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Effects of TiO 2 on microstructural, mechanical properties and in-vitro

bioactivity of plasma sprayed yttria stabilised zirconia coatings for dental
application

Article  in  Ceramics International · December 2017

DOI: 10.1016/j.ceramint.2017.12.008

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 Ceramics International 44 (2018) 4271–4281

Contents lists available at ScienceDirect

Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Effects of TiO2 on microstructural, mechanical properties and in-vitro T

bioactivity of plasma sprayed yttria stabilised zirconia coatings for dental
application
⁎
A. Jemata, M.J. Ghazalia, , M. Razalib, Y. Otsukac, A. Rajabia
a
Department of Mechanical and Materials Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 UKM, Bangi, Selangor,
Malaysia
b
Department of Periodontology, Faculty of Dentistry, Universiti Kebangsaan Malaysia, Jalan Raja Muda Abdul Aziz, 50300 Kuala Lumpur, Malaysia
c
Department of System Safety, Nagaoka University of Technology, 1603-1 Kamitomioka Nagaoka, Niigata 940-2188, Japan

A R T I C L E I N F O A B S T R A C T

Keywords: One of the most compatible coatings, known as yttria-stabilised zirconia polycrystal (YZP) is deposited on
Dental material metallic Ti alloys due to its excellent hardness and aesthetic value as well as its low affinity for plaques.
Mechanical properties However, poor bioactivities of YZP and the existence of micro crack propagations due to the aging of YZP may
Yttria stabilised zirconia (YZP) result in spontaneous implant failure thus limiting its clinical use. In this work, YZP coating reinforced titania
TiO2
(TiO2), which is formed via a plasma spray technique was investigated in order to enhance the bioactivity and
Bioactivity
the mechanical properties of YZP coatings for dental implants. Based on microstructural studies performed on
the deposited coating, a distinguished lamellar structure comprising YZP and TiO2 was observed. It was found
that the reinforcement of TiO2 in YZP coating significantly reduced the crack due to the improved densities and
the lamellar structure. The mechanical properties were also found to improve with 90% of hardness, 45% of
adhesion strength and 54% of Young's Modulus with TiO2 addition, which is desirable for dental implants. An in-
vitro bioactivity test was then conducted by immersing the coatings in a simulated body fluid (SBF). As a result,
an apatite formation was found on the YZP/TiO2 coating surface after 3 days of immersion. Besides, it was
verified in an XRD analysis that the crystalline TiO2 was found in a rutile phase which was highly effective in
generating apatite (natural mineral in human bones) on YZP coatings, proving that the bioactivities of the
coating were significantly improved. Further studies were also performed on the SBF treatment, which took up to
14 days also demonstrated that only a small decrease in hardness was noted, indicating that YZP/TiO2 coatings
had reached an excellent mechanical stability.

1. Introduction In addition, zirconia is mechanically stronger than certain bioactive

The development of implants with zirconium oxide (ZrO2) based
materials has become a topic of increasing interest since the past 6
years [1–6]. A biomedical grade zirconia, also known as yttria-stabi-
lised zirconia polycrystal (YZP) [2,7], has more useful mechanical
properties compared to commercial titanium alloys. YZP is widely used
in dentistry applications, especially for endosseous implants. This is due
to its favourable mechanical strength, its resistance to low temperature
degradation [8], low toxicity [9], and low affinity for plaques [10].
Further advantages of YZP include its tooth-like colour and low in-
flammation response [11]. Besides, Cho and Park [12] reported that
hydroxyapatite (HA) reinforced with zirconia coated titanium implants
showed better adhesion strength between the coating and the substrate.
ceramics including calcium phosphate, fluorapatite (FA), HA, and
wollastonite [13].
Despite these desirable mechanical properties, pure YZP ceramics
are still rarely used in dental implants due to their poor bioactivity. This
can be shown from the insufficient chemical bonding between bone
tissue and the implant stimulated by YZP [14]. The direct structural and
functional connection between the living bone and the surface [15] of
dental implants is known as osseointegration. High bioactivity is an
important determinant for this, especially for a long-term success im-
plantation. Based on biochemical point of view, YZP materials do not
easily chemically or biologically bond with surrounding tissues when
implanted. Therefore, bioactive materials are often selected as coatings
on titanium alloy substrates in order to stimulate a direct bond between

