J Therm Spray Tech
https://doi.org/10.1007/s11666-019-00834-8
PEER REVIEWED
Effect of Addition of Multimodal YSZ and SiC Powders
on the Mechanical Properties of Nanostructured Cr2O3
Plasma-Sprayed Coatings
S. M. Hashemi1 • N. Parvin1 • Z. Valefi2
Submitted: 9 July 2018 / in revised form: 5 January 2019
 ASM International 2019
Abstract In this research, the effect of the addition of
multimodal yttria-stabilized zirconia (YSZ) and SiC rein-
forcements on the mechanical properties of Cr2O3 plasma-
sprayed coatings was studied. For this purpose, the starting
powders were ball milled for 5 h and then mixed and
agglomerated, prior to spraying. Cr2O3, Cr2O3-20YSZ
(CZ), and Cr2O3-20YSZ-10SiC (CZS) coatings were then
deposited onto 304L steel substrates using the atmospheric
plasma spray process. Microstructural evaluations of the
initial/milled powders and the plasma-sprayed coatings
were conducted through x-ray diffraction, field emission
scanning electron microscopy (FESEM) equipped with
energy-dispersive x-ray spectroscopy and porosity mea-
surements. The microscopic images indicated that the
multimodal milled powders resulted in nanostructured
coatings. Mechanical tests including adhesive strength,
fracture toughness, and micro-hardness were used to
understand the dependence of the properties of coatings
and their microstructure. Adding tough YSZ particles to the
C coating considerably increased the toughness through the
phase transformation-toughening mechanism of tetragonal
zirconia while decreasing micro-hardness of the coating;
therefore, intrinsically hard SiC particles were added to the
CZ coating to deal with the reduced hardness. Moreover,
when compared to pure C coating, CZ, and CZS Composite
coatings showed comparable bonding strengths and higher
porosities.
& N. Parvin
nparvin@aut.ac.ir
1
Department of Mining and Metallurgical Engineering,
Amirkabir University of Technology, Tehran, Iran
2
Materials Engineering Research Center, Malek Ashtar
University of Technology, Tehran, Iran
Keywords ceramic matrix composite  Cr2O3-YSZ-SiC 
mechanical properties  multimodal  nanostructured
coating  plasma spraying
Introduction
Generally, ceramics are high-melting-point materials hav-
ing high hardness, good corrosion resistance, low ductility,
and low fracture toughness. Due to their high hardness and
low friction coefficient, ceramics are employed to reduce
friction of devices in many industrial applications (Ref 1-
3).
In order to improve properties of conventional ceramics,
reducing their grain size can enhance strength,4 hardness,
ductility (Ref 5, 6) and applicability (Ref 7) of ceramics. In
fact, nanoceramics show higher hardness and fracture
toughness along with lower ductility and elastic modulus,
when compared to conventional ones (Ref 4, 8, 9). The
main weaknesses of nanostructured ceramics and their
coatings are brittleness and low fracture toughness at room
temperature and under stress, which limit their tribological
applications (Ref 1, 3, 4).
Recently, research on nanostructured and nanocompos-
ite materials has become one of the most challenging and
promising fields of study (Ref 10-13). Using nanometric
powders is the fastest, easiest, and low-cost approach for
producing nanostructured coatings (Ref 14). Among vari-
ous processes which produce nanopowder, mechanical
milling has already been widely used and developed for
industrial applications (Ref 12). Using nanopowders in
thermal spraying decreases the presence of structural
defects in the produced coatings and provides a more
homogeneous structure as compared to conventional coat-
ings with micron grain size (Ref 15). Therefore,
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nanostructured ceramic coatings demonstrate better
mechanical properties compared with conventional ones.
The reason is the existence of bimodal microstructures
consisting of fully molten regions accompanying partially
molten ones (Ref 12-16).
Another way to improve the mechanical properties of
ceramics, such as toughness and wear resistance, is the
production of ceramic matrix composite (CMC) by adding
ceramic reinforcements with higher fracture toughness and
hardness (Ref 4, 8, 17).
As a new concept in previous experiments, a multi-
modal-structured composite coating consisting of nano,
submicron and micron structures was deposited from a
feedstock comprising of particles in nano and submicron
ranges. This multimodal coating has exhibited better
mechanical/wear properties compared to conventional
coatings (Ref 18, 19). Even implementation of a multi-
modal feedstock rather than a fully nanostructured feed-
stock can improve the wear resistance of the wear-resistant
coatings (Ref 20).
The atmospheric plasma spray (APS) is a thermal
spraying process that has been applied by many researchers
since the late 1950s to deposit various coatings (Ref 21).
Due to the elevated temperature of plasma, almost any type
of material with a high melting point including ceramics
and CMCs can be deposited on different substrates (Ref
1, 17, 22, 23). Owing to the low cost of the APS process,
the high deposition rate and the reasonable quality of APS
