Wear studies on plasma sprayed Al

2
O
3
40 wt% 8YSZ composite
ceramic coating on Ti6Al4V alloy used for biomedical applications
G. Perumal
a
, M. Geetha
b,n
, R. Asokamani
c
, N. Alagumurthi
d
a
V.R.S. College of Engineering and Technology, Arasur, Villupuram 607107, Tamil Nadu, India
b
Centre for Biomaterials Science and Technology, School of Mechanical and Building Sciences, VIT University, Vellore 632014, Tamil Nadu, India
c
Dhanalakshmi College of Engineering, Anna University, Chennai 601301, Tamil Nadu, India
d
Pondicherry Engineering College, Pondicherry 605104, India
a r t i c l e i n f o
Article history:
Received 13 October 2013
Received in revised form
31 December 2013
Accepted 31 December 2013
Available online 9 January 2014
Keywords:
Thermal spray coatings
Scratch testing
Sliding wear
Joint prostheses
a b s t r a c t
The relative wear resistance of three candidate coatings for titanium alloy-based orthopedic applications
was compared using a reciprocating test method. Micrometer-sized powders of the following composi-
tions were plasma sprayed onto Ti6Al4V (TAV) alloy: (i) Al
2
O
3
(AO), (ii) 8 mol% yttria stabilized zirconia
(8YSZ) and (iii) Al
2
O
3
40 wt% 8YSZ (A4Z). Deposits were characterized using X-ray diffraction (XRD),
scanning electron microscopy (SEM), and porosity measurements. In addition, microindentation hard-
ness measurements and scratch-based adhesive/cohesive strength measurements were also performed.
The composite coating (A4Z) had superior wear resistance. Wear track examination suggests two reasons
for this improvement. First, the A4Z coating had improved cohesive strength between splats, and second,
there was a phase transition toughening mechanism associated with tetragonal zirconia. Results of
contact mechanics calculations support the experimental ndings.
& 2014 Elsevier B.V. All rights reserved.
1. Introduction
Ti6Al4V alloys are found to be increasingly used in load
bearing bio-implants due to their advantageous properties such as
low density, high strength to weight ratio, greater corrosion resis-
tance and excellent biocompatibility. The other added advantage of
Ti alloy is its modulus of elasticity (113 GPa) which is closer to that of
bone (30 GPa), compared to that of other conventional alloys such as
316 stainless steel and CoCr whose modulii of elasticity are 210 GPa
and 240 GPa and it should be noted that the lower modulii results in
the decrease of the stress shielding effect which in turn leads to
enhanced service period. However, poor tribological properties of Ti
alloys restrict their usage for articulating devices used in biomedical
eld. The alloy Ti6Al4V has been widely used despite concerns in
the medical community that Al might be carcinogenic and that V
might lead to Alzheimer disease. This eventually led to the usage of
II/III generation alloys such as V free Ti6Al7Nb and further several
low modulus beta titanium alloys with non-toxic alloying elements
have been developed and extensively investigated by several
researchers all over the world. The metallurgical aspects and
biocompatibility issues of different Ti alloys have been discussed in
detail in the review article written by two of the authors of the
present paper [1]. Amongst different beta titanium alloys, TNZT and
Ti13Nb13Zr alloys have received greater attention and cataloged
under ASTM. In spite of the fact that certain issues related to Ti6Al
4V implant are still relevant, several major manufacturers of
implants continue to offer Ti6Al4V alloy to develop orthopedic
implants. Hence, in this study we have attempted the coatings on
the most widely used Ti6Al4V implant with the aim of choosing
the best coating which has higher wear resistance.
Currently, ceramic materials are considered to be an alternative
for metalpolyethylene based implants or metalmetal articulating
devices due to their unique features of high hardness, superior
tribological performance along with the excellent biocompatibility.
Further, the recent works in this area reveals that, the wear rates are
reduced signicantly when ceramic femoral head is made to move
either over polyethylene or ceramic cup [27]. Though many
previous works have reported that Al
2
O
3
and ZrO
2
ceramic materials
have withstood the harsh environment in the human body, brittle-
ness and low fracture toughness of pure alumina and hydrothermal
instability of zirconia implants limit their usage for biomaterial
implants [9,10] and therefore more recently aluminazirconia
toughened composites have been proposed for the fabrication of
the acetabular cup and femoral heads, as they provide the superior
combination of mechanical properties and wear resistance. The
increase in the fracture toughness of these composites is attributed
to the presence of zirconia as the fracture strength of zirconia
ceramic is approximately double that of alumina and the enhanced
tribological properties due to the addition of hard alumina [3,8]. Hip
simulator experiments carried out on different compositions of
aluminazirconia (ranging from 0% to 80%) clearly demonstrated
Contents lists available at ScienceDirect
journal homepage: www.elsevier.com/locate/wear
Wear
0043-1648/$ - see front matter & 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.wear.2013.12.027
n
Corresponding author. Tel.: 91 9840896296.
E-mail addresses: perumal_harish@yahoo.com (G. Perumal),
gmv1225@yahoo.com, geethamanivasagam@vit.ac.in (M. Geetha),
asokamanir@yahoo.co.uk (R. Asokamani), alagu_pec@yahoo.co.in (N. Alagumurthi).
Wear 311 (2014) 101113
that aluminazirconia ceramic cup and ball offer the highest wear
resistance with enhanced mechanical properties than pure alumina
[3]. However, susceptibility to slow crack growth, squeaking noises,
stripe wear and headneck taper mismatching are the major
concerns in ceramic-on-ceramic articulating devices [9,10].
