coatings

Article
Porosity Characterization and Its Effect on Thermal
Properties of APS-Sprayed Alumina Coatings
Wolfgang Tillmann, Omar Khalil * and Mohamed Abdulgader
Institute of Materials Engineering, TU Dortmund University, Leonhard-Euler-Str. 2,
D-44227 Dortmund, Germany; wolfgang.tillmann@tu-dortmund.de (W.T.);
mohamed.abdulgader@tu-dortmund.de (M.A.)
* Correspondence: omar.khalil@tu-dortmund.de




Received: 2 July 2019; Accepted: 20 September 2019; Published: 24 September 2019


Abstract: In the thermal spraying process, the porosity of ceramic coatings contributes directly to the
efficiency of the thermal insulation. The size, shape, and distribution of the pores determine the level
of both thermal and sintering resistance. In this work, three different atmospheric plasma sprayed
(APS) alumina coatings were fabricated with the same spraying parameters using alumina powders
with fine, medium, and coarse particle size. The microstructure of the obtained coatings was analyzed
regarding the obtained total porosity, pore size, and pore shape. It was found that it is expedient
to divide the pore size range into fine, medium, and large sizes. The shape was characterized with
regard to the circularity aspect. In this way, all types of cracks can be considered as oblate pores
and were included in the calculation of the total porosity. In the case of using fine feedstock powder,
the densest coatings were produced among all coatings, and the fraction of fine pores and cracks are
thereby substantially higher. However, the total porosity increases with increasing feedstock powder
size. A connection was also made between thermal insulation and porosity fraction which includes
fine pores and cracks.

Keywords: atmospheric plasma spray (APS) process; particle size; thermal insulation; thermal barrier
coating (TBC); thermal diffusivity; coating microstructure; coating porosity

1. Introduction
Thermal spraying technique is designed to add additional thermal and mechanical properties to
base substrate materials. The applied coating enables the substrates to operate in harsh conditions.
Ceramic coatings, for example, are particularly suitable for the use as very good thermal and electrical
insulators. However, atmospheric plasma spraying (APS) is the most appropriate process, due to the
high temperatures that the plasma jet provides, and is used for melting, and thus depositing, ceramic
materials [1]. Ceramic coatings also improve the resistance of steel components against corrosion,
wear, and erosion. For these reasons, they have been widely investigated [2–5]. This kind of coatings
found their use in automotive and aerospace industries, where internal components normally operate
in extreme temperatures [6].
Pores and cracks with various sizes and morphologies are inherent features of thermally
sprayed coatings, which are generated during the deposition process and entrapped between
the splats. The microstructure of ceramic coatings, in particular, exhibit defects such as globular
pores, delaminations or interlamellar pores, and micro-cracks which compose the coating’s porosity.
Incomplete contact between contiguous splats and the presence of unmelted particles result in the
formation of large globular pores [7]. Delaminations in form of crack-like pores between lamella
arise because of the rapid splat solidification and high velocity impingement of the molten particles.
The relaxation of tensile quenching stresses leads to the formation of fine cracks [8,9]. Characterizing

Coatings 2019, 9, 601; doi:10.3390/coatings9100601 www.mdpi.com/journal/coatings

Coatings 2019, 9, 601 2 of 11

these various pores is important, as they influence ceramic coating properties and its behavior in
service, particularly, the thermal conductivity [10,11].
Generally, the level of the obtained porosity in plasma sprayed ceramic coatings may vary from
less than 2 vol.% to more than 20 vol.%. The level of porosity depends on the type and morphology
of the utilized feedstock powder and particle size as well as the used spray parameters [12–14]. In a
wet environment, open pores and cracks may cause local corrosion in the substrate [6]. However,
the presence of such microstructural features with defined levels enhances the thermal insulation of
the coating as well as increases its thermal shock resistance [1,15,16]
Many researchers have studied the effect of porosity on thermal conductivity either by carrying
out theoretical calculations or by conducting experiments. They referred to the fact that total porosity
plays only a secondary role, whereas the size, shape, and spatial distribution of the pores play the
primary role in determining the properties of a coating [17,18]. Chi et al. and Cernuschi et al. [19,20]
reported that the morphology of pores in porous coatings highly affects the thermal conductivity.
Wang et al. [21] built a finite element model, and investigated the effect of pores and splat interfaces
on thermal conductivity. In his model, pores considered as spherical whereas pore orientation and
distribution were estimated. They predicted a reduction up to 50% in the thermal conductivity due
to the variation in porosity levels. Cernuschi et al. [22] modeled the thermal conductivity of plasma
sprayed thermal barrier coatings and determined shape and orientation of the pores as well as the
porosity fractions. They concluded that thermal conductivity of the coating is affected by porosity in
different ways and this effect depends on the morphology and orientation of the pores. Furthermore,
Wang et al. [23] have reported that sizes and shapes of pores affect significantly the effective thermal
conductivity of ceramic coatings. They found that oblate narrow pores with low roundness (indicated
by the circularity factor) show higher thermal resistance than spheroidal pores.
As can be seen, several studies have reported the effect of pores and cracks on thermal properties of
thermally sprayed ceramic coatings through porosity characterization. However, very few information
is available related to the effect of porosity fractions, in terms of size and shape, on thermal insulation
of plasma sprayed ceramic coatings. The present work is based on the study of microstructures of
APS alumina coatings using three feedstock powders of different particle size. The influence of the
particle size on the particle in-flight temperature and velocity as well as the coating’s microstructural
features and properties of the coating were investigated. The microstructural features of alumina
coatings including total porosity, fractions of porosity and crack network were analyzed quantitatively
by means of an image processing tool. The work focuses on the accurate measurement of porosity
fractions based on a clear criterion that distinguishes each porosity component. Moreover, coating
properties such as hardness, phase composition, and thermal insulation were evaluated and related to
the quantified microstructural features.