coatings, this process has so far been developed more than
other deposition processes (Ref 21, 24).
One of the materials previously coated using the APS
process is chromium oxide (Cr2O3). Regarding the high
melting point of Cr2O3 and its excellent wear resistance at
room/high temperatures, it is still among the most suit-
able alternatives for industrial applications. However, the
low fracture toughness of Cr2O3 limits its application in
coating or bulk forms (Ref 24-27).
Zirconium oxide (ZrO2), formerly added to many cera-
mic composites in order to increase their toughness, does
not exhibit the transformation-toughening mechanism (te-
tragonal to monoclinic transformation, T ? M), in its pure
form. To produce tough zirconium oxide, the presence of
the metastable tetragonal phase is required. Adding proper
amounts of some specific compounds, for instance CaO,
MgO, Y2O3, CeO2, and some rare earth oxides can stabilize
this metastable phase in zirconium oxide at room temper-
ature (Ref 28). In this research, yttria-stabilized zirconia
(YSZ) consisting of 8 wt.% Y2O3 (8YSZ) was applied.
Previous studies have indicated that the rapid solidifi-
cation rate during the APS process conserves the non-
equilibrium tetragonal phase of the YSZ without phase
transformation of zirconium oxide into its monoclinic
phase (Ref 29, 30). However, it should be noted that
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applying stress to the YSZ phase and/or increasing its
temperature, can result in the T ? M phase transforma-
tion. As a consequence of this phase transformation, the
coating volume increases about 4% which produces com-
pressive stress in the coating at cracks tips, and therefore,
the generated misfit stress leads to increased strength and
fracture toughness of the coating (Ref 31-33). The stress-
induced martensitic phase transformation (T ? M), the
basis for phase transformation toughening has previously
occurred in both nanostructured and conventional YSZ
coatings after applying grinding and polishing stresses. It
was concluded that larger grains and cracks present in the
conventional coating caused more crack growth and frac-
tures which led to a lower strength and toughness (Ref 34).
In previous studies, ZrO2 reinforcement has been widely
utilized to enhance the composite toughness due to its
intrinsic superior fracture toughness compared to other
ceramics (Ref 35, 36). Former researchers found a con-
siderable increase in the fracture toughness and wear
properties of zirconia-toughened alumina (ZTA) coatings
(Ref 37, 38). YSZ in TBCs exhibited a superior toughness
and better phase stability compared to that of pure Zirconia
(Ref 39, 40); however, the effect of YSZ particles on
properties of the plasma-sprayed Cr2O3 coating still
remains to be investigated. Owing to the high hardness of
SiC, scientists have already applied this reinforcement so
as to increase the hardness, strength and wear resistance of
several matrices, including ceramic matrix composites (Ref
41, 42). In previous research, YSZ and SiC reinforcements
have been mostly added up to 40 vol.% to ceramic matrix
composites in order to enhance their mechanical properties
(Ref 43-46).
In the present study, Cr2O3 and its composite coatings
reinforced by YSZ and SiC particulates were manufactured
via the APS process. The microstructure and mechanical
properties of these coatings were investigated and com-
pared with individual chromium oxide coating. The novelty
of this research is based on improving the toughness of the
Cr2O3 coating (not bulk) toward producing a CZ composite
coating by adding YSZ particles and renovating the
degraded hardness of the CZ coating through adding SiC
reinforcement.
Structural studies and characteristics of initial/milled
powder particles and plasma-sprayed coatings are investi-
gated in further detail, as follows.
Experimental Procedure
Feedstock Preparation
In this study, to prepare the Cr2O3 and its composite
coatings, Cr2O3, YSZ, and SiC powder particles (Powder
J Therm Spray Tech
Alloy Corp., OH, USA) with a particle size distribution
(PSD) of - 70 ? 20, - 60 ? 10, and - 150 ? 100 lm
were applied, respectively. The morphologies of the initial
Cr2O3, YSZ, and SiC powders are shown in Fig. 1.
Mechanical milling was carried out using a high–energy
ball mill model NARYA-MPM 2*250H (Amin Asia
Fanavar Pars Co., Iran), consisting of two cylindrical
containers each with a 250 ml capacity. A combination of
10 and 15 mm in diameters grinding balls was charged into
the container, each of which was 22 and 12 balls, respec-
tively. The balls and the container walls were both made of
hardened steel.
The ball-to-powder mass ratio (BPR) should fall in the
range of 40:1 to 5:1 to supply sufficient energy for milling
powders. It is reported that a 10:1 ratio can lead to the
highest milling efficiency (Ref 21). Accordingly, the BPR
was taken to be 10 to 1 in order to have 65% empty space
in the container. As a result, 25 g of powder as well as
250 g of balls were placed into each container.
Regarding previous research, it is concluded that at a
constant BPR value, a combination of at least two ball sizes