Ceramic coatings on implant materials using different surface
modication techniques are considered to be alternative solutions
to overcome failure of bulk ceramic materials. TiN, DLC and oxide
coatings have been attempted using techniques such as ion
implantation, PVD, CVD etc. [1114]. However, thin layers formed
using these techniques is one of the major disadvantages as they
wear out with time.
Amongst the different surface modication techniques, plasma
spraying which can deposit thick ceramic coating with faster
deposition rate is considered to be the highly efcient technique
by industries to develop different kinds of hard and soft coatings
to prevent the substrate from various surface degradations. Espe-
cially in the eld of aerospace, and navy, thermal sprayed coatings
are very much utilized as they provide high wear resistance to the
substrate material that possesses superior combination of
mechanical properties like ductility and strength [15]. Plasma-
spraying has also been advocated to develop bio-ceramic (Hydro-
xyapatite-HAp) coating on Ti based implants to enhance osseoin-
tegration [16,17] and has also been approved by Food and Drug
Administration (FDA), USA, for coatings on joint prostheses [18].
However, it is also well known that HAp coating on TAV is not the
right combination as the coating does not get adhere well with the
substrate due to mismatch in thermal expansion coefcient and
this has been studied in greater detail [2628].
Amongst the different ceramic powders that are considered for
developing wear resistant coatings, several studies have revealed
that the microhardness, toughness, and wear resistance of the Al
2
O
3
coatings can be further improved by the addition of other oxides like
ZrO
2
or TiO
2
[1924]. Especially, there are many reports which
indicate that Al
2
O
3
coatings with 40 wt% ZrO
2
on steel and stainless
steel substrate developed by plasma spray process yields better
tribological results which has made us to choose such a coating in
the present study [19,22,23]. Though, nanostructured coatings have
become an emerging technique, the associated challenging problems
such as (i) agglomeration of individual nanoparticles into micron
sized particles, (ii) careful control of particle temperature in the
plasma jet in order to develop bimodal microstructure [25] and
(iii) variation in coefcient of thermal expansion of nanomaterials and
micron sized materials have led us to choose micron sized powders
for this present work. To the best of the authors
0
knowledge, even
though alumina with ZrO
2
has been tried to develop ceramic balls,
coating of this combination of ceramic powders on TAV alloy has not
been carried out so far for biomedical load-bearing applications.
Hence, in the present work an attempt has been made to make
use of the advantageous properties of Al
2
O
3
40 wt% ZrO
2
ceramics
and develop a composite coating on TAV alloy using atmospheric
plasma spraying process for articial hip prostheses and to
investigate their tribological properties in simulated body uid
environment. In addition, the coating parameters optimized in this
study for plasma spraying of ceramic powders is applicable for any
Ti alloy. This work was carried out in order to understand the
effects of the novel ceramic composite composition proposed in
this study on the tribological behavior of Ti alloy.
2. Experimental methods
2.1. Materials and processing
Commercially available Al
2
O
3
with particle size 545 m and
8 mol% yttria stabilized ZrO
2
with the same particle size as that of
Al
2
O
3
were used to obtain the composite feed stock powders. The
as-received Al
2
O
3
powders (fused and crushed) are angular and
with irregular shapes, whereas the 8YSZ powders (sintered and
agglomerated) are of spherical morphology. Composite feed stock
powder was obtained by blending 60% of Al
2
O
3
and 40% of 8YSZ
(by weight) powders using planetary ball mill at a speed of
200 rpm for the duration of 3 h. Metco 3MB plasma gun with
40 KW atmospheric plasma spray system was used to develop the
coatings as was done in our earlier studies [30]. All the coatings
were deposited on biomedical grade Ti6Al4V sample of size
30303 mm
3
using the optimized parameters, which were
obtained after conducting several experiments with different
processing parameters. The parameters employed in the present
study which led to thick, dense and adherent coatings are given in
Table 1. Before the deposition, the substrate was sand blasted
using corundum of size # 24 meshes at an air pressure of about
50 psi.
2.2. Characterization
Surface morphology of all the feed stock powders and as-
sprayed coatings were investigated using scanning electron micro-
scope (Hitachi, S-3400N). Surface morphology of the coated
surfaces as well as cross section was investigated using both
optical and scanning electron microscope. For the microstructural
investigation, the samples were mounted using bakelite powder
and then polished using SiC papers of grit sizes ranging from
120 m to 1600 m and followed by mirror polishing with dia-
mond paste of size 1 m.
Phase analysis of the feed stock powders and the as-sprayed
coatings were performed using X-ray diffractrometer (Brucker, D8
Advance) with Cu K radiation. The current and voltage were set at
40 kV and 20 mA and all the readings were collected in the 2
ranges from 101 to 901 in a step scan mode with a step of 21/min.
Vickers microhardness tester was used to nd the microindenta-
tion hardness of the coatings. Microindentation hardness values
were was measured across the polished cross-section of the coated
samples using a load of 200 g for 15 s and the hardness were
measured at ten different points and its average value is reported.
Porosity measurements were performed on the cross section of
the coatings at seven different areas using the optical microscope
(Carl Zeiss, Canada) attached with clemex image analyzer.
2.3. Scratch testing for evaluating adhesion/cohesion strength
The scratch test was performed on the surface of the coatings
to determine the cohesion/adhesion strength using microscratch
tester (DUCOM, India). Scratch test which is commonly used to
determine the adhesion strength of thin coatings is used here to
determine the cohesion strength of thick coatings. The load at
which the coating fails usually determines the adhesion strength
of the coating, while the cohesion strength is determined by
observing the failure within the coating after the scratch test
using optical microscope [31,32]. In the present study, Rockwell
Table 1
Plasma spray parameters of the feedstock.
