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 under-
standing the in-service properties and eventual optimization of the coating. This article dis-
cusses sample preparation and subsequent analytical techniques (LOM, SEM, XRD, WDS,
and QIA) for several cermet thermal spray coatings and provides a detailed analysis of as-
sprayed microstructures in addition to processing trends for several FeCrAIY-carbide coat-
ings. 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 at-
omization 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

Thermal spray coatings have become an
important part of modern industry, offer-
ing customized surface properties for a va-
riety of industrial applications ranging from
thermal barrier coatings for high tech tur-
bine 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. Characteriza-
tion is critical for understanding why ther-
mal spray coatings behave the way they do,
and offering guidelines for improved coat-
ing 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 sub-
strate. Once these molten droplets strike
the substrate they expand out in a radial
fashion and form a splat. As additional par-
ticles impact the specimen splats will even-
tually interact with one another and form a
93
MATERIALS CHARACTERIZATION 42:93–100 (1999)
© Elsevier Science Inc., 1999. All rights reserved.
655 Avenue of the Americas, New York, NY 10010
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 pow-
ders. Consequently, if care is not taken
when preparing a thermal spray coating for
analysis, pullout can cause erroneous po-
rosity, volume %, and even chemistry mea-
surements.
Several papers have dealt with metallo-
graphic preparation and routine analysis of
thermal spray coatings, Blann [1, 2] con-
ducted a thorough study of cutting, grind-
ing, and polishing procedures on the poros-
ity 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 pol-
isher the erroneous porosity levels in ther-
mal spray coatings, especially cermets,
1044-5803/99/$–see front matter
PII S1044-5803(98)00048-5
94 B. S. Schorr et al.

Table 1 Reported Chemistry and Compositions of Pre-Sprayed Powders (all values are wt%)
Powder Type Aluminum Carbon Chromium Iron Nickel Yttrium Other

FeCrAlY 6.5 — 28.50 balance — 0.65 ,1.00

Cr3C2 — 12.75 86.00 — — — ,1.25

could be drastically reduced [1,2]. Addi- tem. The carbide ranges sprayed and chem-
tionally, by adding a fluorescent dye to the ical composition of the pre-sprayed pow-
epoxy mounting material porosity and ders can be found in Tables 1 and 2
pullout can be further separated. Through respectively.
capillary action the fluorescent dye is
pulled into the porosity of the coating and METALLOGRAPHIC PREPARATION
when viewed under fluorescent light, the
Once the samples were sprayed, the coat-
porosity would appear bright while the rest
ings were then sectioned on a Buhler
of the coating, including the pullout, ap-
Isomet low speed abrasive cut off saw and
peared dark.
vacuum mounted in epoxy mixed with a
Although there has been some work on
fluorescent dye, the configuration of the
metallographic preparation and routine ex-
mounted samples can be seen in Fig. 1. The
amination of thermal spray materials, few
samples were mounted coating-to-coating
studies have done thorough examinations
to help maintain the coating’s edge and avoid
of both the chemistry and physical struc-
rounding. The samples were then ground
ture of the as sprayed coating. This paper
through 600 grit using SiC papers, polished
briefly explores some basic sample prepa-
to 1 mm diamond with a low nap cloth on a
ration methodologies and provides in depth
Buhler auto polisher, and finally polished
techniques for analysis of complex as sprayed
with colloidal silica for 15 minutes on a vi-
coatings. The analysis of the coatings centers
bratory polisher. Finally, the coatings were
on quantifying the structure of the coating
etched with various chemicals, Table 3, to
and determining the chemical makeup of
provide different contrast mechanisms.
the various phases in the coating.

EXPERIMENT PROCEDURE

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

Table 2 Starting Powder Compositions

Weight % FeCrAlY Weight % Cr3C2

1 100 0
2 65 35
3 75 25
4 85 15
5 90 10 FIG. 1. Schematic of mounted sample. (A) Epoxy
6 95 5 mount with dye. (B) Low carbon steel substrate. (C)
Thermal spray coating.
Characterization of Thermal Spray Coatings
Table 3 Composition and Use of Etchants
Etchant Composition
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 pro-
vide preliminary phase identification. The
Reikert LOM was used in Nomarski mode
to enhance the contrast of the HVOF coat-
ings and allow detailed analysis of the coat-
ing inter-splat structure. SEM images tend
to be sensitive to differences in atomic
number even in secondary electron imag-
ing, where higher atomic number regions
will be darker.
The chemistry of the individual phases that
comprised each coating were determined
using several complementary methods. X-
ray diffraction patterns of all of the coat-
ings were obtained using a Siemens diffrac-
tometer. In this case, the coatings were re-
moved 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, micro-
hardness 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 threshold-
ing; the missing FeCrAIY appeared black,
the carbides white and the various oxide
95
Use Time
etch FeCrAlY alloy 30 sec
etch FeCrAlY and Fe/Al alloy 10 sec
phases were gray. Figure 2 shows an exam-
ple of the thresholding process for a ther-
mal spray coating.
The volume percent of the FeCrAIY and
Cr3C2 in the various powder blends were
also verified using a similar etching tech-
nique to the final as sprayed coatings men-
tioned 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 re-
maining powder was measured again. The
unetched portion corresponded to the vol-
ume 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 pro-
duced 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
 96

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.