2. Materials and Processes

2.1. Samples Preparation and Deposition Process

Three sets of steel substrates with nominal dimensions with a diameter of 40 mm and a thickness
of 5 mm were grit blasted on one side using alumina (EFK-14). This procedure was followed by an
ultrasonic cleaning for the APS deposition. Three commercial alumina powders (fused and crushed,
high purity; 99.5%) of different particle sizes: fine powder, Amperit 740.000 (+5–22 µm); medium
powder, Amdry 6062 (+22–45 µm); and coarse powder, Amperit 740.002 (+45–90 µm), H.C. Stark,
Germany, were deposited on the grit blasted side of the steel substrates. The median size (vol.50%) of
these powders are 14.00, 35.88, and 77.7 µm, respectively.
SEM images of the utilized powders and their particle size distributions are shown in Figure 1.
An Oerlikon Metco F4-MB gun, with a nozzle with a 6 mm internal diameter and a single powder
feeder, was used for this study. All spray parameters were kept constant for the three powders in
order to investigate the influence of the starting powder’s particle size on porosity fractions in the
Coatings 2019, 9, 601 3 of 11

resulted coatings. Additional samples were produced from the three powders using the same spray
Coatings 2019, 9, x FOR PEER REVIEW 3 of 11
parameters but with variant number of spray passes. The number of spray passes was maintained so
that all coatings have almost the same coating’s thickness. These additional coatings were used for the
that all coatings have almost the same coating’s thickness. These additional coatings were used for
thermal insulation test. The used APS process parameters are given in Table 1.
the thermal insulation test. The used APS process parameters are given in Table 1.

Figure
Figure 1.1. SEM
SEM images
images showing
showing the
the morphology
morphology of of fused and crushed
fused and crushed alumina
alumina powders:
powders: (a)
(a) fine
fine
particle size (+5−22 µm), (b) medium particle size (+22−45 µm), and (c) coarse particle size (+45−90 µm).
particle size (+5–22 µm), (b) medium particle size (+22–45 µm), and (c) coarse particle size (+45–90 µm).

