Materials Science and Engineering A276 (2000) 160 – 166

www.elsevier.com/locate/msea

The effects of ZrO2 on the phase compositions of plasma sprayed

HA/YSZ composite coatings
K.A. Khor a,*, L. Fu a, V.J.P. Lim a, P. Cheang b
a
School of Mechanical and Production Engineering, Nanyang Technological Uni6ersity, Singapore 639798, Singapore
b
School of Applied Science, Nanyang Technological Uni6ersity, Singapore 639798, Singapore

Received 16 April 1999; received in revised form 24 May 1999

Abstract

The low bonding strength of plasma sprayed hydroxyapatite (HA) coating has been a point of potential weakness in its
application as biomedical prosthesis. In the present study, yttria (8wt.%) stabilized zirconia (YSZ) has been used to enhance the
mechanical properties of HA coatings. This paper focused on the effects of YSZ additions (in the range 10 – 50 wt.%) on the phase
composition of plasma sprayed HA/YSZ composite coatings. The results indicated that decomposition of HA during plasma
spraying reduced significantly with the addition of zirconia. The higher the zirconia content, the lower the amount of calcium
oxide (CaO), tricalcium phosphate (TCP), and tetracalcium phosphate (TTCP) that was formed in the coatings. In addition, there
was a trace of calcium zirconate (CaZrO3) formed when 30wt.% or less zirconia was added. Enhancing the plasma arc current
resulted in an increase in the amount of CaO, TCP, and TTCP. The amorphous calcium phosphates and most of the TCP and
TTCP in the as-sprayed coatings transformed into crystalline HA after heat treatment at 800°C for 2 h. The phase of the zirconia
changed from tetragonal to cubic upon plasma spraying. This was due to the stabilization of the cubic phase by CaO. The 1000°C
annealing showed that only cubic zirconia was present in the coatings. © 2000 Elsevier Science S.A. All rights reserved.

Keywords: Hydroxyapatite; Plasma spraying; Yttria stabilized zirconia; Phase composition; Thermal decomposition; Heat treatment.

1. Introduction dynamically stable. Titania additions to HA promote

Hydroxyapatite (HA) is a bio-active material with a
calcium-to-phosphorous ratio that is similar to that of
natural bone, and as a result can encourage early
bonding between bony tissues and an implant surface
[1,2]. Because of the poor mechanical strength, bone
replacement parts made from hydroxyapatite have been
used exclusively in non-load-bearing areas of the hu-
man body such as the ossicles in the middle ear. To
extend the areas of application of hydroxyapatite, many
attempts have been made to improve the mechanical
properties of HA.
Some researchers have tried to improve HA’s
strength and fracture toughness by alloying it with
various oxides such as zirconia, titania, alumina or
titanium alloy [3 – 6]. However, this tends to severely
reduce the temperature range in which HA is thermo-
* Corresponding author. Tel.: +65-7995526; fax: +65-7911859.
E-mail address: mkakhor@ntu.edu.sg (K.A. Khor)
the formation of tricalcium phosphate (TCP) above
800°C [7] whereas the threshold temperature for HA
decomposition in the presence of zirconia partially sta-
bilized with yttria is above 1100°C when processed by
sintering [8].
Another alternative to the application of HA parts in
the human body is its use as a coating on bio-inert
metallic implants [9,10]. Experimental studies in ani-
mals and experience with human implants have sug-
gested that plasma sprayed hydroxyapatite coatings
(HAC) on metal substrates can induce a direct chemical
bond with bone and hence achieve biological fixation of
the implant [9–12]. But the bonding strength of HAC/
metal interface has been a point of potential weakness
in prosthesis. In our study, 10, 30 and 50wt.% yttria
stabilized zirconia (YSZ) has been added into the hy-
droxyapatite to improve the mechanical properties of
the coatings. This paper reports on the effects of zirco-
nia on the phase compositions of plasma sprayed HA/
YSZ composite coatings. The effects following the

