition, high purity material
to a degree not easily achievable by other processing techniques
and the possibility of forming coatings and bodies of complex
shape [140]. Considering all advantages and disadvantages of this
technique, electrophoretic deposition is one of the favorable coat-
ing techniques which can be utilized for hydroxyapatite coating.
2.6.1. Electrophoretic deposition hydroxyapatite (HA) coatings
There is a growing interest in processing of HA powders using
EPD technique, owing to its uniformity and good sinterability of
the deposits, possibility of impregnation of porous substrates, and
composite consolidation [142,148]. However, reports on the use of
EPD for depositing HA on titanium substrate are thus far, relatively
limited. Nie et al. [149] and Soares et al. [150] have used EPD to
deposit HA on Ti–6Al–4V substrates and have obtained uniform
thin coating with good mechanical strength. Stoch et al. [146] have
also coated HA on titanium implants with intermediate layer of
silica. EPD process of HA is a colloidal process where HA powders
are deposited directly from a stable colloid suspension by using a
DC electric field [25].
Electrophoretic deposition of HA can be processed at room
temperature or lower, which avoids problems related to formation
of amorphous phases. The nature of the bond is more metallurgi-
cal rather than mechanical, thus HA coatings using EPD are
expected to have improved adhesion strength as compared to
thermal sprayed techniques. However, a major drawback is the
presence of porosities which may later on leads to corrosion and
delamination of the titanium caused by penetration of body fluids
into the substrate. Post-treatment high temperature sintering can
be utilized to minimize the porosity by increasing the coating
density. Unfortunately, cracks in the coating can form during high
temperature sintering due to the difference in the thermal expan-
sion coefficients and large reduction of the pore volume between
the titanium and HA [151].
For nanostructured materials, the mismatch in thermal expan-
sion coefficient is not a significant problem [152]. In nano-
ceramics, the thermal expansion coefficient is fairly matched with
the metal alloy because the large quantity of atoms located at the
grain boundary improves mobility [152–154]. However, the suc-
cess of electrophoretic deposited HA has been limited to conven-
tional materials in the range of micron-sized grains [134,140,154].
Limitations on the mechanical properties of the micron size HA are
poor fracture toughness, adhesion, and compressive strengths.
There is a need for the HA coating and the substrate to have
sufficient interfacial bond strength since the coating would endure
high interfacial stresses during in vivo service.
2.6.2. Adhesion of electrophoretic deposited hydroxyapatite (HA)
coatings on Ti–6Al–4V
Zhang et al. [151] have developed a unique room temperature
EPD process to deposit nanostructured HA coating having adhe-
sion strength of 50–60 MPa, which is 2–3 times better than
thermal-sprayed HA coating. The interfacial bond strength was
measured in accordance to ASTM Standard F 1501-95 using a
tensile tester [151]. The corrosion resistance of this nanostructured
HA is 50–100 times higher than conventional HA coating. Fig. 8
shows the corrosion resistance results for both EPD coatings and
thermal sprayed coatings, where the corrosion current of n-HA
coating is 50–100 times smaller than the thermal sprayed coating
in simulated human body fluid at room temperature.
High quality HA nano-coating can be produced using EPD
technique. The adhesion stress obtained was 60 MPa, measured
using a direct-pull-tests, which exceeds the 50 MPa requirements
of the food and drug administration (FDA) [155]. A 2 months
in vitro testing also showed that the bonding strength of the EPD
n-HA coating on the titanium alloy was able to be maintained in
the range of 50–60 MPa, which is significantly better than plasma
sprayed HA coatings [151].
Ma et al. [139] reported that HA particles were successfully
deposited onto a titanium substrate via a single electrophoretic
deposition. Good adhesion between the coating and substrate was
verified by scanning electron miscopy examination and shear
Fig. 8. Electro-polarization corrosion curves for both EPD n-HA coating and HA
thermal sprayed coating [151].
 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257
strength tests, following methods outlined by Wei et al. [148] and
ASTM standard F1044-87. The shear stress of the HA coating after
sintering at 1000 1C was 3.34 MPa, indicating a good adhesion of
the coating has been obtained. Figs. 9 and 10 show SEM micro-
graphs of the cross-section and the surface deposit of the 1000 1C
sintered HA coating, respectively. It can be seen that a layer of HA
coating as thick as 400 mm has adhered well into titanium
substrate and no delamination or crack was observed at both the
interface and the surface. The deposition was found to be uniform
with the coating thickness maintained consistently along the
surface of the sample. No observable crack, which is one of the
common problems of EPD, was detected. It is believed that the
good deposition result is due to the stable and dispersed HA
suspension used for the deposition [148].
Studies on EPD coating of HA on titanium alloys show that
particle size is an important factor for the process as the mobility
of the charged particles is proportional to the size of the particles
[156]. Ferrari et al. [157] have also reported that the charges, hence
the conductivity of the suspension, play an essential role and has an
optimum value for the process. Nevertheless, the colloidal stability of
the suspension could also be a main factor to obtain good coating
uniformity and bonding strength in the EPD process [142].
Like many similar techniques for coatings involving ceramics,
EPD coating of HA requires a densification stage involving the
sintering of the coated implants. This requirement poses a
Fig. 9. Cross section SEM micrograph of the EPD deposited under the identified
optimum suspension condition [140].
Fig. 10. SEM micrograph of the uncrack deposit surface [140].
245
Table 3
Adhesion strengths of HA coated samples with and without TiO2 inner layer
deposited using different voltages [160].
Samples (substrateþ inner layer þHa) Shear strength (MPa)
Ti–6Al–4V þ ⋯ þHA 13.8 (s ¼1.8)
Ti–6Al–4V þ TiO2 (50 V) þ HA 11.9 (s ¼1.8)
Ti–6Al–4V þTiO2 (20 V) þHA 13.1 (s ¼1.8)
Ti–6Al–4V þTiO2 (10 V) þ HA 21.0 (s ¼1.8)
s: standard deviation.
dilemma, especially since high sintering temperature is sometime
necessary. Low sintering temperatures results in weak bond with
low-density coatings whereas high sintering temperatures can
lead to the degradation of the HA and the metal substrate
(oxidation and impaired mechanical properties) as a result of the
metal substrate catalyzing decomposition of the HA to anhydrous
calcium phosphates [158,159].
A high sintering temperature may also lead to phase transfor-
mation and grain growth of the metal substrate, causing signifi-
cant decrease in mechanical properties. It has been demonstrated
that the mechanical properties of these titanium alloys degrade
significantly when heated above 1050 1C [138]. Therefore, it is
recommended to keep the densification temperatures below
1000 1C to minimize degradation of the HA and the metal
substrate.
The sintering phase for EPD implants improves densification
and the bonding of the coating. However, HA may decompose in
the process [160]. An interlayer can be used in between the HA
and the metal substrate to moderate the problem of HA decom-
position. Nie et al. deposited a dense layer of titanium dioxide
(TiO2) as the inner layer between HA top layer and titanium alloy
substrate to achieve a very good combination of mechanical
integrity, chemical stability and bioactivity [149].
Kumar and Wang [161] investigated the coating of TiO2 powders
on Ti–6Al–4V substrates as the first layer, followed by the HA–TiO2
composite layers of different weight ratios, coated onto the TiO2 layer.
Wei et al. [138] studied on the adhesion strength of HA coating in
which HA powders are used as both inner and outer layer. Hence, no
change occurred in the structure of coating layers. Sintering was also
applied after the deposition of every single layer. In the HA coating on
TiO2 deposited substrate, the decomposition of HA is decreased; and
generally adhesion of coating, which is tested according to ASTM
F1044-99, was enhanced with the reduction of voltage value used for
TiO2 coating [160]. Table 3 shows the result of adhesion strengths of
HA coated samples with and without TiO2 inner layer deposited using
different voltages.
2.7. Sol–gel derived coating technique
The sol–gel method is one of the simplest technique to
manufacture thin films which can produce almost any single or
multicomponent oxide coating on glass or metals [162,163].
Sol–gel derived coating can be used for optical, electronic, mag-
netic or coating with chemical functions [164]. Sol–gel derived
ceramic films are widely used as a protective layer against
corrosion and oxidation of stainless steel [165], Ag [166], and Al
[167] substrates. The sol–gel process involves the formation of
solid materials, mainly inorganic non-metallic materials from
solution. This can be a solution of monomeric, oligomeric, poly-
meric or colloidal precursors [168].
The sol–gel process, shown in Fig. 11 [169], consist of:
(i) producing a homogeneous solution of purified precursors in
an organic solvent which can be mixed with the reagent used in
the next step or water; (ii) shaping the solution to the ‘sol’ form by
using treatment with a suitable reagent, e.g. water for oxide
246 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257

Fig. 11. Steps in the sol–gel process for ceramic materials [169].

ceramics; (iii) changing the sol to a ‘gel’ by polycondensation; (iv)

converting the gel to the finally preferred shape like thin film,
fiber, and (v) finally converting( sintering) the shaped gel to the
desired ceramic material at temperatures (  500 1C) much lower
than those required in the conventional procedure of the melting
the oxides together [168,170–172].
Olding et al. [172], reports that sol–gel techniques has con-
siderable advantages such as:

1. Ability to produce thin bond-coating to provide excellent

adhesion between the metallic substrate and the top coat.
2. Corrosion resistance performance due to ability to form thick
coating.
3. Ability to shape materials even complex geometries in the
gel state.
4. Production of high purity samples.
5. Low temperature sintering, usually in the range of 200–600 1C Fig. 12. X-ray diffraction of sol–gel coatings preferred to 500 1C on titanium
[173]. substrates and then fired at various temperatures [179].
6. A simple, economic and effective method to produce high
quality coatings.

However, the sol–gel technique has disadvantages such as high

permeability, low wear-resistance, and difficult porosity control,
which has limited its utilization in the industry. For crack-free
coating, the maximum thickness of the coating is only 0.5 μm
[172]. Furthermore, trapped organics during the thermal process
would result in coating failure. Recent advancement in high
substrate sensitive sol–gel also suffers from thermal expansion
mismatch. Nevertheless, there is a wide room for improvement in
the technique and further investigation should be done to improve
this highly potential method for biomaterial coating.

