JTTEE5

DOI: 10.1007/s11666-015-0263-x
1059-9630/$19.00  ASM International

Peer Reviewed
Characterization of Microstructure
and Thermal Properties of YSZ Coatings
Obtained by Axial Suspension Plasma
Spraying (ASPS)
Ashish Ganvir, Nicholas Curry, Stefan Björklund, Nicolaie Markocsan, and Per Nylén

(Submitted February 20, 2015; in revised form May 3, 2015)

The paper aims at demonstrating various microstructures which can be obtained using the suspension
spraying technique and their respective significance in enhancing the thermal insulation property of a
thermal barrier coating. Three different types of coating microstructures are discussed which were
produced by the Axial Suspension Plasma Spraying. Detailed characterization of coatings was then
performed. Optical and scanning electron microscopy were utilized for microstructure evaluations; x-ray
diffraction for phase analysis; water impregnation, image analysis, and mercury intrusion porosimetry for
porosity analysis, and laser flash analysis for thermal diffusivity measurements were used. The results
showed that Axial Suspension Plasma Spraying can generate vertically cracked, porous, and feathery
columnar-type microstructures. Pore size distribution was found in micron, submicron, and nanometer
range. Higher overall porosity, the lower density of vertical cracks or inter-column spacing, and higher
inter-pass porosity favored thermal insulation property of the coating. Significant increase in thermal
diffusivity and conductivity was found at higher temperature, which is believed to be due to the pore
rearrangement (sintering and pore coarsening). Thermal conductivity values for these coatings were also
compared with electron beam physical vapor deposition (EBPVD) thermal barrier coatings from the
literature and found to be much lower.

Keywords axial injection, columnar and feathery columnar

microstructure, micron, MIP, submicron, and
nanometer pores, suspension plasma spraying,
thermal barrier coatings, thermal diffusivity and
conductivity, vertical cracks
1. Introduction
Suspension spraying is a relatively new technique to
produce coatings with a variety of microstructures (Ref 1,
2). Conventional way of spraying solid powder as feedstock
using Atmospheric Plasma Spraying (APS) puts limitation
on the powder size, where it is difficult to spray fine powders.
Suspension spraying is an alternative where the suspension
of a specific powder is used as feedstock, which makes it
possible to spray submicron- and nanometer-sized powder
particles (Ref 3). Suspension spraying can produce highly
porous (Ref 4) coatings with different kinds of microstruc-
tures such as columnar type (Ref 5, 6), feathery columnar
type (Ref 6), and vertically cracked type (Ref 4, 7). Sus-
Ashish Ganvir, Nicholas Curry, Stefan Björklund,
Nicolaie Markocsan, and Per Nylén, Department of
Engineering Science, University West, 46186 Trollhättan,
Sweden. Contact e-mails: gmashish19@gmail.com and ashish.
ganvir@hv.se.
pension sprayed coatings have also shown lower thermal
conductivity than conventional APS coatings (Ref 4, 8).
In a previous screening study, it was shown that feasible
coating microstructures can be achieved by using Sus-
pension High Velocity Oxy-Fuel (S-HVOF) spraying and
Suspension Plasma Spraying (SPS). It was noticed that two
different types of microstructures are predominantly
achieved using the above-mentioned spraying techniques
(Ref 4).
For the S-HVOF coating, the suspension was injected
axially and the resultant microstructure was found to be a
dense, vertically cracked structure with a porosity of
approximately 20% (Ref 4). A gas fuel HVOF TopGun
(GTV) system with a nozzle of diameter of 8 mm and
ethylene as fuel gas, respectively (Fraunhofer IWS,
Dresden) was used. Water-based suspension with particles
in a range of D50 1-10 lm was used. The structure was
similar to a segmented and dense vertically cracked
structure produced by air plasma spraying (Ref 9, 10). A
detailed explanation behind formation of these vertical
cracks in suspension spraying can be found in Ref 4, 7.
Suspension plasma spraying has been shown capable in
producing high porosity coatings which plays a crucial role
in enhancing the thermal insulation (Ref 4, 11) of TBCs.
In order to achieve the desired (higher) porosity con-
tent, another coating type was produced using Suspension
Plasma Spraying (SPS) technique where the water-based
suspension was injected radially. Torch power used to
spray these coatings was between 51 and 52 kW. Particles

Journal of Thermal Spray Technology

 in suspension were in a range of D50 1-10 lm. As expected,
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the resultant microstructure had a higher porosity com-
pared to the S-HVOF coating as can be seen in Ref 4, and
the microstructure found was somewhere in between
columnar and vertical cracked types (Ref 4). The total
porosity of the coatings was around 40% with significant
amount of inter-pass porosity bands. Both coating types
showed good results in terms of thermal properties (Ref 4).