Parameters Al
2
O
3
8YSZ A4Z (composite)
Current (A) 490 510 550
Voltage (V) 70 70 70
Primary (Ar) gas ow rate (l/min) 42 42 42
Secondary (H
2
) gas ow rate (l/min) 7.2 7.2 6.5
Spray distance (mm) 100 100 100
Powder feed rate (g/min) 7 7 9
Carrier gas ow rate (l/min) 5 5 5
G. Perumal et al. / Wear 311 (2014) 101113 102
diamond stylus of radius 200 m was made to slide over the
coatings under ramp loading which ranges from 1 to 100 N at a
rate of 10 N/mmwith a sliding speed of 0.5 mm/s. After the scratch
testing, the onset of coating failure/damage (critical load) as well
as the scratch track at the end of load was observed using optical
microscope in order to determine the load at which failure
occurred and to identify the failure modes respectively. Cohesion
strength of the coating was assessed using the method followed by
Hawthorne et al. [32], who found that the scratch track width,
length of tensile cracking and minimum load at which failure of
the coating occurs to be the good indicators to assess cohesion
strength.
2.4. Friction and wear test
In the present work wear test was carried out using ball-on
plate reciprocating wear tester (TR-285M DUCOM, India) con-
structed in accordance with the provision prescribed by ASTM
G133 standard. Though, ASTM G133 standard was not intended for
screening of bio-implant materials, most of the researchers have
followed the ASTM G133 standard for screening the implant
materials with different load, stroke length and test duration
other than that prescribed by procedure A or B of the standard
[3335,48] as an initial screening test for the selection of materials
or coatings. Further, as far as the selection of the load is concerned,
it has been done on the basis of theoretical calculation made by
comparing the contact pressure on femoral head and contact
pressure on ball in the ball-on-plate conguration. The calculation
was made using the procedure followed by Chikarakara [36]. In
addition, it is found that the contact stress on ball due to selected
load is higher than the maximum contact stress prescribed by the
ASTM F-732 standard (3.54 MPa) which has been specically used
for polymeric materials used in the case of total joint prostheses.
All the wear experiments were performed with 5 mm diameter
Al
2
O
3
ball as a counterpart and the coated Ti6Al4V alloy of
dimension 20 mm20 mm3 mm as the substrate. Wear test
was conducted for the duration of 1,00,000 cycles at a constant
load of 10 N at a frequency of 2 Hz with sliding stroke of 15 mm
[30,48]. All the wear tests were performed in Hank
0
s solution
environment at 37 1C and the constituents of Hank
0
s solution are
presented elsewhere [30]. Before the wear test, the coatings were
ground using 1600 grit SiC papers and then polished using
diamond slurry of size 1 m.The wear experiment was conducted
thrice and the mean weight loss of the ball and the coating were
noted. Both the weight loss method and volume loss method were
used to calculate the wear rate of the ball and the coatings. In the
case of weight loss method, wear rate of the ball and coatings are
calculated by the equation given by Adel et al. [37].
Wear rate
W1W2
Sliding distance
g=cm 1
where, W
1
and W
2
are the weights of the ball or coating before and
after the wear test respectively. The weights of the coatings before
and after the wear test were determined using electronic weighing
balance which has an accuracy of 70.0001 g.
The Klaffke
0
s empirical equation [38] which was used to
calculate wear volume of the ball is given below,
V Wear volume
d
av
8R
d
av
8

4A
3

mm
3
2
where, d
av
is the average transverse diameter of worn surface of
the ball, A is the half of the stroke length and R corresponds to the
radius of the ball used. The volume loss of the coating is calculated
according to ASTM G133 standard, which is given as
V AL mm
3
3
where, A is the average cross sectional area of the wear track and L
is the stroke length. Wear track of all the coatings and balls were
also examined using scanning electron microscope to identify the
wear mechanism.
3. Results and discussion
3.1. Characterization-phase analysis
The objective of performing the XRD studies on the coatings is
to observe the possible phase transformations which would have
been undergone by the particles as they are taken to the molten
state and quenched during the plasma spray process, which will
obviously have a strong bearing on the mechanical properties of
the coatings. Table 2 presents the phases of the powders at
different temperatures and Fig. 1 shows the XRD patterns of both
the as-received feed stock powders and as-sprayed coatings. The
XRD study of Al
2
O
3
feed stocks clearly revealed (Fig. 1a) the
presence of -Al
2
O
3
phase, while the XRD pattern of as-sprayed
Al
2
O
3
coating (Fig. 1d) reveals the presence of the two forms of
Table 2
Phase transition temperature and structure of coating materials.
Material Melting point (1C) Phases Phase transition temperature (1C) Crystal structure Ref
Alumina 2072 RT hcp (Trigonal) [39]
4700 FCC ( Cubic)
4800 FCC (Monoclinic)
41000 FCC (Tetragonal)
41100 hcp (Trigonal)
Zirconia 2700 Monoclinic RT Monoclinic [40]
Tetragonal 41170 Tetragonal
Cubic 42370 Cubic
Fig. 1. XRD pattern of as received powder of (a) Al
2
O
3
, (b) 8YSZ, (c) A4Z composite
and as-sprayed coatings of (d) Al
2
O
3
, (e) 8YSZ and (f) A4Z composite.
G. Perumal et al. / Wear 311 (2014) 101113 103
alumina viz., intermediate metastable -Al
2
O
3
which is the major
phase and smaller traces of -Al
2
O
3
(Fig. 1d).
