Effect of Tribo-layer on the Sliding Wear

Behavior of Detonation Sprayed

Alumina–Titania Coatings

P. Uday Chandra Rao, P. Suresh Babu, D. Srinivasa Rao,

S. V. Gopala Krishna and K. Venkateswara Rao

Abstract Alumina–Titania composite coatings are excellent candidates for provid-

ing protection against abrasive and sliding wear. These coatings have their appli-
cations in textile manufacturing components, tooling, components for the chemical
industry and electrical insulation due to high wear resistance, toughness, good grind-
ability and corrosion resistance. Al2 O3 –TiO2 composite powders having TiO2 from 3
to 40 wt% are deposited on mild steel substrates by advanced detonation spray coat-
ing (ADSC) technique, advanced characterization techniques like SEM, FESEM,
EDS, XRD, were carried to access the coating characteristics. Tribological behavior
of coatings was evaluated under dry sliding wear condition as per ASTM standards,
and the results were summarized and correlated with the coating composition.

1 Introduction

Coatings are applied on to material to form a layer by which it enhances the sur-
face properties of the material by acting as composite. Alumina–Titania coatings
deposited by thermal spray process have been used to enhance the wear, corro-
sion resistance, electrical and thermal conductivity as well as elevated temperature

P. Uday Chandra Rao (B) · S. V. Gopala Krishna · K. Venkateswara Rao

Department of Mechanical Engineering, Sir C.R. Reddy College of Engineering,
Eluru, Andhra Pradesh 534007, India
e-mail: [email protected]
S. V. Gopala Krishna
e-mail: [email protected]
K. Venkateswara Rao
e-mail: [email protected]
P. Suresh Babu · D. Srinivasa Rao
Centre for Engineered Coatings, International Advanced Research Centre for Powder Metallurgy
and New Materials (ARCI), Balapur (PO) Hyderabad, Telangana 500005, India
e-mail: [email protected]
D. Srinivasa Rao
e-mail: [email protected]
© Springer Nature Singapore Pte Ltd. 2020 289
A. N. R. Reddy et al. (eds.), Intelligent Manufacturing and Energy Sustainability,
Smart Innovation, Systems and Technologies 169,
https://doi.org/10.1007/978-981-15-1616-0_28
290 P. Uday Chandra Rao et al.

applications. Thermal spray coatings have their potential applications in automo-

bile, aerospace, oil and textile manufacturing industries as well as refurbishments of
worn-out components to enhance the life without total replacement of component in
cost-effective way. During the sliding wear test of plasma sprayed Al2 O3 –13TiO2
coatings on emery papers (two body abrasion), the presence of Al2 TiO5 phase has
reported as beneficial for the improvement of wear resistance, the coefficient of fric-
tion of Al2 O3 –13TiO2 coatings was in the range of 0.3–0.4 at load range of 10–20 N,
at 30 N load, the worn surface analysis revealed that wear is by deep pits, lateral
cracking and extensive splat fracture [1] plasma sprayed Al2 O3 –TiO2 coatings dur-
ing sliding wear test at normal load of 2 N using ball on disc apparatus, a reduction
of 62% in friction coefficient is observed at 25 wt% TiO2 , and an increase in sliding
wear resistance by 2.6 times with increase in TiO2 content (40 wt% of TiO2 ) was
seen when compared to 13 wt% TiO2 [2]. Plasma sprayed conventional Al2 O3 –3TiO2
coating, during the sliding wear test by using silicon nitride ball at room temperature
to 600 °C range, wear rate is found to be increased at elevated temperatures. An oxide
layer is seemed to be formed on worn surface, as well as brittle fracture was occurred
and elevated due to the desorption of moisture on oxide layer with the increase in
temperature, which resulted in its higher wear rate [3]. In the study of wear behavior
of plasma sprayed CoCrMoSi alloy, coatings on as-coated and coatings oxidized at
different temperatures showed that oxidation temperature enhanced the characteris-
tics of the oxide layer formed on the coatings, where coatings oxidized at 450 °C
exhibited high wear resistance compared to as-coated condition. Continuous layer of
chromium oxide was seen on the coatings oxidized at 700 °C which offered resistance
to sliding wear [4]. While evaluating the sliding wear performance of plasma sprayed
hydro carbon coatings against steel and alumina pins, high friction coefficient was
observed at low load and sliding velocity, and less coating wear was observed as a
result of pin material transfer on to the coating wear surface, due to formation of
carbon-rich tribo-layer with low shear strength resulted in low friction coefficient
[5]. Most studies on plasma sprayed Al2 O3 –TiO2 coatings and no such studies are
reported on detonation sprayed Al2 O3 –TiO2 coatings. Further, a computer-controlled
detonation spray system was developed at ARCI where coatings can deposit at higher
frequencies. In view of above, the present work is aimed to study the influence of
TiO2 content on the sliding wear resistance of Alumina–Titania coatings deposited
by advanced detonation sprayed technique. Coating properties like porosity, micro-
hardness and sliding wear behavior were evaluated. Worn surface was analyzed to
understand the impact of wear mechanisms on the wear rate, also to access optimum
amount of TiO2 attribute for the wear resistance of Alumina–Titania coatings.
Effect of Tribo-layer on the Sliding Wear Behavior … 291