2.7.1. Sol–gel derived hydroxyapatite (HA) coatings

The sol–gel is a low temperature process, thus does not suffer
from the implications of structural instability of hydroxyapatite at
elevated temperatures [174–177]. A major processing stage
involves solution chemistry, whereby a sol is produced from
suitable alkoxides or salts to yield a hydroxyapatite composition
upon heating [178].
Gross et al. [178] described that the production of sol–gel
hydroxyapatite coatings on titanium substrates using alkoxide
precursors requires more control on firing temperature and the
aging time. X-ray diffraction of the coatings heated to various Fig. 13. A scanning electron micrograph of a coating fired to 800 1C for 10 min, the
temperatures, as illustrated in Fig. 12, indicated that the titanium field of view is 250 nm  250 nm [179].
substrate would start to oxidize at temperatures starting at 800 1C.
Thus for sol–gel hydroxyapatite coating, it is suggested that the coating with an average grain size of 50 nm was achieved using
processing temperature should be around 800 1C to reduce possi- this technique. Fig. 13 shows a scanning electron micrograph of a
ble phase transformation in the metallic substrate as well as coating fired to 800 1C for 10 min. Densification of the coating can
the occurrence of oxidation. [178]. Nanograined hydroxyapatite then be obtained with a longer duration of firing at 800 1C.
 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257
Fabrication of sol–gel deposited HA on implants HA [173,
179,180] requires extremely stringent processing parameters,
particularly for the thermal processing phase such as the duration
and calcining temperature, chemical compositions of the precur-
sor, types of substrate, and number of HA-coated layers. Major
issues include the crystalline phases, adhesion strength and
biocompatibility of the resulted coatings.
2.7.2. Adhesion of sol–gel deposited hydroxyapatite (HA) coatings
on Ti–6Al–4V
Tests have shown that pure HA suffers relatively high dissolu-
tion rate in simulated body fluid that would affects its long-term
stability. High dissolution may lead to disintegration of the coat-
ings and hinder the fixation of implant to the host tissue [181,182].
To address this issue, Zhang et al. [183] incorporated fluorine ion,
which exists in human bone and enamel, into HA crystal struc-
tures. Mixing of fluorine into HA, or fluoridation, decreases the
solubility of HA while still maintaining its biocompatibility [184].
Zhang et al. [183] have successfully deposited dense, crack-free
fluoridated hydroxyapatite (FHA, Ca10(PO4)6(OH)2  xFx) coatings
(  1.5 μm) through sol–gel dip coating on Ti–6Al–4V substrates.
Scratch testing has shown an increase of over 35% in the adhesion
strengths of the coating to Ti-alloy. The increase in adhesion is
more prominent for high annealing temperatures. This increase is
most likely due to the formation of chemical bonding at the
interface and the incorporation of fluorine in HA which provided
relief of thermal mismatch.
Fig. 14 illustrates the coefficient of friction in terms of relative
voltage as a function of normal load while scratching (a) pure HA
coating; (b) fluoridate HA (FHA6) coating on Ti–6Al–4V. At the
beginning of the scratch and because of the “soft” nature of the
coating, coefficient of friction increases as load increases. The
fluctuation in the diagram, before point 1, is caused by the surface
roughness. After point 1, the indenter would start to advance into
the coating, resulting in a sharp increase in friction coefficient. The
indenter would completely peel off the coating and scratches the
substrate as the load increases to point 2, or 370 mN for pure HA
(shown in curve a), which results in a sudden increase in friction at
about 470 mN for FHA6.
Comparison of curves (a) and (b) in Fig. 14 shows that curve “b”
appears to have less fluctuation before the indenter completely
digs in and the adhesion of coating and substrate is better since
there is a slower gradient rise after the indenter digs in. A sharp
increase of friction would indicate a brittle peeling-off of the
coating from the substrate surface. Since curve “b” lacks the sharp
Fig. 14. Coefficient of friction in terms of relative voltage as a function of normal
load while scratching: (a) pure HA coating and (b) fluoridate HA (FHA6) coating on
Ti–6Al–4V [174].
247
change in friction, it is thus a more ductile interface and subse-
quently have better coating–substrate bonding than those of
curve “a” (pure HA) [185].
Fig. 15 shows the “upper critical load”, Lc, of all FHA coatings as
a function of firing temperature and fluorine. Both firing tempera-
tures and fluorine content seems to have a significant effect on the
adhesion strength of the coating. Increasing firing temperature or
fluorine concentration results in a dramatic raise of the critical
load. For coatings with the same amount of fluorine content,
higher adhesion is due to higher annealing temperatures. Simi-
larly, at the same firing temperature, adhesion strength increases
with fluorine content.
Zhang et al. [186], in similar studies [183], reported that FHA is
a potential replacement for pure HA coating on metallic implants
due to FHA's significant biocompatibility and resistance to biode-
gradation [184,187]. Ding et al. [188] identified two critical aspects
as the main contributors for long-term stability of the ceramic-
coated implants: high adhesion strength of substrate to coating
and low solubility of the coating. Incorporation of fluoride ions
into HA lattice structure results in reduction of HA solubility.
However, reports on adhesion improvements, especially on adhe-
sion studies after in vitro dissolution test have yet to be studied
extensively. In vitro dissolution tests can be used to investigate the
influence of dissolution behavior on the adhesion. Zhang et al.
[186], evaluated the adhesion of FHA coated on Ti–6Al–4V using
sol–gel technique before and after dissolution tests. The dissolu-
tion tests were conducted by soaking FHA coatings in a Tris-
buffered physiological saline solution (TPS) (0.9%NaCl, pH7.4) at a
fixed temperature of 37 1C for a duration of 3 weeks (Fig. 16). It
worth to mention that the “P” value in Fig. 16 is one-way ANOVA
test was conducted to assess the statistical significance of the
adhesion and toughness results.
Fig. 16 shows the nominal adhesion strength between the
coating and the Ti–6Al–4V substrate. “Adhesion failure” and
“cohesion failure” cannot be recognized by “nominal”. Without
fluoridation (sample F0), the adhesion strength is about 19 MPa.
Fluoridated samples (F1 and F2) show significant increase in
adhesion strength to about 26–27 MPa. Zhang et al. [186] con-
cluded that, the strength range starts from about 19 MPa for pure
hydroxyapatite (x ¼0) up to about 26 MPa for x¼ 1. However, after
21 days of soaking the coating in Tris-buffered physiological saline
solution, the adhesion strength increases to about 30 MPa for pure
HA and to over 40 MPa for FHA.
Fig. 15. Adhesion strength of pure HA and fluoridated HA coatings on Ti-6Al-4V
substrates as indicated by upper critical load in scratch test. Firing temperatures are
indicated [174].
248 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257
Fig. 16. Pull-out adhesion strength of FHA coating before and after soaking in TPS
solutions. *Indicates a significant increase of adhesion strength with respect to F0
(as prepared coatings); **Indicate a significant increase of adhesion strength with
respect to F0 (after soaking in TPS for 21 days) [186].
Fig. 17. Pull-out strength of coatings with different F content [190].
Comparing the sol–gel and thermal spraying methods for the
same FHA coatings on Ti–6Al–4V, Gu et al. [189] described that
after soaking, the adhesion strengths of thermal sprayed speci-
mens tends to decline, with reductions up to 75%. For example the
adhesion strength had decreased from 27 MPa before soaking
down to 19 MPa after soaking in synthetic body fluid (SBF) for
2 weeks. The reduction in adhesion strength of thermal spray
deposited HA coatings is probably due to the presence of cracks in
the coating [83].
Cheng et al. [190] used a pull-out method and scanning scratch
technique to evaluate the bonding strength of FHA coatings on
Ti–6Al–4V. Fig. 17 shows the result of measurements by pull-out
strength, showing the strength is about 11 MPa for pure HA
coating (FHA0), with considering of F content, the strength
intensifies up to about 22 MPa, and then decreases to around
17–18 MPa. Coating peeling-off value is about 390 mN for pure HA.
In contrast, the coating peeling- off increases with increasing F
content, 447 mN for FHA1, 450 mN for FHA2, 449 mN for
FHA3 and 478 mN for FHA4. The result of the study confirms that
the presence of F in FHA coatings has improved the adhesion
strength [190].
2.8. Ion beam assisted deposition technique
Surface modification techniques based on the bombardment
method have been used since the mid-1970s, and many have been
developed and are now widely used for surface engineering of
materials such as ceramics, bioceramics, and metals. Examples of
such methods are ion beam deposition, ion beam mixing and ion
beam assisted deposition (IBAD) [191–195].
IBAD is a vacuum deposition process based on the combination
of ion beam bombardment and physical vapor deposition. The
major characteristic of IBAD is the bombardment with a specific
energy ion beam during coating deposition. Many parameters can
affect the composition, mechanical properties, chemical proper-
ties, and structural properties of the deposited coating in the IBAD
process. The most important processing parameters in IBAD are
evaporation rate or sputtering rate, coating materials, ion species,
ion beam current density and ion energy [196].
IBAD has the ability to prepare bio-coatings with considerably
higher adhesive strength as compared to traditional coating
methods. The high adhesive strength is the result of interaction
between the substrate and coating atoms, assisted by ion bom-
bardment. This results in an atomic intermixed zone in the
substrate–coating interface [196]. IBAD process is highly reliable,
reproducible and is conducted at low substrate temperature,
without unfavorably affecting the bulk substrate characteristics.
Furthermore, the process has superior control over coating micro-
structure and chemical composition [197].
2.8.1. Ion beam assisted deposition of hydroxyapatite (HA) coatings
As it mentioned earlier, there are several methods to make HA
coating on Ti–6Al–4V, among which plasma spraying is the most
frequently used [198,199]. However, long-term clinical follow-up
has demonstrated that there are significant deficiencies in the
plasma-sprayed HA coatings. The limited cohesive strength of the
coatings and the limited strength of the coating–metal substrate
interface are the main problem with plasma-sprayed coting
technique. Moreover, heat treatments in plasma-sprayed HA coat-
ings results in cracks in the coating layer because of thermal
expansion mismatch between the metal substrate and
coated layer. This leads to a severe decreasing in bond strength
[200–203]. In order to produce more permanent bone-bonding
calcium phosphate coatings, ion beam assisted deposition (IBAD)
is introduced as an alternative technique for plasma spraying
technique. Previous studies shows that implants coated with HA
by the IBAD method demonstrate a very good adhesion to the
substrate [204].
2.8.2. Adhesion of ion beam assisted deposition of hydroxyapatite
(HA) coatings on Ti–6Al–4V
In the IBAD process, a wide atomic intermixed zone between
the coatinsg material and the substrate can be created, assisted by
the bombardment with energetic ions during deposition. This
creates a strong adhesion of the coating to the substrate
[205,206]. Ohtsuka et al. first used 50 keV Ca þ implantation into
Ti, followed by CaþIBAD to deposit HA coating on Ti substrate and
has obtained higher adhesive strength than conventional methods
[204]. It has been demonstrated that Ca þ implantation alone into
Ti was unable to provide the bioactive surface.
Cui et al. [207] proposed using Ar þ IBAD to form highly
adhesive hydroxyapatite coatings on titanium alloy. The coatings
prepare by IBAD was compared to those formed by ion beam
sputtering deposition (IBSD) of calcium phosphate coatings.
Scratch test is used to investigate the adhesive strength of the
IBSD and IBAD coatings on the substrates. Fig. 18 shows the typical
Fz–Fy curves of scratch test results for the specimens prepared by
 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257 249

Choi et al. [35] have used an Ar ion beam in the coating of HA

on Ti–6Al–4V deposited by IBAD technique. Fig. 19 illustrates the
bonding strength as a function of the ion beam current, before and
after the heat treatment. Increasing the current would increase the
ion bombardment and broadens the atomic intermixed zone
during the deposition. This results in the increase of adhesion
strength between the substrate and coating layer [207].
Several studies have shown that heat treatments would decrease
the bond strength [200–203]. Fig. 20 shows the SEM micrographs of
the coating layer before and after heat treatments. The morphologies
were found to be relatively similar regardless of the current level.
Before heat treatment, the layer was rather featureless, as shown in
Fig. 20(A). The lines at the interface are Wallner lines frequently
observed when hard coating layers are detached from a metal
substrate [208]. However, after heat treatment, the layer became
severely cracked, as shown in Fig. 20(B). This is probably due to the
thermal expansion mismatch between the coating and the substrate
[209]. These cracks are the main reason for the reduction in bond
strengths. The micrograph also reveals that the metal surface was
slightly oxidized, presumably by OH in the coating layer [209]. Overall
significant improvement in the bond strength is resulted by Choi et al.
Fig. 18. Fz–Fy curve of scratch test from specimen prepared by (a) IBSD and
[35] using an Ar ion beam while deposition.
(b) IBAD [207].
Hamdi and Ide-Ektessabi [197] have proposed the deposition of
hydroxyapatite layer using a combination of technique of IBAD and
simultaneous vapor deposition (SVD), namely ion-beam-assisted
simultaneous vapor deposition (IBASVD). Fig. 21 illustrates the

Fig. 19. Layer–metal substrate bond strengths, before and after heat treatment, as a
function of ion beam current [207].