Table 1.
Table Atmospheric plasma
1. Atmospheric plasma sprayed
sprayed (APS)
(APS) process
process parameters
parameters for
for alumina
alumina powders.
powders.
Parameter
Parameter Value
Value
Current
Current [A][A] 600
600
Voltage
Voltage[V][V] 74 ±±33
74
Argon [L·min−1 ]−1 41
Argon [l.min ] 41
Hydrogen [L·min−1 ] −1 12
Power carrier gas[l.min
Hydrogen [NLPM] ] 12
3.4
Power
Nozzlecarrier gas[mm]
diameter [NLPM] 3.4
6
Nozzle diameter
Spray distance [mm] [mm] 6
120
Step height
Spray [mm]
distance [mm] 1204
Number of spray passes [mm] 10
Step height [mm] 4
Number of spray passes [mm] 10
2.2. Porosity Analysis
2.2. Porosity Analysis evaluate the porosity of the produced depositions, cross-sectional metallographic
To quantitatively
samples
To were prepared for
quantitatively the investigations.
evaluate the porosity A series
of the of SEM images depositions,
produced with differentcross-sectional
magnification
factors for each cross-section were taken by a field-emission scanning
metallographic samples were prepared for the investigations. A series of SEM images with different electron microscope (Joel,
JSM-7001F FESEM).
magnification factorsFor theeach
for porosity measurements,
cross-section ten images
were taken by a along the cross-section
field-emission scanningwere taken
electron
randomly, central to the coating’s thickness, for a cross-section of each
microscope (Joel, JSM-7001F FESEM). For the porosity measurements, ten images along the cross-coating type. The images were
magnified with a magnification factor of 1000×, which enables the detection
section were taken randomly, central to the coating’s thickness, for a cross-section of each coating of 0.1 µm-sized features.
The
type.image brightness
The images were was reduced,with
magnified whereas the contrast factor
a magnification was increased
of 1000×,towhich
facilitate the image
enables analysis
the detection
software to accurately detect the porosity. Additionally, a very low accelerating
of 0.1 µm-sized features. The image brightness was reduced, whereas the contrast was increased voltage (1.0 kV) andtoa
low probethe
facilitate current
image(8–10 µA) were
analysis softwareusedtosoaccurately
that the contrast
detect between the pores
the porosity. and coating’s
Additionally, a very matrix
low
was enhanced.
accelerating Furthermore,
voltage (1.0 kV)backscattering
and a low probe electrons
currentfeature
(8–10were
µA)used
were to used
enhance the quality
so that of the
the contrast
obtained the
between SEM images.
pores An imagematrix
and coating’s analysis waswas performed
enhanced. using Jimage
Furthermore, J1.49r software
backscattering (provided
electrons by
feature
the National
were used toInstitutes
enhance of theHealth,
qualityBethesda, MD, USA)
of the obtained SEM[24] on SEM
images. Animages
image at 1000×. was
analysis Image filtering
performed
was applied to remove noise followed by image segmentation by thresholding,
using Jimage J1.49r software (provided by the National Institutes of Health, Bethesda, MD, USA) [24] which have produced
binary
on SEM images;
imagesthe atzero-threshold
1000×. Image levelfiltering
(black) was
wasassigned
appliedtototheremove
pores and the one
noise level (white)
followed by imagewas
assigned to theby
segmentation alumina solid state.
thresholding, which Subsequently,
have produced the pores
binary were measured
images; and categorized
the zero-threshold according
level (black)
to three area ranges: Fine (0–1 µm 2 ), medium (1–10 µm2 ), and large (>10 µm2 ). Moreover, the medium
was assigned to the pores and the one level (white) was assigned to the alumina solid state.
pore size rangethe (1–10 2 ) for the porosity of the three coatings was further classified in terms of
µmwere
Subsequently, pores measured and categorized according to three area ranges: Fine (0–1
their
µm 2),circularity
medium (1–10 (Cir. <0.5),
µm2), where
and large circularity
(>10 µmis2).a Moreover,
measuring the unitmedium
of pore spheroids. The more
pore size range (1–10a µm
pore2)

becomes spherical, the circularity approaches unity and when pores become more
for the porosity of the three coatings was further classified in terms of their circularity (Cir. <0.5), elongated or narrow,
circularity
where decreases.
circularity is aThe circularity
measuring is defined
unit of pore as [24]
spheroids. The more a pore becomes spherical, the
circularity approaches unity and when pores become more elongated or narrow, circularity decreases.
The circularity is defined as [24] Cir. = 4π (A/p2) (1)

Cir. = 4π (A/p2) (1)

Coatings 2019, 9, 601 4 of 11

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9, xx FOR
FOR PEER
PEER REVIEW
REVIEW 44 of
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11

where “A”
where “A”
is is
“A” is
the pore
the pore
area
pore area
and
area and
“p”
and “p”
isisthe
“p” is
pore
the pore
perimeter.
pore perimeter.
Variousshapes
perimeter. Various
shapesofofpores
Various shapes
poresand
and cracks
cracks of
of
of
where the the of pores and cracks
different sizes
different sizes in
sizes in a cross-sectional
in aa cross-sectional SEM
cross-sectional SEM image
SEM image for
image for typical
for typical ceramic
typical ceramic coating
ceramic coating are
coating are identified
are identified
identified in in Figure
in Figure 2, 2,
Figure 2,
different
whereas
whereasthethe
process
process ofofpore
poreclassification
classificationisis
isshown
shown inin Figure 3.
Figure 3.
3.
whereas the process of pore classification shown in Figure

Figure
Figure
Figure 2.
2. 2. Cross-sectionalSEM
Cross-sectional
Cross-sectional SEMimage
SEM image showing
image showing the
showing the shapes
the shapes
shapesand and relative
andrelative sizes
relativesizes (area)
sizes(area) ofof
(area)
of pores and
pores
pores cracks;
and
and cracks;
cracks;
fine:
fine:
fine: <1µm
<1<1 µm
µm ; medium:
medium: 111 to
2 ;22;medium: to 10
10 µm
µm222;;;and
and large:
andlarge: >10
>10
large:>10 µm
µm 2.. 2 .
2
µm