Table 1 Description of
Coating Composition Average particle size
Alumina–Titania powders
(μm)
used in coatings
AT-3 Al2 O3 –3 wt% TiO2 15.4
AT-13 Al2 O3 –13 wt% TiO2 14.3
AT-40 Al2 O3 –40 wt% TiO2 45.4

2 Methodology

2.1 Sample Preparation

Coatings are deposited on to mild steel samples of standard sizes to access the coating
characterization and to conduct the tribological studies of coatings. Those include
pins of size Ø 6 mm × 30 mm length for sliding wear test and 10 × 12 × 5 mm size
samples for SEM and XRD analysis. These specimens are sand blasted using alumina
grit (24 mesh size) to attain a surface roughness of 3–4 μm and are ultrasonically
cleaned with acetone to remove the dirt particles from the surface prior to coating
deposition.

2.2 Powder Preparation

Commercially available fused/crushed powders of Alumina–Titania having angu-

lar morphology with TiO2 from 3 to 40 wt% are chosen to form coating by using
advanced detonation spray coating process. Powders are slightly heated in a cru-
cible to remove the moisture content before introducing into powder hopper of spray
equipment, and the description of powders is provided in the Table 1.

2.3 Process Parameters

The process parameters are optimized for advanced detonation spray process to melt
and hurtle the powder particles onto the substrate. The process parameters used in
the spray process are given in Table 2.

2.4 Coating Characterization

The Alumina–Titania-coated samples having thickness of 250–300 μm were sec-

tioned and mounted in bakelite and are fine polished using SiC emery papers further
292 P. Uday Chandra Rao et al.

Table 2 Process parameters of Alumina–Titania coatings used in ADSC process

Process parameter Powder
AT-3 AT-13 AT-40
Oxygen [SLPH] 5120 5040 4960
Acetylene [SLPH] 2240 2240 2240
Powder feed rate [SLPH] N2 as carrier gas 720 720 720
Spray distance, mm 180 180 180

cloth polished with diamond suspension (1 μm) to carry microstructural analysis

and microhardness measurement.
The coating microstructure and worn surface analysis was carried out using
scanning electron microscope (S-3400N Hitachi), FESEM attached with EDS.
The phase analysis of coatings was carried out on X-Ray diffractometer (Bruker
D8) using Cu Kα radiation by scanning the specimen between range of 20° and 100°
at rate of 3°/m, and the phases were identified using Match software attached to XRD
system and International Center for Diffraction Data (ICDD) cards.
The surface roughness of coatings was measured by using contact stylus surface
roughness tester (MitutoyoSJ-210). Microhardness test was conducted on coating
cross section of mounted samples using Vickers hardness tester by making series
of indentations with pyramidal diamond indenter, and under a load of 300 g with a
dwell time of 14 s, an average of five readings on each specimen was taken.
Dry sliding wear behavior of coated pins was studied using pin on disc apparatus
according to ASTM G 99 standard [6]. Pins were slided over a rotating disc of
higher hardness (1913 HV10) [7], sliding speed was maintained as 1 m/s by choosing
the track dia of disc as 72 mm and with a rotating speed of 190 rpm by a normal load
of 30 N, for a sliding distance of 1000 m. Test was carried at room temperature and
with 35% of relative humidity, up to five laps until the steady state in the wear rate is
attained, the corresponding friction coefficient is recorded on friction monitor. The
disc and pins were cleaned after each test to remove wear debris. The samples are
weighed using analytical balance to an accuracy of 0.01 mg to measure the weight
loss.