IBSD and IBAD. Markers “A” and “B” indicate the points of the first
occurrence of coating detachment from the substrate. Fz and Fy, as
the normal and tangential forces respectively, are affecting the
diamond indenter during the test. A load speed of 2000 gf/min
was chosen for the tests. The results have shown that the critical
loads were 660 gf for IBSD and 1050 gf for IBAD samples. Gen-
erally, it was seen that the adhesive strength of the coatings
prepared by IBAD technique is almost twice that of the IBSD
coatings.
It has been shown that the adhesion strengths of coatings
prepared by IBSD and plasma sprayed technique are generally
similar [127]. Thus, it can be deduced from the comparative results
between IBSD and IBAD that the adhesive strength of IBAD
coatings would be reasonably higher than that of plasma sprayed
depositions. The main benefit of IBAD is the improved adhesion
strength due to the wide atomic intermixed zone at the interface
of the coating and substrate [204,206]. Thus, the issue of low
adhesion strength, which exists in plasma sprayed coatings can be Fig. 20. SEM micrographs of the coating layer (A) before and (B) after the heat
significantly eliminated by using the IBAD technique [207]. treatment [208].
250 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257

2.9.2. Adhesion of sputter coating of hydroxyapatite (HA) coatings

Fig. 21. Adhesion strength of the IBASVD samples at different elevated tempera-
tures [197].
result of coating detachments for two sets of IBASVD samples as
function of different annealing temperatures. Both types of sam-
ples resulted in similar curve patterns with the minimum detach-
ment forces recorded at 700 1C annealing temperature and the
maximum adhesion strength at 1200 1C. In all cases the adhesion
strength for the 260 mA/cm2 sample was higher than the 180 mA/
cm2 sample. In general, the recorded data for both samples are
extremely higher than the maximum adhesion strength obtainable
by the SVD samples, which was less than 100 mN [210]. It is
suggested that the increase in adhesion strength was the result of
the formation of a mixed layer between the substrate and the HA
film, consisting of a gradient fill of Ca, P and the element of the
substrate [207,211]. Hamdi and Ide-Ektessabi [197] described that
the energetic ions assisted the reactions between the migrated
atoms and the substrate atoms to generate an intermixed layer,
which have specific properties different from the deposited films
and the substrate. It was also understood that high current density
of ion beam resulted in a wider atomic intermixed zone, which
consequently improved the overall adhesion strength.
on Ti–6Al–4V
Ozeki et al. [217] compared the thermal treatments of the HA
coated on titanium alloy substrate prepared by sputter coating
with those prepared by plasma spraying technique. The substrates
were sandblasted using Al2O3 (125–180 mm) abrasive before coat-
ing. The specimens were post-treated with a hydrothermal process
for 24 h. The film thickness obtained for sputter coating was
1.2 mm while the thickness for plasma spraying was 60–100 mm.
Fig. 22 shows the shear strength results of the sputter coating,
the plasma sprayed coatings and the non-coated columns over a
period of time. The sputter coating showed the highest bonding
strength overall with recorded strengths of 3.3 7 0.2, 5.7 7 0.5, and
8.6 71.6 MPa after two, four, and 12 weeks, respectively. The
plasma sprayed coatings resulted in strength values of 1.97 0.25,
4.0 70.3, and 6.6 70.7 MPa, respectively, for the same period of
time. The strength values of the non-coated columns were
0.4 70.3 and 1.1 70.3 MPa after four and 12 weeks, respectively.
The strength of the sputter coating exceeded that of the plasma
sprayed coating by more than 70%, 40%, and 30% after a period of
two, four and 12 weeks, respectively. De Groot et al. reported that
coating thicknesses above 100 μm were associated with fatigue
failure under tensile loading [218]. According to Hasegawa et al.
thin plasma sprayed coatings are bound more strongly than thick
coatings [219].
Ding et al. [220] investigated on a series of thin ( o10 μm),
single layered HA/Ti coatings deposited on Ti–6Al–4V substrate
using an RF magnetron-assisted sputtering system. For the experi-
ments, six HA/Ti targets with different compositions (95HA/5Ti,
90HA/10Ti, 85HA/15Ti, 75HA/25Ti, 50HA/50Ti, and 25HA/75Ti)
were prepared. Generally it was found that the coating with
higher Ti contents resulted higher adhesion strengths. The highest
adhesion strength (of the 25HA/75Ti coating), evaluated using a
Sebastian adhesion test system (Sebastian Five, Quad Group,
Spokane, WA) [127] was even higher than 80 MPa, which
exceeded the maximum value achievable using the bonding resin
in the pull-out test. Table 4 reports the adhesion strength and their

2.9. Sputter coating technique

Sputter deposition is a physical vapor deposition (PVD) method

of depositing thin films by sputtering. This involves ejecting
material from a source, known as a “target”, onto a “substrate”
such as a silicon wafer. It was reported that initial sputtering using
multi-component ceramic targets such as superconducting oxides,
HA and other CaP materials would produce coatings whose
chemistries were different upon deposition than the bulk target
[212,213]. Sputtering utilizes a gas plasma (argon, neon, krypton or
xenon) to remove material from a negatively charged target which
is then deposited as a thin film coating onto the substrate. Studies
have shown successful deposition of thin HA layers on titanium
substrates using RF magnetron sputtering [214].

2.9.1. Sputter coating of hydroxyapatite (HA) coatings

Sputtering techniques have been used to deposit homogeneous
thin films coatings of high adhesion strength with thicknesses
ranging from 0.5 to 3 μm. However, sputter coated HA films on
metals were found to be of low crystallinity [214–216]. The low
crystallinity increases the rate of dissolution of the coating in the
living body. Post-treatment thermal process can be used to
crystallize the film, hence reducing the possibility of dissolution.
However, conventional thermal treatment in the electric furnace
increases the likely formation of cracks and may degrade the
HA films. Fig. 22. Bone bonding strengths of sputtered films [217].
 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257 251

corresponding failure point for different compositions and Fig. 23 [26]. Moreover, the determination of the adhesion between the
shows the adhesion strength for each composition. coating and the substrate has been always a main concern when
The high adhesion strength of sputtered monolithic HA coating using plasma spraying technique [59]. High spraying power results
is higher than most plasma sprayed HA coatings [221,222], and is in high adhesion strength of HACs due to significant melting of the
believed to be attributed to the sputter cleaning and ion bombard- coating material which forms dense microstructure. However, the
ing processes. The sputter cleaning process would remove con- high-temperature process can lead to phase transformation and
taminants and adsorbed gas molecules from the surface of the grain growth of the metal substrate which may cause significant
substrate to produce a clean, highly active surface [223]. The ion decrease in the mechanical properties of the metal.
bombarding process during sputtering would enhance atomic Results of the study [61] has established the relationship
diffusion and mixing near the interface region [207,224]. Mechan- between residual stress and bonding strength especially for
ical interlocking effect may have contributed to the higher average plasma sprayed hydroxyapatite coatings. This stress in the coating
adhesion strength of coating sputtered on the rougher surface is influenced by the spraying parameter, coating thickness [67,68],
(Ra ¼0.7 mm) as compared to the lower value obtained for the and substrate cooling effect (i.e. temperature of substrate) [62,63].
smoother surface (Ra ¼0.06 mm). However this effect was not as Generally, the residual stresses increase with the increase in the
significant for sputtering with Ti-containing targets. thickness of coating and the temperature of the specimen during
Results from Ding et al. [220] have shown that all coatings had plasma spraying. Moreover, high-power sprayed HA coatings
adhesion strengths between 60 and 80 MPa. Furthermore if the generally possess higher adhesion strength than those sprayed
sputtering uses a target comprising of more than 15 vol% Ti, the with lower power. In some cases, the adhesion of the plasma
resulting coating adhesion strength and hardness were signifi- sprayed HA can be significantly improved by a subsequent hot
cantly higher than those of monolithic HA coating. isostatic pressing operation.
The adhesion strength is a reflection of the combination of
cohesive (within the coating layers themselves) and adhesive
3. Discussion (coating to substrate) strengths of a coating [61]. The cohesive
strength is obtained by coating properties, such as the micro-
There have been numerous studies on coatings of hydroxyapa- structure and crystallinity, but the adhesive strength is mostly
tite (HA) onto Ti–6Al–4V because of its significant utilization in influenced by coating properties, such as surface roughness,
orthopedic prostheses and implants. Table 5 summarizes the residual stress, and the mechanical interlocking between substrate
previous discussion on the various techniques for coating of HA and HACs [61].
on Ti–6Al–4V, with comparison on their advantages and Overall, it was found that plasma sprayed coating has not
disadvantages. improved the service-life performance of uncoated implants. In
Plasma spraying is the most frequently investigated method to addition, there are issues with poor reliability and mechanical
coat HA onto Ti–6Al–4V specimen [198,199]. Plasma spray is the integrity [56,57]. The pulsed laser deposition (PLD) is a better
first method used for HA coating, owing to its ease of application alternative than the plasma spray technique because the PLD
transfers sintered HA stoichiometrically to deposit a thin adherent
Table 4 coating onto titanium substrate surface [58]. The substrate tem-
Adhesion strength and failure mode of coatings [220]. perature is lower in PLD as compared to plasma spray and
Coating Adhesion strength (MPa) Failure mode
different calcium phosphate compositions can be deposited by
Code (Ra ¼ 0.06 lm) changing the parameters of deposition [112,114,225]. In addition,
(Ra ¼0.06 mm) (Ra ¼0.7 mm) undesirable phases of HA coatings by PLD are reduced under
optimal conditions and generally have better coating to substrate
HA 59.9 7 12.4 (41) 71.8 7 14.7 (25) R/C, C/S
adhesion [54,106].
95HA/5Ti 59.5 7 6.5 (20) 60.7 7 5.8 (23) R/C, C/S
90HA/10Ti 58.4 7 6.2 (18) 54.5 7 6.1 (12) R/C, C/S TiO2 and TiN layers can be used as an interfacial layer between
85HA/15Ti 64.87 6.2 (17) 69.5 7 10.3 (19) R/C, C/S coating and the metal substrate as reported in studies related to
75HA/25Ti 64.07 6.9 (32) 65.3 7 6.5 (50) R/C, C/S the adhesion of crystalline PLD HA thin films on Ti–6Al–4V
50HA/50Ti 75.17 5.5 (22) 72.9 7 5.4 (28) R/C substrates [20]. Some authors consider that this interfacial layer
25HA/75Ti 81.9 7 5.2 (19) 79.8 7 6.3 (17) R/C
Ti 79.5 7 9.1 (15) 85.17 5.1 (34) R/C
favours adhesion due to better bonding of HA to TiN which is then,
directly bonded to the substrate [125,126]. These layers can be

Fig. 23. Adhesion strength of coatings [220].