Suspension trajectory while injecting the suspension in
SPS was perpendicular to the flow of plasma as in con-
ventional radial injection plasma spraying process. How-
ever, in S-HVOF and Axial Suspension Plasma Spraying
(ASPS) (coatings produced in this work) techniques, sus-
pension was injected axially that is parallel to the plasma
flow. Detailed difference in two trajectories can be found
elsewhere (Ref 12).
Although both techniques S-HVOF and SPS showed
several advantages, they also showed some limitations.
S-HVOF has the limitation of achieving the desired high
porosity due to the high particle velocity involved, and
radial injection SPS showed overspray problems due to
the radial injection. It should be noted here that this
overspray problem can be minimized with the radial
injection upon proper optimization of SPS process. In an
attempt to overcome these problems, in this work it was
decided to use axial suspension plasma spraying (ASPS).
The aim of the work presented in this paper was to
investigate the microstructures of the TBCs which can be
sprayed by axial SPS and further to correlate these
microstructures to the thermal properties of the obtained
coating.
Three coatings of varying microstructure were pro-
duced for this study. Characterization techniques utilized
in this work were optical and scanning electron micro-
scopy (SEM) for microstructure evaluations; x-ray
diffraction (XRD) for phase analysis; water impregnation
(WI), image analysis (IA), and mercury intrusion
porosimetry (MIP) for porosity analysis, and laser flash
analysis (LFA) for thermal diffusivity measurements.
2. Experimental
2.1 Coating Production
Three different types of coatings (top coats) which are
designated as C1, C2, and C3 were sprayed with ASPS
technique using the Axial III high power plasma torch
(Northwest Mettech Corp., Vancouver, Canada) and
Nanofeed 350 suspension feed system. Partially stabilized
zirconia with 8 wt.% yttria suspension (INNOVNANO,
Table 1 Different spray parameters used to produce coatings C1, C2, and C3
Coating ID Spray distance, mm Surface speed, cm/s
C1 50 216
C2 100 75
C3 50 75
Coimbra, Portugal) was used to spray these coatings. The
particle size distribution and the solid loading were
(D10 = 241 nm, D50 = 492 nm, and D90 = 1.082 lm) and
25 wt.% powder in ethanol respectively. Mixture of Ar,
H2, and N2 was used to form the plasma with a gas flow in
a range of 200-300 L/min. Suspension injector of 250 lm
and exit nozzle of 0.375 inch was used. A summary of
deposition parameters used for C1, C2, and C3 is dis-
played in Table 1. It should be noted that the spraying
conditions were not optimized.
Prior to spraying the top coats, a metallic bond coat was
sprayed on HastelloyX substrates. The bond coats were
produced using a CoNiCrAlY material; AMDRY 9951
(Oerlikon Metco, Wholen, Switzerland) and were de-
posited using a high velocity air-fuel (HVAF) spray sys-
tem (Uniquecoat, Richmond, USA). The bond coat
thickness was kept constant for all the three types of
coatings with a target thickness of 200 lm. Both plates
(25 mm 9 25 mm 9 1.6 mm) and buttons (25 mm diam-
eter and 6 mm thickness) substrates were used.
2.2 Microstructure Characterization
In order to study the microstructure of the coatings, the
samples were first sectioned using a diamond cutting
blade, and then the cross sections for each coating were
mounted in a low viscosity epoxy resin. Mounting was
done using a vacuum impregnation technique. A standard
procedure was used to polish the mounted samples semi-
automatically using a Buehler PowerPro 5000 (Buehler,
USA). Mirror polished samples were used for the optical
and scanning electron microscopes (SEM) evaluations.
Gold sputtering was used prior to SEM in order to reduce
the charging effect on ceramic layer in the coating.