Figure 3.
Figure 3. Pore
Pore classification
classification process:
process: (a)
(a) SEM
SEM gray
gray image,
image, (b) total
total porosity (binary
(binary image),
image), (c)
(c) fine
fine
Figure 3. Pore classification process: (a) SEM gray image,(b) (b) totalporosity
porosity (binary image), (c) fine
pores,
pores, (d) medium pores, (e) medium pores with a circularity <0.5, and (f) large pores.
pores, (d)(d) mediumpores,
medium pores,(e)
(e)medium
mediumpores
poreswith
with aa circularity
circularity <0.5,
<0.5,and
and(f)
(f)large
largepores.
pores.
2.3.
2.3.2.3. Characterization
Characterization
Characterization
A thermal
thermal spray
spray sensor
sensor (AccuraSpray
(AccuraSpray G3, G3, Tecnar
Tecnar Co.,
Co., St-Bruno-de-Montarville,
AA thermal spray sensor (AccuraSpray G3, Tecnar Co., St-Bruno-de-Montarville,
St-Bruno-de-Montarville, QC, Canada)
QC,
QC,Canada)
Canada)
was
was used
used to measure the temperature and velocity of in-flight particles prior the process of samples
was used toto measurethe
measure thetemperature
temperatureand and velocity
velocity of
of in-flight
in-flightparticles
particlesprior
priorthe
theprocess of of
process samples
samples
deposition. The
deposition. The system—the
system—the thermal
thermal sensor—was
sensor—was positioned
positioned so so that
that measurements
measurements are are taken
taken exactly
exactly
deposition. The system—the thermal sensor—was positioned so that measurements are taken exactly
at the spray
spray distance
distance listed
listed in Table
Table 1.
1.
at at
thethespray distance listed ininTable 1.
The additionally
The additionally produced
produced samples,
samples, which
which represent
represent the
the three powders
powders and have have the
the same
same
The additionally produced samples, which represent thethree three powdersand and have the same
coating thickness, were used in the thermal insulation test. Coating surface
coating thickness, were used in the thermal insulation test. Coating surface was subjected to anwas subjected to an
coating thickness,
increasing heat were (oven)
source used inup the
to thermal
950 °C insulation
with a rate of test.
15 °C Coating
per surface
minute, and a was subjected
holding time ofto
60an
increasing heat source (oven) up to 950 °C with a rate of 15 °C per minute, and a holding time of 60
increasing heat source (oven) up to 950 ◦ C with a rate of 15 ◦ C per minute, and a holding time of
Coatings 2019, 9, 601 5 of 11

60 min. The temperature on both sides of samples that represent the three types of coatings were
simultaneously
Coatings 2019, 9,measured
x FOR PEER by means of two thermocouples.
REVIEW 5 of 11
Microhardness measurements were carried out at room temperature on polished cross-sections
min. The temperature on both sides of samples that represent the three types of coatings were
that represent the three as-sprayed coatings using a Vickers micro-indenter (Leco M-400, Ebersbach an
simultaneously measured by means of two thermocouples.
der Fils, Germany). The indentations were performed with a load of 2.94 N for a dwell time of 15 s.
Microhardness measurements were carried out at room temperature on polished cross-sections
Standard spacing was
that represent usedas-sprayed
the three between the indentations
coatings (at least
using a Vickers three times the
micro-indenter diagonal)
(Leco to ensure that
M-400, Ebersbach
no further stresses were produced by the interaction between the consecutive indentations.
an der Fils, Germany). The indentations were performed with a load of 2.94 N for a dwell time of 15
s. Standard spacing was used between the indentations (at least three times the diagonal) to ensure
3. Results
that noand Discussion
further stresses were produced by the interaction between the consecutive indentations.