can result in a higher milling efficiency (Ref 47-49). In
fact, an increase in the size distribution of the balls, led to
an improvement in the rate of powder breakdown and
therefore the proper functioning of the mill (Ref 50).
To prevent powder oxidation or nitration, mechanical
milling was performed in an Argon gas atmosphere. Fur-
thermore, agglomeration of the powder particles during
milling was avoided by adding 2 wt.% stearic acid (Merck,
Fig. 1 SEM images of as-
received powder particles:
(a) Cr2O3, (b) YSZ, and (c) SiC
Germany), along with 10 ml ethanol, as a process control
agent (PCA).
In this research, to achieve nanosized/multimodal pow-
ders, milling was carried out at a maximum rotational
speed of 500 rpm, and each initial powder was individually
milled for 5 h. Powder PSDs were measured by a particle
size analyzer (PSA) using dynamic light scattering tech-
nique (DLS, Malvern Instruments, United Kingdom).
Afterward, three types of feedstock with different compo-
sitions and percentages of the initial powders are prepared
as listed in Table 1. Each powder mixture was then gran-
ulated using polyvinyl alcohol (PVA, Sigma-Aldrich,
USA) binder. To do this, each 5 g of the powder mixture
was mixed with 1 g of PVA and subsequently heated at
80 C for 10 min using a heater so as to obtain dried
powder granules. Afterward, powder particles with 20 to
125 lm diameters were obtained by sieving the agglom-
erated particles. A schematic of the manufacturing process
for making the sprayable feedstock is drawn in Fig. 2.
Plasma Spraying
Atmospheric plasma spraying equipment with an F4
plasma gun (Sulzer Metco, Switzerland) was used to apply
the coatings. Prior to spraying the top coat, a Ni-5 wt.%Al
(AMDRY 956, Sulzer Metco, Switzerland) bond coat was
deposited onto the substrate. APS parameters for deposit-
ing bond and top coatings are listed in Table 2. Due to the
fact that all three feedstocks were entirely/mainly
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composed of chromium oxide, therefore, C, CZ, and CZS respectively (Ref 52). In thermal spraying, the bonding
top coats were deposited using the same spraying strength of coating/substrate is related to the surface
parameters. roughness prior to spraying and also residual thermal misfit
The 304L steel substrates used in this research were cut stress caused by coating shrinkage during solidification. In
into disks with 25 mm and 10 mm in diameter and height, thick coatings, if the coating and substrate materials have
respectively. The samples were then mounted on a fixture different coefficients of thermal expansion, large residual
with a diameter of 110 mm (Fig. 3). Due to the diameter mismatch stresses will be developed in the coating after
and rotational speed of the fixture, its linear speed was cooling to room temperature (Ref 16, 53). The residual
calculated to be 576 mm/s. stress reaches its maximum value next to the coating/sub-
To achieve high coating adhesion and good mechanical strate interface which can lead to failure at the interface
bonding of coatings to substrate, the surfaces of the sub- region (Ref 54). To reduce these stresses, the substrate
strates were roughened (Ref 51). Prior to spraying, the should be preheated or coating material with a lower
substrates were degreased by acetone and grit blasted with coefficient mismatch of coating/substrate thermal expan-
alumina. Then, to remove any pollution that could prevent sions should be selected (Ref 16, 53, 55). Considering all
coating/substrate adhesion, dust was eliminated from the mentioned above, in this research the coatings were
substrate surface using compressed air and ethanol. sprayed after preheating the substrates up to about 200 C.
A Mitutoyo SJ-201 instrument (Mitutoyo Corporation, Preheating treatment was performed using several passes of
Japan) was used to determine the linear surface roughness no-powder plasma flame just before spraying the coating
of the coatings. The mean roughness value for substrates (Ref 56). Temperature measurements were carried out
was measured to be around 7.35 lm prior to spraying. Each
roughness value was the result of averaging 5 linear mea-
Table 2 APS parameters
surements performed on different areas of the samples.
During plasma spray process, the molten particles are Feedstock type F4 Sulzer Metco
rapidly solidified after impacting the substrate. As an out- Bond coating Top coating
come, the tensile stress and its balancing compressive
Current, A 600 600
stress, commonly known as quenching stresses, are pro-
Voltage, V 57 57
duced in the sprayed layer and underlying material,
Spray distance, mm 110 60
Ar gas flow rate, l/min 65 45
Table 1 Composition of different feedstocks prepared for APS H2 gas flow rate, l/min 10 10
process Carrier gas flow rate, l/min 3.2 2.9
Code Cr2O3 YSZ SiC Powder feed rate, g/min 51 12
Torch transfer speed, mm/s 7 7
(vol.%) (wt.%) (vol.%) (wt.%) (vol.%) (wt.%)
Fixture rotating speed, rpm 100 100
C 100 100 0 0 0 0 Number of passes 1 28
CZ 80 78.6 20 21.4 0 0 Substrate thickness, mm 10 10
CZS 70 71.5 20 22.23 10 6.27 Coating thickness, lm 100-120 280-310