252 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257

Table 5
Different techniques to deposit HA coating.

Technique Thickness Advantages Disadvantages

Plasma spraying o 20 mm Rapid deposition; sufficiently low cost; fast bone
healing, less risk for coating degradation
Thermal spraying 30–200 mm High deposition rates; low cost;
Sputter soating 0.5–3 mm Uniform coating thickness on flat substrates;
dense coating; homogenous coating; high adhesion
Pulsed laser 0.05–5 mm Coating with crystalline and amorphous; coating with
deposition dense and porous; ability to produce wide range of
multilayer coating from different materials; ability to
produce high crystalline HA coating; ability to restore
complex stoichiometry; high degree of control on
deposition parameters
Dip coating o 1 mm Inexpensive; coatings applied quickly; can coat
complex substrates; high surface uniformity; good
speed of coating;
Sol–gel 0.1–2.0 mm Can coat complex shapes; Low processing
temperatures; relatively cheap as coatings are very
thin; simple deposition method; high purity; high
corrosion resistant; fairly good adhesion
Electrophoretic 0.1–2.0 mm Uniform coating thickness; rapid deposition rates; can
deposition coat complex substrates; simple setup, low cost, high
degree of control on coating morphology and thickness,
good mechanical strength; high adhesion for n-HA
Hot isostatic 0.2–2.0 mm Produces dense coatings; produce net-shape ceramics;
pressing good temperature control; homogeneous structure;
high uniformity; high precision; no dimensional or
shape limitation
Ion beam assisted o 0.03 mm Low temperature process; high reproducibility and
deposition reliability; high adhesion; wide atomic intermix zone
are coating-to-substrate interface
Poor adhesion, alternation of HA structure due to
coating process; non-uniformity in coating density;
extreme high temperature up to 1200 1C, phase
transformation and grain grow of substance due to
high temperature procedure; increase in residual
stress; unable to produce complete crystalline HA
coating
Line of sight technique; high temperatures induce
decomposition; rapid cooling produces amorphous
coatings; lack of uniformity; crack appearance; low
porosity; coating spalling and interface separation
between the coating and the substrate
Line of sight technique; expensive time consuming;
produces amorphous coatings; low crystallite which
accelerates the dissolution of the film in the body
Line of sight technique; splashing or particle
deposition; need surface pretreatment; lack of
uniformity
Requires high sintering temperatures; thermal
expansion mismatch; crack appearance
Some processes require controlled atmosphere
processing; expensive raw materials; not suitable for
industrial scale; high permeability; low wear
resistance; hard to control the porosity;
Difficult to produce crack-free coatings; requires high
sintering temperatures; HA decomposition during
sintering stage
Cannot coat complex substrates; high temperature
required; thermal expansion mismatch; elastic
property differences; expensive; removal/interaction
of encapsulation material
Crack appearance on the coated surface