3.1. Image Processing

3. Results Analysis
and Discussion
The SEM images of the as-sprayed coatings were used to analyze the porosity of the coatings
3.1. Image Processing Analysis
produced from the three powders.
The SEMlevel
The porosity images of the as-sprayed
variation in the three coatings were
coatings used toin
is shown analyze
Figurethe4. porosity
It can beofobserved
the coatings
that fine
produced from the three powders.
pores with an almost spherical shape are uniformly distributed along the coating produced from the
The porosity level variation in the three coatings is shown in Figure 4. It can be observed that
fine powder. As the particle size increases with medium and coarse powders, more pores of larger
fine pores with an almost spherical shape are uniformly distributed along the coating produced from
sizes are visible and the porosity distribution becomes nonuniform. The image analysis performed
the fine powder. As the particle size increases with medium and coarse powders, more pores of larger
on SEM images of coating’s cross sections showed that the average total porosity of fine-, medium-,
sizes are visible and the porosity distribution becomes nonuniform. The image analysis performed
and coarse-powder
on SEM images of coatings
coating’sare 0.93%,
cross 2.47%,
sections andthat
showed 5.55%
the of coating
average area,
total respectively.
porosity It should be
of fine-, medium-,
notedandhere that, in the coatings
coarse-powder presentare
work, the2.47%,
0.93%, measurement
and 5.55% unit usedarea,
of coating is the area percentage
respectively. It should(area
be %),
whichnoted
is almost the same
here that, in theas the volume
present percentage
work, the (vol.%).
measurement unitThe
usedlower
is thelevels of measured
area percentage porosities
(area %),
which for
(especially is almost the same as the
the fine-powder volumecould
coating) percentage (vol.%).
be related to The lowermelting
the high levels of degree
measured of porosities
the deposited
(especially for the fine-powder coating) could be related to the high melting degree of
particles and also to the metallurgical preparation process of the cross sections used to get SEM images the deposited
particles
in which part and
of thealso to the
open metallurgical
porosity preparation
disappeared, process
leading of theevaluate
to under cross sections used tomeasurement.
the porosity get SEM
images in which part of the open porosity disappeared, leading to under evaluate the porosity
Taking this into consideration, the porosity measurements are in agreement with the reported data for
measurement. Taking this into consideration, the porosity measurements are in agreement with the
porosity range of ceramic coatings [12–14].
reported data for porosity range of ceramic coatings [12–14].

Figure 4. Cont.
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Figure
Figure 4. Cross-sectional
4. Cross-sectional SEMSEMmicrographs
micrographs of of as-sprayed
as-sprayed alumina
aluminacoatings indicating
coatings the coating
indicating the coating
porosity and cracks deposited with: (a) fine powder, (b) medium powder, and (c) coarse powder.
porosity and cracks deposited with: (a) fine powder, (b) medium powder, and (c) coarse powder.
In general, the total porosity levels for all coatings increases when increasing the feedstock
In general, the total porosity levels for all coatings increases when increasing the feedstock powder
powder particle size is increased. This increase is mainly due to the simultaneous increase of both the
particle size is increased. This increase is mainly due to the simultaneous increase of both the number
number and size of large pores, whereas fine and medium pores decrease.
and size of Aslarge pores,
all spray whereaswere
parameters fine and
kept medium
constant forpores
the decrease.
three powders, fine-powder particles were
As all spray parameters were kept constant
exposed to a higher in-flight temperature and velocity for the three
(2620 °C,powders,
415 m/s onfine-powder
average) thanparticles
medium-were
exposed to a higher in-flight temperature ◦
and coarse-powder particles (2530 °C and and velocity
365 m/s, (2620
and 2390 °C andC, 330
415m/sm/son
onaverage,
average) than medium-
respectively).
and coarse-powder particles
Also, thickness (2530 ◦ Cofand
measurements the365
threem/s, and 2390
coatings ◦ C and
revealed 330 m/s on average,
that coarse-powder produce respectively).
thicker
coatings
Also, than medium-
thickness measurementsand fine-powders
of the three (average
coatings thicknesses
revealed that were 668, 475, and
coarse-powder 180 µm,
produce thicker
respectively).
coatings than medium- and fine-powders (average thicknesses were 668, 475, and 180 µm, respectively).
The porosity
The porosity of the
of the three
three coatingswas
coatings wasevaluated
evaluated quantitatively
quantitatively and classified
and intointo
classified threethree
area area
ranges. Subsequently, the average of each pore range was calculated. The porosity evaluation was
ranges. Subsequently, the average of each pore range was calculated. The porosity evaluation was
based on ten measurements of ten different SEM images for each coating sample. Given the average
based on ten measurements of ten different SEM images for each coating sample. Given the average
of each pore range and average total porosity for each sample, the fraction of each pore range was
of each pore range
calculated. and average
Additionally, total porosity
the medium for each
pore range (1–10sample,
µm2) forthe fraction
each sampleofwas
each pore
also range was
classified
calculated. Additionally, 2
the medium pore range (1–10 µm ) for each sample was also classified
according to the pore’s circularity.
accordingFor to the pore’s circularity.
the medium pore range of each coating type, the shape of the pores is crucial with regard to
For the medium
the thermal poreproperty
insulation range of as each
porescoating
with a lowtype, the shape
circularity of the pores
(circularity is crucial
<0.5) highly with to
contribute regard
to the thermal insulation property as pores with a low circularity (circularity <0.5) highly contribute
the thermal insulation property in comparison to pores with a high circularity (circularity >0.5). These
to themeasurements are visualized
thermal insulation property in Figure 5. It can be
in comparison to seen
pores that
withthe afine-powder coating
high circularity possesses a>0.5).
(circularity
higher percentage of fine-pores and medium-pores ranges (34.4% and 62.3%, respectively) than the
These measurements are visualized in Figure 5. It can be seen that the fine-powder coating possesses
medium-powder and coarse-powder coatings (15% and 45%, and 6% and 27%, respectively). While
a higher percentage of fine-pores and medium-pores ranges (34.4% and 62.3%, respectively) than
more than 60% of the medium-pore range for fine-powder coatings exhibit a circularity of <0.5,
the medium-powder and coarse-powder coatings (15% and 45%, and 6% and 27%, respectively).
medium-powder and coarse-powder coatings exhibit less than half (48.2% and 48%, respectively) of
Whilemedium-pore
more than 60% rangeofwith
the medium-pore range for fine-powder coatings exhibit a circularity of <0.5,
the same circularity.
medium-powder and coarse-powder coatings exhibit less than half (48.2% and 48%, respectively) of
medium-pore range with the same circularity.
In contrast, coarse-powder coatings possess a higher percentage of large-pore ranges (67%) than
medium-powder and fine-powder coatings (40% and 3.3%, respectively).
The measurements above for porosity fractions (considering medium- and coarse-powder coatings)
are well in agreement with the recorded literature data [25,26]. Deshpande et al. [25] prepared APS
alumina and YSZ coatings by powders of different size distributions and morphologies. They reported
that for the APS alumina coatings prepared by 15–50 µm particle size and spherical morphology
powder, the crack network and fine pores together represent only one-third of the total porosity.
Huang et al. [26] prepared different YSZ coatings using different spray parameters and measured
the total porosity and number of pores in a prespecified scanning area. They also classified pores in
terms of aspect ratio (big & small pores) and orientation (horizontal & vertical) to investigate their
influence on thermal conductivity of the coatings. They reported that large pores (pore area greater
than 2 µm2 ) represent ~80% of the total porosity, whereas only 20% is the porosity fraction of small
pores (pore area less than 2 µm2 ).
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Figure 5.
Figure 5. Relative
Relative pore
pore range
range contributions out of
contributions out of total
total porosity.
porosity.