⁎
Corresponding author.
E-mail address: mariyam@ukm.edu.my (M.J. Ghazali).

https://doi.org/10.1016/j.ceramint.2017.12.008
Received 16 September 2017; Received in revised form 30 November 2017; Accepted 1 December 2017
Available online 05 December 2017
0272-8842/ © 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
A. Jemat et al.
the bone-like surface and tissues [16].
A bioactive TiO2 is always employed as a strengthened material for
dental implant coatings due to its high biological activity. This char-
acteristic not only enhances the osteoblast adhesion of the dental im-
plant, but also possess self-healing characteristics and the ability to
achieve a direct chemical bond to the surrounding tissues [17]. On the
other hand, the TiO2/yttria-tetragonal stabilized zirconia (Y-TZP)
composites are produced via a sol–gel process in order to improve the
TiO2 properties [18]. In the recent study by Kaluđerović et al. [19], the
anodic plasma-electrochemical coating process was used in order to
produce a zirconia/titania-based composite for dental applications.
However, their studies were mainly focused on improving the me-
chanical properties rather than enhancing the bioactivity of the YZP.
The bioactivity characteristic of biomaterial can be assessed by
immersion in a simulated body fluid (SBF). A material cannot be de-
fined as bioactive unless the formation of apatite occurs on its surface
after being soaked in SBF for a certain duration [14]. Furthermore,
apatite formations comprise of nucleation and the development of ac-
tive layers which is affected by factors such as morphology, composi-
tion, and roughness. Based on previous work [14], the rapid formation
of apatite were observed on a surface of plasma-sprayed ZrO2 re-
inforced HA composite coatings after being soaked in a SBF solution.
Moreover, researchers [15,17] found the presence of TiO2 induced in-
vitro bone-like apatite formation that stimulated in-vivo osteo-
conductivity. Moreover, several studies [13,17] discovered that TiO2
surfaces were more bioactive and able to spontaneously induce apatite
in the SBF solution. Besides, an in-vitro test had confirmed an excellent
bioactivity of titania with rutile phase [18]. On the other hand, the
ability of titania to bond well to bone [19] which is desirable for dental
implants was observed in the in-vivo test. The existence of anatase and
rutile phases in titania gels significantly improved the apatite-forming
ability in the SBF [20,21]. In other work, titania-Y-TZP composites were
fabricated by a sol–gel precipitation exhibiting bioactivity. This was
resulted from anatase/rutile titania phases preservation [22]. In short,
various methods are available in order to improve mechanical proper-
ties of YZP with bioactive ceramics like HA, fluorapatite (FA) and cal-
cium phosphate [17,20,22].
A plasma spray method is a highly effective technique for composite
coating. This technique is frequently used to enhance surface roughness
which originates from the presence of pores to reduce the healing time
[23] and inhibited cell growth [24], whilst maintaining its excellent
mechanical properties. In addition, surface roughness and porosity are
the important parameters that play crucial roles in implant tissue in-
teraction and osseointegration [25]. Evaluation of the implant coatings
by the plasma spraying technique found that surface roughness had
significant effects not only on the hardness and bonding strength [26],
but also on the adhesion of osteoblasts cells to the substrate surface
[27]. The interlocking between the bone and the implant surface was
improved by the micro rough surface ranging from 1 to 10 µm [25].
However, it was reported that failures of osseointegration as well as
implant failure were subject to the ineffective roles of the coating/
substrate interfaces when immersed in the SBF [13,28]. This attributed
to the porosity within the coating layer, poor particle bonding and low
