Scripta Materialia 55 (2006) 179–182

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Hot corrosion performance of a NiCr coated Ni-based alloy

T.S. Sidhu,* S. Prakash and R.D. Agrawal
Metallurgical and Materials Engineering Department, Indian Institute of Technology Roorkee, Roorkee, 247667 Uttranchal, India
Received 25 January 2006; revised 24 March 2006; accepted 24 March 2006
Available online 4 May 2006

The hot corrosion performance of high velocity oxy-fuel sprayed Ni–20Cr wire coating on a Ni-based superalloy is evaluated for
1000 h at 900 C under cyclic conditions in a coal-fired boiler. The performance of bare and Ni–20Cr coated Superni 75 is assessed
via thermogravimetric data, metal thickness loss corresponding to the corrosion scale formation, scale thickness loss and the depth
of internal corrosion attack. The better hot corrosion resistance of the coated alloy is mainly attributed to the formation of a thick
band of chromium oxide just above the scale–substrate interface and chromium oxide stringers along the splat boundaries, as well as
to the nickel oxide and the dense and uniform fine grain structure of the as sprayed coating.
 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: HVOF; Ni–20Cr; Coal fired boilers; Hot corrosion; Wire coating

A dynamic surface layer consisting of a mechanical
mixture of particles from the boiler gases and oxide scale
growing from the base metal is formed on boiler tubes.
This layer is constantly refurbished and removed at a rate
that results in an essentially constant thickness of the de-
posit/scale layer during steady state operation of the boi-
ler [1]. The accumulation of these low melting-point salts
from flue-gas containing sulfates of sodium and potas-
sium on the fire side surface of boiler tubes induces hot
corrosion and is considered a root cause for the severe
wastage of tube materials used for superheaters and
reheaters in ‘‘advanced’’ steam-generating systems [2–6].
Wang and Luer [7] reported that nickel chromium
coatings can be used to protect the heat exchanger tubes
of fluidized bed combustors and Hocking [8] also sug-
gested the use of corrosion resistant alloys as coatings
to protect substrate alloys, having good mechanical
properties. The high velocity oxy-fuel (HVOF) process
is a continuous and most convenient way of applying
coatings to industrial installations on site and has been
widely adopted by many industries due to its flexibility,
cost effectiveness, and the superior quality of the coat-
ings produced [9–14].
Little work has been published on HVOF sprayed
Ni–20%Cr wire coatings to the best of knowledge of
the authors. An evaluation of hot corrosion perfor-
mance of HVOF sprayed Ni–20Cr wire coating is not
* Corresponding author. Mobile: +91 94129 68912; fax: +91 1332
285243; e-mail: tssidhu@rediffmail.com
currently available in the literature. Therefore, an
attempt was made to evaluate the hot corrosion perfor-
mance of HVOF Ni–20Cr wire coating on a nickel-
based superalloy in an actual industrial environment
of a coal-fired boiler. X-ray diffractometry (XRD), scan-
ning electron microscopy/energy-dispersive X-ray analy-
sis (SEM/EDAX) and electron probe microanalysis
(EPMA) techniques were used for analyses.
The Ni-based substrate material Superni 75 (19.5Cr–
3Fe–0.3Ti–0.1C–Balance Ni) selected for the present
study was provided by Mishra Dhatu Nigam Ltd,
Hyderabad (India) in a rolled sheet form. The specimens
with dimensions of approximately 20 mm · 15 mm ·
5 mm were cut from the alloy sheets, polished with SiC
papers down to 180 grit and subsequently grit blasted
with alumina powders (Grit 45) before spraying of the
coatings using the HVOF process.
Coatings were deposited at M/S Metallizing Equip-
ment Co. Pvt. Ltd, Jodhpur, India, with a Hijet-9600
HVOF wire spraying system, using liquefied petroleum
gas as the fuel. Commercially available Ni–20%Cr wire,
3.17 mm diameter, was used as the feedstock material
and the coating was deposited on all sides of the speci-
mens. Standard spray parameters, as described in the
manual of the Hijet-9600 HVOF system, were used for
depositing the Ni–20%Cr wire coatings. All the process
parameters, including the spray distance, were kept con-
stant throughout the coating process. The specimens
were cooled with compressed air jets during and after
spraying. The spray parameters and characterisation of
the coating have been reported by the author elsewhere