Fig. 1b and e present the XRD results of 8YSZ feedstock and its
corresponding coating respectively. XRD results show that both
coating and powder are composed of pure metastable tetragonal
zirconia which is the stable phase at higher temperature. However,
discrepancy in the peak intensities among the feed stocks and
coating was observed. The peak corresponding to tetragonal
zirconia at 230.21 in the feed stock disappears in the coating
and few new peaks appeared in the coating at different 2 values
when compared to that of the powders.
The XRD pattern of both as-blended composite powders and
as-sprayed composite coatings are shown in Fig. 1c and f respec-
tively. The presence of high temperature stable tetragonal-ZrO
2
phase and -Al
2
O
3
phase were observed in powders (Fig. 1c),
while, the tetragonal phase of ZrO
2
along with major amount of
-Al
2
O
3
with lower intensity of -Al
2
O
3
is observed in the
composite coating (Fig. 1f). However, the intensity of -Al
2
O
3
in
the composite coating is found to be higher than that of the
alumina coating (Fig. 2d) which indicates that Al
2
O
3
powder in the
alumina coating has undergone extensive melting than in the
composite powders. The formation of -Al
2
O
3
in the alumina and
alumina/zirconia composite coating is a typical phase formed in
plasma sprayed alumina coatings, as this technique is associated
with high temperature and rapid splat quenching. The reason for
the formation of -Al
2
O
3
phase from -Al
2
O
3
has been discussed
by Dejang et al. [41]. Small traces of -Al
2
O
3
in the coating are
attributed to the unmelted or partially melted particles and these
results are in good agreement with the earlier reports on similar
types of coatings [22,23,4143]. Extensive melting and subsequent
high quenching rate of splat favors the presence of high tempera-
ture stable tetragonal-ZrO
2
in the 8YSZ coatings as well as in the
aluminazirconia composite coating in addition to the presence
of -Al
2
O
3
.
3.2. Microstructure of the feed stock powders and coatings
Fig. 2 shows the SEM micrographs of as received micron sized
Al
2
O
3
, 8YSZ, and Al
2
O
3
40 wt% 8YSZ composite blend. Al
2
O
3
powders (Fig. 2a) were of angular shape and of uniform size with
mean particle size of 10 mm and 8YSZ powders (Fig. 2b) exhibit
porous spherical morphology with non-uniform particles whose
size ranged from 5 to 45 mm. The size and morphology of both
powders conform to the details supplied by the manufacturer.
After blending the micron sized Al
2
O
3
with 8YSZ powders using
ball milling process as described earlier, the SEM micrograph
(Fig. 2c) of composite powder shows the uniform distribution of
alumina and zirconia.
Figs. 3 and 4 present the SEM micrographs of surface of the as-
sprayed coatings. The SEM pictures of the surface of the Al
2
O
3
coating are shown in Fig. 3a and at a higher magnication in
Fig. 3b. It is found that the coating consists of smoother disk-like
splats of size varying from 10 to 25 mm. SEM of the surface of the
Al
2
O
3
coating also reveals very small traces of partially melted
particles with uniform distribution of small pores of size ranging
from 2 to 5 mm. Smoothness of splats in the Al
2
O
3
coating surface
is also consistent with the surface roughness values which is given
in Table 3. Formation of these smoother splats in the Al
2
O
3
coating
with uniform distribution of smaller sized pores is due to exten-
sive melting of in-ight particles during the spray and attening of
the molten droplet upon impact on the substrate.
In the case of A4Z composite coating, SEM studies revealed the
presence of certain degree of partially melted particles with fully
molten splats of size 1035 mm (Fig. 4a) and the presence of these
splats with partially melted particles has contributed to the higher
surface roughness of the composite coating compared to alumina
coatings as shown in Table 3. SEM micrograph of alumina coatings
taken at higher magnication clearly indicated the absence of
microcracks (Fig. 4b) and presence of few unmelted particles with
ZrO
2
100m 100m
Fig. 2. SEM morphology of as-received (a) Al
2
O
3
powders, (b) 8YSZ powders and (c) blended A4Z composite powders.
G. Perumal et al. / Wear 311 (2014) 101113 104
very small size of uniformly distributed pores of sizes about 2 mm.
This suggests that most of the particles in the composite feed stock
experienced high degree of melting and spreading upon impact on
the substrate.
Figs. 5 and 6 show the SEM micrographs of cross section of
as-sprayed Al
2
O
3
, 8YSZ and A4Z composite coatings. It was found
that all the coatings are formed by layered structure and all of
them exhibit dense microstructure with less porosity with pores of
smaller size. Porosity values measured using image analyzer are
given in Table 3 and the values obtained also agreed fairly well
with the values obtained from SEM micrographs. The SEM micro-
graph of the Al
2
O
3
coating (Fig. 5a) shows that only a very small
amount of unmelted particles being present compared to that of
8YSZ coating (Fig. 5b) indicating that alumina particles have
experienced the greatest extent of melting. SEM image of 8YSZ
coating (Fig. 5b) reveals the presence of microcracks in the coat-
ing/substrate interface and between the splats. It is obvious that
the adhesion strength of the 8YSZ coating on TAV alloy is less and
this is attributed to the high residual stress resulting from
mismatch of the coefcient of thermal expansion (CTE) between
tetragonal-ZrO
2
and TAV alloy whose CTE values are 12 10
6
K
1
and 8.910
6
K
1
respectively [44,40]. Among the three coat-
ings, mismatch of coefcient of thermal expansion is the least for
the case of aluminazirconia composite coating and TAV as the
CTE value of the composite coat is found to be 8.5 10
6
K
1
[29]
which is very close to that of TAV which will obviously lead to
minimal residual tensile stress along the coating/substrate inter-
face which is the cause for the better adhesion strength of this
system and absence of microcracks.