strength between the lamellar inside the plasma sprayed coatings.
Therefore, a composite coating with material reinforcement as a new
phase [29] is highly important in order to mitigate this problem [30].
For this reason, selection of bioactive materials is crucial for the in-
crease of the microstructural, mechanical properties, and bioactivity
characteristics of the YZP coatings for dental implants.
In order to address both bioactivity and mechanical performance
issues of YZP, deposited composite coatings with TiO2 via plasma
spraying technique seems to be desirable. The main hypothesis of the
study is the addition of TiO2 to YZP coating may result in better per-
formance compared to a pure YZP coating layer.
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Ceramics International 44 (2018) 4271–4281
Table 1
Ball milling parameter for YZP/TiO2 powders mixing.
Parameter Value
Speed (r.p.m) 100
Time (h) 3
Time off (min) 10
Powder (g) 100
Powder: Ethanol ratio 1:1
2. Material and method
2.1. Preparation of YZP/TiO2 powder
The mixture of YZP and TiO2 feedstock powders was made ball
milled [21] in a ceramic jar, with an ethanol as a dispersant to form
YZP/xTiO2 (x = 0, 10, 20 and 30 wt%) mixing powders. The parameter
for the ball milling process is shown in Table 1. The average after-
milled powder size was found to be in the range of 45–90 µm. YZP
particles were spherical whilst the TiO2 particles were angular in shape
as shown in Fig. 1. Based on an XRD analysis, both powders were
confirmed well-crystallised with relatively high purity.
2.2. Plasma spray process
The Ti-6Al-4V alloy substrates were sectioned into thin plates with
measurement of 150 mm × 10 mm × 3 mm dimensions. In order to
remove any traces of surface impurities, the plates were ground using
silica carbide papers (1000 and 1200 grit). Then they were cleaned in
an ethanol solution, and dried in an air furnace at 60 °C for 10 min.
Prior to the plasma spraying process, substrate surfaces were grit
blasted using alumina powders (400–600 µm) in order to enhance the
mechanical bonding between the coating and the substrate [14]. Fol-
lowing that, atmosphere plasma spraying (APS) by Sulzer Metco func-
tioned to deposit the ceramic coatings. The coating consisted of a
powder mixture, which was designated according to what is listed in
Table 2. Fig. 2 illustrates the schematic layout of the YZP/TiO2 coating
process. Meanwhile the spraying parameters are summarised in
Table 3.
2.3. Morphology and surface characterisation
All coating surfaces were metallographically prepared according to
ASTM E 1920 – 03 standards. The microstructures of polished coatings
were observed by scanning electron microscopy (SEM) and the surface
and cross section porosity measurement were in accordance with ASTM
E 2109 standards [31]. The grayscale SEM micrographs was taken for
image analysis and conducted with the Image J software [32]. The
phase composition of the coatings was examined using an x-ray dif-
fractometer (XRD), whilst the surface roughness measurement (Ra) was
carried out using a profilometer (Model Formtracer SV-C3100). Last but
not least, the surface microstructure and composition after the im-
mersion in SBF were examined using SEM-EDS analysis.
2.4. Nanoindentation test
Hardness evaluation is an important parameter in identifying the
strength and mechanical stability of a coating layer. In this study,
hardness and elastic modulus strength of the coating layers were
measured using the nanoindentation tester with a Berkovich indenter.
As a result, the loading rate was 0.5 mN/min and the dwell period at
maximum load (10 mN) was 10 s for every reading. The average value
of 10 readings was taken.
A. Jemat et al. Ceramics International 44 (2018) 4271–4281

Fig. 1. SEM micrograph of powders, a) YZP, b) TiO2 and c)

mixture of YZP and TiO2.

Table 2 Table 3
Plasma spraying parameter for YZP/TiO2 coatings. Composition and designation of YZP/TiO2 coating.