3 Results and Discussion

3.1 Surface Roughness, Microstructure and Porosity Values

of Coatings

The average surface roughness (Ra) values of coatings were AT-3 (2.369 μm), AT-13
(2.824 μm) and AT-40 (3.124 μm), respectively. The surface roughness of AT-40
Effect of Tribo-layer on the Sliding Wear Behavior … 293

Fig. 1 SEM microstructures of Alumina–Titania coatings a AT-3, b AT-13 and c AT-40

seems slightly increased which may be due to its higher average particle size (45 μm)
compared to AT-3 (15.4 μm) and AT-13 (14.3 μm) powders.
SEM micrographs of Alumina–Titania coating cross sections are shown in Fig. 1.
Coatings exhibited good interference bonding and dense microstructure which are a
characteristic of DSC process. AT-3, AT-13 coatings exhibited gray color with few
bright (Ti rich) regions, and in AT-40 coating, successive layers of dark gray (Al2 O3 )
and light gray (TiO2 ) rich regions were observed.
The porosity values of coatings were AT-3 (0.38%), AT-13 (0.58%) and AT-40
(0.69%). It is observed that porosity in all coatings is less than 1% which is a capability
of DSC process that empowers to form dense coatings.

3.2 XRD Analysis

XRD analysis of coatings showed that in AT-3, AT-13 γ-Al2O3 is a major phase with
little amount of α-Al2O3 along with Rutile TiO2 , whereas AT-40 coating exhibited
higher amount of mixed oxide phase (Al2 TiO5 ). The absence of peaks corresponds
to TiO2 may due to more reactive nature of TiO2 with Al2 O3 , which is consistent
with the earlier reports [8] (Fig. 2).

3.3 MicroHardness Values

The typical microhardness values of coatings are presented in Table 3 and are found
around AT-3 (1080 HV0.3), AT-13 (1028 HV0.3) and AT-40 (909 HV0.3) and that
of substrate material is 123 ± 6 HV200, it seems that hardness is getting decreased
at higher amount of TiO2 content in coatings, and this is basically due to the lowest
hardness of TiO2 (942 HV) compared to Al2 O3 (1500 HV). In addition, the amount
of porosity will also influence the hardness of coatings. However, the porosity of
coatings is very less in the present study as against high porosity plasma sprayed
coatings where an increase in porosity resulted in the decrease in microhardness of
plasma sprayed Alumina–Titania coatings [8].
294 P. Uday Chandra Rao et al.

Fig. 2 XRD patterns of Alumina–Titania coatings

Table 3 Microhardness
Coating Hardness (HV0.3)
values of coatings
AT-3 1080
AT-13 1028
AT-40 909

3.4 Sliding Wear Behavior

During sliding wear test, the pins were made to slide over rotating disc (WC-6Co)
having hardness (1913 HV10) [7] for a sliding distance of 1000 m in each lap, at a
normal load of 30 N, and the results were presented as cumulative mass loss versus
sliding distance are in Fig. 3. It is well known that hardness has high impact on
wear resistance of coatings, and it is reported that increase in hardness resulted in the
improvement in the wear resistance of Alumina–Titania coatings [9]. Wear resistance

Fig. 3 Cumulative mass loss comparison of coatings

Effect of Tribo-layer on the Sliding Wear Behavior … 295

Fig. 4 Coefficient of friction comparison of coatings

of coatings was in the order of AT-13(0.7 mg), AT-3(0.9 mg) and AT-40(1.19 mg), and
in case of AT-3 and AT-40, the wear resistance of coatings was proportional to their
microhardness, whereas AT-13 coating possessed the lowest mass loss among the
coatings may be attributed to material removal mechanisms and tribo-layer formation
which will deal in detail in later part of the article.