2.2.1 Coating Thickness, Inter-columnar Spacing or
Vertical Crack Density, and Column Width Measure-
ment. Coating thickness was measured using optical
micrographs. Around 200 measurements were performed
across the 25-mm coating cross section. Inter-columnar
spacing, inter-feathery spacing, or vertical crack density
determination was done using SEM micrographs which
were then analyzed with an ImageJ public domain free
software (Ref 13). From now onward in the further dis-
cussion, inter-columnar spacing or inter-feathery spacing
will be referred as vertical cracks. A total of 35 SEM
micrographs were taken for each sample at 9300 magni-
fication across the 25-mm sampleÕs cross section. A
straight line of fixed length was drawn at half of the
coating thickness. All the vertical cracks intercepting the
line in the micrograph were counted. The vertical crack
density was calculated from each micrograph using
Suspension feed
Power, kW Total gas flow, L/min rate, mL/min
101 200 100
120 300 45
147 300 100
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cracks
Vertical crack density
mm
No: of vertical cracks intercepted the line
¼ :
True length of the line
The final vertical crack density was taken as an average of
35 vertical crack density measurements. The distance be-
tween two cracks or columns was also calculated during
the same procedure. This distance will be referred as
column width in the further discussion. Column width was
measured at the half of the coating thickness for all
micrographs. Final column width results were the average
of all column sizes from 35 micrographs.
2.3 Phase Analysis
Phase analysis was performed using XRD technique on
coatings in the as-sprayed state. Measurements were car-
ried out using a D8 Discover diffractometer (Bruker AXS,
Germany) using Cu Ka radiation. 1D LynxEye detector
and double laser system were used for precise sample
height positioning. Beam knife was placed above the
samples in order to minimize the air scattering. The
scanned range was from 20 to 90 2h with 0.03 2h
increment and 115 s scanning time in each step. Rietveld
refinement of the obtained diffraction pattern was done
with TOPAS 4.2 software.
The crystallite sizes, or more precisely average sizes of
coherently scattering domains, were determined according
to the Fundamental Parameters Approach (Ref 14). Since
Bragg-Brentano geometry was used in this study, the
instrumental function was calculated pursuant direct
convolution approach. Weight fractions were determined
according to quantitative Rietveld refinement (Ref 15)
with the structural data of the identified phases taken from
the ICSD database.
2.4 Porosity Analysis
Measuring the porosity in SPS coatings is a big chal-
lenge due to the presence of different scaled porosities
starting from micrometric vertical cracks to submicron and
nanometer pores. Hence, porosity analysis was done using
three different techniques. Open porosity (pores which are
accessible by a fluid) measurement was done using water
impregnation and mercury infiltration techniques. Also,
image analysis was carried out to see the content of closed
porosity in the coating. These techniques are described
individually in detail below.
2.4.1 Image Analysis. Porosity measurement was done
using a public domain free software ImageJ (Ref 13).
Porosity measurement for SPS coatings using ImageJ
software was also found in the literature (Ref 16, 17).
Since the coatings studied in this work showed porosity at
varied scale (micrometric, submicron, and nanometer
pores); two different magnifications were utilized for
analysis in the software one of one thousand times mag-
nification, 91000 (91K) and one of ten thousand times
magnification, 910,000 (910K). These two magnifications
were selected such that 91K magnification should capture
Journal of Thermal Spray Technology
features like column gaps, big cracks, and micrometric
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pores, whereas 910K should capture features like sub-
micrometric and nanometer pores. While capturing the
higher magnification micrographs (910K), it was made
sure that the micrographs should not contain any big
features in order to avoid repetition.
For each coating, a total of 20 SEM micrographs were
captured across the 25-mm coating cross section for both
low and high magnification settings, respectively. It has to
be noted that a larger number of micrographs at higher
magnification may lead to a better statistical estimation of
porosity. However, in this work, the number was limited
to 20 micrographs since the purpose was to determine the
relative porosity values among these three coatings and
not the absolute value for each coating. All the images
were then threshold appropriately and converted into
binary images to calculate the porosity. The image analysis
technique adopted for this work is time-consuming but can
provide an estimate of all types of pores (connected, non-
connected, vertical cracks, branching cracks etc.) present
in the coating which may not be possible using other
techniques like water impregnation or mercury intrusion
porosimetry.