1359-6462/$ - see front matter  2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.scriptamat.2006.03.054
180 T. S. Sidhu et al. / Scripta Materialia 55 (2006) 179–182

[15]. The equipments and procedures used for analysing

Weight change/area (mg/cm2)

5
Bare Superni 75
the corrosion products have also been already reported 4
Ni-20Cr coated

[16]. The deposited coating had a porosity of less than 3

1%, and microhardness and coating thickness in the 2

range of 600–630 Hv and 200–250 lm, respectively [15]. 1

The samples were hung through the soot blower 0
dummy points in the middle zone of the platen super- 0 100 200 300 400 500 600 700 800 900 1000
Number of hours
heater of the Stage-II boiler, where the temperature
was 900 ± 10 C, at the Guru Nanak Dev Thermal Figure 1. Weight change vs. time plots time plots for coated and
Plant, Bathinda, Punjab, India. A 1 mm hole was pro- uncoated Superni 75 after 1000 h exposure to platen superheater zone
vided to hang these specimens in the boiler for experi- of the coal fired boiler at 900 C.
mentation with the help of stainless steel wire. The
gain squared (mg2/cm4) verses time plot (Fig. 2) for
studies were conducted for 10 cycles; each cycle con-
the bare alloy shows significant deviations from the par-
sisted of 100 h exposure followed by 1 h cooling at ambi-
abolic rate law, while the fluctuations in data are less for
ent conditions. Cyclic study provides the severest testing
the coated specimen. The coated alloy followed a nearly
conditions and may best represent the real plant opera-
parabolic behaviour up to 10 cycles. The parabolic rate
tion, where breakdown or shutdown occurs frequently
constants (kp in 1012 g2 cm4 s1) for the bare and
depending on the power requirement. The average volu-
coated Superni 75 on the basis of 10 cycles were calcu-
metric flow of flue gases was around 122 m3/s. The SOx
lated as 4.45 and 4.15, respectively.
and NOx values of the flue gases were 280.53 mg/m3 and
The light grey scale appeared on the surfaces of the
1166.67 lg/m3, respectively. Flue gases contained by
bare and coated superalloy after first cycle of 100 h
vol. 12% CO2 and 7% O2.
turned to brownish grey during the subsequent cycles
At the end of each cycle, the specimens were visually
(Fig. 3). The brownish appearance of the scale may be
observed for any change on the surface and the weights
attributable to ash deposition in the boiler environment.
of the specimens were measured subsequently. After
From the back scattered electron (BSE) images
1000 h exposure under cyclic conditions, the samples
shown in Figure 4, the average scale thicknesses for bare
were subjected to analysis by XRD, SEM, EDAX,
and Ni–20Cr coated Superni 75 were measured as
EPMA and the scale thickness and depth of internal cor-
56.43 lm and 209 lm, respectively. The uncoated alloy
rosion attack were measured. The hot corrosion perfor-
showed internal corrosion attack and scale thickness
mance of bare and HVOF Ni–20Cr coated Superni 75
loss as 10 lm and 80 lm, respectively. The coated alloy
was assessed using thermogravimetric data, metal thick-
showed no internal corrosion attack as well as scale
ness loss corresponding to the corrosion scale forma-
thickness loss.
tion, and the depth of internal corrosion attack.
Both the uncoated and coated alloy showed the for-
Degradation of the specimens was assessed by mea-
mation of Cr2O3, Fe2O3, Al2O3 and SiO2 as the major
suring the weight change per unit area and the extent of
phases in X-ray diffraction analysis. In addition to these
corrosion. The weight change consists of weight gain
phases, the uncoated alloy also shows the formation of
owing to the formation of oxide scale and weight loss
FeS. The presence of Al2O3 and SiO2 phases indicates
due to the suspected spalling and fluxing of the oxide
the incorporation of ash deposit in the outer layer of
scale. The net weight change represents the combined ef-
the scale.
fects of these two processes.
The extent of corrosion was assessed by measuring: (i)
(Weight change/area)2 mg2 cm-4