FIG. 2. Thresholding process for a typical cermet thermal spray coating: (A) LOM of coat-
ing, (B) Coating with porosity highlighted, (C) Coating with second phase highlighted,
(D) Coating with matrix highlighted, (E) Thresholding of entire coating.
B. S. Schorr et al.
Characterization of Thermal Spray Coatings
FIG. 3. (a) HVOF FeCrAIY - Chromium carbide ther-
mal spray coating (etched) and (b) Etched FeCrAIY
powder used to make coating shown in (a).
FIG. 4. Example of a columnar structure in a plasma sprayed coating.
97
columnar type structure similar to most
plasma sprayed coatings as seen in Fig. 4.
X-RAY ANALYSIS (XRD AND WDS)
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 Ta-
ble 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 com-
plex 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, cor-
responding to the FeCrAIY matrix, while
region 2 appears to be rich in Cr and car-
bon, delineating a possible carbide. Finally,
the region 3 of the coating contains Fe, Al,
Cr, C and O identifying a mixture of vari-
ous metal carbides and oxides. Microhard-
ness measurements of the various constitu-
ents 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
98 B. S. Schorr et al.

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

Table 4 Unknown X-ray and Possible Matching Data

Unknown (d-space) Fe Cr FeCr Cr2O3 Cr3O4 Fe2O3 Fe2O3-beta Al2Fe2O6 Maghemite (Fe3O4)

1.11 X X X X X
1.17 X X X X X X X X
1.20 X X X X X X X X
1.25 X X X X X X
1.27 X X X X X
1.31 X X X X
1.43 X X X X X X X
1.47 X X X X
1.60 X X X X X X
1.70 X X X X
1.80 X X X X
2.03 X X X
2.08 X X X
2.40 X X
2.51 X X X X
2.94 X
4.81 X X
15.83 X
Characterization of Thermal Spray Coatings 99

FIG. 7. Reported volume % of Cr3C2 in the pre- FIG. 8. Volume % of FeCrAIY in the final as sprayed
sprayed powder versus measured Cr3C2 content in the coating versus starting measured alpha content in the
pre-sprayed powder. pre-sprayed powder.

to the FeCrAIY matrix while the higher sured and plotted versus starting carbide
value is most likely a carbide particle. Fi- powder composition in Figs. 8–10. As can
nally, area 3 had a hardness reading of be seen in Fig. 8, the FeCrAIY alpha phase
about 800 DPH, which is comparable to increases after spraying when compared to
hardness values for various oxides [3]. the as-sprayed powder content, while Fig. 9
shows that initial powder carbide content
QUANTITATIVE IMAGE ANALYSIS (QIA) was not retained in the coating. It was in-
teresting to note that the FeCrAIY matrix
Prior to determining the volume percent of
was somewhat above the 1:1 correspon-
the various coatings, the pre-sprayed pow-
dence line drawn in Fig. 8 while the chro-
der was analyzed to make sure the re-
mium carbide was significantly below its 1:1
ported compositions were accurate. Figure
line in Fig. 9. Consequently, a greater per-
7 contains a plot of the reported volume
centage of the FeCrAIY was incorporated
percent versus the actual powder composi-
into the coating than was the Cr3C2 powder,
tions as measured via the LECO image
or in other words, the spray efficiency of
analysis system. As Fig. 7 shows the re-
the FeCrAIY was superior to that of the
ported and actual powder compositions
Cr3C2. Also, Fig. 10 shows that as the chro-
were in good agreement, consequently, the
mium carbide in the pre-sprayed powder
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 fur-
ther analysis of the coatings since the vari-
ous oxides had similar gray levels and
would have been difficult to distinguish be-
tween 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 prop-
erties of the coating. FIG. 9. Volume % of Cr3C2 in the final as sprayed coat-
The volume percent of each constituent ing versus starting Cr3C2 content in the pre-sprayed
(FeCrAIY, carbide, and oxide) was mea- powder.
100
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 coat-
ing also increased. Combining the trends
present in Figs. 8–10 with the previous
phase identification it becomes clear that
the HVOF process results in the breakdown
of the carbides into a mixture of metal car-
bides 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 at-
tributed to the constant spray parameters
that were used to produce all of the coat-
ings for this study. Since the spray efficien-
cies of the FeCrAIY was much better than
FIG. 11. Thickness of the final as sprayed coating ver-
sus starting Cr3C2 content in the pre-sprayed powder.
B. S. Schorr et al.
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:
1. Sample preparation: Careful sample prep-
aration, including proper mounting, pol-
ishing, and etching procedures, yielded ac-
curate microstructures that could be
readily analyzed.
2. Light optical microscopy: LOM revealed
that HVOF coatings tend to retain the as-
cast 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 compo-
nents of the coatings are FeCrAIY, car-
bides, 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 separa-
tion and quantification of the various
phases present in the thermal spray coat-
ings tested were determined. From the
image analysis measurements it was
found that as the carbide content of the
pre-sprayed powder increased, the car-
bide and oxide in the coating was also in-
creased while the FeCrAIY matrix (al-
pha) content was reduced.
References
1. Blann, G. A. and D. J. Diaz: Raising the standards
for image analysis. Adv. Mat. Proc. 145:31–36.
2. Blann, G. A.: The important role of microstructure
evaluation in each phase of thermally sprayed
coatings application. Thermal Spray Conference Pro-
ceedings, June 1992, pages 959–966.
3. Richerson, D. W.: Modern Ceramic Engineering.
Marcel Decker Inc., New York, 1992.
Received March 1998; accepted October 1998.