An analysis of t h e protection of boiler steel tube with thermal spray

coatings from hot corrosion

Bablu yadav a,⇑, B r i j e s h , Veresh c, Vivak d
a Department of Mechanical Engineering, Reva University, Bangalore 560063, Karnataka, India

ABSTRACT

ARTICLE INFO
Traditional steels and their alloys cannot resist corrosion at high temperatures seen in
Keywords: thermal power plant boilers. Due to higher working temperatures for boilers, the issue of
Thermal hot corrosion has grown more straightforward. Several researchers have recently attempted
spray to use surface coatings to lessen heat corrosion of boiler steels. It's been a while since I've
Microstruc done this, but I've been able to get a few hours in the past few days. These coating processes
ture have been demonstrated to improve boiler steels' corrosion resistance and boost their
Corrosion performance at high working temperatures, which has subsequently prolonged their
Porosity lifespan. The development of surface coatings with remarkably superior corrosion
Mechanical properties
resistance qualities is the consequence of developments and advancements in thermal
spraying processes.

1. Introduction
Steels and other materials go through a variety of working
situations at high temperatures. Corrosion is an issue as a result
of using steels in this high-temperature application. Steels and
other materials go through a variety of working situations at
high temperatures. Corrosion is an issue as a result of using
steels in this high-temperature application. According to Rapp
and Zhang [1], the oxidation of material at high temperatures
that's what allows boiler steel to corrode. The contaminants in
the coal used in the boilers encompass oxide of vanadium,
sodium, and Sulphur. These contaminants combine with oxygen
to form oxides, which can corrode metals. Sulphur combines
with oxygen to produce SO2, which partially oxidizes to
produce SO3. According to Srikanth et al.[2] sodium and
vanadium react with oxygen to create sodium and vanadium
oxides. These oxides combine to form complex oxides of Na
and V, which are commonly known as vanadates. Eliaz et al.[3]
define hot corrosion as accelerated corrosion based on the
presence of salt
Contamination, mostly NaCl, and V2O5, which combined to
produce molten deposits that destroy the protective coatings. In
energy generation systems, residual fuel oil and coal are
frequently used due to the lack of high-quality fuels, as well as
the reason for financial gain. These fuels include impurities that
form compounds on the material’s surface at low melting points
and cause corrosion.
Such compounds are commonly referred to as Ash. The said ash
settles on the material surface and causes corrosion. Material
degradation happens when these melted compounds dissolve the
protective oxide layers which form naturally on the materials
during the boiler/gas turbine operation[4-8]. Many situations
that resulted in fatalities and property damage were due
to a failure to prevent or at least detect hot corrosion at an
early stage. Tens of millions of dollars are frequently
spent to restore deteriorated structures, machinery, and
equipment in addition to the immediate expenses
associated with shutdown and productivity loss.
Moreover, abrupt material degradation can result in
human handicaps or even risk to life [9,10]. When boiler
tubes and other parts are corroding, power plants may need to
shut down. Boiler steam temperature and thermal efficiency are
both reduced by corrosion.
Conventional steels, which are used extensively in thermal
power plants, cannot tolerate corrosion issues. In recent years,
scientists have improved the oxidation and corrosion protection
of steel by using several types of coatings. Thermal spray
coating techniques are now widely used to increase abrasive
wear resistance and extend the useful life of products. [11–14].
Over recent years, these coatings have gained significant
importance
to improve the life span of steels in high-temperature application
environments. Innovations in the manufacturing of powder and wire
alongside advancements in thermal spraying methods have led to the
development of surface coatings with high corrosion resistance
properties [15-17]. Such techniques have no particular shortcomings
in the surface and core composition [18]. High-hardness coatings can
be developed at a few millimetres of thickness. Flame, arc, plasma,
and HVOF methods are mostly used to protect boiler components
[19]. Owing to the remelting, the flame system is rarely used, and the
plasma method is relatively expensive[20-22].
In the recent past, various researchers have used thermal
spraying
techniques to develop various types of coatings on boiler steels
to increase corrosion resistance. In the following section, work done
by various researchers has been discussed.
A. Literature review
Bala et al. [23] studied the coating behaviour of Ni-50Cr cold spray
coating on boiler steel. The cold spray method was used for coating the
substrate T-22 and SA 516. The results were examined using XED and
SEM/EDAX analysis. The XED analysis shows the formation of Ni as
a principal phase for Ni-50Cr coating on T-22 and SA 516. SEM/EDAX
show the dominance of Ni and Cr in the coating composition which
forms oxides of Ni and Cr whereas, in the uncoated specimen, there was
the formation of Fe2O3 which result in corrosion. The coated and the
uncoated specimen were examined in the salt environment of Na2SO4-
60%V2O5 for 50 cycles. It was seen that coated specimen shows no
spallation whereas the uncoated specimen has porosities in the
specimen. Hence, the coating prevents the oxygen to diffuse into the
material thus it helps prevent corrosion.
