Characterization of Thermal Spray Coatings

Brian S. Schorr, Kevin J. Stein, and Arnold R. Marder

Department of Materials Science and Engineering, Lehigh University, Bethlehem, PA 18015-3195
The ability to characterize fully the microstructure of a coating is paramount for understanding the in-service properties and eventual optimization of the coating. This article discusses sample preparation and subsequent analytical techniques (LOM, SEM, XRD, WDS,
and QIA) for several cermet thermal spray coatings and provides a detailed analysis of assprayed microstructures in addition to processing trends for several FeCrAIY-carbide coatings. It was found that the splats produced in these high velocity oxy-fuel (HVOF) coatings
tended to exhibit a predominantly dendritic structure most likely retained from the gas atomization process that produced the original powder. Chemical analysis showed that the
carbides tend to breakdown during spraying producing a complex mixture of oxides and
various carbides. Finally, image analysis revealed that as the carbides in the pre-sprayed
powder were increased, more carbides and oxides with less FeCrAIY and thinner coatings
were found. These techniques allow the thorough characterization of thermal spray cermet
coatings, which in turn should further the understanding of the thermal spray processes
and help provide superior coatings in the future.
Elsevier Science Inc., 1999. All rights
reserved.
INTRODUCTION

continuous coating. Splat-to-substrate, as

well as splat-to-splat, bonding tends to be
weak, providing little resistance to pullout
during the mechanical processing (cutting,
grinding, and polishing) of the coating for
metallographic preparation. In addition,
multi-phase coatings, such as cermets, can
have enhanced pullout due to the different
sizes and densities of the as-sprayed powders. Consequently, if care is not taken
when preparing a thermal spray coating for
analysis, pullout can cause erroneous porosity, volume %, and even chemistry measurements.
Several papers have dealt with metallographic preparation and routine analysis of
thermal spray coatings, Blann [1, 2] conducted a thorough study of cutting, grinding, and polishing procedures on the porosity levels of various thermal spray coatings.
Blann discovered that by using a low speed
cut off saw, diamond lapping discs, low
nap polishing clothes, and a vibratory polisher the erroneous porosity levels in thermal spray coatings, especially cermets,

Thermal spray coatings have become an

important part of modern industry, offering customized surface properties for a variety of industrial applications ranging from
thermal barrier coatings for high tech turbine blades to erosion resistant coatings for
boiler tubes. Although the usage of thermal
spray coatings has increased dramatically,
the characterization and analysis of these
coatings has lagged behind. Characterization is critical for understanding why thermal spray coatings behave the way they do,
and offering guidelines for improved coating performance in the future.
Thermal spray coatings are formed by
melting materials in particulate form or
wire feed stock and accelerating the molten
or partially molten droplets toward a substrate. Once these molten droplets strike
the substrate they expand out in a radial
fashion and form a splat. As additional particles impact the specimen splats will eventually interact with one another and form a
93
MATERIALS CHARACTERIZATION 42:93100 (1999)
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B. S. Schorr et al.

94

Table 1 Reported Chemistry and Compositions of Pre-Sprayed Powders (all values are wt%)
Powder Type

FeCrAlY
Cr3C2

Aluminum

Carbon

Chromium

Iron

Nickel

Yttrium

Other

6.5

12.75

28.50
86.00

balance

0.65

,1.00
,1.25

could be drastically reduced [1,2]. Additionally, by adding a fluorescent dye to the

epoxy mounting material porosity and
pullout can be further separated. Through
capillary action the fluorescent dye is
pulled into the porosity of the coating and
when viewed under fluorescent light, the
porosity would appear bright while the rest
of the coating, including the pullout, appeared dark.
Although there has been some work on
metallographic preparation and routine examination of thermal spray materials, few
studies have done thorough examinations
of both the chemistry and physical structure of the as sprayed coating. This paper
briefly explores some basic sample preparation methodologies and provides in depth
techniques for analysis of complex as sprayed
coatings. The analysis of the coatings centers
on quantifying the structure of the coating
and determining the chemical makeup of
the various phases in the coating.