Parameter Composition (powder) Designation

Plasma gas/flow rate Argon/42 L min−1 Pure YZP YZP

Carrier gas/flow rate Argon/7–8 L min−1 YZP + 10 wt% TiO2 0.1 T
Powder feed rate 10 g/min YZP + 20 wt% TiO2 0.2 T
Current 600 A YZP + 30 wt% TiO2 0.3 T
Spray distance 120 mm

Fig. 2. Fabrication of YZP/TiO2 composite coatings

by atmospheric plasma spraying.

Voltag
ge Powderr feeder

Coolinng
water

Plasm
ma Molten/ Unmellted
Gas particles
Substrate
Coating

Electrodee

Nozzle

Insulationn

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A. Jemat et al.
2.5. Adhesion test
Another important mechanical property for the coating on metallic
implants is bonding strength. In this study, the adhesion or substrate/
coating interface strength was evaluated according to ASTM C633. The
bonding strength was measured at a tensile strain rate of 0.5 mm/min.
Prior to the adhesion test, both coating and grit-blasted surfaces were
glued onto a 16-mm diameter aluminium cylinder using an epoxy resin
adhesive. Five measurements were taken and an average value
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Ceramics International 44 (2018) 4271–4281
Fig. 3. XRD patterns of the YZP/TiO2 coatings; (a)
YZP, (b) 0.1 T, (c) 0.2 T and (d) 0.3 T.
calculated.
2.6. In-vitro test in SBF
The effect of TiO2 addition on the in-vitro bioactivity of YZP/TiO2
coatings was studied by characterising the apatite growth on the
coatings surface via a SBF immersion. The ion concentration of SBF
solution was found to be similar to human blood plasma which was
strictly prepared according to the Kokubo's protocol [33] for 1, 3, 7 and
A. Jemat et al.
14 days at 37 °C. The ion concentration of the solution was maintained
by refreshing the SBF every 24 h. After a certain period of immersion,
the coatings were taken out and thoroughly washed with distilled water
and air-dried. The SEM-EDS was used to observe the change in surface
morphology and composition of the apatite nuclei. The changes in the
pH value of the SBF solution were also recorded using pH meter
(Mettler Toledo).
3. Results and discussion
3.1. Structural and morphological analysis
Fig. 3. shows the X-ray diffraction results of the YZP/TiO2 ceramic
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Ceramics International 44 (2018) 4271–4281
Fig. 4. Surface morphologies of coating; a) YZP, b)
0.1 T, c) 0.2 T, d) 0.3 T and at higher magnification
(e-h).
coatings. It was noted that the diffraction peaks for all the coatings
mostly composed of crystalline YZP with the peak intensity being
constantly sharp and high. Furthermore, the tetragonal peaks with
higher intensity were shown from the XRD pattern for YZP indicating
the pure phase of YZP which was in agreement with other studies
[21,23]. Another phase in the XRD pattern was ZrTiO4, which occurred
as a result of the reaction between YZP and TiO2 [34,35]. This showed
that with higher ratios of YZP-TiO2, a complete transformation of
ZrTiO4 can be achieved. Therefore, desired mechanical and thermal
properties of sintered porous ceramics can be produced [36].
The SEM views of the surface morphologies of YZP, 0.1 T, 0.2 T and
0.3 T coatings are presented in Fig. 4. Typical plasma sprayed features
with the presence of splats, cracks and micro porosity were observed on
A. Jemat et al. Ceramics International 44 (2018) 4271–4281

Fig. 5. Cross-sectional observations of YZP/TiO2

coatings; a) YZP, b) 0.1 T, c) 0.2 T and d) 0.3 T.

Table 4
Surface properties of YZP/TiO2 coatings.

Properties YZP 0.1 T 0.2 T 0.3 T

Roughness, Ra (μm) 7.06 ± 0.24 6.96 ± 0.78 9.12 ± 0.33 5.86 ± 0.29
Surface porosity (%) 5.28 5.69 4.81 6.43
Cross section porosity 0.96 2.50 1.80 1.42
(%)

Fig. 7. Adhesion strength of the YZP/TiO2 composites coatings as a function of the TiO2
content.