The SEM pictures taken in the back scattered electron mode of
A4Z composite coating is shown in Fig. 6a. It can be seen from the
micrographs that the coating is composed of alternative layers of
bright and dark lamella. EDX analysis (Fig. 6c and d) shows that
the bright lamella corresponds to ZrO
2
with negligible amount of
alumina while dark lamella corresponds to the mixture of major
amount of alumina and small amount of zirconia and these
features are the same as that have been reported by earlier
workers [19,23,41,43].
SEM micrograph at a higher magnication of composite coating
(Fig. 6b) reveals that the ZrO
2
splats in the form of at stripes
(bright layer) are embedded in the alumina matrix (dark layer).
The absence of microcracks between the two splats in the coating
clearly demonstrated that there is a strong bonding among the
splats. Composite coating also reveals uniformly distributed smal-
ler pores with partially melted or unmelted particles. However,
presence of partially melted particles in the composite coating is
not high as compared to the ZrO
2
coatings. The presence of
unmelted particles can be attributed to the melting state of feed
stock which in turn is determined by the temperature distribution
of the in-ight particles. It should be noted that the temperature
distribution depends on the powder size, injecting velocity and
plasma spray parameters [43,45].
3.3. Scratch test for adhesion/cohesion strength
The results obtained from the scratch test performed on the
surfaces of plasma sprayed coatings viz; onset of coating damage
(critical load), type of failure and nature of cracks as well as crack
length are presented in Table 4. Generally, severe aking and
25m
Fully melted
splat
50m
Pores
Fig. 3. SEM surface morphology of (a) Al
2
O
3
coating and (b) at higher magnication.
10m
Fully melted
splats
Partially melted
p articles
pores
50m
Fig. 4. SEM surface morphology of (a) Al
2
O
3
40 wt% 8YSZ coating and (b) at higher magnication.
Table 3
Roughness, porosity and microhardness of the coatings.
Coatings Roughness (lm) Porosity (vol%) Microhardness (GPa)
Al
2
O
3
3.67 2.42 9.4373.5
8YSZ 4.75 3.41 5.6772.1
A4Z composite 4.52 1.34 8.8671.8
G. Perumal et al. / Wear 311 (2014) 101113 105
delamination are often observed during the scratching of hard
coatings [42]. In the present study, the scratch track of plasma
sprayed Al
2
O
3
coating reveals the presence of large number of
tensile cracks only on the surface of the Al
2
O
3
coating layer and
underlying substrate was not exposed as the coating did not spall
(Fig. 7a and b).
Formation of these tensile cracks are due to the tensile
frictional stress present behind the trailing edge of the stylus
and these stresses are balanced by the compressive frictional
stresses ahead [32]. On the other hand, scratch track of A4Z
composite coating (Fig. 7e and f) exhibits many short micro cracks
on the coating surface instead of long tensile cracking. The scratch
test on the plasma sprayed 8YSZ coatings (Fig. 7c and d) resulted
in severe spallation and delamination with the exposure of
underlying substrate. In addition, the formations of large number
of long tensile cracks were also observed. Thus, the scratch track of
8YSZ coating/TAV system reveals the cohesive and adhesive failure
as given in Table 4. Obviously, the TAV alloy substrate underwent
severe ductile deformation during the scratch testing on 8YSZ
coated Ti alloy. Presence of microcracks and large volume of
partially melted particles can be attributed to the poor cohesion
strength between the splats in the 8YSZ coating. Severe aking
and delamination that were observed in the case of 8YSZ coating
were not observed in the plasma sprayed Al
2
O
3
and A4Z composite
coatings. Instead of severe aking and delamination, spallation
was observed in the vicinity of the scratch track and also both the
coatings show plastic deformation to some degree. Thus, the
plasma sprayed Al
2
O
3
and A4Z composite coatings possess higher
Fig. 6. SEM morphology of polished cross section of (a) A4Z composite coating, (b) at higher magnication, (c) and (d) EDAX at point A and B respectively.
Table 4
Results of scratch test.
Coating Critical load (N) Nature of the crack Crack length (mm) Type of coating failure
Al
2
O
3
41.62 Tensile cracks 50.38 Cohesive
8YSZ 15.39 Tensile cracks 125.42 Adhesive and cohesive
A4Z composite 46.02 Tensile cracks 33.83 Cohesive
Unmelted/partially
melted particles
Substrate
50m
Pores
50m
Coating
Fig. 5. SEM morphology of polished cross section of (a) Al
2
O
3
coating and (b) 8YSZ coating.
G. Perumal et al. / Wear 311 (2014) 101113 106
bonding strength among the splats than that of the plasma
sprayed 8YSZ coating.
Further, interbonding strength of the coating is also character-
ized by the onset of failure (critical load) and the widths of the
scratch tracks. Widths of scratch tracks of both alumina and
alumina/zirconia coatings are much narrower than those for the
plasma sprayed 8YSZ coatings, indicating that the plasma sprayed
Al
2
O
3
and A4Z composite coatings presented better scratch and
wear-resistance property and high ability for plastic deformation
than the 8YSZ coating. The most important conclusion that we
arrive at from the above Table 4 is that the critical load required is
maximum for the A4Z composite coating which indicates max-
imum cohesive strength of composite coating with the substrate
compared to other two coatings.