tem. The carbide ranges sprayed and chemical composition of the pre-sprayed powders can be found in Tables 1 and 2
respectively.
METALLOGRAPHIC PREPARATION
Once the samples were sprayed, the coatings were then sectioned on a Buhler
Isomet low speed abrasive cut off saw and
vacuum mounted in epoxy mixed with a
fluorescent dye, the configuration of the
mounted samples can be seen in Fig. 1. The
samples were mounted coating-to-coating
to help maintain the coatings edge and avoid
rounding. The samples were then ground
through 600 grit using SiC papers, polished
to 1 mm diamond with a low nap cloth on a
Buhler auto polisher, and finally polished
with colloidal silica for 15 minutes on a vibratory polisher. Finally, the coatings were
etched with various chemicals, Table 3, to
provide different contrast mechanisms.

EXPERIMENT PROCEDURE
COATING FABRICATION
FeCrAIY-Cr3C2 cermet coatings were applied to low carbon steel substrates using a
high velocity oxy-fuel (HVOF) spray sys-

Table 2 Starting Powder Compositions

1
2
3
4
5
6

Weight % FeCrAlY

Weight % Cr3C2

100
65
75
85
90
95

0
35
25
15
10
5

FIG. 1. Schematic of mounted sample. (A) Epoxy

mount with dye. (B) Low carbon steel substrate. (C)
Thermal spray coating.

Characterization of Thermal Spray Coatings

95

Table 3 Composition and Use of Etchants

Etchant

Composition

Use

Boiling Picric (electrolytic) 5g picric, 2ml HCl, & 100ml H2O

HCl-HNO3 mixture
12ml HNO3, 20ml HCl,
20ml H2O, & 40ml H2O2

COATING CHARACTERIZATION
The coatings were first photographed using
both a Zeis and Reikert-Jung light optical
microscope (LOM) in addition to a JEOL
scanning electron microscope (SEM) to provide preliminary phase identification. The
Reikert LOM was used in Nomarski mode
to enhance the contrast of the HVOF coatings and allow detailed analysis of the coating inter-splat structure. SEM images tend
to be sensitive to differences in atomic
number even in secondary electron imaging, where higher atomic number regions
will be darker.
The chemistry of the individual phases that
comprised each coating were determined
using several complementary methods. Xray diffraction patterns of all of the coatings were obtained using a Siemens diffractometer. In this case, the coatings were removed from their substrates and broken up
using liquid nitrogen prior to testing. WDS
dot maps were also used to help with phase
determination and confirm the x-ray data
using a JEOL Superprobe. Finally, microhardness measurements of each phase were
also conducted to complete the qualitative
chemical analysis of the various coatings.
Once the chemical nature of each phase
had been determined the coatings were
then quantified using a LECO 2001 image
analysis system. The volume percent of
each phase, in addition to the thickness of
each coating, was determined. Since the
carbide and FeCrAIY matrix had similar
gray levels the matrix had to be etched
away using a HC1-HNO3 etch (see Table 3
for the composition of this etch). With the
FECrAIY matrix gone all of the phases
could be easily distinguished by thresholding; the missing FeCrAIY appeared black,
the carbides white and the various oxide

Time

etch FeCrAlY alloy

30 sec
etch FeCrAlY and Fe/Al alloy 10 sec

phases were gray. Figure 2 shows an example of the thresholding process for a thermal spray coating.
The volume percent of the FeCrAIY and
Cr3C2 in the various powder blends were
also verified using a similar etching technique to the final as sprayed coatings mentioned above. The powders were vacuum
mounted and a region of the mount was
scribed with a 50 mm circle. The volume
percent of the powder within the circle was
then measured, the FeCrAIY was etched
away, and the volume percent of the remaining powder was measured again. The
unetched portion corresponded to the volume percent of carbide present and when
subtracted from 100 produced the volume
percent of FeCrAIY.