Table 5
The Ca/P ratio for all coatings after SBF immersion.

Coatings Immersion (day) Atomic (%) Ca/P ratio

Ca P

YZP 1 1.10 9.51 0.12

3 1.32 4.05 0.33
7 3.20 5.54 0.58
14 8.97 8.88 1.01
Fig. 6. Hardness and Young's Modulus of the YZP/TiO2 composites coatings as a function 0.1 T 1 3.97 9.47 0.42
of the TiO2 content. 3 12.01 9.84 1.22
7 12.88 9.13 1.41
14 13.10 8.45 1.55
the YZP/TiO2 coating. Meanwhile the cross-sections of all coatings are 0.2 T 1 1.21 4.84 0.25
depicted in Fig. 5. It was observed that the lamellar structure of the 3 4.17 4.85 0.86
coatings was constructed due to the impact of molten YZP and TiO2 7 11.05 8.70 1.27
particles on the substrate surface. These particles consequently spread 14 4.02 2.73 1.47
0.3 T 1 3.83 5.80 0.66
out, flattened and rapidly solidified, then cooled and solidified to form
3 11.78 8.86 1.33
the lamellar [37] for YZP/TiO2 composite coatings. However, there was 7 14.04 9.24 1.52
no distinct interface between the substrate and coating, which signified 14 18.67 11.29 1.65
excellent interfacial locking [38]. Overall, the deposition layer of
coatings with TiO2 content possessed a very uniform and dense mi-
crostructure compared to those not containing TiO2. Moreover, the