2.4.2 Water Impregnation and Mercury Intrusion
Porosimetry. Water impregnation technique was used to
measure the open porosity (i.e., pores which are accessible
by water) and it is based on Archimedes principle. The
detailed experimental procedure can be found elsewhere
(Ref 4). Porosity measurement and pore size distributions
were also determined by MIP carried out on a PoreMaster
33 GT (Quantachrome Corporation, Boynton Beach, FL)
equipment. Free-standing coatings were used for MIP
which were cut (10 mm 9 24 mm) from a 25-mm button
and then detached from substrate using nitro-hydrochloric
acid which dissolved the metallic bond coat. Samples were
washed then dried in a furnace at 130 C for 45 min to
remove adsorbed water from the inner surfaces of the
coating. Due to the small sample volumes, blank cell
correction was applied to increase accuracy of the mea-
surements. The samples were analyzed in a pressure re-
gime which was from 12 kPa to 230 MPa. It has to be
noted here that WI does not provide information about
the pore size but just the volume fraction of the pores
based on the weight difference of wet (immersed in water)
and dry (as-sprayed) coating. However, MIP can detect
pores of the order of a nanometer. The smaller the open
pores, the higher the required intrusion pressure for the
mercury to impregnate into the pore. Resolution for MIP
in this work was sample volume (3.2 cc), intrusion capacity
(0.5 cc), and volume resolution 3 9 105 cc.
2.5 Characterization of Thermal Properties
Thermal diffusivity was measured using laser flash
analysis. A Netzsch Laser Flash Apparatus LFA 427 sys-
tem (Netzsch Gerätebau GmbH, Germany) was used to
measure the thermal diffusivity. A complete three layer
system (top coat-bond coat-substrate) was used to mea-
sure the diffusivity. The diffusivity was measured both at
room temperature as well as across the complete tem-
 perature range 25-1190 C. This range will be referred as
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one cycle during the further discussion in this work. One
cycle here refers to the time taken to bring the sample
temperature from room temperature to 1190 C which
was approximately 4 h and then cool it back to room
temperature which was approximately 2 h. After high
temperature exposure, coatings were allowed to cool
down and re-measured at room temperature in order to
see the short-term sintering effect in the coating. Thermal
conductivity was then mathematically calculated using the
following formula (Ref 18):
k ¼ qaCp :
Here k (W/(m K)) is thermal conductivity, q (g/cm3) is
coating density which was measured from water impreg-
nation technique, a (mm2/S) is thermal diffusivity mea-
sured using LFA technique, and Cp (J/g/K) is the specific
heat capacity which was measured previously. The test
specimens for LFA were 10-mm diameter disks which
were water jet cut from 25-mm square plates. A thin layer
of graphite was applied on the top of the coating before
the measurement to enhance the absorption of the applied
infrared light pulse. As YSZ is transparent to IR radiation
wavelengths used in LFA equipment, the graphite layer
prevents the IR detector from measuring temperature
increase of the bond coat surface, rather than the YSZ
layer itself. The detailed experimental procedure for
thermal diffusivity and conductivity measurement is
described elsewhere (Ref 4, 18, 19).
3. Results and Discussion
3.1 Microstructure Analysis
Coating C1 showed porous structure with some
columnar features which can be seen from both cross
section and top view of the surface of the coating, Fig. 1. It
should be noted that this coating does not contain discrete
inter-columnar spacing unlike other columnar-type struc-
tures. It was found that the vertical crack density and the
column width was around 12 cracks/mm and (80 ± 34)
lm, respectively, Table 2. Column width can also be
Fig. 1 Cross section of coating C1 (a) and top view of the surface of coating C1 (b)
confirmed from both cross section and top view of the
coating from Fig. 1. Also, it is obvious from the cross
section that C1 is highly porous, Fig. 1(a).
Processing parameters for coating C1 utilized relatively
low power and total gas flow settings. Under such condi-
tions, the atomizing effect of the plasma is reduced rela-
tive to conditions C2 and C3. It should, therefore, be
expected that the C1 conditions will generate larger ato-
mized droplets and consequently larger ceramic droplets
once the solvent has evaporated. The high suspension feed
rate and consequently high total volume of solvent for
evaporation within the plasma further reduces the energy
available for particle heating. The combination of plasma
conditions, suspension feed and the 50 mm spray distance
results in larger particles that are arriving at the substrate
without complete melting. This can be observed in the
resultant microstructure that contains a large quantity of
pores and spherical particles.
Coating C2 (Fig. 2) has shown feathery columnar-type
microstructure. This can be seen from both the cross
section and top surface of the coating, Fig. 2. Calculation
of cracks or in this case inter-columnar spacing was found
to be similar as in coating C1 which is 12 cracks/mm.
However, the size of these feathers or column width was
found to be (86 ± 38) lm.