3.5 Coefficient of Friction Values

In the present study, it is observed that coatings with higher wear resistance possessed
higher values of coefficient of friction. The increase in COF is due to the resistance
(frictional force) offered by the coatings during sliding. COF values obtained during
sliding wear tests on coatings are shown in Fig. 4. It is observed that coatings exhibited
coefficient of friction (COF) of 0.58 in AT-3, 0.57 in AT-40 coatings and 0.68 in AT-13
coatings. From EDS analysis of worn surfaces, the elements of counterpart (W, Co)
having hardness [1913 HV10] are attached on the tribo-layer formed during sliding
of AT-13 coating, and these high-hard elements attribute for the formation of stable
and harder tribo-layer which has shown clear impact on COF values. Generally,
tribo-layer was expected to originate due to raise in temperature of sliding surface
which is a characteristic behavior of cobalt-base alloys [4], and thus, AT-13 coating
exhibited high COF compared to other two coatings.

3.6 Wear Mechanisms

SEM images of worn-out regions of coating under sliding wear are shown in
Fig. 5a–c. From the SEM micrographs of worn surfaces, formation of tribo-layer
originated from wear debris was noticed on all three coatings. However, the stability
296 P. Uday Chandra Rao et al.

Fig. 5 SEM micrographs of worn surfaces of coatings a AT-3, b AT-13, c AT-40 subjected to sliding
wear

and delamination of tribo-layer as a function of TiO2 have shown variation in wear

rates among coatings. It is clear from micrograph of AT-3 (Fig. 5a), pullouts were
seen in addition to delamination which is a main cause in its wear. The tribo-layer
formation is minimum in AT-3 coating, which may be due to low amount of TiO2 in
the coating. While in case of AT-13 (Fig. 5b) and AT-40 (Fig. 5c) coatings the mate-
rial removal is by cracking, fragmentation and delamination of tribo-layer formed
during sliding. However, the degree of cracking, fragmentation and delamination is
very less in AT-13 coating compared to AT-3, AT-40 coatings.

3.7 EDS Analysis of Worn Surfaces

EDS analysis was performed on the worn-out regions of pins to trace out the elements
formed on the regions as a result of wear, and from the EDS analysis of AT-13
(Fig. 6a), elements of counterpart WC-9Co disc, i.e., (W, Co) were observed in
the tribo-layer. It has been reported that the presence of tribo-layer on the coating
influenced the friction properties of HVOF sprayed WC-17Co coatings [9]. Higher
COF value was noticed in the WC-17Co coating with stable tribo-layer. The COF
values observed in the present study are consistent with the literature report where the
stable tribo-layer noticed on AT-13 coating exhibited higher COF values compared
to AT-3 and AT40 coatings. In case of AT-3, the tribo-layer is not seen due to low
TiO2 .
Though the tribo-layer formed in case of AT-40 coating during sliding, the layer
is not stable, and counter body always experiences the coating surface than tribo-
layer. Hence, the observed higher COF value in AT-13 coating in the present study
is attributed stable tribo-layer formed on the coating.
The wear debris resulted from sliding wear adhered to form a tribo-layer which
decreases the direct contact between tribo-pair, thereby decreases the wear rate of
contact surfaces. Although a continuous tribo-layer was formed in AT-40 (Fig. 6b)
Effect of Tribo-layer on the Sliding Wear Behavior … 297

Fig. 6 EDS analysis of worn surfaces of AT-13 a and AT-40 b coatings during sliding wear test

but due to the presence of higher amount of brittle phase Al2 TiO5 (refer Fig. 2),
cracks are originated in tribo-layer, with rapid increase in crack intensity material
detached as wear fragments. This resulted in its higher wear rate, whereas a thin
tribo-layer is partially observed in AT-3 which may be due to less amounts of TiO2
and high melting point (2040 °C) of Al2 O3 [10, 11]. It is reported that thin tribo-layer
may not influence the wear behavior of tribo-pair [12].