RESULTS AND DISCUSSIONS

LIGHT OPTICAL MICROSCOPY (LOM)
Figure 3a shows the etched microstructure
of a 60% FeCrAIY-40% carbide coating.
From Fig. 3a it is clear that the heat input
(time and temperature) involved in the
HVOF process was not high enough to melt
the FeCrAIY or carbide powder. Due to the
lack of melting the FeCrAIY structure produced during powder fabrication, dendrites,
remained in the final coating. To verify the
presence of the dendrites during powder
fabrication, the mounted powder was etched
as shown in Fig. 3b. Figure 3b clearly
shows the same dendritic structure found
in the final coating (Fig. 3a), consequently,
it is safe to assume that little, if any, melting
has occurred and the dendritic structure is
retained from gas atomization processing
of the powder. It would also be expected
that any melting would tend to produce a

FIG. 2. Thresholding process for a typical cermet thermal spray coating: (A) LOM of coating, (B) Coating with porosity highlighted, (C) Coating with second phase highlighted,
(D) Coating with matrix highlighted, (E) Thresholding of entire coating.

FIG. 6. EDS/WDS dot map of a portion of the 85% FeCrAIY-15% Cr3C2 coating (1500x):
Area 1 - FeCrAIY matrix, Areas 2, 3a and 3b chromium carbides, and Areas 3c and 3d oxides.

96
B. S. Schorr et al.

Characterization of Thermal Spray Coatings

97

columnar type structure similar to most

plasma sprayed coatings as seen in Fig. 4.
X-RAY ANALYSIS (XRD AND WDS)

FIG. 3. (a) HVOF FeCrAIY - Chromium carbide thermal spray coating (etched) and (b) Etched FeCrAIY
powder used to make coating shown in (a).

A sample x-ray spectra can be found in Fig.

5, the peaks from this spectra, in addition to
possible matching peaks, are located in Table 4. From Table 4, it can be seen that the
coating may contain a range of Fe, Cr and
Al based oxides in addition to the FeCrAIY
matrix. Further confirmation of the complex nature of the as sprayed coating can be
seen in the WDS dot map found in Fig. 6.
There are 3 distinct regions marked in Fig.
6 corresponding the three basic phases in
the coating: matrix, carbides and oxides.
Region 1 has high Fe and Al content, the
dot maps for Fe and Al appear bright, corresponding to the FeCrAIY matrix, while
region 2 appears to be rich in Cr and carbon, delineating a possible carbide. Finally,
the region 3 of the coating contains Fe, Al,
Cr, C and O identifying a mixture of various metal carbides and oxides. Microhardness measurements of the various constituents of the coating were done to finalize the
phase identities mentioned above. It was
found that the hardness of the areas 1 and 2
ranged from a low of about 150 DPH to a
high of over 1200 DPH, respectively, the
lower value (150 DPH) should correspond

FIG. 4. Example of a columnar structure in a plasma sprayed coating.

B. S. Schorr et al.

98

FIG. 5. X-ray diffraction spectra of FeCrAIY-Cr3C2 coating.

Table 4 Unknown X-ray and Possible Matching Data

Unknown (d-space)

1.11
1.17
1.20
1.25
1.27
1.31
1.43
1.47
1.60
1.70
1.80
2.03
2.08
2.40
2.51
2.94
4.81
15.83

Fe

Cr

FeCr

X
X

X
X

X
X

Cr2O3

X
X
X
X

Cr3O4

X
X

X
X

X
X
X

Fe2O3

Fe2O3-beta

Al2Fe2O6

Maghemite (Fe3O4)

X
X
X
X
X
X

X
X
X
X
X
X
X
X
X
X
X

X
X
X
X
X
X
X
X

X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X

X
X

X
X

X
X

X
X

X
X
X
X

X
X

Characterization of Thermal Spray Coatings

99

FIG. 7. Reported volume % of Cr3C2 in the presprayed powder versus measured Cr3C2 content in the
pre-sprayed powder.