Fig. 2 Schematic illustration of the manufacturing process of multimodal sprayable feedstocks: (a) ball milling, (b) agglomeration, and
(c) sieving

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Fig. 3 Schematic drawing of (a) plasma gun (b) rotating fixture, and (c) coating sample
using an infrared thermometer model MS6550A (MAS-
TECH, CA, USA).
Characterization
A field emission scanning electron microscope (FESEM,
Tescan, Czech Republic) was used to study the
microstructure and morphology of the initial powders,
agglomerated mixed particles, and as-sprayed coatings.
Moreover, energy-dispersive x-ray spectroscopy (EDS)
was utilized to carry out elemental analysis of the powders
and coatings.
In order to characterize phase composition of the pow-
ders and as-sprayed coatings, XRD investigations were
done by the X’PERT PRO MPD instrument (PANalytical,
Netherlands) at filament voltage and current of 40 kV and
40 mA, respectively. In all recordings, a CuKa x-ray source
with a wavelength of 1.54 Å was used. A Step size of
0.026, scan step time of 48 s and scanning range of 20 to
90 were chosen.
The porosity of the coatings was measured using image
analysis method performed on cross-sectional images of
the coatings taken by a research-level optical microscope
(BX51, Olympus Inc., Japan) at a magnification of 400X.
This method relies on differences between various colors
and calculating the percentages of each color. This analysis
was conducted using medical image processing (MIP)
software through the Cloud computing method. The
porosity value for each coating is the average of mea-
surements obtained from 10 different image analyses.
The Vickers micro-hardness test was carried out using
an OSK 14218-1 micro-hardness tester (OGAWA SEIKI
CO., LTD, Tokyo, Japan). The indentations were applied
on the coatings cross sections with a 200 g load and a dwell
time of 15 s. Each micro-hardness value is the average of
10 measurements.
A pull-off test based on ASTM C633 was performed
with a Zwick Z050 universal tensile test machine (Zwick/
Roell Group, Germany) to determine the bonding strength
of the coatings. Each strength value was the average of 5
measurements.
The best approach for measurement of fracture tough-
ness of brittle materials is the Vickers indentation fracture
(VIF) method in which a load is applied by the Vickers
indenter on the polished coatings surface (Ref 4, 57, 58).
Vickers indentation was carried out using a universal
hardness tester model Koopa UV1 (Koopa Instruments,
Iran).
Two types of cracks are produced by a Vickers indenter,
namely the Palmqvist crack system with a half-ellipse sub-
structure and the median or half-penny crack system
(Fig. 4). Generally, a tough material exhibits the Palmqvist
crack system. Palmqvist cracks extend from the corner
points of the Vickers indent outwards. Typically, a Vickers
indentation gives rise to four Palmqvist cracks. Median
cracks extend both into the depth beneath the indentation
and in the diagonal direction beyond the corner points.
Typically, a Vickers indentation gives rise to two median
cracks. However, most materials will present both crack
systems depending on the applied load. For a number of
brittle materials, the Palmqvist cracks were formed in the
low-load regime. On the other hand, Palmqvist cracks were
formed only at large loads for reasonably tough materials
(Ref 59-61).
There are two ways to distinguish the crack system
present in the analyzed material. One way to define the
crack system is the verification of the c/a ratio (‘‘c’’ is the
crack length from the center of the indent to the crack tip
and ‘‘a’’ is the half value of the indentation diagonal, as
shown in Fig. 4). If it is less than 2.5, then the material
shows a Palmqvist crack system. Another approach to
differentiate between the two types of crack system is to
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Fig. 4 Schematic idealized top view and cross-sectional view of Vickers indent (a) radial ‘‘Median’’ or ‘‘Half-penny’’ crack system and
(b) radial ‘‘Palmqvist’’ crack system