VanEvery et al. has proposed column formation in SPS
coating depending on the suspension droplet trajectory in
the plasma plume just before the final impact. Droplets
with diameters of the order of 1 lm and having low
momentum are influenced by the drag of the plume in the
boundary layer close to the substrate. Such particles will
be influenced by the plasma flow and deposit at shallow
Table 2 Vertical crack density, column width, and
coating thickness for coating C1, C2, and C3
Vertical
crack density, Column Coating
Coating ID cracks/mm size, lm thickness, lm
C1 12.1 ± 2.3 80 ± 34 132 ± 11
C2 12 ± 2.3 86 ± 38 253 ± 18
C3 6.3 ± 1.6 176 ± 83 192 ± 9
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Fig. 2 Cross section of coating C2 (a) and top view of the surface coating C2 (b)
Fig. 3 Cross section of coating C3 (a) and top view of the surface coating C3 (b)
angles on surface asperities. This shadowing effect results
in the formation of columnar structures (Ref 6).
Since coating C2 was produced utilizing higher power
(energy), higher total gas flow and lower suspension feed
rate than coating C1; hence results in stronger atomization
of the suspension on injection and well treated particles in
flight. The longer stand-off distance of 100 mm compared
to 50 mm used for coating C1 results in lower particle
velocity when the plasma plume interacts with the sub-
strate surface. The lower momentum particles are thus
greatly influenced by the flow of the boundary layer effect
of the plasma and result in oblique deposition trajectories
and formation of feathery columnar structures.
Coating C3 has shown vertically cracked type
microstructure which can be seen from the cross section of
the coating, Fig. 3. Vertical crack density for this coating
was around 6 cracks/mm which is half of the crack density
of coatings C1 and C2. Similarly, the column width was
found to be (176 ± 83) lm which is double than coating
C1 and C2. This can also be seen in the microstructure of
coating C3, Fig. 3. Uniform inter-pass porosity bands were
also found in these coatings.
Higher power (energy) and total gas flow involved
during spraying of coating C3 results in strong atomization
and melting of the particles in the plasma plume despite
the high suspension feed rate of 100 ml/min. However,
Journal of Thermal Spray Technology
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due to the short stand-off distance, the particles arrive at
the substrate with very high velocity resulting in a planar
deposition structure that cracks during spraying. This,
then, as VanEvery et al. discussed may generate lamellar
structure similar to APS. In such a lamellar structure,
presence of micro cracks can form the vertical crack as the
splats overlaps during the coating growth. Vassen et al.,
however, has shown that driving force for vertical crack
growth in SPS coating is the higher tensile stresses present
in the coating. Increased tensile stresses in SPS coating
than APS are due to the presence of less microcracks than
in APS. Minimized microcracks can then increase tensile
stresses in the SPS coating. Again, formation of such
vertical cracks in suspension sprayed coatings is explained
elsewhere in detail (Ref 4, 7).
3.2 Phase Analysis
XRD analysis of coatings C1, C2, and C3 was also
carried out in the as-sprayed state. Results showed that
the major phase present in all coatings is tetragonal along
with some monoclinic, Table 3. Coating C3, however, did
not show any other phases and it was pure tetragonal. The
crystallite size was also determined and found to be almost
in similar range for all C1, C2, and C3 coatings around
100 nm, Table 3.
 Table 3 Various phases present in the as-sprayed state
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and crystallite size for C1, C2, and C3
Phase, wt.%
Coating ID Tetragonal Monoclinic Crystallite size, nm
C1 96.28 3.61 99 ± 2
C2 97.18 2.82 90 ± 2
C3 100 0 105 ± 2
Fig. 4 Open porosity content (in vol.%) using water impreg-
nation (WI) and mercury infiltration porosimetry (MIP)
techniques
3.3 Porosity and Pore Distribution Analysis
Porosity and pore architecture determination is a big
challenge for SPS TBCs due to the high porosity of the
coatings and also due to the presence of a varied scale of
the pores size from micron- to nano-scaled pores (Ref 11).
Hence, in this work, three of the existing methods to
measure the porosity were used and the results are dis-
cussed. Results for open porosity measurements are
shown in Fig. 4. Both results from WI and MIP follow the
same trend with coating C1 having highest porosity,
whereas C2 and C3 having almost similar total open
porosity. This can also be observed from the microstruc-
tures of these coatings, Fig. 1, 2, and 3.
Porosity by WI for coating C3 and C2 is almost same as
shown in Fig. 4, since the error bars are overlapping.
However, porosity by MIP shows that coating C2 is
slightly higher than the porosity of coating C3. This slight
increase in the porosity of coating C2 than C3 can be due
to the presence of relatively larger submicron and nano-
pores in C2 which is also shown in Fig. 5. The difference in
the trend for coating C2 and C3 from two techniques can
be due to the fact that WI may not be able to impregnate
very small pores as in MIP due to the higher pressure used
in MIP.