4 Conclusions

1. Thick, dense Al2 O3 –TiO2 coatings were deposited using advanced detonation
spray technique. Al2 O3 –3 wt% TiO2 and Al2 O3 –13 wt% TiO2 coatings exhibited
homogeneous coating structure, whereas the successive layers of rich in Al2 O3
and TiO2 formed in case of Al2 O3 –40 wt% TiO2 coatings.
2. From XRD analysis, the presence of composite oxide phase Al2 TiO5 in addition
to Al2 O3 phase was noticed in all coatings. The amount of composite phase is
increasing with increase of TiO2 content in the coatings.
3. Addition of TiO2 in Al2 O3 has shown impact on mechanical properties of coat-
ings. The hardness is decreased with increasing TiO2 content in the coating from
1082 HV in 3 wt% TiO2 coating to 909 HV in 40 wt% TiO2 coating.
4. In Al2 O3 –3 wt% TiO2 and Al2 O3 –40 wt% TiO2 , sliding wear behavior of coatings
followed the coating hardness trend. However, the low wear rate and the highest
COF values noticed in Al2 O3 –13 wt% TiO2 coating are due to stable and hard
tribo-layer formation.
298 P. Uday Chandra Rao et al.

5. In the EDS analysis of worn surface of AT-13 coating, the elements of counter-
part (W, Co) seem to be attached on worn regions which may attribute for the
formation of hard and stable tribo-layer.
6. In the EDS analysis of worn surfaces of coatings, elements of base metal (Fe, C)
were not detected on the worn regions at normal load of 30 N and 5000 m sliding
distance, so it can be concluded that the life time of Alumina–Titania coatings
was more than 5000 m at a normal load of 30 N.

Acknowledgements P. Uday Chandra Rao would like to thank Director, ARCI and Center for
Engineered Coatings, ARCI for permitting to carry out the work.

References

1. Bagde, P., Sapate, S.G., Khatirkar, R.K., Vashishtha, N.: Friction and abrasive wear behavior
of Al2O3-13TiO2 and Al2O3-13TiO2+Ni Graphite coatings. Tribol. Int. 121, 353–372 (2018)
2. Klyatskina, E., Espinosa-Fernandez, L., Darut, G., Segovia, F., Salvador, M.D., Montavon, G.,
Agorges, H.: Sliding wear behavior of Al2O3-TiO2 coatings fabricated by suspension plasma
spraying technique. Tribol. Lett. 59, 8 (2015)
3. Narulkar, V.V., Prakash, S., Chandra, K.: Effects of temperature on tribological properties of
Al2O3-TiO2 coating. Defence Sci. J. 58(4), 582–587 (2008)
4. Claros, J.M., do Nascimento, E.M., D Oliveira, A.S.C.M.: Effect of the oxide film on the
sliding wear behavior of a CoCrMoSi alloy hard facing coating. In: 24th ABCM International
Congress of Mechanical Engineering, 3–8 Dec 2017, Curitiba, PR, Brazil
5. Ronkainen, H., Likonen, J., Koskinen, J., Varjus, S.: Effect of tribofilm on the tribological
performance of hydrogenated carbon coatings. Surf. Coat. Technol. 79, 87–94 (1996)
6. ASTM International: ASTM G 99–95a: Standard Test Method for Wear Testing with a Pin-on-
Disk Apparatus (2000). http://www.astm.org
7. Bonny, K., De Baets, P.: EDM machinability and dry sliding friction of WC-Co cemented
carbides. Int. J. Manuf. Res. 4(4) (2009)
8. Sapra, P.K., Singh, S., Prakash, S.: Evaluation of detonation gun sprayed alumina titania
coatings. Int. J. Surf. Sci. Eng. 2(5) (2008)
9. Katranidis, V., Kamnis, S., Allcock, B., Gu, S.: Effects and interplays of spray angle and stand-
off distance on the sliding wear behavior of HVOF WC-17Co coatings. J. Therm. Spray Tech.
28, 514–534 (2019)
10. Sert, Y., Toplan, N.: Tribological behavior of a plasma-sprayed Al2O3-TiO2-Cr2O3 coating.
Mater. Technol. 47(2), 181–183 (2013)
11. Material product data sheet. DSMTS-0006.6–Alumina 3% Titania Thermal Spray Powders.
https://www.oerlikon.com/metco
12. Navas, C., Cadenas, M., Cuetos, J.M., de Damborenea, J.: Microstructure and sliding wear
behaviour of tribaloy T-800 coatings deposited by laser cladding. Wear 260, 838–846 (2006)