the average scale thickness formed after 1000 h of expo- 30

sure to the boiler environment (the depth from the surface 25

20
Bare Superni 75

Ni-20Cr coated

to scale–substrate interface up to which the oxygen has 15

penetrated almost uniformly is taken as the scale thick- 10

ness); (ii) the scale thickness loss due to spallation or pos- 5

0
sible evaporation during experimentation; and (iii) the 0 100 200 300 400 500 600 700 800 900 1000
Number of hours
depth of internal corrosion attack which is taken as the
2
distance from the scale–substrate interface up to which Figure 2. (Weight change/area) vs. time plots for coated and uncoated
corrosive species penetrated into the substrate. Superni 75 after 1000 h exposure to platen superheater zone of the coal
The sum of the average scale thickness, scale thick- fired boiler at 900 C.
ness loss and depth of internal corrosion attack provide
an estimate of the material depth affected by the hot cor-
rosion and thereby of the remaining sound metal.
The weight change plots are shown in Figure 1.
After 1000 h of study, the coated alloy showed little
more weight change than the bare substrate. The lower
weight change for the bare alloy might be due to spalla-
tion of the oxide scale, as suspected spallation symptoms
and cracks were observed on the surface scale at the end
of each cycle. The coated alloy showed negligible spall- Figure 3. Macrographs of the (a) bare (b) Ni–20Cr coated Superni 75
ation behaviour and did not show the presence of any after 1000 h exposure to platen superheater zone of the boiler at
cracks during the course of study. Further, the weight 900 C.