3.3.1 Pore size Distribution Analysis Using MIP.
From the cumulative plot of MIP measurements, Fig. 5,
it can be seen how the pores are distributed in several size
ranges. Three important regions are marked in Fig. 5,
these are pores in nanometer, sub-micrometer, and
micrometer range. Pores above 10 lm can be considered
as globular pores, large inter-columnar spacing, larger
vertical, and horizontal cracks etc.
Fig. 5 Cumulative distribution of pores in different size ranges
(micron, submicron, and nanometer) performed using mercury
infiltration porosimetry (MIP) technique for coatings C1, C2, and
C3
Comparing C1, C2, and C3, it is shown from the plot in
Fig. 5 that C1 and C3 did not show the significant presence
of nanometer-sized pores compared to C2. However,
submicron-sized pores were found in all three coatings
with C1 having the highest content and C2 and C3 a
similar content. Pores in micron scale were almost negli-
gible (around 0.6 vol.%) in coatings C2 and C3, whereas
some (around 1.5 vol.%) of micron-sized pores were
noticed in coating C1. Pores and other features which are
considered in the category larger than 10 lm are found in
all three coatings. These bigger pores contributed around
37% in C2, 50% in C3, and 57% in C1 of their total
porosity content. The large scale features measured here
may be related then to the column spacing in the C2
coating, segmentation cracks in the C3 coating, and large
scale pores in the C1 coating (due to absence of column
gaps). Comparing C2 and C3, C2 showed relatively larger
content of submicron and nanometer pores than C3.
3.3.2 Image Analysis (IA). Image analysis is an
extensively used tool to analyze the porosity in thermal
barrier coatings. However, this technique can have some
difficulty in analyzing porosity in SPS coatings due to the
presence of pores in various size ranges from micron to
nanometer range (Ref 11). Small pores such as submicron
and nanometer pores may not be captured using low
magnification images. Hence, in this study, porosity mea-
surement was carried out at two different magnifications
to see the overall porosity content from both micron as
well as submicron and nanometer scales. Figure 6 presents
the SEM micrographs from coating C2 at two different
magnifications (91K and 910K) used for IA. It can be
seen from these micrographs that two different scaled
porosities are present in the coating.
Figure 7 summarizes the IA results on all three coat-
ings at two different magnifications 91K and 910K.
Comparing coatings C1, C2, and C3, it can be seen that
coating C1 showed the highest porosity content at both
magnifications, whereas coating C3 showed the lowest.
This can also be seen from the microstructure pictures,
Fig. 1, 2, and 3.
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Fig. 6 SEM pictures analyzed in image analysis (IA) technique to measure the porosity content at two different magnifications 91000
(91K) (a) and 910,000 (910K) (b), respectively, showing two different scaled porosities for coating C2
Fig. 7 Porosity content (in vol.%) using image analysis (IA)
technique at two different magnifications 91000 (91K) and
910,000 (910K) to capture large-scaled pores and small-scaled
pores, respectively
Comparing each coating at two different magnifica-
tions, it can be seen that coating C1 has shown both small-
scaled porosity (at 910K) and large-scaled porosity (91K)
in significant amounts which is around 24 and 42 vol.%,
respectively. Coating C2 has shown similar amount of
small- and large-scaled porosity which is around 13 vol.%.
However, Coating C3 has shown almost negligible small-
scale porosity; at around 2 vol.% and significantly low
large-scale porosity at around 6 vol.%.
Comparing porosity results from two different standard
techniques WI and MIP, it is seen from Fig. 4 that WI
shows higher porosity than MIP for all coatings. This can
be due the fact that WI does not neglect the surface
roughness of the top coat which then can be counted in the
overall porosity. However, in MIP, influence from the
surface roughness can be minimized by doing correction
prior to the measurement in the machine. Important fact
to be noted here is that, this difference does not relate to
the porosity results from image analysis since image
analysis considers 2D images where surface roughness
does not have any role.
3.4 Thermal Diffusivity and Conductivity
For a TBC system, higher the porosity, higher the
amount of air present in the coating which will result in
greater thermal insulation of the coating (Ref 4, 8). This
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study also reveals the importance of vertical cracks or
inter-columnar spacing and uniform inter-pass porosity
bands in affecting the thermal conductivities of the coat-
ings.