0921-5093/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 9 2 1 - 5 0 9 3 ( 9 9 ) 0 0 4 9 5 - 5
 K.A. Khor et al. / Materials Science and Engineering A276 (2000) 160–166
addition of different contents of zirconia and with
different plasma arc currents (600, 800, 1000 A) were
studied.
2. Experimental methods and materials
Hydroxyapatite and 8wt.% yttria-stabilized zirconia
were obtained commercially (Plasmalloy from Miller
Thermal, USA) with an average particle size of 34
Fig. 1. Particle size distribution of the ball-milled HA/YSZ mixture
powders.
Fig. 2. XRD patterns of as-sprayed coatings obtained at 600 A. (a)
50wt.% ZrO2, (b) 30wt.% ZrO2, (c) 10wt.% ZrO2.
161
Fig. 3. XRD patterns of as-sprayed coatings obtained at 1000 A. (a)
50wt.% ZrO2, (b) 30wt.% ZrO2, (c) 10wt.% ZrO2.
and 30 mm, respectively. The HA particles were
spherical in shape while the ZrO2 were angular. Both
powders had a purity of 99% and were 100% crys-
talline. In order to study the effects of ZrO2 on the
HA coatings, the powders were mechanically ball-
milled together in three different weight proportions,
namely 10, 30, 50wt.% of ZrO2 for 3 h at a speed of
100 rpm in a planetary ball mill (Fritsch P-5, Ger-
many). The particle size distribution was obtained af-
ter milling using a laser particle sizer (Analysette 22
Compact from Fritsch). Fig. 1 is the particle size dis-
tribution of the ball milled HA/YSZ mixture pow-
ders. The mean particle size of the ball-milled
powders is 13.6 mm.
The substrates used for the coatings were Ti-6Al-
4V. They were sand blasted using SiC particles and
then ultrasonically cleaned. A 100-kW net energy
computerized control plasma system coupled with a
six-axis robot unit (Praxair Surface Technologies,
USA) was used to ensure repeatability of the plasma
spraying process. Three different plasma arc currents
(600, 800 and 1000 A) were used to study the effects
of the plasma energy. The plasma working gas was a
mixture of argon and helium. The gases’ flow-rates
162 K.A. Khor et al. / Materials Science and Engineering A276 (2000) 160–166

were 1.70 and 1.10 m3/h, respectively. The powder feed

rate was 10 g/min and the spray distance was 10 cm.
The phase analysis was carried out using Philips
MPD 1880 X-ray diffractometer with Ni-filtered Cu Ka
radiation at 40 kV and 30 mA. A 2u range from 20 to
80° was covered at a step size of 0.02° min − 1. Heat
treatments in the furnace at 800°C for 2 h were applied
to verify the phase transformation and to check the
final phases in the coatings.

Fig. 6. XRD patterns of the coatings in the {400} region after

annealing at 1000°C for 1 h: (a) 10wt.% ZrO2; (b) 30wt.% ZrO2; (c)
50wt.% ZrO2.

3. Results

Figs. 2 and 3 show the XRD patterns of the as-

sprayed coatings obtained at arc currents of 600 and
1000 A, respectively: (a) XRD pattern with 50wt.%
ZrO2 addition, (b) pattern with 30% ZrO2 addition, (c)
Fig. 4. XRD patterns of the coatings heat treated at 800°C for 2 h. 10wt.% ZrO2 addition. Referring to the XRD patterns,
it can be seen that the coating with 50wt.% ZrO2
Table 1
Relative phase ratios of as-sprayed coating at 1000 A
consisted of ZrO2, HA and amorphous phase; at
30wt.% ZrO2 the main phases were ZrO2, HA and
10% ZrO2 30% ZrO2 50% ZrO2 amorphous phase with a small amount of CaO, TCP,
and TTCP; at 10wt.% ZrO2 the phase compositions
ICaO/IHap (%) 8.89 6.21 2.62 were ZrO2, HA, CaO, TCP, and TTCP with a trace of
IHAc/IHAp (%) 35.38 16.66 10.17
CaZrO3. Fig. 4 shows the XRD results for the heat-
ITTCP/IHAp (%) 28.34 18.06 3.26
ITCP/IHAp (%) 16.70 8.63 1.35 treated coatings obtained at an arc current of 1000 A.
ICaZrO/IHAp(%) 2.06 0.87 0.08 The heat-treated coatings consisted of HA, ZrO2 and
CaO. No TCP appeared in the coatings with any of the
zirconia additions. Only a trace of TTCP existed in the
coatings with 30wt.% zirconia and some at 10wt.%
zirconia. The results indicated that the amorphous cal-
cium phosphate, some TCP and TTCP transformed
into the crystalline phase of HA during heat treatment.