created using pre-treatment processes, such as laser surface
nitriding and etching on titanium, which have been reported to
improve the bonding strength of the coating. Thus, laser surface
nitriding and subsequent etching of the substrate is an effective
pre-treatment method for improving the adhesion strength of HA
coated onto Ti–6Al–4V by PLD [119].
EPD is a technique which is gaining attention due to its ability
to economically produce films of a wide range of thicknesses as
compared to conventional methods such as thermal spraying, sol–
gel deposition, and sputtering [139]. Moreover, EPD of HA has
ability to be processed at room temperature, reducing the possi-
bility of formation of the amorphous phase in HA. The good
uniformity and bonding strength results is mostly due to the
colloidal stability of the suspension [142]. The EPD technique can
also produce nanostructured HA coating having bond strength 2–3
times better than thermal sprayed HA coating.
Similar to PLD, studies have shown that an intermediate layer,
such as silica or TiO2, improves the adhesion strength of coating
fabricated using EPD [146]. Dense titanium dioxide (TiO2) films
possess a very good combination of bioactivity, chemical stability
and mechanical integrity [149]. A TiO2 inner layer would also
reduce the decomposition of HA and increases the and overall
adhesion strength of coating [160].
The sol–gel technique is a simple technique which can create
single or multicomponent oxide coating on glass or metals
[162,163]. However, there is a coating thickness limit of 0.5 μm
[172]. Fluoridation of HA can enhance the coating's resistance to
biodegradation while still maintaining good biocompatibility
[184,187]. An increase in fluoridation ratio would increase the
adhesion strength by about 40%. The strength range for FHA is
about 26 MPa which is higher than the value of the bonding
strength of 19 MPa for pure hydroxyapatite. The fracture tough-
ness increases about 200–300% and the scratch test results in
adhesion improvement of 35% for fluoridated HA coatings as
compared to pure hydroxyapatite coating [183,186,190]. The
enhancement in adhesion strength is believed to be caused by
the formation chemical bonding at the interface and the relief of
thermal mismatch resulting from the incorporation of fluorine
(F) into the HA structure.
Dip coating can be generally compared with sol–gel coating
technique. The technique is simple, economical and is able to
generate high coating quality. Dip coating process is rapid, where
the complete transition can be completed within a few seconds or
less if volatile solvents are used.
IBAD technique can deposit highly adhesive HA coating on Ti–
6Al–4V due to atomic interactions between the substrate and
coating materials, assisted by ion bombardment [196]. The main
advantage of IBAD compare to other methods, such as IBSD or
plasma spraying, is that there is a wide atomic intermixed zone at
the coating–substrate interface which significantly improves the
adhesive strength of the coating. Heat treatment of IBAD coated
samples reduces the adhesion strength, due formation of cracks in
the layer and the thermal expansion mismatch between the
coated layer and the metal substrate [200–203].
 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257
Fig. 24. Quantative comparison of different coating techniques.
Fig. 24 shows adhesion strength values of HA coatings on Ti–
6Al–4V coated using various techniques. The sputtering technique
has the highest adhesion of coating to the substrate compares to
other methods which can be attributed to the sputter cleaning and
ion bombardment processes.
4. Conclusion
Adhesion strength of HA on Ti–6Al–4V substrate has been
reviewed in detail. Nine common techniques of deposition such as
plasma sprayed deposition, hot isostatic pressing, thermal spray, dip
coating, pulsed laser deposition (PLD), electrophoretic deposition
(EPD), sol–gel, ion beam assisted deposition (IBAD), and sputtering
were evaluated and discussion were made on the coating parameters
affecting the adhesion strength of the coating. Advantages and
disadvantages of each method were discussed and a quantitative
comparison was made on the different techniques of HA coating on
Ti–6Al–4V substrate. Based on this review, the best adhesion of HA
coating to substrate is obtained by sputtering deposition technique
while the worse bonding strength was obtained by PLD at 1000 laser
pulses. Using an interfacial layer (such as TiO2 or TiN) as the initial
coating layer on the substrate followed by HA coating layer can
enhance the bonding strength. Pretreatments such as nitriding,
followed by etching, can enhance the adhesion strength in PLD.
Moreover, post-treatments also have similar effects on other techni-
ques such as IBAD and thermal spray.
Acknowledgment
The authors would like to acknowledge the University of
Malaya for providing the necessary facilities and resources for this
research. This research was fully founded by the Ministry of Higher
Education, Malaysia with the high impact research Grant no. of
um.c/625/1/HIR/MOHE/ENG/27.
References
[1] Jaffe WL, Scott DF. Current concepts review-total hip arthroplasty with
hydroxyapatite-coated prosthesesn. The Journal of Bone & Joint Surgery
1996;78:1918–34.
[2] Thomas KA. Hydroxyapatite coatings. Orthopedics 1994;17:267.
[3] Ducheyne P, Cuckler JM. Bioactive ceramic prosthetic coatings. Clinical
Orthopaedics and Related Research 1992;276:102–14.
253
[4] Corpe RS, Steflik DE, Whitehead RY, Wilson MD, Young TR, Jaramillo C.
Correlative experimental animal and human clinical retrieval evalua-
tions of hydroxyapatite (HA)-coated and non-coated implants in ortho-
paedics and dentistry. Critical Reviews in Biomedical Engineering
2000;28:395–8.
[5] Sakkers R, Dalmeyer R, Brand R, Rozing P, Van Blitterswijk C. Assessment of
bioactivity for orthopedic coatings in a gap-healing model. Journal of
Biomedical Materials Research 1998;36:265–73.
[6] Tadic D, Peters F, Epple M. Continuous synthesis of amorphous carbonated
apatites. Biomaterials 2002;23:2553–9.
[7] Holmes RE, Bucholz R, Mooney V. Porous hydroxyapatite as a bone-graft
substitute in metaphyseal defects. A histometric study. The Journal of Bone
and Joint Surgery. American volume 1986;68:904.
[8] Bucholz RW, Carlton A, Holmes R. Interporous hydroxyapatite as a bone graft
substitute in tibial plateau fractures. Clinical Orthopaedics and Related
Research 1989:53.
[9] Hench LL, Wilson J. An introduction to bioceramics. World Scientific; 1993.
[10] Thomas M, Doremus R, Jarcho M, Salsbury R. Dense hydroxylapatite: fatigue
and fracture strength after various treatments, from diametral tests. Journal
of Materials Science 1980;15:891–4.
[11] With G, Dijk H, Hattu N, Prijs K. Preparation, microstructure and mechanical
properties of dense polycrystalline hydroxy apatite. Journal of Materials
Science 1981;16:1592–8.
[12] Hsieh M-F, Perng L-H, Chin T-S. Hydroxyapatite coating on Ti6Al4V alloy
using a sol–gel derived precursor. Materials Chemistry and Physics
2002;74:245–50.
[13] Kawagoe K, Saito M, Shibuya T, Nakashima T, Hino K, Yoshikawa H.
Augmentation of cancellous screw fixation with hydroxyapatite composite
resin (CAP) in vivo. Journal of Biomedical Materials Research 2000;53:
678–84.
[14] Luckey HA, Kubli Jr F. Titanium alloys in surgical implants, 1st ed. ASTM
International; 1983.
[15] Brunette DM. Titanium in medicine: material science, surface science, engineer-
ing, biological responses, and medical applications. Springer Verlag Engineering
Materials; 2001.
[16] Koch C, Johnson S, Kumar D, Jelinek M, Chrisey D, Doraiswamy A, et al.
Pulsed laser deposition of hydroxyapatite thin films. Materials Science and
Engineering: C 2007;27:484–94.
[17] Nelea V, Morosanu C, Iliescu M, Mihailescu I. Microstructure and mechanical
properties of hydroxyapatite thin films grown by RF magnetron sputtering.
Surface and Coatings Technology 2003;173:315–22.
[18] Wang S, Lacefield WR, Lemons JE. Interfacial shear strength and histology of
plasma sprayed and sintered hydroxyapatite implants o i4 in vivo o /i4.
Biomaterials 1996;17:1965–70.
[19] Silva P, Santos J, Monteiro F, Knowles J. Adhesion and microstructural character-
ization of plasma-sprayed hydroxyapatite/glass ceramic coatings onto Ti–6A1–4V
substrates. Surface and Coatings Technology 1998;102:191–6.
[20] Blind O, Klein LH, Dailey B, Jordan L. Characterization of hydroxyapatite films
obtained by pulsed-laser deposition on Ti and Ti–6Al–4V substrates. Dental
Materials 2005;21:1017–24.
[21] Poser R, Magee F, Kay J, Hedley A. In-vivo characterization of a hydroxyla-
patite coating. In: Transactions of the 16th annual meeting of the society for
biomaterials; 1990. p. 170.
[22] Tong W, Yang Z, Zhang X, Yang A, Feng J, Cao Y, et al. Studies on diffusion
maximum in x‐ray diffraction patterns of plasma‐sprayed hydr-
oxyapatite coatings. Journal of Biomedical Materials Research
1998;40:407–13.
[23] Garcia F, Arias J, Mayor B, Pou J, Rehman I, Knowles J, et al. Effect of heat
treatment on pulsed laser deposited amorphous calcium phosphate coatings.
Journal of Biomedical Materials Research 1998;43:69–76.
[24] Watson C, Tinsley D, Ogden A, Russell J, Mulay S, Davison E. Implants: a 3 to
4 year study of single tooth hydroxylapatite coated endosseous dental
implants. British Dental Journal 1999;187:90–4.
[25] Wang C, Ma J, Cheng W, Zhang R. Thick hydroxyapatite coatings by
electrophoretic deposition. Materials Letters 2002;57:99–105.
[26] De Groot K, Geesink R, Klein C, Serekian P. Plasma sprayed coatings of
hydroxylapatite. Journal of Biomedical Materials Research 2004;21:1375–81.
[27] Gross KA, Berndt CC. Thermal processing of hydroxyapatite for coating
production. Journal of Biomedical Materials Research 1998;39:580–7.
[28] Ding S-J. Properties and immersion behavior of magnetron-sputtered multi-
layered hydroxyapatite/titanium composite coatings. Biomaterials
2003;24:4233–8.
[29] Cleries L, Martınez E, Fernandez-Pradas J, Sardin G, Esteve J, Morenza J.
Mechanical properties of calcium phosphate coatings deposited by laser
ablation. Biomaterials 2000;21:967–71.
[30] Yoshinari M, Ohtsuka Y, Dérand T. Thin hydroxyapatite coating produced by
the ion beam dynamic mixing method. Biomaterials 1994;15:529–35.
[31] Kaciulis S, Mattogno G, Napoli A, Bemporad E, Ferrari F, Montenero A, et al.
Surface analysis of biocompatible coatings on titanium. Journal of Electron
Spectroscopy and Related Phenomena 1998;95:61–9.
[32] Li P, Groot Kd, Kokubo T. Bioactive Ca10(PO4)6(OH)2  TiO2 composite coating
prepared by sol–gel process. Journal of Sol–Gel Science and Technology
1996;7:27–34.
[33] Han Y, Fu T, Lu J, Xu K. Characterization and stability of hydroxyapatite
coatings prepared by an electrodeposition and alkaline‐treatment process.
Journal of Biomedical Materials Research 2000;54:96–101.
254 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257
[34] Habibovic P, Barrere F, Blitterswijk CA, Groot K, Layrolle P. Biomimetic
hydroxyapatite coating on metal implants. Journal of the American Ceramic
Society 2002;85:517–22.
[35] Choi J-M, Kim H-E, Lee I-S. Ion-beam-assisted deposition (IBAD) of hydro-