Firstly, looking at the first combination C1 and C2, It
can be seen from the porosity results, Fig. 4, that C1 has
higher porosity content than C2 but similar vertical crack
density, Table 2. Thermal diffusivity and conductivity are
hence following the inverse porosity trend where it can be
seen that C1 has shown lower thermal diffusivity and
conductivity values than C2.
Looking at the C2 and C3 combination, it can be seen
that C2 has shown comparatively similar content of overall
porosity as C3, Fig. 4. However, the vertical crack density
for C2 was found to be double than C3, Table 3. Now,
even though the overall porosity content was similar for
C2 and C3, thermal diffusivity and conductivity values
were significantly higher for C2 than C3, Fig. 8(a) and (b).
This trend can be explained due to the higher vertical
crack density in coating C2 than C3. These results are also
confirmed by literature which showed that higher vertical
crack density increased the thermal diffusivity and con-
ductivity in coatings (Ref 20, 21). This is because these
vertical cracks allow the hot gases to pass through them
which leads to easy heat flow and hence increase the
thermal diffusivity and conductivity of the coating
(Ref 22).
Also, lower thermal diffusivity and conductivity in C3
than C2 can be due to the presence of uniform inter-pass
porosity bands in C3 which can be clearly seen from the
microstructure, Fig. 3(a). These porosity bands are per-
pendicular to the direction of the heat flow in the coating,
which then may affect the overall heat flow. So, it can be
said that these porosity bands may act as barriers for the
easy heat flow in the coating. This then may decrease the
overall thermal diffusivity and thermal conductivity of the
coating.
Finally, looking at the combination C1 and C3 where
C1 showed both higher overall porosity content and
higher vertical crack density than C3, thermal diffusivity
and conductivity were found to be lower for C1 than C3,
Fig. 8(a) and (b). Hence, it can be said that the effect of
porosity content might be higher than the effect of vertical

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Fig. 8 (a) Thermal diffusivity values in the as-sprayed and just
after completion of one cycle at room temperatures for coatings
C1, C2, and C3. (b) Thermal conductivity values in the
as-sprayed and just after completion of one cycle at room
temperatures for coatings C1, C2, and C3
cracks density on thermal diffusivity and conductivity.
Looking at the microstructure, Fig. 1(a), it can be seen
that C1 did not actually show the vertical cracks as dis-
crete as C3 and C2. Hence, comparing C1 with either C2
or C3, the effect of porosity may be much significant than
effect of the vertical cracks. Hence, it can be said that
higher porosity content may be the reason behind lower
thermal diffusivity and conductivity of coating C1 than C3.
One important thing to be noted here is the sudden
increase in the diffusivity values after one cycle in coating
C2. On the contrary, C1 and C3 showed almost the same
diffusivity and conductivity, Fig. 8(a) and (b). The reason
behind this sudden increase could be some rearrangement
of pores in coating C2. Guignard et al. showed that at
higher temperatures, YSZ SPS coatings undergo pore
structure rearrangement. It was shown that pores below
0.6 lm undergo sintering, on the other hand pores larger
than 0.6 undergo pore coarsening (Ref 23).
Coating C2 has shown almost similar thermal diffusiv-
ity and conductivity in the as-sprayed state with C3.
Having the similar amount of porosity in coating C2 and
C3, the trend in diffusivity and conductivity is not sur-
prising. However, C2 showed significant increase in dif-
fusivity and conductivity, whereas C3 did not after treating
the coating for one cycle. This behavior can be explained
based on the pore structure rearrangement in the coating.
As it can be seen from porosity results by image analysis at
910K, Fig. 7, coating C3 has negligible small-scaled pores,
whereas C2 has shown significantly higher amount of
small-sized pores than C3. This can also be seen from
cumulative porosity plot by MIP, Fig. 5. Due to a larger
fraction of small-scaled pores in coating C2 than C3, a
larger amount pores might have undergone sintering as
well. This could be the reason behind the abrupt increase
in diffusivity after one cycle compared to C3.