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A. Jemat et al.
Fig. 8. Failure surface images for YZP/TiO2 coatings; (a) YZP, (b) 0.1 T, (c) 0.2 T and (d) 0.3 T ( Ø = 16 mm, Co: cohesive failure; Ad: adhesive failure).
thickness of the coating layers in the present work was found around
75–120 µm (Fig. 5), which was consistent to the previous literature by
Hung et al. [28]. They found that the thickness with the value between
47 and 130 µm was considered sufficient for a good adhesion in
coating-substrates.
Table 4 shows that the YZP/TiO2 coating displayed a rougher sur-
face varying from 5.86 to 9.12 µm. In a similar case [17], micro rough
surface (4.23 ± 0.2 µm) was obtained in order to reduce the healing
period upon implantation. The high values of YZP coating surface
roughness reflected the state of unmelted powder particles. In fact,
various factors such as the process of surface preparation, the presence
of porosity, and the distribution of cracks within the coating had strong
influences on the roughness values. Since the living cell tissue favoured
porosity from 1 to 10 µm [37], the current result suggested that the
surface roughness of YZP/TiO2 coatings may have better initial cell
responses [39], as well as promote good osseointegration. Furthermore,
it was noted that all cross-sectional views of the coatings showed less
than 2.5% porosity (Table 4) indicating that the plasma sprayed powder
was deposited favourably [40]. A direct relationship was proven be-
tween porosity, the cell growth and cell adhesion on ceramic materials
through the in-vitro evaluation of cell–material interaction [41]. The
occurrence of porosity on coating surfaces significantly enhanced both
cell adhesion and proliferation in zirconia ceramics. In addition, higher
interconnection between the smaller pores inside the coatings resulted
to a better circulation of nutrient medium for the cells [42].
As observed in Table 4, the cross section porosity value decreased
with the increase of TiO2 content increased. Similar effects, which were
also observed in Al2O3 coating toughened by TiO2 [43]. They found
that the decreased porosity was due to the increase of TiO2. This can be
explained by the low melting point of the dispersed TiO2 in the high
melting point of YZP coating. These dispersedly distributed TiO2 were
responsible for the coverage of the pores.
A large number of fine pores which ranged between 0.1 and 3 µm in
size were also observed on 0.1 T and 0.2 T coating surfaces. These pores
were attributed to the small voids originated from gas entrapment, the
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Ceramics International 44 (2018) 4271–4281
microcracks, and micropores formed in intersplats [44]. According to
previous literature [45], porosities with sizes less than 5 µm were re-
sponsible for the cell proliferation and growth of osseous tissue. Thus a
good bond between the implant materials and the bone was formed. At
a higher magnification, cracks and unmelted particles (Fig. 4e) were
observed on the YZP coating. This was attributed to small particles of
YZP which underwent rapid melting, whereas the larger particles were
stuck inside the melting particles, thereby resulting in unmelted parti-
cles.
3.2. Nanohardness studies
Fig. 6 shows that the addition of TiO2 in the coating gradually in-
creases the hardness. This was due to the compact coating with fewer
cracks and pores. There was a direct relationship between hardness and
the porosity [46], which was also comparable in the present coating
results. The hardness values of 0.1 T, 0.2 T and 0.3 T were found to
increase by approximately 13.6%, 35.5% and 90% respectively com-
pared to the YZP coating. This was attributed to the reduction in por-
osity value by adding TiO2. The 0.3 T coating presented the highest
value of 20.9 GPa and similar trends were also obtained for Young's
modulus. Corresponding to earlier works [47], it was well-observed
that the surface roughness had no significant effect on the hardness
value. Besides, the observed lower value of the hardness of YZP coat-
ings can be ascribed to the physical presence of the crack network in-
side the coating as shown in Fig. 5a. In comparison, the microhardness
of commercial dental materials such as IPS Empress 2 was 5.9 GPa [48].
Meanwhile, the microhardness of Cerabone® was 6.8 GPa [49] and
ceramic coatings that consist of HA reinforced by YZP and Ti–6Al–4 V
was 3.92 GPa [21]. As shown in Fig. 6, the hardness values for YZP/
TiO2 coatings were between 11 and 20.9 GPa, which proved that the
current chosen materials were harder than the commercial ones. Apart
from that, they were capable of being used in dental implant.
In regards to the hardness, the low Young's modulus values for
plasma sprayed coatings were associated with porosity, pore, cracks
A. Jemat et al.
Fig. 9. Apatite nucleation morphology induced on different coating surfaces in the function of time (scale: 1 µm for all figures).
and interlamellar structure [47]. In fact, an increase in the elastic
modulus strength of the YZP/TiO2 coatings had eliminated the effects of
surface microstructure with the relatively high amount (4.81–6.43%) of
pores on the surface (refer to Table 4).