3.1. Effects to calcium oxide and bioresorbable phases

formation

The experimental results showed that the addition of

Fig. 5. Relationship of HA crystallinity with different ZrO2 additions
after heat treatment. Spraying current: 1000 A.
ZrO2 reduced the presence of CaO detected by XRD
after plasma spraying. There was no (Fig. 1) or a small
amount (Fig. 2) of CaO formed with addition of
50wt.% ZrO2. The coatings with 10wt.% ZrO2 consisted
of some (Fig. 1) or quite a lot (Fig. 2) of CaO. That is,
at the same plasma spraying parameters, the more ZrO2
that was added, the less the amount of CaO. Figs. 1
and 2 also indicate that the addition of ZrO2 decreases
 K.A. Khor et al. / Materials Science and Engineering A276 (2000) 160–166
the formation of TTCP and TCP. There were none or
a trace amount of TCP and TTCP formed with speci-
mens containing 50wt.% zirconia. The amount of TCP
and TTCP increased with decreasing amounts of zirco-
nia. The most TCP and TTCP appeared in the coatings
containing 10wt.% zirconia. XRD patterns showed that
CaZrO3 formed with the addition of 10wt.% zirconia
while there was no trace of CaZrO3 in the composite
coating with 50wt.% zirconia, indicating that increasing
the content of zirconia reduces the formation of
CaZrO3.
It was difficult to obtain the relative phase ratio of
crystalline HA for the as-sprayed coatings because of
Fig. 7. Cross-section microstructures of HA/ZrO2 coating: (a) region
A (gray region); (b) region B (white region); (c) region C (black
region).
163
the formation of an amorphous phase in the coatings.
A comparison of crystalline HA (IHAc), CaO (ICaO),
TTCP (ITTCP), TCP (ITCP) and CaZrO3 (ICaZrO) in the
as-sprayed coatings to the crystalline HA (IHAp) in the
raw powders with the same contents of zirconia, was
used to evaluate the relative amount crystalline HA,
CaO, TTCP, TCP and CaZrO3, respectively. Table 1
shows the relative phase ratios of ICaO/IHAp, IHAc/IHAp,
ITTCP/IHAp, ITCP/ IHAp, ICaZrO/ IHAp in the coating
sprayed at 1000 A. The results indicate that the content
of CaO, TCP, TTCP and CaZrO3 decreases with in-
creasing amounts of zirconia for the same spraying
parameters.
3.2. Effects of YSZ on HA crystallinity
Some of the crystalline HA solidified as an amor-
phous phase while some decomposed into various cal-
cium phosphate phases during plasma spraying. The
HA peak in the XRD pattern of as-sprayed coatings
represents the crystalline phase of HA which did not
decompose and solidify as an amorphous phase. It can
be seen from Figs. 1 and 2 and Table 1 that HA
crystallinity decreased with increasing the contents of
zirconia.
The extent of decomposition of crystalline HA could
not be quantified directly by XRD patterns of as-
sprayed coatings due to the presence of amorphous
calcium phosphate. After heat treatment, the amor-
phous calcium phosphate transformed to crystalline
HA, but CaO remained. Referring to the XRD results
of the heat-treated coatings, the amount of crystalline
HA could be evaluated. The main peak intensity (area
of the peak) of HA, CaO, TCP and TTCP in the
heat-treated coatings, which was integrated by com-
puter software using the XRD patterns, had been ob-
tained. Fig. 5 shows the relative phase ratios of the HA
crystallinity for different contents of zirconia in the
heat treated coatings. It indicates an upward slope
trend with the highest phase ratio of HA occurring at
50wt.% zirconia addition regardless of the spraying
current. It was also noted that the decomposition of
HA decreased with increasing contents of zirconia.
3.3. Effects of plasma arc current
Fig. 3 indicates that the amount of phases such as
CaO, TCP, TTCP and CaZrO3 increased with increas-
ing plasma arc current. A trace of CaO formed with the
addition of 50wt.% zirconia at 1000 A. Quite a lot of
CaO, TCP and TTCP formed in the coatings sprayed at
1000 A as compared to XRD patterns at 600 A with
10wt.% zirconia. A trace of CaZrO3 formed at 600 A
with 10wt.% zirconia and the content increased at 1000
A. The coating sprayed at 1000 A was annealed at
1000°C for 1 h. The heating and cooling rates were
164 K.A. Khor et al. / Materials Science and Engineering A276 (2000) 160–166

Fig. 8. Elemental analysis as measured by EDX.