Further, according to Pan et al. [24], the anti-scratch resistance
of the coating (W
R
), which is a measure of wear resistance is given
as
W
R
p
H
1=2
v
K
2
IC
F
3=2
n
L
4
where, H
v
, F
n
and L respectively refer to the hardness, normal force
exerted on the substrate by the sliding ball and the sliding
distance. As fracture toughness K
IC
is directly proportional to crack
growth resistance (), the above can be rewritten as
W
R
p
H
1=2
v

2a
F
3=2
n
L
5
is the crack growth resistance which is equal to reciprocal of the
crack length and the exponent a (a40), is a property related to the
coating. The crack lengths measured using SEM images for different
coatings are presented in Table 4 and these values were correlated
with the anti-scratch resistance using Eq. (5). This correlation leads to
a very signicant conclusion viz; that the wear resistance of the
composite coating is maximum as the corresponding crack length is
the minimum even though its hardness value is somewhat lower.
3.4. Microindentation hardness
From the Vickers microindentation hardness values of Al
2
O
3
,
8YSZ and A4Z composite coatings (Table 3), it is clearly evident
Tensile cracks
Fig. 7. Scratch track of the coatings of (a) OM image and (b) SEM of Al
2
O
3
, (c) and (d) OM image of 8YSZ, (e) OM image and (f) SEM of A4Z composite.
G. Perumal et al. / Wear 311 (2014) 101113 107
that alumina coating exhibits higher hardness (9.4373.5 GPa)
which was 1.65 times and 1.2 times higher than 8YSZ and A4Z
composite coatings respectively. YSZ coating possesses good
combination of hardness and fracture toughness [46], whereas,
alumina coating possessed higher hardness. Hence, addition of YSZ
in Al
2
O
3
can give the composite coatings having optimum combi-
nation of hardness and fracture toughness which makes the
composite coating more suitable for tribological applications
[4,9,46]. The obvious decrease in the hardness of alumina compo-
site coating arises due to lower hardness of YSZ which is
consistent with the previous reports [43,46]. Presence of pores
and distribution of partially melted or unmelted particles also
seem to be responsible for the reduction in hardness of the
composite coatings.
3.5. Wear rate of the coatings
Amongst the three different coatings, Al
2
O
3
and A4Z composite
coated specimens which were subjected to wear test for 1,00,000
cycles while for 8YSZ coating, the experiment was stopped after
30,000 cycles as the coating got completely removed. Table 5
presents the wear rate and friction coefcient of the all the
coatings against alumina ball in Hank
0
s solution environment. In
the present work, the coefcient of friction and wear rate of TAV
alloy performed in Hank
0
s solution are found to be 0.454 and
3.7510
4
mm
3
/Nm respectively. Qu et al. [47] who has studied
the wear behavior of TAV alloy against alumina ball under dry
condition obtained the coefcient of friction to be 0.49 and wear
rate as 5.7 10
4
mm
3
/Nm. It can be noted that the wear rate
observed with Hank
0
s solution as has been done in the present
work is lesser than those that were observed in the dry condition
which is obviously expected as the intermediate medium acts like
a lubricant. It can also be observed from Table 5 that coefcient of
friction and wear rate of all the three coatings are substantially
lesser compared to the wear of the bare substrate of the TAV alloy.
Further, it is obvious from Table 5 that the wear rates calculated by
both weight loss and volume loss methods show the increasing
trend of wear resistance in the order of A4Z composite coating,
Al
2
O
3
coating and nally 8YSZ coating. The wear rates of both the
coatings as well as the ball measured in terms of the weight loss or
the volume loss show obviously the same trends. It can be seen
that wear rates of the coatings determined from weight loss
method vary from 0.66 10
9
to 4410
9
g/cm. This result
clearly suggests that the wear resistance of the plasma-sprayed
A4Z composite coating on TAV alloy is superior to other coatings.
Many earlier reports in this connection show that porosity
directly inuences the wear resistance of the coating [48,49].
Obviously, though all the coatings posses the dense microstruc-
ture, the well bonded splats and higher microhardness of the
alumina and A4Z composite coatings are the benecial factors for
the improvement of the wear resistance. Evidently, this feature is
consistent with what has been observed and discussed in connec-
tion with the studies made on scratch resistance. Further, there are
reports which show that the wear resistance of plasma-sprayed
ceramic coatings increases with improved hardness and toughness
[5052]. In the present study, the hardness of the A4Z composite
coating is slightly lower than that of the Al
2
O
3
coating, whereas,
the fracture toughness of the A4Z composite coating is found to be
higher from previous reports [25,29] compared with that of the
Al
2
O
3
coating. This combined property of optimum hardness and
fracture toughness of the composite coating are attributed to its
higher wear resistance.
The wear rate of counterpart (alumina ball) was also deter-
mined by both methods in order to obtain cumulative wear (which
refers to the wear rate of both counterpart and coating). The wear
rate of counterpart against the composite coating shows lower
wear resistance than the alumina coating.
Cumulative wear rates of all the coatings are shown in Fig. 8.
It is found that the cumulative wear of 8YSZ coating increased
Table 5
Wear rate of coating and ball.
Coating Wear loss (g) Wear rate (g/cm) (wt loss method) Wear rate (mm
3
/N m) (vol. loss method) Friction
co-efcient (m)
Coating Ball Coating 10
9
Ball 10
9
Coating 10
6
Ball 10
6
Al
2
O
3
0.0015 0.00015 5.00 0.50 12.60 1.26 0.314
8YSZ 0.0132 0.00032 44.00 1.06 25.00 9.01 0.414
A4Z 0.0002 0.00025 0.66 0.83 1.48 2.52 0.342
TAV 0.0149 0.01100 165.00 122.00 375.00 30.10 0.454
Fig. 8. Cumulative wear of (a) 8YSZ coating, (b) Al
2
O
3
coating, (c) A4Z composite coating, and (d) cumulative wear rate of different pair of coating and ball.