In contrast,
Table 2 lists coarse-powder
porosity fractionscoatings
measuredpossess a higher
through the percentage
present work of compared
large-poretoranges (67%)data.
literature than
medium-powder and fine-powder coatings (40% and 3.3%, respectively).
Table 2. Measurementsabove
The measurements of porosity
for fractions
porosityfrom literature
fractions compared to medium-
(considering present work measurements
and coarse-powder
for coatings prepared by medium and coarse particle size.
coatings) are well in agreement with the recorded literature data [25,26]. Deshpande et al. [25]
prepared APS alumina and YSZ coatings by powders
Ref. [25]
of different
Ref. [26] size distributions and morphologies.
This Study
Porosity Fraction
They reported that for the APS alumina coatings prepared by 15–50 µm25–45particle
15–50 µm Powder Size Not Specified µm size45–90and spherical
µm
morphology powder,
Large pores
the crack network
≈65%
and fine pores together
2 represent only
40%
one-third of the total
80% (>2 µm ) 67%
porosity.
Fine + Medium pores ≈35% n/a * 55% 33%
HuangMediumet al. [26] prepared
pores n/a *different YSZ coatings n/a * using different45% spray parameters
27% and
measured Fine poresporosity andn/a
the total *
number of pores20% in a(<2 µm2 )
prespecified scanning15%area. They also 6%classified
pores in terms of aspect ratio (big & small pores) * = not applicable.
and orientation (horizontal & vertical) to investigate
their influence on thermal conductivity of the coatings. They reported that large pores (pore area
3.2. Microhardness
greater than 2 µm2) represent ~80% of the total porosity, whereas only 20% is the porosity fraction of
smallMicrohardness
pores (pore area less
tests than 2the
showed µmeffect
2).
of the coating porosity on microhardness values of the three
TableTable
coatings. 2 lists porosity
3 lists fractions
the average measured through
microhardness values the present
of the three work compared
coatings to literature
along with data.
the deviations
of these measurements. In comparison to medium- and coarse-powder coatings, fine-powder coatings
Table 2. Measurements of porosity fractions from literature compared to present work measurements
have the highest microhardness value due to their denser microstructure and lower total porosity.
for coatings prepared by medium and coarse particle size.
It is noticeable that the deviation value associated with the average microhardness value for the
coarse-powder coating is higher than
Ref. 25 that of the medium-
Ref. 26 and fine-powder Thiscoatings.
Study This can
Porosity Fraction
be attributed to the nonuniform distribution
15–50 µm Powder of large-
Size and medium-range
not Specified pores
25–45 µm along the
45–90 coating.
µm
In contrast,Large
fine-powder
pores coatings possess
≈65% the lowest deviation
80% (>2 µm ) 2 in microhardness
40% value,
67% to the
due
relativeFine
low+distribution
Medium pores of pore-size
≈35%and the very low n/a*
fraction of large-range55%pores (3.3%).
33%
Medium pores n/a* n/a* 45% 27%
Table
Fine pores 3. Average microhardness
n/a* measurements
20% (<2 µm )and
2 associated deviations.
15% 6%
Coating of * = not
Average applicable. (HV0.3)
Microhardness Deviation
Fine-powder 944 16.2
3.2. Microhardness
Medium-powder 881 32.3
MicrohardnessCoarse-powder 829
tests showed the effect of the coating 71.4
porosity on microhardness values of the
three coatings. Table 3 lists the average microhardness values of the three coatings along with the
3.3. Phase Analysis
deviations of these measurements. In comparison to medium- and coarse-powder coatings, fine-
powder coatings have the highest microhardness value due to their denser microstructure and lower
To justify the different ranges of the pore size distribution in the coatings, the phase composition of
total porosity. It is noticeable that the deviation value associated with the average microhardness
the three coatings was investigated and the measurements are given in Figure 6. The three as-sprayed
value for the coarse-powder coating is higher than that of the medium- and fine-powder coatings.
coatings consist of a mixture of α-Al2O3 and γ-Al2O3. However, the main phase was the γ-phase,
This can be attributed to the nonuniform distribution of large- and medium-range pores along the
coating. In contrast, fine-powder coatings possess the lowest deviation in microhardness value, due
to the relative low distribution of pore-size and the very low fraction of large-range pores (3.3%).
Coatings 2019, 9, 601 8 of 11