10°C/min. Fig. 6 shows the X-ray diffraction patterns Ca10(PO4)6(OH)2 − 2x Ox x

from {400} of c-ZrO2. It shows only cubic zirconia
= Ca10(PO4)6O+ (1− x)H2O (2)
indicating that the tetragonal zirconia transformed to
cubic zirconia upon plasma spraying. Ca10(PO4)6O= 2Ca3(PO4)2 + Ca4[O(PO4)2] (3)
Followed by,

4. Discussion Ca4[O(PO4)2]“ Ca3(PO4)2 + CaO (4)

This decomposition normally takes place above
The decomposition of HA powders without oxide 1200°C over a long period of time. The mechanism of
additives can be described by the following three-step HA decomposition with the addition of zirconia has
reaction equations [13] for 05x 51: been studied recently. Post-sintering HIP of HA ceram-
ics with tetragonal ZrO2 showed that the CaO in HA
Ca10(PO4)6(OH)2 = Ca10(PO4)6(OH)2 − 2x Ox
x + xH2O diffuses into the ZrO2 causing tetragonal ZrO2 to trans-
(1) form into cubic ZrO2. The loss of CaO then accelerates
 K.A. Khor et al. / Materials Science and Engineering A276 (2000) 160–166
the decomposition of HA to beta-tricalcium phosphate
above 800°C [3]. Ioku et al. and Tamari et al. [14]
investigated hot pressed bulk materials at 1300 –1400°C
and also found the transformation of tetragonal ZrO2
into cubic ZrO2 after sintering, but a-TCP was the
decomposition product rather than the b-TCP phase.
Another study by Wu and Yeh [15] indicated that at
sintering temperatures over 1150°C, HA will decom-
pose into b-TCP and CaO. ZrO2 then reacts further
with CaO to produce a new CaZrO3 phase. All of the
above studies were carried out at temperatures less than
1400°C and sintering times more than 1 h. Therefore
there was sufficient time for HA to decompose into
TCP and CaO, and CaO reacts with ZrO2.
Plasma sprayed hydroxyapatite are known to contain
other bio-resorbable phases such as a-TCP, b-TCP,
TTCP, amorphous calcium phosphate and CaO [16,17].
These phases come from the decomposition of the
apatite induced by the high temperature plasma spray-
ing process. Chang et al. [18] studied the plasma spray-
ing of zirconia reinforced HA composite coatings with
the addition of 5 and 10wt.% of ZrO2 stabilized by
Y2O3. The results showed that ZrO2 reacted with CaO
in HA to form CaZrO3 and accelerated HA decomposi-
tion to a-TCP and TTCP during plasma spraying.
In our study, there is an absence of tetracalcium
phosphate (TTCP), tricalcium phosphate (TCP), and
CaO in the XRD pattern of the as-sprayed coating with
50wt.% zirconia. On the other hand, significantly higher
amounts of TTCP, TCP and CaO were found with
10wt.% zirconia suggesting that reactions (3) and (4)
are restrained by adding more zirconia.
In contrast to the previous work on bulk materials
[3,14,15] and plasma sprayed HA coatings with less
than 10wt.% zirconia [18], the present study of plasma
spraying found that CaO, a-TCP and the TTCP phase
in the coatings could be reduced by increasing the
content of zirconia. Meanwhile, a trace of CaZrO3
appeared in the coatings. It was assumed that two steps
had taken place during plasma spraying. The first step
was that the Ca dissolved into the zirconia to form a
solid solution. This dissolution induced the crystalline
HA to transform into an amorphous phase. The second
was that HA decomposed to form CaO that reacted
with ZrO2 to form CaZrO3. The first step played a very
important role during plasma spraying. Because the
particles’ resident time in the high temperature plasma
was quite short, there was insufficient time for the HA
to decompose after the Ca dissolution in zirconia. The
higher the content of zirconia addition, the greater the
dissolution of HA. At the same time, more crystalline
HA transformed to amorphous calcium phosphate.
Fig. 7 shows the cross-section microstructures of an
HA/ZrO2 composite coating obtained by SEM. It can
be seen that there are different regions in the coatings.
Fig. 8 shows the EDX results of the white, gray and
165
dark regions. The EDX results indicate that the gray
area represents a mixture of HA/ZrO2. In the white