3.3. Adhesion strength
The bonding strength of each coating is presented in Fig. 7. It is
interesting to note that all coatings were well-adhered to the substrate.
This was possibly due to mechanical interlocking and sufficient
roughness on the substrate surface. The adhesion strength evaluation
revealed that the average value of adhesion strength increased from
5.22 to 8.51, 9.28 and 12.0 MPa as the coating content was amounted
to 10, 20 and 30 wt% TiO2, respectively. The findings of the current
study were consistent with the findings from the study conducted by of
Yugeswaran and co-workers [49]. In their study, it was found that the
value of yttria stabilized zirconia reinforced hydroxyapatite (HA) have
increased between 3.43 and 5.39 MPa. Evidently, by adding TiO2 in
YZP coating a greater adhesion strength compared to pure YZP mate-
rials was acquired. Moreover, the ultimate adhesion strength
(12.0 MPa) of 0.3 T coating was in agreement with the ones from the
earlier study which found that the HA coatings with the lowest porosity
had a higher tensile adhesion strength [30]. Nevertheless, YZP pre-
sented the lowest value of adhesion strength. This could be due to the
presence of unmelted particles [38] and a crack network that conse-
quently increased the internal stresses [44] inside the coating and
weakening the interface strength between coating and substrate
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Ceramics International 44 (2018) 4271–4281
(Table 5).
According to ASTM C633, there are three types of failure that can
occur during the adhesion test; adhesive, cohesive and a combination of
these two. Generally, cohesive failure occurs within the coating layer
whilst adhesive failure occurs at the coating and substrate interface.
Fig. 8 shows the coating surfaces after an adhesion strength test was
carried out. It can be seen that the area with majority of the coating
failure was at the interface between coating and substrate, indicating a
predominant adhesive failure. However, some coatings remained on the
surface such as 0.1 T (Fig. 8b) and 0.3 T (Fig. 8d) coatings showing that
the failures were classified as a combination of these. The weaker in-
tersplats and particle bonding of YZP/TiO2 powders might lead to co-
hesive failure. Accordingly, TiO2 not only enhanced the adhesive
strength but also improved the cohesive strength between the lamellar
in the coating. In fact, the low porosity (< 2.5%) and fewer cracks in
the cross section led to a better adhesion of the YZP/TiO2 coatings.
Furthermore, the 0.3 T coating shows the highest adhesion strength
which positively corresponded with the hardness value which is also
identified as the highest value compared to other coatings. Most im-
portantly, similar trends are observed for both graphs; adhesion
strength and hardness. Based on the current study, it was confirmed
that with the increase of hardness, the adhesion for YZP coating with
TiO2 addition also increased. Thus, these surfaces had achieved an
excellent mechanical stability which significantly led to the long term
improvement of the integration of implant surface with the surrounding
tissues.
A. Jemat et al.
Fig. 10. EDS spectra for a) YZP; b) 0.1 T; c) 0.2 T and d) 0.3 T after 14 days of SBF immersion.
Fig. 11. Variation of pH as a function of immersion time in simulated body fluid (SBF).
3.4. Bioactivity studies
The bioactivity of YZP/TiO2 coatings was assessed by investigating
the surface morphology and apatite-forming ability on the coating
surface. This assessment was performed via SBF immersion method.
Fig. 9 shows the surface morphology of all coated specimens after being
immersed in SBF for 1, 3, 7 and 14 days. As a result, the apatite formed
on the YZP coatings surface showed a remarkable increase with the
increasing TiO2 content. At an initial stage of day 3, all coated speci-
mens exhibited the distribution of small apatite nucleation all over the
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Ceramics International 44 (2018) 4271–4281
surface. It was confirmed through EDS analysis that apatites nucleation
was composed of Ca and P elements (Fig. 10). Furthermore, it was
found that the value of calcium to phosphate (Ca/P) ratio for all coat-
ings in current result ranged from 0.12 to 1.65. This value was sig-
nificantly close to the Ca/P ratio of stoichiometric HA (1.67) [50]. As
the immersion time increased, the surface was constituted by many
particle networks as seen on the surface of 0.2 T and 0.3 T coatings. In
contrast, no apatite formation [13,34] was detected on the Y-TZP
ceramic composite, even after one month of immersion in SBF. More-
over, the apatite nuclei formed on the YZP coating were found to be
smaller than YZP/TiO2 coating.
At a longer time of immersion (Fig. 9) all coated surfaces exhibited a
large amount of apatite nuclei formation, hence improving the apatite
layer. This resulted to the apatite's forming ability for a good bioactive
response. It was apparent that the apatite nucleus was much faster in
the coatings containing bioactive TiO2. Based on the current work, the
SEM analysis on immersed coated samples in SBF proved that the sur-
face with TiO2 content could improve the biocompatibilities of the YZP