Also comparing C1 and C2, again, there was not sig-
nificant increase in thermal diffusivity and conductivity in
C1 as in C2 after one cycle. Like C2, C1 also showed
significant small-scaled porosity, Fig. 5 and 7. However,
C1 did not show the presence of nanometer pores as in C2,
which can be seen from the cumulative plot of MIP, Fig. 5,
but C1 did show significant submicron porosity which were
also considered as small-scaled pores which are prone to
sintering (Ref 23). Considering the fact that if a coating
has significant small-scaled porosity but still does not show
significant increase in thermal diffusivity and conductivity
after one cycle, it can be explained by taking into con-
sideration the larger pores which may undergo pore
coarsening at higher temperatures while small pores sinter
(Ref 23). The coarsening of larger pores and sintering of
small-scaled pores can then balance the change in thermal
diffusivity and conductivity. In C1, as it can be seen from
MIP cumulative plot, Fig. 5, the percentage of larger pores
is in the same range with small-scaled pores. Hence, in
coating C1, larger pores coarsening and smaller pores
sintering may be balancing the thermal diffusivity and
conductivity increase. However, the complete behavior of
pore rearrangement under heat loads is complicated and
further investigations are needed to better understand its
impact on the thermal properties of the coatings.
Motivation for generating columnar structure in sus-
pension plasma sprayed thermal barrier coatings comes
from the well-known EBPVD TBCs. Hence, thermal
conductivity values of coatings from this study were also
compared with EBPVD coatings from the literature. It
was found that EBPVD coatings showed thermal con-
ductivity around 1.4 W/mK (Ref 24) and 1.5 W/mK (Ref
25) which is higher than ASPS coatings produced in this
work.
Figure 9(a) and (b) show the thermal diffusivity and
the thermal conductivity of the as-sprayed coatings,
respectively, against temperature during one heating
cycle. Both curves follow the same trend as it was
observed at room temperature in the as-sprayed state.
Coating C1 shows the lowest diffusivity and conductivity,
whereas C2 shows the highest throughout the temperature
range. The increased trend of conductivity curve right
from the room temperature is not similar with the stan-
dard APS coatings. In standard APS YSZ TBCs, the
conductivity first decreases until 600-800 C and then in-
creases (Ref 26, 27) which is shown to be the result of
sintering in those coatings. However, in this study, the
presence of fine-scaled microstructural features (submi-
cron and nanometer pores) for all coatings is believed to
produce multiple interfaces that overall offer better ther-
mal resistance. These fine features on the other hand may
favor phenomena like sintering and pore coarsening by
relatively shortening the surface diffusion distance in the
coating. These fine features then can offer considerable
scope for the surface diffusion to occur through grain
Journal of Thermal Spray Technology

Fig. 9 (a) Thermal diffusivity values at higher temperatures
(during one cycle) for coatings C1, C2, and C3. (b) Thermal
conductivity values at higher temperatures (during one cycle) for
coatings C1, C2, and C3
boundaries and free surfaces (Ref 22). Hence, it can be
said that the nature of the conductivity curve in coatings
C1, C2, and C3 which is increasing might be driven by
some micro or nano-structural changes in the
microstructure. It is also shown in the literature that SPS
coatings can have significant microstructural changes due
to the surface diffusion in the coating (Ref 28). Also, a
steep jump in the conductivity curve for all coatings is
shown in Fig. 9(b) after 1000C, which can be due to the
enhanced heat transport by radiation (Ref 29).
4. Conclusion
The study presented in this paper was focused on three
different types of microstructures obtained by axial sus-
pension plasma spraying (ASPS) as well as the impact of
these microstructures on the thermal properties of the
coatings. It has been shown that ASPS can generate a
variety of microstructures which can be categorized in
porous type, feathery columnar type, and vertically
cracked type. These coatings have shown a large variation
of pores size from micrometer scale, to nanometer scale,
confirmed by mercury infiltration porosimetry and image
analysis techniques.
It was also shown that the presence of higher porosity,
lower density of inter-columnar spacing or vertical cracks,
and large column width decreases the thermal diffusivity
and hence thermal conductivity of the coating. Also, it was
found that the presence of uniform inter-pass porosity
Journal of Thermal Spray Technology
bands helps in reducing the overall thermal diffusivity and
Peer Reviewed
hence the thermal conductivity of the coating. Significant
increase in thermal diffusivity and conductivity was found
after heat treating the coatings at higher temperatures,
due to the rearrangement of the pore structure, which is
believed to be due to the coarsening of larger pores and
sintering of submicron and nanometer pores. However,
further detailed investigation behind the pore rearrange-
ment due to coarsening and sintering in SPS coatings is
needed.
Acknowledgments
Authors sincerely thank Monika Vilemova and Zdenek
Pala from IPP Prague, Czech Republic for helping out
with MIP and XRD experiments, respectively. Authors
are also thankful to Toni Bogdanoff from Jönköping
University and Narayanan Venkateswaran from India for
helping with LFA measurements and image analysis for
microstructural characterization respectively.
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Journal of Thermal Spray Technology