xyapatite coating layer on Ti-based metal substrate. Biomaterials
2000;21:469–73.
[36] Wie H, Herø H, Solheim T. Hot isostatic pressing-processed hydroxyapatite-
coated titanium implants: light microscopic and scanning electron micro-
scopy investigations. The International Journal of Oral & Maxillofacial
Implants 1998;13:837.
[37] M. Mittal, S. Nath, S. Prakash, Improvement in mechanical properties of
plasma sprayed hydroxyapatite coatings by Al2O3 reinforcement, Materials
Science and Engineering: C, (2013).
[38] Sun L, Berndt CC, Gross KA, Kucuk A. Material fundamentals and clinical
performance of plasma‐sprayed hydroxyapatite coatings: a review. Journal
of Biomedical Materials Research 2001;58:570–92.
[39] Wang RR, Welsch GE, Monteiro O. Silicon nitride coating on titanium to
enable titanium–ceramic bonding. Journal of Biomedical Materials Research
1999;46:262–70.
[40] Man H, Zhao N, Cui Z. Surface morphology of a laser surface nitrided and
etched Ti–6Al–4V alloy. Surface and Coatings Technology 2005;192:341–6.
[41] Herman H. Plasma spray deposition processes. MRS Bulletin 1988;13:60–7.
[42] Ong JL, Chan D. Hydroxyapatite and their use as coatings in dental implants:
a review. Critical Reviews in Biomedical Engineering 2000;28:667.
[43] Herman H. Plasma-sprayed coatings. Scientific American; (USA) 1988;259.
[44] Filiaggi M, Coombs N, Pilliar R. Characterization of the interface in the
plasma-sprayed HA coating/Ti–6Al–4V implant system. Journal of Biomedi-
cal Materials Research 1991;25:1211.
[45] Palka V, Poštrková E, Koerten H. Some characteristics of hydroxylapatite
powder particles after plasma spraying. Biomaterials 1998;19:1763–72.
[46] Ellies L, Nelson D, Featherstone J. Crystallographic changes in calcium
phosphates during plasma-spraying. Biomaterials 1992;13:313–6.
[47] Lemons J. Hydroxyapatite coatings. Clinical Orthopaedics and Related
Research 1988:220.
[48] Buser D, Schenk R, Steinemann S, Fiorellini J, Fox C, Stich H. Influence of
surface characteristics on bone integration of titanium implants. A histo-
morphometric study in miniature pigs. Journal of Biomedical Materials
Research 2004;25:889–902.
[49] Jansen J, Van De Waerden J, Wolke J, De Groot K. Histologic evaluation of the
osseous adaptation to titanium and hydroxyapatite‐coated titanium
implants. Journal of Biomedical Materials Research 2004;25:973–89.
[50] Søballe K, Hansen ES, Brockstedt-Rasmussen H, Pedersen CM, Bünger C.
Hydroxyapatite coating enhances fixation of porous coated implants: a
comparison in dogs between press fit and noninterference fit. Acta Ortho-
paedica 1990;61:299–306.
[51] Cook SD, Thomas KA, Kay JF, Jarcho M. Hydroxyapatite-coated porous
titanium for use as an orthopedic biologic attachment system. Clinical
Orthopaedics 1988;230:303–12.
[52] Moroni A, Caja V, Sabato C, Egger E, Gottsauner-Wolf F, Chao E. Bone
ingrowth analysis and interface evaluation of hydroxyapatite coated versus
uncoated titanium porous bone implants. Journal of Materials Science:
Materials in Medicine 1994;5:411–6.
[53] Lacefield W, Ducheyne P, Lemons J. Bioceramics: material characteristics versus
in vivo behavior. New York: The New York Academy of Science; 1988; 72.
[54] Fernández-Pradas J, Garcıa-Cuenca M, Cleries L, Sardin G, Morenza J. Influence of
the interface layer on the adhesion of pulsed laser deposited hydroxyapatite
coatings on titanium alloy. Applied Surface Science 2002;195:31–7.
[55] Ducheyne P, Cuckler J, Radin S, Nazar E. Plasma sprayed calcium phosphate
lining on porous metal coatings for bone in growth. Handbook of bioactive
ceramics, vol II, 9th ed. Boca Raton, FL, USA: CRC Press; 1990.
[56] Khor K, Gu Y, Quek C, Cheang P. Plasma spraying of functionally graded
hydroxyapatite/Ti–6Al–4V coatings. Surface and Coatings Technology
2003;168:195–201.
[57] Morales JG, Clemente RR, Armas B, Combescure C, Berjoan R, Cubo J, et al.
Controlled nucleation and growth of thin hydroxyapatite layers on titanium
implants by using induction heating technique. Langmuir 2004;20:5174–8.
[58] Lo W, Grant D, Ball M, Welsh B, Howdle S, Antonov E, et al. Physical,
chemical, and biological characterization of pulsed laser deposited and
plasma sputtered hydroxyapatite thin films on titanium alloy. Journal of
Biomedical Materials Research 2000;50:536–45.
[59] Matejka D, Benko B. Plasma spraying of metallic and ceramic materials.
Chichester, West Sussex, UK: John Wiley and Sons; 1989; 280p.
[60] Mittal K. Adhesion measurement of thin films, thick films and bulk coatings.
ASTM International (ASTM Specical Technical Publication); 1978.
[61] Yang Y-C, Chang E. Influence of residual stress on bonding strength and
fracture of plasma-sprayed hydroxyapatite coatings on Ti–6Al–4V substrate.
Biomaterials 2001;22:1827–36.
[62] Scardi P, Leoni M, Bertamini L. Residual stresses in plasma sprayed partially
stabilised zirconia TBCs: influence of the deposition temperature. Thin Solid
Films 1996;278:96–103.
[63] Takeuchi S, Ito M, Takeda K. Modelling of residual stress in plasma-sprayed
coatings: effect of substrate temperature. Surface and Coatings Technology
1990;43:426–35.
[64] Brown S, Turner I, Reiter H. Residual stress measurement in thermal sprayed
hydroxyapatite coatings. Journal of Materials Science: Materials in Medicine
1994;5:756–9.
[65] Noutomi A, Kodama M, Inoue Y, Ono T, Kawano M, Tani N. Residual stress
measurement on plasma sprayed coatings. Welding International
1989;3:947–53.
[66] Eigenmann B, Scholtes B, Macherauch E. Determination of residual stresses
in ceramics and ceramic–metal composites by X-ray diffraction methods.
Materials Science and Engineering: A 1989;118:1–17.
[67] Evans A, Crumley G, Demaray R. On the mechanical behavior of brittle
coatings and layers. Oxidation of Metals 1983;20:193–216.
[68] Mencik J. Mechanics of components with treated or coated surfaces.
Dordrecht, Netherlands: Kluwer Academic Publishers; 1996.
[69] Tsui Y, Doyle C, Clyne T. Plasma sprayed hydroxyapatite coatings on titanium
substrates Part 1: Mechanical properties and residual stress levels. Bioma-
terials 1998;19:2015–30.
[70] Mohammadi Z, Ziaei-Moayyed A, Mesgar A. Adhesive and cohesive proper-
ties by indentation method of plasma-sprayed hydroxyapatite coatings.
Applied Surface Science 2007;253:4960–5.
[71] Kweh S, Khor K, Cheang P. An in vitro investigation of plasma sprayed
hydroxyapatite (HA) coatings produced with flame-spheroidized feedstock.
Biomaterials 2002;23:775–85.
[72] Larker HT, Larker R. Hot isostatic pressing. Materials Science and Technology
1991.
[73] Herø H, Wie H, Jørgensen RB, Ruyter I. Hydroxyapatite coatings on Ti
produced by hot isostatic pressing. Journal of Biomedical Materials Research
1994;28:343–8.
[74] Nakamura M, Kaieda Y. Microstructure and mechanical properties of
sintered TiAl. Powder Metallurgy 1988;31:201–9.
[75] Sheppard LM. Fabrication of ceramics; the challenge continues. American
Ceramic Society Bulletin; (USA) 1989;68.
[76] Shin DW, Orr K-K, Schubert H. Microstructure-mechanical property relation-
ships in hot isostatically pressed alumina and zirconia-toughened alumina.
Journal of the American Ceramic Society 1990;73:1181–8.
[77] Lange FF. Powder processing science and technology for increased reliability.
Journal of the American Ceramic Society 1989;72:3–15.
[78] Fu Y, Batchelor A. Hot isostatic pressing of hydroxyapatite coating for
improved fretting wear resistance. Journal of Materials Science Letters
1998;17:1695–6.
[79] Khor K, Yip C, Cheang P. Post-spray hot isostatic pressing of plasma sprayed
Ti’ 6Al’ 4V/hydroxyapatite composite coatings. Journal of Materials
Processing Technology 1997;71:280–7.
[80] Heimann RB. Thermal spraying of biomaterials. Surface and Coatings
Technology 2006;201:2012–9.
[81] Liang H, Shi B, Fairchild A, Cale T. Applications of plasma coatings in artificial
joints: an overview. Vacuum 2004;73:317–26.
[82] Yang Y, Kim K-H, Ong JL. A review on calcium phosphate coatings produced
using a sputtering process—an alternative to plasma spraying. Biomaterials
2005;26:327–37.
[83] Cheang P, Khor K. Addressing processing problems associated with plasma
spraying of hydroxyapatite coatings. Biomaterials 1996;17:537–44.
[84] Hanyaloglu C, Aksakal B, Bolton J. Production and indentation analysis of
WC/Fe–Mn as an alternative to cobalt-bonded hardmetals. Materials Char-
acterization 2001;47:315–22.
[85] Hamdi M, Hakamata S, Ektessabi A. Coating of hydroxyapatite thin film by
simultaneous vapor deposition. Thin Solid Films 2000;377:484–9.
[86] Zyman Z, Weng J, Liu X, Zhang X, Ma Z. Amorphous phase and morpho-
logical structure of hydroxyapatite plasma coatings. Biomaterials
1993;14:225–8.
[87] Shunyan T, Heng J, Chuanxian D. Effect of vapor-flame treatment on plasma
sprayed hydroxyapatite coatings. Journal of Biomedical Materials Research
2000;52:572–5.
[88] Weng J, Liu X, Zhang X, Ma Z, Ji X, Zyman Z. Further studies on the plasma-
sprayed amorphous phase in hydroxyapatite coatings and its deamorphiza-
tion. Biomaterials 1993;14:578–82.
[89] Zyman Z, Weng J, Liu X, Li X, Zhang X. Phase and structural changes in
hydroxyapatite coatings under heat treatment. Biomaterials 1994;15:151–5.
[90] Roome CM, Adam CD. Crystallite orientation and anisotropic strains in
thermally sprayed hydroxyapatite coatings. Biomaterials 1995;16:691–6.
[91] Hsiung J, Tzeng J, Kung K, Chen H. A study of thermal spray coating on
artificial knee joints. Life Science Journal 2013;10.
[92] Hsiung J, Kung H, Chen H, Chang K-Y. Applications of thermal spray coating
in artificial knee joints. Life Science Journal 2012;9.
[93] Standard A. G65. Standard test method for measuring abrasion using the dry
sand/rubber wheel apparatus. Annual book of ASTM Standards, vol. 3; 2008.
p. 245–56.
[94] Aegerter MA, Mennig M. Sol–gel technologies for glass producers and users.
Springer, Springer Science; 2004.
[95] Li T, Lee J, Kobayashi T, Aoki H. Hydroxyapatite coating by dipping method,
and bone bonding strength. Journal of Materials Science: Materials in
Medicine 1996;7:355–7.
[96] Mavis B, Taş AC. Dip coating of calcium hydroxyapatite on Ti–6Al–4V
substrates. Journal of the American Ceramic Society 2000;83:989–91.
[97] Weng W, Baptista JL. Preparation and characterization of hydroxyapatite
coatings on Ti6Al4V alloy by a sol–gel method. Journal of the American
Ceramic Society 1999;82:27–32.
[98] Lahoz R, Espinós JP, de la Fuente GF, González-Elipe AR. in situ XPS studies of
laser induced surface cleaning and nitridation of Ti. Surface and Coatings
Technology 2008;202:1486–92.
 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257
[99] Delgado-Ruíz R, Calvo-Guirado J, Moreno P, Guardia J, Gomez‐Moreno G,
Mate-Sánchez J, et al. Femtosecond laser microstructuring of zirconia dental
implants. Journal of Biomedical Materials Research Part B: Applied Bioma-
terials 2011;96:91–100.
[100] Zavestovskaya I. Laser nanostructuring of materials surfaces. Quantum
Electronics 2010;40:942–54.
[101] Kurella A, Dahotre NB. Review paper: surface modification for bioimplants:
the role of laser surface engineering. Journal of Biomaterials Applications
2005;20:5–50.