area, the main elements are zirconium, oxygen and a
small amount of calcium. It can be inferred that some
CaO mixed with the zirconia. In the dark region, the
main elements are calcium, phosphorous and oxygen. It
represents the mixture of HA and TCP, TTCP and
CaO.
With the addition of zirconia, the additional reac-
tions occurring during plasma spraying are assumed to
be:
Ca10(PO4)6(OH)2 + ZrO2
“ Ca10(PO4)6O doped ZrO2 + H2O (5)
CaO+ ZrO2 “ CaZrO3 (6)
Eq. (5) plays an important role in the reaction during
plasma spraying when more zirconia is added to HA.
Eq. (6) occurs at a lower content of zirconia.
After heat treatment, most of the additional calcium
phosphates (TCP, TTCP) were converted to HA. It was
found that the hydrolysis reactions, which are the ce-
ment-setting reactions in self-setting calcium phosphate
cements, led to the formation of HA [19]. Absorbed
water molecules in the atmosphere easily reacted with
amorphous calcium phosphate, TCP and TTCP to
transform into HA during heat treatment. The reac-
tions can be described as the following equations:
3Ca4P2O9 + 3H2O“ 2Ca5(PO4)3(OH)+ 2Ca(OH)2 (7)
5Ca3(PO4)2 + 3H2O“ 3Ca5(PO4)3(OH)+ H3PO4 (8)
Heat treatment in a humid atmosphere can transform
TTCP and TCP into crystalline HA.
5. Conclusions
The effects of zirconia on the phase compositions of
plasma sprayed HA/ZrO2 composite coatings have been
studied. The main phases of as-sprayed coatings were
HA, ZrO2 including CaO, TCP, TTCP, and CaZrO3
with associated different contents of zirconia. The re-
sults showed that the content of the phases CaO, TCP
and TTCP decreased with increasing amounts of zirco-
nia from 10 to 50wt.%. The higher the content of
zirconia, the lower the amount of CaO formed. The
amounts of CaO, TCP, TTCP and CaZrO3 increased
with increasing plasma arc current. Some HA formed a
solid-solution mixture with the zirconia during plasma
spraying and this increased the degree of amorphous
phase formation. Meanwhile, CaO in the hydroxyap-
atite reacted with the zirconia to form a new phase of
CaZrO3 in compositions containing less than 30wt.%
zirconia. Tetragonal zirconia transformed to cubic zir-
conia upon plasma spraying. The addition of zirconia
to the HA can improve the phase compositions of the
166 K.A. Khor et al. / Materials Science and Engineering A276 (2000) 160–166
composite coatings. Heat treatment played an impor-
tant role in transforming TTCP and TCP into crys-
talline HA.
Acknowledgements
Financial assistance in the form of research grant JT
ARC 4/96 from National Science and Technology
Board (NSTB) and Ministry of Education is much
appreciated.
References
[1] J.D. De Bruijn, C.A. Van Blitterswilk, J.E. Davis, J. Biomed.
Mater. Res. 29 (1995) 89.
[2] M. Jarchol, J. Bioeng. 1 (1997) 79.
[3] K. Ioku, S. Somiya, M. Yoshimura, J. Ceram. Soc. Jpn. 99
(1991) 196.
[4] J. Li, S. Forberg, L. Hermansson, Biomaterials 12 (1991) 438.
[5] J. Li, B. Farasah, L. Hermansson, Interceram. 39 (1990) 20.
[6] K.A. Khor, P. Cheang, Y. Wang, JOM 49 (1997) 51.
[7] J. Weng, X. Liu, X. Zhang, X. Ji, J. Mater. Sci. Lett. 13 (1994)
159.
[8] A.J. Ruys, B.K. Milthorpe, C.C. Sorreti, Interceram. 43 (1994)
7.
[9] K. De Groot, R. Geesink, C. Klein, P. Serekian, J. Biomed.
Mater. Res. 21 (1988) 1375.
[10] S.D. Cook, K. Thomas, J.F. Kay, M. Jarcho, Clin. Orthop.
Relat. Res. 232 (1988) 225.
[11] J.A. Jansen, J.P.C.M. Van De Waerden, J.G.C. Wolk, K. De
Groot, J. Biomed. Mater. Res. 25 (1991) 973.
[12] B.C. Wang, E. Chang, C.Y. Yang, D. Tu, J. Mater. Sci. Mater.
Med. 4 (1993) 394.
[13] K.A. Khor, P. Cheang, J. Thermal Spray Tech. 3 (1994) 45.
[14] W.D. Tong, J.Y. Chen, X.D. Zhang, Biomaterials 16 (1995) 829.
[15] N. Tamari, M. Mouri, I. Kondo, J. Jpn. Ceram. Soc. 95 (1987)
806.
[16] J.M. Wu, T.S. Yeh, J. Mater. Sci. 23 (1988) 3771.
[17] E. Chang, W.J. Chang, B.C. Wang, C.Y. Yang, J. Mater. Sci.
Mater. Med. 8 (1997) 193.
[18] R.B. Heimann, T.A. Vu, J. Mater. Sci. Lett. 16 (1997) 437.
[19] J. Chen, W. Tong, Y. Cao, J. Feng, X. Zhang, J. Biomed. Mater.
Res. 34 (1997) 15 – 20.