polish the surface layers away. The median crack system
will always remain connected to the inverted pyramid of
the indent (the ratio value of c/a is higher than 2.5), while
the Palmqvist cracks will detach from the indentation (Ref
60-64).
There are many empirical equations which have already
been developed by previous researchers for the determi-
nation of fracture toughness using the Vickers indenter
(Ref 65-69). All of these equations are based on Palmqvist
or half-penny crack models which emphasize the existence
of crack length. Some commonly used equations used to
calculate KIC are tabulated in Table 3, where KIC is the
fracture toughness (MPam1/2); P is the indentation load
(N); c is the radial crack length (m); a is the half-diagonal
of the indent (m), E is Young’s modulus (GPa) and HV is
Vickers hardness (GPa).
Crack Propagation Resistance (CPR) as a means of
characterizing fracture toughness has mostly been used for
comparing the fracture toughness of different coatings (Ref
70), i.e., fracture toughness is directly proportional to the
CPR values (Ref 60, 61). Each CPR value is calculated as
follows:
P
CPR ¼ ðMPam1=2 Þ
c =2
3
The fracture toughness tests were performed under a
load of 100 kg and each of the CPR and KIC values is the
average of 5 measurements.

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Table 3 Some equations
No. Crack type
developed for the determination
of fracture toughness in brittle
1 Half-penny Lawn & Fuller (1975)
materials
2 Half-penny Charles & Evans (1976)
3 Half-penny Evans & Wilshaw (1976)
4 Half-penny Tanaka (1987)
5 Palmqvist Niihara (1982)
6 Palmqvist Shetty (1985)
Results and Discussion
Figure 5 and 6 display powder morphologies and PSDs
after 5 h of milling, respectively. As seen, morphologies of
the milled powders differed from the ones of the initial
powders. After milling, the Cr2O3 particle size was 50 to
90 nm, which is a narrow range of nano sizes, and the YSZ
particle size lay mostly between 90 and 120 nm. Moreover,
the size of the milled SiC particles was mainly in the fine
range of 160 and 220 nm. The larger size of the milled SiC
particles is attributed to the larger size of the initial SiC
powders.
The main drawback in spraying the nanosized particles
is their low deposition efficiency due to the low mass and
the poor flowability of the particles. So agglomeration of
the fine particles to produce agglomerates with a diameter
of 10–100 lm for using in the APS process is unavoidable
(Ref 15, 71). Figure 7 shows SEM images of C, CZ, and
CZS agglomerated powders with a diameter of 20–50 lm,
appropriate for spraying (Ref 24).
To evaluate the purity and the probability of phase
transformation of the initial powders during milling and
spraying, an XRD analysis was carried out. As observed in
Fig. 8, the characteristic peaks of Cr2O3, YSZ, and SiC
particles exist in the patterns while no new phase or
impurity was formed during milling. As seen, there is also
no newly appeared phase in the coating patterns and the
peaks still belong to the initial powders. Also, the lack of
any deviation in the coating peak positions implies that no
solid solution has been created during spraying. Former
studies have also concluded that the presence of oxygen in
the APS process might change the Cr-to-O ratio of chro-
mium oxide negligibly, but it does not alter its stoichio-
metric ratio and chemical composition (Ref 72).
The most important difference between the XRD pat-
terns of the milled and initial powders is that the XRD
peaks of the milled powders are broader. Peak broadening
and the lower peak intensities of the milled powders can be
related to the grain size reduction and increase in the lattice
strain (Ref 73, 74). In addition, the milling of powders
Author(s) Equation References
 
KIC ¼ 0:0726 CP3=2 Ref 54
 
KIC ¼ 0:0752 CP3=2 Ref 46
 

KIC P
¼ 0:0790 a3=2  log 4:5a Ref 55
C
 
KIC ¼ 0:0725 CP3=2 Ref 53
 2=5 Ref 57
KIC ¼ 0:0089 HEV P
al1=2
KIC ¼ 0:0319 alP1=2 Ref 56
resulted in peak shifts toward higher angles. Since there
were no reinforcement particles or measurable impurities
in the starting powders, the shift in the position of peaks
was due to the compressive stress produced during milling
(Ref 75, 76).
XRD patterns of C and CZ coatings revealed that the
characteristic peaks of YSZ at 30, 35, and 60 degrees,
related to (002), (200), and (302) planes, respectively, were
added to the XRD pattern of the C coating. The only dif-
ference between XRD patterns of the CZ and CZS coatings
relates to the presence of the (101) plane of SiC particles,
around 34 degrees, in the CZS coating pattern. It is
important to note that the other peaks of SiC have over-
lapped with Cr2O3 and YSZ peaks. Furthermore, it can be
observed that the coating peaks were broader than the
peaks of the milled powders. This fact is associated with
enhanced amorphism and grain size reduction in the molten
particles due to the rapid solidification of the coatings upon
collision of the molten powder particles with the substrate.
The grain size of Cr2O3 phase in the coatings was cal-
culated by means of the Williamson-Hall method using
(012), (014), (110), and (116) reflections. Cr2O3 grain sizes
for C, CZ, and CZS coatings were calculated to be 54, 58,
and 68 nm, respectively. However, because of the over-
lapping peaks of YSZ and SiC, the Scherrer method was
employed to calculate the grain size of these two phases,
using (002) and (006) reflections, respectively. The YSZ
grain size was calculated to be 31 and 37 nm for CZ and
CZS coatings, respectively. The SiC grain size in the CZS
coating was also obtained as 32 nm.
The coating deposition efficiency in the APS process is
defined as the mass ratio of the deposited coating to the
consumed powder (Ref 77). The calculated deposition
efficiencies of the C, CZ, and CZS coatings are summa-
rized in Table 4. The coating net weight is the differences
in the mass of the samples before and after spraying.
Since the agglomerated powders include pores, any
coating produced using these agglomerated powders would
also be porous. Regarding the fact that the fully molten
region does not completely surrender the un-molten or
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Fig. 5 SEM images of milled
powders after 5 h of milling:
(a) Cr2O3, (b) YSZ, and (c) SiC
partially molten particles; the coating structure will be
porous. However, if plasma spraying parameters are opti-
mized, diffusion takes place properly on the surfaces of the
particles, and fully dense coatings with low porosity con-
tent and excellent mechanical properties will be obtained
(Ref 12, 15).
The critical plasma spraying parameter (CPSP), an
indicator of plasma flame temperature, can be calculated
via the below equation. The units of measurement for
voltage, current intensity, and primary gas flow rate are V,
A and SCFH,1 respectively.
Voltage  Current
CPSP ¼
Primary Gas Flow Rate
CPSP is a fundamental factor which controls spraying
temperature affecting quality and properties of the coat-
ings. Increasing CPSP values up to a definite value (about
350 to 400 V A SCFH-1) increases the wear resistance of
materials while much higher values cause a decrease in the
coating wear resistance. Hardness values, as well, increase
through increasing CPSP values (Ref 14, 64). In fact,
increasing this parameter promotes the amount of fully
molten regions compared with the partially molten ones
and reduces cracks in the coatings (Ref 78, 79).
Given the plasma spray parameters, the applied plasma
spray current intensity, arc voltage and Argon flow rate
were 600 A, 57 V and 45 L min-1 (each ft3 equals
1
Standard cubic feet per hour.
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0.4719 L), respectively. Therefore, CPSP was calculated to
be 358 V.A.SCFH-1.
According to the previous studies (Ref 14), the CPSP
factor for the APS with the highest deposition efficiencies
must be in the range of 350–400 V.A.SCFH-1. As seen, in
this research the CPSP value also lies in the above-men-
tioned range.
Finally, surface morphologies and the cross sections of
the coatings (Fig. 9 and 10, respectively) were character-
ized by FESEM. As shown in Fig. 9, spraying multimodal
powders led to the nanostructured coatings consisting of
thousands of micro-sized particles; however, each
microparticle itself can be also an assembly of tens of
nanoparticles. As seen in Fig. 10, there are four regions
with white, light gray, dark gray and black colors that have
homogenously been distributed throughout the coatings,
defined by arrows in Fig. 10c. There are some micro pores
in these regions.
Figure 11 shows the EDS analysis on different phases in
the CZS coating, formerly referred to in Fig. 10. Regarding
the penetration depth of EDS, about 1 lm, the existence of
all elements in the analysis of each region is related to
receiving elemental analysis information from the
nanoparticles as well as their surroundings (Ref 80).
Figure 11a depicts the elemental analysis of the light
gray region. Since this region contains a high percentage of
chromium, it seems to be chromium oxide. The CZS
coating contains a significant fraction of this phase.
Therefore, this region can be considered as the matrix of
J Therm Spray Tech