G. Perumal et al. / Wear 311 (2014) 101113 108
linearly with number of cycles and is completely peeled off even at
30,000 cycles. In the case of alumina coating, wear rate increases
upto 20,000 cycles and thereafter reaches more or less a steady
state. On the other hand A4Z composite coating attains a steady
state even at lesser number of cycles indicating that the cumula-
tive wear is minimal among the three coatings which can be
obviously seen from Fig. 8c.
Fig. 8d also shows the cumulative wear rate of different pairs.
Among these, the cumulative wear for the pair A4Z/alumina ball is
much lower than the cumulative wear rate of the other two pairs.
The above study makes us to come to a denitive conclusion that
the A4Z composite coating is the best choice as it shows minimum
wear rate.
3.6. Wear mechanism
This section deals with the possible wear mechanisms involved
in the coatings which support the observed wear data. Figs. 911
show the SEM and optical micrographs of wear track on Al
2
O
3
,
8YSZ and A4Z composite coatings and their counter parts respec-
tively. SEM micrograph of worn surfaces of alumina coating is
shown in Fig. 9a and b. Worn surface of alumina coating consists of
grooves, microcracks, and plowing marks. It indicates that the
material removal in the alumina coating is due to abrasive wear
and gets enhanced by the dislodgement of grain boundaries
fracture of the surface splats. This kind of wear mechanism is
consistent with the observations made by other researchers
[53,54]. Worn surfaces of 8YSZ coatings are examined by optical
microscope and are shown in Fig. 10. The worn surface of 8YSZ
coating shows that a large amount of delaminated micron sized
particles has ultimately resulted in the delamination of the coat-
ing. Fig. 11 depicts the wear track morphology of the plasma
sprayed A4Z composite coating tested against alumina ball at
different magnications. A network of ne cracks and chipping
was observed over the zirconia rich splat. These cracks nucleated
and propagated along the splat/splat boundaries and this should
be the obvious reason for the delamination of composite coating.
In addition to chipping and pullouts, brittle fracture was also
observed in the composite coating. The same features of wear
mechanism were noticed by Dejang et al. on Al
2
O
3
20 wt% ZrO
2
coating sliding against WC/Co ball [41]. Fig. 11a shows some
unusual color in the wear track of composite coating unlike what
is being observed in the other regions. In order to probe the above
mentioned difference, EDX analysis was carried out on the worn
surface and the reason for coloration is found to be due to the
presence of the constituents of Hank
0
s solution (Ca, Na, and Cl)
along with wear debris of alumina and zirconia.
In general, in the case of thermal spray ceramic coatings the
detailed study made by Hawthorne et al. [55] shows that the
material removal occurs via three processes viz; (i) microchipping
and plowing, (ii) debonding at splat boundaries and (iii) splat
fractures in association with porosity. In the case of the coating
with poor inter-splat bonding, the major material removal
Fig. 9. SEM micrographs of wear track of (a) Al
2
O
3
coating, (b) at higher magnication, (c) wear track of alumina ball against Al
2
O
3
coating and (d) wear track of alumina ball
at higher magnications.
Fig. 10. Optical micrographs of wear track of 8YSZ coating.
G. Perumal et al. / Wear 311 (2014) 101113 109
mechanism is debonding at splat boundaries. Typical plasma
sprayed ceramic coating is built up by random stacking of
impacted droplets, resulting in imperfect contact between splats
and weak interbonding between splats. Hence, the cracks devel-
oped preferentially at weak-bonding splat boundaries result in
detachment of the coatings and an increase in wear rate [57].
When the cohesion between splats is improved, this changes the
wear mechanism of debonding of splat into splat fracture and
microchipping. This kind of feature has also be observed from the
earlier works [54,56].
In the present work, the wear track of 8YSZ coating exhibits
coating delamination and this can be attributed to the poor inter
bonding of the splats. This further led to higher coefcient of friction
and wear rate than the Al
2
O
3
and A4Z composite coatings. On the
other hand, the wear tracks of Al
2
O
3
and A4Z composite coatings
show the progressive changes in the wear mechanism of coating
delamination into microcracking and microchipping. It demonstrates
the higher inter-splat cohesion strengths of Al
2
O
3
and A4Z composite
coating, which improves the wear resistance than 8YSZ coatings. The
good cohesion strengths of Al
2
O
3
and A4Z composite coating should
be due to the extensive melting and deforming of the molten
particles upon impact leading to more points of contact between
splats which in turn improve the wear resistance. Further, the wear
rate of A4Z composite coating is too much reduced due to the
presence of tetragonal-ZrO
2
in addition to the strong bonding of
splats. Tetragonal-ZrO
2
exhibits the phase transformation toughening
mechanism which resists the crack propagation or deects the crack
which postpones the splat delamination [41].
The wear tracks of counterface against alumina coating and
A4Z composite coating are presented at different magnications in
Figs. 9 and 11. The counterface wears less against the alumina
coating (Fig. 9c) than against the composite coating (Fig. 11d).This
result is consistent with the wear rate of alumina ball as shown in
Table 5.Further, the wear mechanism of counterface against both
coatings, appears to be abrasive wear (Figs. 9d and 11e) owing to
high frictional force developed on the wear surface combined with
the action of wear debris.