Figure 4. BSEIs for the (a) bare and (b) HVOF coated Superni 75 after
1000 h exposure to platen superheater zone of the coal fired boiler at
900 C.
A continuous, uniform and adherent granular scale
with embedded ash particles rich in silica and alumina is
formed on the Ni–20Cr coated Superni 75 without any
indication of cracks (Fig. 5). The EDAX analysis shows
mainly the presence of ash deposits in the surface scale
along with very small amounts of Cr2O3 and NiO. The
chemical composition of these deposits is similar to the
ash composition. The presence of TiO2 and Fe2O3 in
the surface scale indicates their outward diffusion from
the substrate though the coatings.
The BSE images and EDAX analysis at some
selected point of interest across the cross section of
Ni–20Cr coated Superni 75 exposed to the actual boiler
environment for 1000 h under cyclic conditions at
900 C are shown in Figure 6. A continuous and adher-
ent oxide scale formed on the coated alloy has retained
the lamellar structure of the as sprayed coatings. There
is no indication of any crack in the scale. The absence
of degrading species near the scale–substrate interface
(Point 1 of Fig. 6) is symptomatic of the protective
behaviour of the coating. The scale formed at point 2
was rich in chromium and oxygen whereas nickel had
decreased significantly. It implies that a thick layer of
Cr2O3 is formed just above the scale–substrate interface.
The white phase in the scale (Point 3) consisted of Ni-
rich splats which seem to be surrounded by oxides of
chromium. The scale formed at Points 4 and 5 was
mainly composed of nickel, chromium and oxygen, indi-
cating that the uppermost scale possibly consisted of
oxides of Ni and Cr.
80
Ni
Si
60
Weight %
40
20
0 due to their low melting temperatures: 624 C for
1 2
43% SiO2
45% SiO2
36% Al2O3
34% Al2O3
09% Fe2O3
05% TiO2
08% Fe2O3
1 2
06% TiO2
02% Cr2O3
02% CaO
01% K2O
02% NiO
01% NiO
01% K2O
0.5% CaO
50 µm
30 µm Fig. 5
Figures 5 and 6. These show the SEM/EDAX analysis (elemental
composition, wt.%) at the surface and across the cross section of Ni–
20Cr coated Superni 75, respectively, after 1000 hrs exposures to the
boiler at 900 C.
T. S. Sidhu et al. / Scripta Materialia 55 (2006) 179–182 181
BSEI O-Kα
Substrate 200 µm 200 µm
Cr-Kα Ni-Kα
200 µm 200 µm
Figure 7. EPMA analysis across the cross-section of Ni–20Cr coated
Superni 75 after 1000 h exposure to boiler at 900 C.
The elemental mappings for Cr, Ni and O show that
Cr and O co-exist mostly at splat boundaries suggesting
the formation of Cr2O3, whereas Ni-rich splats generally
remains unoxidised (Fig. 7). Chromium also formed a
Cr-rich band just above the scale–substrate interface.
The absence of oxygen below the scale–substrate inter-
face indicates that the Ni–20Cr coating provided the
necessary protection to the Superni 75 in the actual
working environment of the boiler.
The lower weight gain of bare Superni 75 than its
coated counterpart might be attributed to spallation of
the oxide scale in the actual environment of the coal
fired boiler and fluxing action of the molten salt. The
(weight gain/area)2 plot for the bare alloy shows signif-
icant deviations from the parabolic rate law (Fig. 2)
indicating that spallation occurred on the surface of
the bare specimen. The XRD and EDAX analyses show
the presence of ash deposition on the surface of the spec-
imens. The sodium, potassium and sulfur present in ash
deposits may react with iron oxides (coming from oxide
scales or ashes) in the presence of SO3 (resulting from
the oxidation of SO2) to form alkali-iron trisulfates
(Na,K)3Fe(SO4)3 according to the following reactions.
They are held responsible for the degradation of coal-
Cr O Fe Mn fired plant superheaters.
S K Na Al
2Fe3 O4 þ 9M2 SO4 þ 9SO3 þ 1=2O2 ¼ 6M3 FeðSO4 Þ3 ðiÞ
Fe2 O3 þ 3M2 SO4 þ 3SO3 ¼ 2M3 FeðSO4 Þ3 where
M ¼ Na or K ðiiÞ
They are molten at operating conditions of boiler
3 4 5
Point of Analysis Na3Fe(SO4)3 and 618 C for K3Fe(SO4)3 and 552 C
for the mixed compounds (Na,K)3Fe(SO4)3 [17,18].
These molten compounds can take part in fluxing caus-
ing dissolution of the scale, or they react with the metal
to form internal sulfides as per the reaction given below:
4 5
3
2M3 FeðSO4 Þ3 þ 6Fe ¼ 3=2FeS þ 3=2Fe3 O4
þ Fe2 O3 þ 3M2 SO4 þ 3=2SO2 : ðiiiÞ
Fig. 6
The BSE image of bare Superni 75 shown in Figure
4a seems to indicate well the fluxing action of the molten
salt and the spallation tendency of the scale. The oxides
detected by XRD/EDAX analyses of bare alloy
appeared to be porous due to reprecipitation by fluxing
182 T. S. Sidhu et al. / Scripta Materialia 55 (2006) 179–182
action (Fig. 4a) and less protective as internal corrosion