with the α phase only occurring as a secondary phase. The α-phase is associated with un-melted
sprayed powder particles or with melted particles cooled at a low rate. Generally, a high cooling
rate leads to a high composition of a γ-phase [27]. The broad, flat area on the curve representing the
fine-powder coating (Figure 6c) indicates that larger amounts of particles were fully melted and their
phase changed into a γ phase when compared to medium- and coarse-powders. This implies that
higher fraction of fine-powder particles was fully melted when impinging at the substrate than those
in medium- and coarse-powders, which is represented by the γ-phase.

Figure 6. X-ray powder diffraction (XRD) patterns of APS alumina coatings deposited with (a)
coarse-powder, (b) medium-powder, and (c) fine-powder particle sizes.

Un-melted and partially melted particles of coarse- and medium-powders within the coatings
were the source of large pores formations. Therefore, the α-phase, which represents these particles in
coarse- and medium-powder coatings (Figure 6a,b), has a higher level in the composition than that of
fine-powder coatings (Figure 6c).

3.4. Thermal Insulation

The thermal insulation test applied on coatings of the same thickness (200 ± 10 µm) and produced
from the three powders is shown in Figure 7. It can be seen that the fine-powder coating possesses
a comparable thermal insulation value when compared to the medium-powder coatings, although
its total porosity (0.93%) is much lower than the total porosity of medium-powder coatings (2.47%).
At the same time, coarse-powder coating exhibits the lowest thermal insulation although it has the
highest porosity content among other coatings. This can be attributed to the high porosity fraction of
large pores (67%) and to the low porosity fraction of medium-size pores (13%) that has a circularity
factor less than 0.5.
As the porosity of fine-powder coatings consists mainly from pores and cracks of fine- and
medium-range (96.7%), and it can be concluded that these ranges of pore sizes and shapes contribute
largely to the thermal insulation property and play the primary role in determining thermal insulation
value of coatings. The high thermal insulation exhibited by fine-powder coatings can be related to
the greater number of interfaces between the pores and the matrix of the coating [16]. In addition,
the relative high thermal insulation of fine-powder coatings can be related to the higher fine pore
density (number of fine pores per unit area), as can be noticed in SEM images in Figure 4.
has been reported that the number of pores plays a significant role in reducing the thermal
conductivity of ceramic coatings [26]. They measured the thermal conductivity of plasma sprayed
YSZ coatings and found that thermal conductivity is reduced from 1.4 to 0.8 W/(m.K), for coatings of
higher pore number, although all coatings were having almost the same total porosity. This implies
Coatings 2019, 9, 601
that a coating 9 of 11
with big number of fine pores has lower thermal conductivity than a coating with small
number of large pores.