Fig. 6 Powder particle size

distribution after 5 h of milling:
(a) Cr2O3, (b) YSZ, and (c) SiC

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Fig. 7 SEM morphological

images of agglomerated
powders: (a) C, (b) CZ, and
(c) CZS

Fig. 8 XRD patterns of

elemental/milled powders and
plasma-sprayed coatings

the coating while the other phases are distributed in this
region. Figure 11b illustrates the elemental analysis of the
white region distributed throughout the matrix. In this
region, the increased percentage of zirconium is attributed
to the formation of the YSZ phase. Figure 11c shows the
elemental analysis of the dark gray region in which the Si
percentage is high. As aforementioned, 10 vol.% SiC was
used in this composite. This region occupying a low frac-
tion of the coating must be SiC particles. Since SiC par-
ticles are brittle, they have been possibly crushed into

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Table 4 Mean values of the coatings deposition efficiencies

Coating code Coating thickness, lm Coating mass, g Consumed powder mass, g Deposition efficiency, %

C 290 ± 8 27 ± 0.74 59 ± 0.33 46 ± 1.25

CZ 310 ± 9 28 ± 0.81 50 ± 0.12 56 ± 1.62
CZS 280 ± 8 26 ± 0.73 70 ± 0.37 37 ± 1.06

Fig. 9 FESEM morphological

images of (a, b) C, (c, d) CZ,
and (e, f) CZS coatings in two
magnifications

123

Fig. 10 FESEM cross-sectional
images of APS coatings: (a) C,
(b) CZ, and (c) CZS
smaller pieces by milling and appeared as finer particles in
the images. The black regions of FESEM images corre-
spond to the porosities mostly created owing to the
inability of un-molten or partially molten particles to fill
the empty space during coating deposition. Overheating
and evaporation of very fine particles due to the high
temperature of the plasma flame or capturing of air bubbles
during spraying could be another reason for the formation
of porosities in the coatings.
The temperature and velocity of the powder particles
while passing through the plasma zone influence the extent
of splat formation in the coatings (Ref 81). The higher the
thermal conductivity of the powders, the higher the mean
temperature is and the lower the temperature gradient is
across the powder particle. In fact, particles with high
thermal conductivity can retain more heat, so more melting
and flattening will occur in spite of this, in materials with
lower thermal conductivity, greater temperature gradients
would result in thermal shock and concentrated stress
during melting and solidification (Ref 9). Based on previ-
ous results, the following relationship exists between
thermal conductivities of the powder particles:
SiC [ Cr2O3 [ YSZ (Ref 82-84). Therefore, the
123
J Therm Spray Tech
temperature of Cr2O3 particles compared to that of YSZ
particles would increase further due to its higher thermal
conductivity.
Figure 12 demonstrates optical microscope images of
the polished surface of the coatings cross section. The layer
structures in the bond coating can be obviously seen.
Mechanical bonds in the coating-substrate interface,
specifically in the C sample, have been well established
while low porosity and no crack were observed in the
coating/substrate interfaces. According to this figure, the
surface of as-sprayed coatings, as well as coating/substrate
interface, are rough. The reason for interface roughness is
grit blasting of the substrate surface. However, the surface
roughness of the as-sprayed coatings is one of the char-
acteristics of plasma-sprayed coatings due to the presence
of splats with different degrees of flattening in the coatings.
The thickness of the coatings, an average of 10 measure-
ments, was also obtained as 280 ± 15 lm.
Mean porosity fractions of the C, CZ, and CZS coatings
were calculated to be 8.7 ± 2.2, 10.2 ± 2.7, and
12.8 ± 3.1%, respectively.
The melting points of YSZ and SiC are about 400 C
higher than that of chromium oxide. Adding YSZ and SiC
J Therm Spray Tech
Fig. 11 EDS analyses on different phases of CZS coatings: (a) Cr2O3, (b) YSZ, and (c) SiC
provides a lower degree of splat flattening since their
melting points are higher than the matrix material. High
amount of porosities in the CZS coating can also be
attributed to the larger size of SiC particles compared with
other particles and therefore the high amount of un-molten
SiC particles in the coating (porosity content: CZS [
CZ [ C). This result is consistent with the results of
porosity measurements carried out by image analysis.
One of the effective factors for improving the quality of
microstructures is selecting powder particles with the
proper sizes for APS. Using smaller powder particles
causes a decrease in stacking faults of splats, gas bubble
trapping, and un-molten particles and therefore reduces the
mean size of the porosities (Ref 22). Consequently, by
using nanosized powders, denser plasma-sprayed coatings
can be produced. However, due to the high melting points
of ceramics, it is always hard to achieve a fully dense
ceramic coating with low porosity content (Ref 85).
Hardness, an important factor for evaluating the prop-
erties of plasma-sprayed coatings, is dependent on their
inherent hardness and microstructure. The percentage of
molten and un-molten particles can affect porosity
distribution, splat cohesion and adhesion. The Vickers
micro-hardness of C, CZ, and CSZ coatings was 823, 799,
and 910 HV0.2, respectively. As seen, the hardness of
coating C decreased by adding the YSZ particles while,
conversely, subsequent addition of SiC particles to the
coating enhanced the degraded hardness. SiC and Cr2O3
particles have almost the same hardness. As outcome
result, the higher hardness of CZS coating, compared with
C and CZ coatings, is owing to the high hardness of SiC.
On the other hand, the lower hardness of CZ coating could
be attributed to the lower hardness of YSZ, compared to
those of other particles (coating hardness: CZS [ C [
CZ). Furthermore, regarding higher SiC and Cr2O3 thermal
conductivities, SiC and Cr2O3 splats solidify faster than
YSZ splats, resulting in a higher hardness of CZS and C
coatings compared with the CZ coating.
Given the high hardness and low toughness of the
ceramic coatings, cracking and spallation are the main
reasons for failure in these coatings. This is why CPR is as
importance to evaluate and compare the fracture toughness
of the coatings. It should be mentioned that the Vickers
micro-indentation was firstly applied at loads of 25, 50, and
123