[102] Gaggl A, Schultes G, Müller W, Kärcher H. Scanning electron microscopical
analysis of laser-treated titanium implant surfaces—a comparative study.
Biomaterials 2000;21:1067–73.
[103] Kaczmarek SM. Pulsed laser deposition—today and tomorrow. Proceedings of
the SPIE 1997;11:129–34.
[104] Karl H, Stritzker B. Reflection high-energy electron diffraction oscillations
modulated by laser-pulse deposited YBa_ {2} Cu_ {3} O_ {7-x}. Physical
Review Letters 1992;69:2939–42.
[105] Cotell CM, Chrisey DB, Grabowski KS, Sprague JA, Gossett CR. Pulsed laser
deposition of hydroxylapatite thin films on Ti–6Al–4V. Journal of Applied
Biomaterials 2004;3:87–93.
[106] Bao Q, Chen C, Wang D, Ji Q, Lei T. Pulsed laser deposition and its current
research status in preparing hydroxyapatite thin films. Applied Surface
Science 2005;252:1538–44.
[107] Boyd IW. Thin film growth by pulsed laser deposition. Ceramics International
1996;22:429–34.
[108] Kelly R, Miotello A. Mechanisms of pulsed laser sputtering. Pulsed Laser
Deposition of Thin Films 1994:55–85.
[109] Cheung JT. History and fundamentals of pulsed laser deposition. Pulsed Laser
Deposition of Thin Films 1994:14–5.
[110] Nelea V, Ristoscu C, Chiritescu C, Ghica C, Mihailescu I, Pelletier H, et al.
Pulsed laser deposition of hydroxyapatite thin films on Ti-5Al-2.5Fe sub-
strates with and without buffer layers. Applied Surface Science
2000;168:127–31.
[111] Fernández-Pradas J, Cleries L, Martinez E, Sardin G, Esteve J, Morenza J.
Calcium phosphate coatings deposited by laser ablation at 355 nm under
different substrate temperatures and water vapour pressures. Applied Physics
A: Materials Science & Processing 2000;71:37–42.
[112] Fernández-Pradas J, Sardin G, Clèries L, Serra P, Ferrater C, Morenza J.
Deposition of hydroxyapatite thin films by excimer laser ablation. Thin Solid
Films 1998;317:393–6.
[113] Tucker B, Cottell C, Auyeungt R, Spector M, Nancollas G. Pre-conditioning
and dual constant composition dissolution kinetics of pulsed laser
deposited hydroxyapatite thin films on silicon substrates. Biomaterials
1996;17:631–7.
[114] Fernandez-Pradas JM, Cleries L, Sardin G, Morenza J. Hydroxyapatite coatings
grown by pulsed laser deposition with a beam of 355 nm wavelength. Journal
of Materials Research 1999;14:4715–9.
[115] Cleries L, Fernández–Pradas J, Morenza J. Bone growth on and resorption of
calcium phosphate coatings obtained by pulsed laser deposition. Journal of
Biomedical Materials Research 1999;49:43–52.
[116] Zeng H, Lacefield WR. XPS, EDX and FTIR analysis of pulsed laser deposited
calcium phosphate bioceramic coatings: the effects of various process
parameters. Biomaterials 2000;21:23–30.
[117] Ball M, Downes S, Scotchford C, Antonov E, Bagratashvili V, Popov V, et al.
Osteoblast growth on titanium foils coated with hydroxyapatite by pulsed
laser ablation. Biomaterials 2001;22:337–47.
[118] Rau JV, Generosi A, Laureti S, Komlev VS, Ferro D, Cesaro SN, et al.
Physicochemical investigation of pulsed laser deposited carbonated hydro-
xyapatite films on titanium. ACS Applied Materials & Interfaces
2009;1:1813–20.
[119] Man H, Chiu K, Cheng F, Wong K. Adhesion study of pulsed laser deposited
hydroxyapatite coating on laser surface nitrided titanium. Thin Solid Films
2009;517:5496–501.
[120] Dinda G, Shin J, Mazumder J. Pulsed laser deposition of hydroxyapatite thin
films on Ti–6Al–4V: effect of heat treatment on structure and properties.
Acta Biomaterialia 2009;5:1821–30.
[121] Rajesh P, Muraleedharan C, Komath M, Varma H. Pulsed laser deposition of
hydroxyapatite on titanium substrate with titania interlayer. Journal of
Materials Science: Materials in Medicine 2011;22:497–505.
[122] Kim H, Camata RP, Chowdhury S, Vohra YK. In vitro dissolution and
mechanical behavior ofo i 4 c o /i4-axis preferentially oriented hydro-
xyapatite thin films fabricated by pulsed laser deposition. Acta Biomaterialia
2010;6:3234–41.
[123] Pelletier H, Nelea V, Mille P, Muller D. Nano-scratch study of pulsed laser-
deposited hydroxyapatite thin films implanted at high energy with N þ and
AR þ ions. Journal of Materials Science 2004;39:4185–92.
[124] Cotell C. Pulsed laser deposition and processing of biocompatible hydro-
xylapatite thin films. Applied Surface Science 1993;69:140–8.
[125] Park E, Condrate RA. Graded coating of hydroxyapatite and titanium by
atmospheric plasma spraying. Materials Letters 1999;40:228–34.
[126] Kummer FJ, Jaffe WL. Stability of a cyclically loaded hydroxyapatite coating:
effect of substrate material, surface preparation, and testing environment.
Journal of Applied Biomaterials 1992;3:211–5.
[127] Ong J, Lucas L, Lacefield W, Rigney E. Structure, solubility and bond strength
of thin calcium phosphate coatings produced by ion beam sputter deposition.
Biomaterials 1992;13:249–54.
255
[128] Garcia-Sanz F, Mayor M, Arias J, Pou J, Leon B, Perez-Amor M. Hydroxyapatite
coatings: a comparative study between plasma-spray and pulsed laser
deposition techniques. Journal of Materials Science: Materials in Medicine
1997;8:861–5.
[129] Wang C, Lin J, Ju C, Ong H, Chang R. Structural characterization of pulsed
laser-deposited hydroxyapatite film on titanium substrate. Biomaterials
1997;18:1331–8.
[130] Chen M, Yang X, Liu Y, Zhu S, Cui Z, Man H. Study on the formation of an
apatite layer on NiTi shape memory alloy using a chemical treatment
method. Surface and Coatings Technology 2003;173:229–34.
[131] ASTM C 633-79. Standard Test Method for Adhesion or Cohesive Strength of
Flame Sprayed Coatings. Annual book of ASTM Standards Section 2;1979.
[132] Rajesh P, Muraleedharan C, Komath M, Varma H. Laser surface modification
of titanium substrate for pulsed laser deposition of highly adherent hydro-
xyapatite. Journal of Materials Science: Materials in Medicine 2011;22:
1671–9.
[133] I.O.f. Standardization, I.E. Commission, Information technology: security techni-
ques: code of practice for information security management. ISO/IEC; 2005.
[134] Sarkar P, Nicholson PS. Electrophoretic deposition (EPD): mechanisms,
kinetics, and application to ceramics. Journal of the American Ceramic
Society 1996;79:1987–2002.
[135] Maiti H, Datta S, Basu R. High-Tc superconductor coating on metal substrates
by an electrophoretic technique. Journal of the American Ceramic Society
2005;72:1733–5.
[136] Sarkar P, Huang X, Nicholson PS. Zirconia/alumina functionally gradiented
composites by electrophoretic deposition techniques. Journal of the Amer-
ican Ceramic Society 2005;76:1055–6.
[137] Fischer R, Fischer E, De Portu G, Roncari E. Preparation of ceramic micro-
laminate by electrophoresis in aqueous system. Journal of Materials Science
Letters 1995;14:25–7.
[138] Wei M, Ruys A, Milthorpe B, Sorrell C, Evans J. Electrophoretic deposition of
hydroxyapatite coatings on metal substrates: a nanoparticulate dual-coating
approach. Journal of Sol–Gel Science and Technology 2001;21:39–48.
[139] Ma J, Liang C, Kong L, Wang C. Colloidal characterization and electrophoretic
deposition of hydroxyapatite on titanium substrate. Journal of Materials
Science: Materials in Medicine 2003;14:797–801.
[140] Ducheyne P, Radin S, Heughebaert M, Heughebaert J. Calcium phosphate
ceramic coatings on porous titanium: effect of structure and composition on
electrophoretic deposition, vacuum sintering and o i 4 in vitroo/i 4
dissolution. Biomaterials 1990;11:244–54.
[141] Yamashita K, Nagai M, Umegaki T. Fabrication of green films of single-and
multi-component ceramic composites by electrophoretic deposition techni-
que. Journal of Materials Science 1997;32:6661–4.
[142] Zhitomirsky I, Gal-Or L. Electrophoretic deposition of hydroxyapatite. Journal
of Materials Science: Materials in Medicine 1997;8:213–9.
[143] Ducheyne P, Van Raemdonck W, Heughebaert J, Heughebaert M. Structural
analysis of hydroxyapatite coatings on titanium. Biomaterials 1986;7:97–103.
[144] Kim C, Ducheyne P. Compositional variations in the surface and interface of
calcium phosphate ceramic coatings on Ti and Ti–6Al–4V due to sintering
and immersion. Biomaterials 1991;12:461–9.
[145] Yamashita K, Kitagaki K, Umegaki T. Thermal instability and proton con-
ductivity of ceramic hydroxyapatite at high temperatures. Journal of the
American Ceramic Society 1995;78:1191–7.
[146] Stoch A, Brożek A, Kmita G, Stoch J, Jastrzebski W, Rakowska A. Electro-
phoretic coating of hydroxyapatite on titanium implants. Journal of Mole-
cular Structure 2001;596:191–200.
[147] Singh RK, Qian F, Nagabushnam V, Damodaran R, Moudgil B. Excimer laser
deposition of hydroxyapatite thin films. Biomaterials 1994;15:522–8.
[148] Wei M, Ruys A, Swain M, Kim S, Milthorpe B, Sorrell C. Interfacial bond
strength of electrophoretically deposited hydroxyapatite coatings on metals.
Journal of Materials Science: Materials in Medicine 1999;10:401–9.
[149] Nie X, Leyland A, Matthews A. Deposition of layered bioceramic hydroxya-
patite/TiO2 coatings on titanium alloys using a hybrid technique of micro-arc
oxidation and electrophoresis. Surface and Coatings Technology
2000;125:407–14.
[150] Soares G, de Sena LÁ, Rossi AM, Pinto M, Muller CA, de Almeida Soares GD.
Effect of electrophoretic apatite coating on osseointegration of titanium
dental implants. Key Engineering Materials 2004;254:729–32.
[151] Zhang Z, Dunn MF, Xiao T, Tomsia AP, Saiz E. Nanostructured hydroxyapatite
coatings for improved adhesion and corrosion resistance for medical
implants. In: MRS proceedings. Cambridge University Press; vol 703, 2001.
[152] Gleiter H. Materials with ultrafine microstructures: retrospective and per-
spectives. Nanostructured Materials 1992;1:1–19.
[153] Siegel R., Eastman J. Synthesis, characterization, and properties of nanophase
ceramics. In: MRS proceedings. Cambridge University Press; 1988.
[154] Yamashita K, Yonehara E, Ding X, Nagai M, Umegaki T, Matsuda M.
Electrophoretic coating of multilayered apatite composite on alumina cera-
mics. Journal of Biomedical Materials Research 1998;43:46–53.
[155] Nahler G, Mollet A. Dictionary of pharmaceutical medicine. Springer; 2009.
[156] Yamashita K, Matsuda M, Inda Y, Umegaki T, Ito M, Okura T. Dielectric
depression and dispersion in electrophoretically fabricated BaTiO3 Ceramic
films. Journal of the American Ceramic Society 1997;80:1907–9.
[157] Ferrari B, Sanchez-Herencia A, Moreno R. Aqueous electrophoretic deposition
of Al2O3/ZrO2 layered ceramics. Materials Letters 1998;35:370–4.
[158] Ruys A, Wei M, Sorrell C, Dickson M, Brandwood A, Milthorpe B. Sintering
effects on the strength of hydroxyapatite. Biomaterials 1995;16:409–15.
256 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257
[159] We M, Ruys A, Swain M, Milthorpe B, Sorrell C. Hydroxyapatite-coated
metals: interfacial reactions during sintering. Journal of Materials Science:
Materials in Medicine 2005;16:101–6.
[160] Albayrak O, El-Atwani O, Altintas S. Hydroxyapatite coating on titanium
substrate by electrophoretic deposition method: effects of titanium dioxide
inner layer on adhesion strength and hydroxyapatite decomposition. Surface
and Coatings Technology 2008;202:2482–7.
[161] Roop Kumar R, Wang M. Functionally graded bioactive coatings of hydro-