Figure 7.7.Comparison
Comparisonof of thermal
thermal insulation
insulation of as-sprayed
of as-sprayed alumina
alumina coatings
coatings produced
produced by fine,
by fine, medium,
and coarse particle size for a hold time of 60 min.
medium, and coarse particle size for a hold time of 60 min.

Furthermore, large pores and medium pores of circularity >0.5 are of low significance and play
4. Conclusions
only a secondary role in determining the thermal insulation property of coatings, although their
In this study, it was shown that the particle size of the feedstock starting powder has a
presence in medium- and coarse-powder coatings increases greatly the overall porosity.
fundamental effect on the porosity level as well as pore-size distribution, pore shape, and distribution
This finding is consistent with the reported data for thermal conductivity of ceramic coatings. It has
of the overall porosity which highly influence the ultimate thermal coating properties, such as the
been reported that the number of pores plays a significant role in reducing the thermal conductivity of
thermal insulation and strain tolerance. According to the obtained results, the following conclusions
ceramic coatings [26]. They measured the thermal conductivity of plasma sprayed YSZ coatings and
can be drawn.
found that thermal conductivity is reduced from 1.4 to 0.8 W/(m·K), for coatings of higher pore number,
although
 all coatings
Coatings were by
produced having almost the same
fine-powders (i.e., total
fine porosity. This implies
particle size) exhibitthat
morea coating
uniform withpore
big
number of fine pores
distribution thanhas lower thermal
coatings produced conductivity
using medium- than aand coating with small number
coarse-powders. The poreof large pores.
size was in
the range from few tenth nanometers to approximately 10 µm . More than 95% of this range
2
4. Conclusions
contributes highly to the coating’s thermal insulation property due to the uniform distribution,
pore
In thissize, and
study, it pore shape.that the particle size of the feedstock starting powder has a fundamental
was shown

effectAson the
the starting
porosity powder’s particle
level as well size increases,
as pore-size the percentage
distribution, pore shape,ofandfine and medium
distribution of thepore size
overall
ranges (0–1 and 1–10 µm 2) decreases, whereas the percentage of large pore-size ranges (>10 µm2)
porosity which highly influence the ultimate thermal coating properties, such as the thermal insulation
increases.
and strain The increment
tolerance. Accordingintolarge pores greatly
the obtained increases
results, the total
the following porosity with
conclusions can berelatively
drawn. low
contribution to the coating’s thermal insulation.
• Coatings
APS coatings produced by fine-powders
fabricated (i.e., finehave
by fine-powders particle size) micro
higher exhibithardness
more uniform
valuespore distribution
than coatings
than
fabricated by medium- and coarse-powders due to their denser coatings. At the same time,range
coatings produced using medium- and coarse-powders. The pore size was in the fine-
from fewcoatings
tenth nanometers to approximately 10 µm 2 . More than 95% of this range contributes
powder exhibit thermal insulation value comparable to thermal insulations of coatings
highly to the coating’s thermal insulation property due to the uniform distribution, pore size,
and pore shape.
• As the starting powder’s particle size increases, the percentage of fine and medium pore size
ranges (0–1 and 1–10 µm2 ) decreases, whereas the percentage of large pore-size ranges (>10 µm2 )
increases. The increment in large pores greatly increases the total porosity with relatively low
contribution to the coating’s thermal insulation.
• APS coatings fabricated by fine-powders have higher micro hardness values than coatings
fabricated by medium- and coarse-powders due to their denser coatings. At the same time,
fine-powder coatings exhibit thermal insulation value comparable to thermal insulations of
coatings produced by medium-powders despite of higher total porosity owned by medium-powder
coatings. This is due to the higher contribution of the “effective porosity” in fine-powder coatings,
represented by fine pores and cracks, and their homogeneous distribution within the coatings.
Coatings 2019, 9, 601 10 of 11

In addition, coarse-powder coatings exhibit the lowest thermal insulation although it has the
highest porosity content among other coatings.

Author Contributions: Conceptualization, O.K. and M.A.; Methodology, O.K.; Validation, O.K. and M.A.; Formal
Analysis, O.K.; Investigation, O.K.; Resources, O.K.; Data Curation, O.K.; Writing—Original Draft Preparation,
O.K.; Writing—Review and Editing, O.K and M.A.; Visualization, O.K.; Supervision, W.T.; Project Administration,
O.K.; Funding Acquisition, W.T.
Funding: This research received no external funding.
Acknowledgments: We acknowledge financial support by Technische Universität Dortmund/TU Dortmund
University within the funding program Open Access Publishing.
Conflicts of Interest: The authors declare no conflicts of interest.

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