coating as the rutile phase of TiO2 played an important role in gen-
erating apatite (natural mineral present in bone) formation. Further-
more, the rutile structure in titania gels exhibited an excellent apatite-
forming ability in the SBF [51]. Up to 7 days of SBF immersion, the size
and amount of the apatite nuclei on the surface increased. With a fur-
ther increase of the immersion period to 14 days, the apatite nuclei
became crystallised and agglomerated. Apart from that, it began to
form a layer on the surface of the coatings. On the other hand, an is-
land-like apatite crystal agglomerate was observed on 0.2 T and 0.3 T
surfaces after 14 days of immersion in the SBF. The nucleation of the
A. Jemat et al.
apatite favours occurred more intensely near/in the pores (Fig. 9d3) or
cracks (Fig. 9c7). Moreover similar results were observed in the work of
Ning et al. [52] on ceramic surface. This finding reflects the ideas of
other researchers, who have suggested that the micro-cracks and pores
resulted from dissolution acts as nucleation sites for the nuclei to an-
chor [53].
In general, there is a close relation between bioactivity, porosity and
pore size [24,54]. As porosity increased, surface area also increased,
which resulted to the increase of apatite nuclei formation. This state-
ment was also in agreement with the findings of other study [24]
whereby the pores on the surface facilitated the solute to reach the
bottom of the pores easily, so the apatite nuclei could grow. This was
due to their ability to continuously absorb Ca2+ and HPO2- 4 ions. Based
on the present result, there was a high potential of reducing the healing
time for implantation as well as improving the implant success rates
[23]. To illustrated this, the YZP coating with the highest content of
TiO2 (0.3 T) displayed an excellent behaviour of apatite-forming po-
tential. In short, all coating surfaces in this study could form an apatite
in SBF. Therefore, by modifying the YZP coating surface with TiO2
addition significantly could improve the positive effect on bioactivity
properties.
The effect of TiO2 on the bioactivity behaviour of the YZP coating
was also supported by the change in the pH value of SBF. Changes of pH
in SBF as a function of immersion time are represented in Fig. 11. The
pH value of the SBF solution slightly decreased on the first day of im-
mersion. However, it increased gradually throughout the immersion
process. All coated surfaces showed a similar trend in the pH value.
These results corresponded well with the previously reported data [51]
which described that a small increase in the pH or the concentration of
calcium or phosphate ions in the SBF can result to a noticeable accel-
eration of the apatite formation.
The chemical reaction occurred once the YZP/TiO2 coatings were
immersed into the SBF solution. The origin of Ti-OH groups caused the
coating surface to become slightly altered to a negative charge.
Subsequently, this attracted the calcium and phosphate ions released
from SBF which formed the apatite nuclei [55]. As the SBF was su-
persaturated towards an apatite, the process of apatite nuclei occurred
rapidly, in order to transform into an apatite layer. The purpose of this
was to increase the pH value of the SBF. The increase of the pH value,
which was up to 7.86 after 14 days of immersion in SBF, suggested that
the coating reinforced by TiO2 possessed better apatite-forming ability
as compared to pure YZP. In short, the bioactivity of YZP/TiO2 coatings
strongly depended on the availability of Ti–OH groups and the occur-
rence of rutile crystal structure on the coating surface.
4. Conclusions
The effects of TiO2 on the microstructure, mechanical and bioac-
tivity properties of YZP coating have been successfully studied.
Interestingly, the addition of TiO2 in YZP coatings could significantly
reduce cracks and consequently enhanced the hardness and the adhe-
sion strength. Furthermore, the hardness and adhesion strength of YZP
coatings increased with the addition of TiO2. The highest hardness
value (20.9 GPa) and adhesion strength (12.0 MPa) were achieved for
the composite coating with 30 wt% of TiO2 content. Furthermore, the
rutile phase of TiO2 played a significant role in inducing apatite nu-
cleation, thus producing YZP/TiO2 coating with superior bioactivity
characteristics as dental materials. In overall, coatings with 30 wt% of
TiO2 content were most preferable as they exhibited excellent me-
chanical properties and appropriate surface roughness and micro-
structures. With these coatings, the bioactivity properties of the YZP
coating could be enhanced, aside from the high potential of them to be
used in future dental implant system.
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Ceramics International 44 (2018) 4271–4281
Acknowledgments
The authors would like to acknowledge the Ministry of Higher
Education of Malaysia for financial support under exploratory research
grant number ERGS/1/2012/STG05/UKM/02. Special thanks are
dedicated to the group of Assoc. Prof. Dr. Yuichi Otsuka (Nagaoka
University of Technology) for performing the plasma spray and the
fruitful discussions.
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