xyapatite/titanium oxide composite system. Materials Letters 2002;55:
133–7.
[162] Uhlmann D, Suratwala T, Davidson K, Boulton J, Teowee G. Sol–gel derived
coatings on glass. Journal of Non-crystalline Solids 1997;218:113–22.
[163] Guglielmi M. Sol–gel coatings on metals. Journal of Sol–Gel Science and
Technology 1997;8:443–9.
[164] Hu L, Yoko T, Kozuka H, Sakka S. Effects of solvent on properties of sol–gel-
derived TiO2 coating films. Thin Solid Films 1992;219:18–23.
[165] Miyazawa Ki, Suzuki K, Wey MY. Microstructure and oxidation-
resistant property of sol–gel-derived ZrO2–Y2O3 films prepared on austenitic
stainless steel substrates. Journal of the American Ceramic Society
1995;78:347–55.
[166] Young DG, Duran MA. Guide to the identification and geographic distribution
of Lutzomyia sand flies in Mexico, the West Indies, Central and South
America (Diptera: Psychodidae). DTIC Document; 1994.
[167] Innocenzi P, Guglielmi M, Gobbin M, Colombo P. Coating of metals by the
sol–gel dip-coating method. Journal of the European Ceramic Society
1992;10:431–6.
[168] Brinker CJ, Scherer GW. Sol–gel science: the physics and chemistry of sol–gel
processing. Academic Press; 1990.
[169] Mehrotra RC. Chemistry of alkoxide precursors. Journal of Non-crystalline
Solids 1990;121:1–6.
[170] Brinker CJ, Ashley CS, Cairncross RA, Chen KS, Hurd AJ, Reed ST, et al. Sol–gel
derived ceramic films—fundamentals and applications. Metallurgical and
ceramic protective coatings. Springer; 1996; 112–51.
[171] Troczynski T, Yang Q. Process for making chemically bonded sol–gel ceramics.
Google Patents; 2001.
[172] Olding T, Sayer M, Barrow D. Ceramic sol–gel composite coatings for
electrical insulation. Thin Solid Films 2001;398:581–6.
[173] Varma H, Kalkura S, Sivakumar R. Polymeric precursor route for the
preparation of calcium phosphate compounds. Ceramics International
1998;24:467–70.
[174] Hench LL. Bioceramics: from concept to clinic. Journal of the American
Ceramic Society 1991;74:1487–510.
[175] Chai CS, Gross KA, Ben-Nissan B. Critical ageing of hydroxyapatite sol–gel
solutions. Biomaterials 1998;19:2291–6.
[176] Deptuła A, Łada W, Olczak T, Borello A, Alvani C, Di Bartolomeo A. Preparation
of spherical powders of hydroxyapatite by sol–gel process. Journal of Non-
crystalline Solids 1992;147:537–41.
[177] Van Raemdonck W, Ducheyne P, De Meester P. Calcium phosphate ceramics.
Metal and Ceramic Biomaterials 1984;2:143–66.
[178] Gross K, Chai C, Kannangara G, Ben-Nissan B, Hanley L. Thin hydroxyapatite
coatings via sol–gel synthesis. Journal of Materials Science: Materials in
Medicine 1998;9:839–43.
[179] Layrolle P, Ito A, Tateishi T. Sol–gel synthesis of amorphous calcium
phosphate and sintering into microporous hydroxyapatite bioceramics.
Journal of the American Ceramic Society 2005;81:1421–8.
[180] Hsieh M-F, Perng L-H, Chin T-S, Perng H-G. Phase purity of sol–gel-derived
hydroxyapatite ceramic. Biomaterials 2001;22:2601–7.
[181] Gineste L, Gineste M, Ranz X, Ellefterion A, Guilhem A, Rouquet N, et al.
Degradation of hydroxylapatite, fluorapatite, and fluorhydroxyapatite coat-
ings of dental implants in dogs. Journal of Biomedical Materials Research
1999;48:224–34.
[182] Overgaard S, Lind M, Josephsen K, Maunsbach AB, Bünger C, Søballe K.
Resorption of hydroxyapatite and fluorapatite ceramic coatings on weight-
bearing implants: a quantitative and morphological study in dogs. Journal of
Biomedical Materials Research 1998;39:141–52.
[183] Zhang S, Xianting Z, Yongsheng W, Kui C, Wenjian W. Adhesion strength of
sol–gel derived fluoridated hydroxyapatite coatings. Surface and Coatings
Technology 2006;200:6350–4.
[184] Barinov S, Tumanov S, Fadeeva I, Bibikov VY. Environment effect on the
strength of hydroxy-and fluorohydroxyapatite ceramics. Inorganic materials
2003;39:877–80.
[185] Zhang S, Bui XL. Adhesion improvement of magnetron-sputtered amorphous
carbon coating on cemented carbide. Adhesion aspects of thin films, vol. 2
autofilled  . p. 37.
[186] Zhang S, Wang Y, Zeng X, Khor K, Weng W, Sun D. Evaluation of adhesion
strength and toughness of fluoridated hydroxyapatite coatings. Thin Solid
Films 2008;516:5162–7.
[187] Kim H-W, Kong Y-M, Bae C-J, Noh Y-J, Kim H-E. Sol–gel derived fluor-
hydroxyapatite biocoatings on zirconia substrate. Biomaterials
2004;25:2919–26.
[188] Ding S, Ju C-P, Lin JC. Morphology and immersion behavior of plasma-
sprayed hydroxyapatite/bioactive glass coatings. Journal of Materials Science:
Materials in Medicine 2000;11:183–90.
[189] Gu Y, Khor K, Cheang P. In vitro studies of plasma-sprayed hydroxyapatite/
Ti–6Al–4V composite coatings in simulated body fluid (SBF). Biomaterials
2003;24:1603–11.
[190] Cheng K, Ren C, Weng W, Du P, Shen G, Han G, et al. Bonding strength of
fluoridated hydroxyapatite coatings: a comparative study on pull-out and
scratch analysis. Thin Solid Films 2009;517:5361–4.
[191] Zhang Q, Long Z, Ren C, Guo B, Xu D, Ma T. Multi-beam mixing implantation
system and its applications. Surface and Coatings Technology
1998;103:195–9.
[192] Ektessabi A. Ion beam processing of bio-ceramics. Nuclear Instruments and
Methods in Physics Research Section B: Beam Interactions with Materials and
Atoms 1995;99:610–3.
[193] Bambauer R, Mestres P, Schiel R, Schneidewind J, Goudjinou R, Latza R, et al.
Surface treated large bore catheters with silver based coatings versus
untreated catheters for extracorporeal detoxification methods. ASAIO Journal
1998;44:303–8.
[194] Ektessabi A. Surface modification of biomedical implants using ion-beam-
assisted sputter deposition. Nuclear Instruments and Methods in Physics
Research Section B: Beam Interactions with Materials and Atoms
1997;127:1008–14.
[195] Sioshansi P, Tobin EJ. Surface treatment of biomaterials by ion beam
processes. Surface and Coatings Technology 1996;83:175–82.
[196] Cui F, Luo Z. Biomaterials modification by ion-beam processing. Surface and
Coatings Technology 1999;112:278–85.
[197] Hamdi M, Ide-Ektessabi A. Preparation of hydroxyapatite layer by ion beam
assisted simultaneous vapor deposition. Surface and Coatings Technology
2003;163:362–7.
[198] Geesink RG, Manley MT. Hydroxylapatite coatings in orthopaedic surgery.
Raven Press, (ISBN 0781700051); 1993.
[199] Aoki H. Science and medical applications of hydroxyapatite. Ishiyaku Euro-
america 1991.
[200] Ji H, Marquis P. Effect of heat treatment on the microstructure of plasma-
sprayed hydroxyapatite coating. Biomaterials 1993;14:64–8.
[201] Chen J, Wolke J, De Groot K. Microstructure and crystallinity in hydroxyapa-
tite coatings. Biomaterials 1994;15:396–9.
[202] Brossa F, Cigada A, Chiesa R, Paracchini L, Consonni C. Post-deposition
treatment effects on hydroxyapatite vacuum plasma spray coatings. Journal
of Materials Science: Materials in Medicine 1994;5:855–7.
[203] Chen J, Tong W, Cao Y, Feng J, Zhang X. Effect of atmosphere on phase
transformation in plasma-sprayed hydroxyapatite coatings during heat
treatment. Journal of Biomedical Materials Research 1997;34:15–20.
[204] Ohtsuka Y, Matsuura M, Chida N, Yoshinari M, Sumii T, Dérand T. Formation
of hydroxyapatite coating on pure titanium substrates by ion beam dynamic
mixing. Surface and Coatings Technology 1994;65:224–30.
[205] Kant R, Sartwell B. Ion beam modification of TiN films during vapor
deposition. Materials Science and Engineering 1987;90:357–65.
[206] Smidt F. Use of ion beam assisted deposition to modify the microstructure
and properties of thin films. International Materials Reviews 1990;35:
61–128.
[207] Cui F, Luo Z, Feng Q. Highly adhesive hydroxyapatite coatings on titanium
alloy formed by ion beam assisted deposition. Journal of Materials Science:
Materials in Medicine 1997;8:403–5.
[208] Choi J-M, Kong Y-M, Sona K, Kim H-E, Lee I. Formation and characteriza-
tion of hydroxyapatite coating layer on Ti-based metal implant by
electron-beam deposition. Journal of Materials Research-Pittsburgh
1999;14:2980–5.
[209] Choi JW, Kong YM, Kim HE, Lee IS. Reinforcement of hydroxyapatite
bioceramic by addition of Ni3Al and Al2O3. Journal of the American Ceramic
Society 1998;81:1743–8.
[210] Hamdi M, Ektessabi A. Influence of annealing temperature on simultaneous
vapor deposited calcium phosphate thin films. Journal of Vacuum Science &
Technology A: Vacuum, Surfaces, and Films 2001;19:1566–70.
[211] Liu J, Luo Z, Cui F, Duan X, Peng LM. High-resolution transmission electron
microscopy investigations of a highly adhesive hydroxyapatite coating/
titanium interface fabricated by ion-beam-assisted deposition. Journal of
Biomedical Materials Research 2000;52:115–8.
[212] Ong JL, Harris LA, Lucas LC, Lacefield WR, Rigney D. X-ray photoelectron
spectroscopy characterization of ion-beam sputter-deposited calcium phos-
phate coatings. Journal of the American Ceramic Society 1991;74:2301–4.
[213] Lacefield W, Rigney E, Lucas L, Ong J, Gantenberg J. Sputter deposition of Ca–P
coatings onto metallic implants; 1990.
[214] Ozeki K, Yuhta T, Aoki H, Nishimura I, Fukui Y. Crystal chemistry of
hydroxyapatite deposited on titanium by sputtering technique. Bio-Medical
Materials and Engineering 2000;10:221–7.
[215] Ozeki K, Yuhta T, Fukui Y, Aoki H. Phase composition of sputtered
films from a hydroxyapatite target. Surface and Coatings Technology
2002;160:54–61.
[216] Ozeki K, Yuhta T, Aoki H, Nishimura I, Fukui Y. Push-out strength of
hydroxyapatite coated by sputtering technique in bone. Bio-medical Materi-
als and Engineering 2001;11:63–8.
[217] Ozeki K, Fukui Y, Aoki H. Hydroxyapatite coated dental implants by sputter-
ing. Biocybernetics and Biomedical Engineering 2006;26:95–101.
[218] De Groot K, Wolke J, Jansen J. Calcium phosphate coatings for medical
implants. Proceedings of the Institution of Mechanical Engineers, Part H:
Journal of Engineering in Medicine 1998;212:137–47.
[219] S. Hasegawa, K. Furuya, Y. Ukegawa, M. Fushimi, H. Aoki, M. Akao, et al.,
Osteocompatibility of hydroxyapatite-coated titanium by thermal decom-
position method. In: Proceedings of the first international symposium on
apatite; 1991. p. 259–66.
 E. Mohseni et al. / International Journal of Adhesion & Adhesives 48 (2014) 238–257
[220] Ding SJ, Ju CP, Lin JHC. Characterization of hydroxyapatite and titanium
coatings sputtered on Ti‐6Al‐4V substrate. Journal of Biomedical Materials
Research 1999;44:266–79.
[221] Brossa F, Cigada A, Chiesa R, Paracchini L, Consonni C. Adhesion properties of
plasma sprayed hydroxylapatite coatings for orthopaedic prostheses. Bio-
medical Materials and Engineering 1993;3:127–36.
[222] Lin JC, Liu M, Ju C. Structure and properties of hydroxyapatite-bioactive glass
composites plasma sprayed on Ti6Al4V. Journal of Materials Science:
Materials in Medicine 1994;5:279–83.
View publication stats
257
[223] Lacefield W. Hydroxyapatite coatings. Annals of the New York Academy of
Sciences 1988;523:72–80.
[224] Koski K, Hölsä J, Ernoult J, Rouzaud A. The connection between sputter
cleaning and adhesion of thin solid films. Surface and Coatings Technology
1996;80:195–9.
[225] Cleries L, Fernandez-Pradas J, Morenza J. Behavior in simulated body fluid of
calcium phosphate coatings obtained by laser ablation. Biomaterials
2000;21:1861–5.