attack to a depth of 10 lm has been observed.
The HVOF sprayed Ni–20Cr coating proved to be
very effective in providing hot corrosion resistance for
Superni 75. The BSE images of coated alloy (Fig. 4b
and Fig. 6) show the formation of uniform, continuous
and adherent oxide scale without indications of any
internal corrosion attack. The weight gain curves for
coated Superni 75 followed nearly a parabolic behav-
iour. The small deviations from the parabolic rate law
might be due to cyclic scale growth. The higher weight
gain of the coated specimens during the first few cycles
might be attributed to the rapid formation of oxides at
the splat boundaries and within open pores due to the
penetration of the oxidizing species, but the subsequent
increase in weight is gradual. These oxides once formed
might have blocked the pores and splat boundaries, and
acted as barriers to further inward diffusion of oxidizing
species. As a consequence, the growth of the oxides be-
comes limited mainly to the surface of the specimens.
Therefore the steady state of oxidation might have been
reached with the progress of exposure time.
The better hot corrosion resistance of Ni–20Cr coat-
ing might be attributed to the presence of oxides of chro-
mium and nickel, and the thick band of Cr2O3 as revealed
by cross-sectional EDAX analysis (Fig. 6) and supported
by X-ray mapping (Fig. 7). Selective oxidation of chro-
mium along the nickel-rich splats boundaries, as revealed
by EDAX/EPMA analysis, might have acted as a diffu-
sion barrier to the inward diffusion of corrosive species.
The mechanism of Cr2O3 formation in Ni–20Cr is
described as follows: though NiO and Cr2O3 are stable
oxides at 1 atm pressure of oxygen, various factors, par-
ticularly thermodynamics and kinetics, influence the
overall scale development. Chromium has a higher affin-
ity for oxygen than nickel and forms a more stable oxide.
NiO is a less stoichiometric oxide than Cr2O3 [19]. This
implies that the oxidation of Ni–Cr coating is solely
based on the formation of Cr2O3. The threshold concen-
tration required to form Cr2O3 is around 15%. In the
present coating the concentration of chromium was
20% and its concentration was not reduced by diffusion.
In earlier studies, the Ni–20Cr powder coatings showed
the high amount of Fe diffusion from the substrate to
the coating and Ni diffusion from the coating to the sub-
strate [19,20]. However, in the present case of HVOF
sprayed Ni–20Cr wire coating, the diffusion of Fe and
Ni was found to be negligible (Fig. 7). This can be attrib-
uted to the formation of a thick layer of Cr2O3 just above
the scale–substrate interface as Cr and O coexist in this
region of the scale (Fig. 7). The very low porosity, uni-
form fine grain and flat splat microstructure of the HVOF
sprayed Ni–20Cr wire coating as reported earlier [15],
might also be partly responsible for imparting hot corro-
sion resistance; this is the desired structure when coatings
have to perform in corrosive environment at high temper-
atures, since corrosive species mostly propagate along the
splat boundaries and through the pores and voids. Due to
the dense and flat splat structure of the coatings, the dis-
tance from the coating surface to the coating/substrate
interface along the splat boundaries is very long.
In the O elemental map, a higher concentration was
noticed at the interface. These islands do not match with
the elements of the substrate alloy or coating materials.
These islands were identified as Al2O3, possibly formed
due to the incorporation of aluminium powder during
polishing. This additionally confirms the adherent nat-
ure of the oxide scale with the substrate alloy. Therefore
the HVOF sprayed Ni–20Cr coatings do not initiate
scale at the interface until 1000 h of hot corrosion study
and demonstrated their protective behaviour.
In conclusion:
1. HVOF sprayed Ni–20Cr wire coating was found to
be effective in imparting hot corrosion resistance to
Superni 75 in the actual working environment of a
coal fired boiler.
2. The formation of a continuous and thick Cr2O3-rich
band just above the scale–substrate interface and
the stringers of chromium oxide along the nickel-rich
splats boundaries mainly contributed to the better
performance of the Ni–20Cr coating. The oxide of
chromium along the nickel-rich splats boundaries
acted as a diffusion barrier to the inward diffusion
of corrosive species.
3. The hot corrosion resistance of the coating is also
partly attributable to the formation of nickel oxide,
the presence of very low porosity, uniform fine grains
and the flat splat microstructure of as the sprayed Ni–
20Cr wire coating.
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