3.7. Contact pressure and stress distribution in the coatings
The wear mechanism connected with all the coatings was
correlated using Hertzian contact mechanics, according to which
Fig. 11. SEM micrographs of wear track of (a) A4Z composite coating, (b) at higher magnication, (c) EDX analysis at point A, (d) wear track of alumina ball against A4Z
composite coating and (e) wear track of alumina ball at higher magnications.
G. Perumal et al. / Wear 311 (2014) 101113 110
all the stresses in the contact region are directly related with the
maximum contact pressure at the contact interface and it is given
by the expression [63]
P
0

6pE
n

3
R
2
" #
1=3
7
where p is the normal applied load, R is the ball radius and E
n
is
the reduced elastic modulus for ball and disc which is calculated
from
1
E
n

1
1
2
E
1

1
2
2
E
2

8
Radius of contact circle a
3PR
4E
n

1=3
9
where, E
1
, E
2
are the elastic modulii of ball and disc and
1
,
2
are
Poisson
0
s ratio of ball and disc respectively. For the present work,
E
1
and E
2
for all the coatings were taken from the literature and
are given in Table 6 and Poisson
0
s ratio is chosen as 0.25 from the
work of Shackelford et al. [60].
It should be noted that density functional method has been
found to be very useful in evaluating theoretically the values of
Young
0
s modulus as well as Poisson
0
s ratio as has been done by
Iordanova et al. [16] and one of the authors has done extensive
work along this line on Ti alloys [61,62] which in principle can be
performed for these systems as well. Using the above relations, the
values of contact pressure and contact area were determined for
different mating pairs and the values are given in Table 7.
The values of contact pressure (P
0
) and contact radius (a) are
used to determine the shear stress distribution along x, y and z
directions for the two surfaces which are in contact using the
following expressions [63] and the values of
max
is presented in
Table 7.
s
x
s
y
P
0
1 1
z
a
h i
tan
1
a
z
h i n o

1
2
1
z
2
a
2
1
10
s
z
P
0
1
z
2
a
2
1
11
Table 7
Reduced elastic modulus and maximum contact pressure.
Mating pairs E
n
(GPa) P
0
(MPa) a (mm) Max shear stress
max
(MPa) Depth of max shear stress (mm)
Al
2
O
3
/Al
2
O
3
ball 135.11 1611 0.0243 556.14 0.0245
8YSZ/Al
2
O
3
ball 44.615 775 0.0353 265.69 0.0354
A4Z/Al
2
O
3
ball 114.72 1446 0.0257 498.67 0.0259
Fig. 12. Shear stress distribution in the (a) alumina coating, (b) 8YSZ coating and (c) A4Z composite coating.
Table 6
Elastic modulus of coatings poisson.
Coatings Elastic modulus (GPa) Ref
Al
2
O
3
190740 [58]
8YSZ 47 [59]
A4Z composite 150722 [23]
G. Perumal et al. / Wear 311 (2014) 101113 111

max

s
x
s
z
2

or 0:30P
0
at a depth of 0:48a for 0:3 12
Fig. 12 shows the maximum shear stress (
max
) and its dis-
tribution obtained using Hertzian contact theory of mating pairs.
When two surfaces are under sliding motion, the maximum shear
stress lies at a certain distance below the surface which causes
fatigue cracks initiated at the surface and being propagated to the
subsurface regions. These cracks may be connected to each other
which will lead to separation and delamination of material pieces
[64]. Cai et al. [65] have also addressed this question and found
that dominant wear occurs at the bonding interface due to shear
stress. Cracks observed in the substrate are initiated and propa-
gated mainly due to repeated shear stress subjected to the
bonding interface. From the present work, it is obvious that higher
cohesion strength with lesser contact pressure and shear stress of
the composite coating contributes for its lower wear rate than the
other coatings. The above nding which stems from the theory of
contact mechanics corroborates to the observation made by wear
track studies discussed earlier.
4. Conclusions
The experimental and theoretical studies performed on the
coatings developed on TAV alloy with Al
2
O
3
, ZrO
2
and A4Z
composite powders lead us to make the following conclusions.
Amongst the three different coatings (Al
2
O
3
, 8YSZ and A4Z),
wear resistance is found to be superior for the A4Z composite
coating. The wear resistance of A4Z composite coating is about
8 times higher than the alumina coating and more than 60 times
higher than the 8YSZ coating. Superior wear resistance of the
composite coating is attributed to its dense microstructure and
enhanced bonding strength among the splats. In addition, phase
transformation toughening mechanism due to the presence of
tetragonal-ZrO
2
in the composite coating is also a contributory
factor for its higher wear resistance. Wear track examination of the
coatings reveal that the main wear mechanism in the case of the
composite coating is due to microcracking and microchipping,
whereas, the wear mechanism of 8YSZ coating is due to the de-
bonding of splat. In the case of alumina coating one nds abrasive
wear and dislodgement of splat. SEM micrographs observed at the
cross section of all the coatings, scratch test results and calculation
based on contact mechanics is in agreement with the observed
wear mechanism and wear data. The present study clearly
demonstrates that the A4Z composite coating can be a suitable
choice for enhancing the wear behavior of TAV alloy for articial
implant applications.
Acknowledgments
One of the authors (GP) wishes to thank the chief executive
ofcer MJF.Ln. M. Saravanan and Dr. N. Anbazhaghan of V.R.S.
College of Engineering and Technology for providing their con-
tinuous support and cooperation to carry out the present work. Dr.
Geetha Manivasagam expresses her deep sense of gratitude to the
Department of Science and Technology, India for funding the
Project on Tribology of Coatings on Ti Alloys which led to the
conceptualization of the current work.
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