FIG. 8. Volume % of FeCrAIY in the final as sprayed

coating versus starting measured alpha content in the
pre-sprayed powder.

to the FeCrAIY matrix while the higher

value is most likely a carbide particle. Finally, area 3 had a hardness reading of
about 800 DPH, which is comparable to
hardness values for various oxides [3].

sured and plotted versus starting carbide

powder composition in Figs. 810. As can
be seen in Fig. 8, the FeCrAIY alpha phase
increases after spraying when compared to
the as-sprayed powder content, while Fig. 9
shows that initial powder carbide content
was not retained in the coating. It was interesting to note that the FeCrAIY matrix
was somewhat above the 1:1 correspondence line drawn in Fig. 8 while the chromium carbide was significantly below its 1:1
line in Fig. 9. Consequently, a greater percentage of the FeCrAIY was incorporated
into the coating than was the Cr3C2 powder,
or in other words, the spray efficiency of
the FeCrAIY was superior to that of the
Cr3C2. Also, Fig. 10 shows that as the chromium carbide in the pre-sprayed powder

QUANTITATIVE IMAGE ANALYSIS (QIA)

Prior to determining the volume percent of
the various coatings, the pre-sprayed powder was analyzed to make sure the reported compositions were accurate. Figure
7 contains a plot of the reported volume
percent versus the actual powder compositions as measured via the LECO image
analysis system. As Fig. 7 shows the reported and actual powder compositions
were in good agreement, consequently, the
reported compositions will be used in the
rest of the article.
With a rough idea of the identities of the
various phases present in the coatings it
was decided that all the oxides would be
termed generic oxides and grouped as such
for the quantitative analysis of the coatings.
This decision was made to simplify the further analysis of the coatings since the various oxides had similar gray levels and
would have been difficult to distinguish between them. In addition, the various oxides
were also lumped together since it was felt
that they would most likely contribute in a
similar manner to the final in-service properties of the coating.
The volume percent of each constituent
(FeCrAIY, carbide, and oxide) was mea-

FIG. 9. Volume % of Cr3C2 in the final as sprayed coating versus starting Cr3C2 content in the pre-sprayed
powder.

B. S. Schorr et al.

100

that of the Cr3C2 it would be expected that the

higher Cr3C2 coatings would not be as thick.
CONCLUSIONS
The complex structure of a series of thermal
spray cermet coatings was characterized
utilizing a series of analytical techniques:

FIG. 10. Volume % of various oxides in the final as

sprayed coating versus starting Cr3C2 content in the
pre-sprayed powder.

increased, the measured oxide in the coating also increased. Combining the trends
present in Figs. 810 with the previous
phase identification it becomes clear that
the HVOF process results in the breakdown
of the carbides into a mixture of metal carbides and various oxides.
The thickness of the various coatings was
also measured with the LECO system and
plotted versus pre-sprayed carbide content
in Fig. 11. From Fig. 11, it is apparent that
as the carbide content was increased the
thickness of the coatings was reduced. The
reduction in coating thickness could be attributed to the constant spray parameters
that were used to produce all of the coatings for this study. Since the spray efficiencies of the FeCrAIY was much better than

1. Sample preparation: Careful sample preparation, including proper mounting, polishing, and etching procedures, yielded accurate microstructures that could be
readily analyzed.
2. Light optical microscopy: LOM revealed
that HVOF coatings tend to retain the ascast dendritic structure produced during
powder processing due to the lack of
melting of some of the powders during
spraying.
3. X-ray analysis: From the XRD and WDS
data, it is clear that the major components of the coatings are FeCrAIY, carbides, and oxides. The oxide phase was
comprised of a multitude of Fe, Al, and
Cr based oxides, corresponding to both
the FeCrAIY and Cr3C2 powder being
oxidized during spraying.
4. Quantitative image analysis: The separation and quantification of the various
phases present in the thermal spray coatings tested were determined. From the
image analysis measurements it was
found that as the carbide content of the
pre-sprayed powder increased, the carbide and oxide in the coating was also increased while the FeCrAIY matrix (alpha) content was reduced.

References

FIG. 11. Thickness of the final as sprayed coating versus starting Cr3C2 content in the pre-sprayed powder.

1. Blann, G. A. and D. J. Diaz: Raising the standards

for image analysis. Adv. Mat. Proc. 145:3136.
2. Blann, G. A.: The important role of microstructure
evaluation in each phase of thermally sprayed
coatings application. Thermal Spray Conference Proceedings, June 1992, pages 959966.
3. Richerson, D. W.: Modern Ceramic Engineering.
Marcel Decker Inc., New York, 1992.
Received March 1998; accepted October 1998.