Fig. 12 Optical images of
coatings cross sections: (a) C,
(b) CZ, and (c) CZS
200 g on the polished surface of the cross section. No crack
was found since the microcracks were so tiny and easily
arrested in the microstructure. Afterward, 30, 60, and
100 kg loads were applied on the top surface of the coat-
ings while no crack was observed under loads of 30 and
60 kg, as well.
Figure 13 shows the Vickers indentation mark on the
coating surface at a load of 100 kg under two different
magnifications. Four cracks at the tips of indenter marks
were detected. The cracks and their length (l) are shown in
the figure. As seen in Table 5, an average of four cracks
lengths for each indentation was obtained. The CPR values
for C, CZ, and CZS coatings were then calculated as 104,
110.2, and 106.5 MPam1/2, respectively. As seen, CZ and
CZS composite coatings indicated higher CPRs than pure
C coating while CZ coating had the highest CPR value.
In this research, since the values of the c/a ratio for the
coatings (as mentioned in Table 5) are less than 2.5, the
coatings show the Palmqvist crack system. In previous
studies, to evaluate the fracture toughness of brittle mate-
rials showing the Palmqvist crack system, the Shetty
equation has been mostly used (Ref 63, 68, 86, 87). The
mean values of the coatings fracture toughness were cal-
culated using the Shetty equation as already aforemen-
tioned in Table 3. Adding YSZ particles to the chromium
oxide coating increased its fracture toughness from 11.06
to 13.81 MPam1/2. According to previous studies, intrinsic
fracture toughness values of bulk Cr2O3, YSZ, and SiC
123
J Therm Spray Tech
materials are equal to 3.9–4.4, 7.0–12.0, and
2.6–4.4 MPam1/2, respectively (Ref 88-90). The higher
fracture toughness of CZ compared to C coating was
attributed to the addition of tough YSZ particles to the C
coating as well as the YSZ transformation-toughening
mechanism. Moreover, YSZ particles can act as obstacles
to crack propagation and therefore enhance the coatings
strength and fracture toughness (Ref 91). The higher
quantity of porosities in the CZ coating compared to that of
the C coating may also increase the fracture toughness (Ref
92). Comparison between CZ and CZS coatings reveals
that addition of SiC particles to the CZ coating has
degraded its fracture toughness from 13.81 to
12.85 MPam1/2. Since the CZS coating porosity is higher,
such decrease in fracture toughness can be attributed to the
low fracture toughness of SiC particles. It seems that the
effect of SiC on decreasing fracture toughness of the CZS
coating is dominant when compared with the effect of
porosity content.
Applying a load on surface of ceramic coating com-
posed of smaller particles due to increased number of
particles, the stress shared on each particle decrease and,
therefore, their fracturing would be hard. On the other
hand, since ceramic particles are intrinsically hard mate-
rials, strengthening through size reduction is the most
effective parameter. Accordingly, to obtain high strength
and remarkable fracture toughness, powder particles with
smaller sizes should be used (Ref 93). Therefore, fracture
J Therm Spray Tech

Fig. 13 SEM images of

indentation effects (left) and
cracks (right) in (a, b) C, (c, d)
CZ, and (e, f) CZS coatings
under IF test at a load of 100 kg

Table 5 Mean calculated

Coating code a, lm l, lm C, lm CPR, MPam1/2 KIC, MPam1/2
values of crack propagation
resistance and coatings fracture C 400 ± 2 52 ± 2 452 ± 4 104.0 ± 1.3 11.06 ± 0.27
toughness
CZ 402 ± 2 33 ± 2 435 ± 4 110.2 ± 1.5 13.81 ± 0.51
CZS 408 ± 3 37 ± 3 445 ± 6 106.5 ± 2.1 12.85 ± 0.65

toughness of coatings produced using nano/multimodal
particles are expected to be higher than those of coatings
deposited using microparticles. Considering the fracture
toughness of the initial powder particles (YSZ [ Cr2O3
[ SiC), fracture toughness values of CZ and C coatings are
expected to be the highest and the lowest, respectively, in
accordance with the results obtained from the IF test.
Several researchers have already indicated that partially
molten particles in the coatings act as obstacles to crack
growth which results in an increase in the coating fracture
toughness (Ref 15, 78). Therefore, higher fracture tough-
ness of the CZS coating compared to the C coating can be
attributed to its lower number of partially molten particles
as well as higher hardness and porosity content.
Mean values of bonding strength of the coatings are
reported in Table 6. As seen in Fig. 14, fractures have
occurred at the coating/substrate interface; therefore the
reported strengths refer to the bonding strength of the
coatings. The results revealed that all the plasma-sprayed
coatings have high and comparable bonding strengths,
while C and CZS coatings showed the highest and the
lowest values, respectively. The higher bonding strength of
the C coating is attributed to the lower melting point of
Cr2O3 particles as well as lower coating porosity.

123

Table 6 Mean values of
Coating code Test 1
bonding strength of the coatings
(MPa) C 53
CZ 38
CZS 41
Fig. 14 Fracture surface of (a) C, (b) CZ, and (c) CZS samples after
bonding strength test
Regarding previous studies, high toughness and tensile
strength of nanostructured coatings prevent crack propa-
gation throughout the coating/substrate interface, which
results in their higher bonding strength when compared to
conventional coatings (Ref 15).
In bonding strength tests, fracture can take place as a
result of cohesion or adhesion failure. Adhesive failure
happens when the coating entirely separates from the
substrate. A fully pure adhesive fracture rarely occurs, due
to the surface roughness of the substrate. In adhesive fail-
ure, fracture takes place in the regions adjacent to the
coating/substrate interface and uncoated surfaces might be
observed in the fractured surface. If the fracture occurs
completely throughout the coating, then the fracture is
based on cohesion failure (Ref 55).
Difference between thermal expansion coefficients
of coatings and substrates generates residual thermal
123
J Therm Spray Tech
Test 2 Test 3 Test 4 Test 5 Mean value
48 45 49 51 49 ± 4
48 44 39 45 43 ± 5
45 35 35 43 40 ± 5
misfit stress. If the total residual stress exceeds the
tensile strength of the coating, the crack propagates
which can lead to the coating fracture or delamination.
Therefore, it can be concluded that the coating/sub-
strate adhesion is mainly affected by the residual stress
generated at the coating/substrate interface (Ref 94). In
this research, the authors tried to deposit the coatings
with acceptable thickness so as to maintain the stress
concentration value lower than the coatings tensile
strength.
Conclusions
In the present work, the authors’ effort was aimed at
evaluating the microstructure, phase composition and
mechanical properties of atmospheric plasma-sprayed
Cr2O3, Cr2O3-20YSZ, and Cr2O3-20YSZ-10SiC nanos-
tructured ceramic coatings. The results are summarized
below:
• No impurity or interaction between initial powders was
found during ball milling and also after spraying the
agglomerated powders.
• Considering XRD patterns, Coatings synthesized from
5-hour ball-milled multimodal powders, possessed
nano structures as well.
• Considering microstructural studies, all coatings
included 8–12% porosities whereas coatings C and
CZS showed the lowest and highest porosity contents,
respectively.
• Adding tough YSZ to coating C, caused a considerable
increase in the coating resistance to crack propagation,
and consequently the mean values of coating toughness
from 11.06 to 13.81 MPam‘.
• Regarding the high hardness of the SiC particle,
subsequent addition of SiC reinforcements to the
coating, increased coating micro-hardness, while the
mean hardness of the CZS coating was measured to be
about 910 HV.
• Due to the lower melting point of Cr2O3 particles
compared to YSZ and SiC ceramics, as well as the
lower porosity content of the C coating in comparison
with CZ and CZS composite coatings, coating C
showed the highest value of 49 MPa as the coating
bonding strength.
J Therm Spray Tech
Data availability The authors are willing to firstly publish this
research paper through the highly prestigious journal of ‘‘Thermal
Spray Technology’’. Therefore the datasets generated and analyzed
during the current study have not already been available in public.
However, it can be available from the corresponding author on a
reasonable request.
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