Sidhu and Prakash [24] investigated the effect of HVOF coatings
in increasing ASTM-SA210 GrA1 steel’s hot corrosion resistance in the
presence of salt deposits of Na2SO4-V2O5. With the HVOF process,
Cr3C2-NiCr, Ni-Cr, WC-Co and stellite-6 metallic coatings had been
deposited on ASTM SA-210 grade A1 steel. LPG had been used as the
fuel gas. The porosity measurements have been conducted to determine
the surface properties. Hot corrosion experiments were carried out after
the samples were exposed under cyclic conditions to molten salt at 900
°C. NiCr Coating was found to be the most efficient backed up by the
Cr3C2-NiCr coating. WC-Substrate steel coating would have been least
effective in protecting from corrosion. The uncoated steel continued to
suffer from corrosion in the form of intense spalling and scale peeling.
Chatha et al. [25] examined the efficiency and application of Cr3C2-
NiCr thermal spray coatings in different conditions for corrosion erosion
and explored the microstructure and mechanical properties. The authors
concluded that voids were created at the edges of the splat due to thermal
sprayed coatings, and they were primarily targeted through these voids
of the Cr3C2-NiCr coatings. This was established that HVOF, Plasma
Spray processes, and detonation device processes would deposit carbide
coatings with effectiveness.
Gond et al. [26] studied the corrosion-resistant behaviour of bare T-
22 and T-91 steel in t h e molten salt environment at 900 °C. 75
wt%Na2SO4 + 25 wt% NaCl molten salt environment was used for
placing the bare steel specimens. The results were analyzed using
weight change, x-ray diffraction, and Energy Dispersive and cross-
sectional analysis. It was found that T-91 steel was superior in
preventing hot corrosion than T-22 steel as T-22 steel has a layer of NiO
which was not as much protective because it has loosely structured on
the other hand T-91 steel had a layer of chromium oxide which acts as a
barrier against corrosion as the result given by XRD technique.
Moreover, in T-22 steel pits formed were
deep and large whereas in T-91 it was small. Hence, it shows that T-
91 steel was better than T-22 steel in a molten salt environment. Bala
et al. [27] studied the high temperature and oxidation condition of Ni-
20Cr and Ni-50Cr coatings on SAE 213 (T22) steel in a simulation
model boiler situation at 900oC for 50 cycles in cyclic conditions. This
was observed that uncoated steel gained weight by oxidation in the
air along with salt conditions for 50 cycles of 900 °C. The Ni-Cr
coating had been found to have greater resist-
stance to corrosion in the simulated environment.
Varis et al. [28] investigated the corrosion actions of NiCr and FeCr
coatings within simplified situations for the combustion of biomass.
HVOF thermal spraying was used to apply the coatings. The researchers
used KCl-K2SO4 blend as synthetic biomass ash. This ash was imposed
on coated material and heat treated in two separate gas atmospheres (air
and air +%H2O) for 168 h at 550 °C and 600 °C. It had been found there
was no depletion of chromium from the coatings at 550 °C nor was
there infiltration of chlorine in the coatings. At 600 °C, significant
depletion of chromium was observed in ambient and humid conditions.
Fe-based HVOF CJS Fe25Cr coatings have been found to have strong
corrosion resistance, but no chlorine penetration was found through this
coating.
Fernandez et al. [29] analyzed the corrosion of laser-treated Cr- Ni
base coatings inside a steam boiler with 3–3.5 vol% free oxygen at
temperatures of 773 K and 1073 K and especially compared the final
results with Cr-Ni plasma sprayed coatings and AISI 304 stainless steel.
The researchers were using a laser process to combine all plasma spray
coating with base Ni alloy pearl forming. Laser treatment has resulted
in decreased porosity and a homogenous coating has been obtained.
Singh and Singh [30] investigated corrosion in real boiler conditions
of Al2O3-coated T-91 boiler steel. The detonation gun thermal spraying
process had been used for Al2O3 powder coating. Cyclic conditions
have been observed for the coated and uncoated samples. It had been
observed that coated T-91 exhibited a weight loss of 2.96 per cent due
to the degradation of the scale of the samples. In realistic conditions, the
erosion-corrosion risk of Al2O3-coated T-91 was found to be greater
than those of uncoated T-91.
Somasundaram et al. [31] developed a composite powder by infusing
Si alloy products with Cr3C2-35% NiCr powder. The composite powder
with HVOF on SA213-T22, MDN-310, and SUPERFER 800H steels had
been deposited. Under cyclic conditions, these coated steels were
examined in the air at 700 °C. The coated steels have been shown to have
better corrosion resistance to oxidation. Cr3C2-35 % NiCr + 5% Si
coating had been found to have a better resistance to oxidation thanks to
the formation of Cr2O3, SiO2, NiCr2O4 and Ni2(SiO4) oxide layers. At
the substratum and coating interface, oxygen was not present which
meant that oxidizing elements had not penetrated the inside of the
coatings.
Sidhu et al. [9] studied HVOF-sprayed solid particle degradation
from WCCo/NiCr-FeSiB coatings. It had been found that WCCo/NiCr-
FeSiB sprayed high-velocity oxy-fuel (HVOF) coatings on GrA1 boiler
tube steel show composite ductile and brittle erosion modes with angular
silica sand erodent size 125–180 mm impacting at 40 m/s. The HVOF
spraying results in high WC retention in the substrate matrix
accompanied by lower porosity.
Singh et al. [12] deposited different carbon nanotubes mixed with
zirconium yttrium coatings on boiler steel and observed their corrosion
behaviour at 600 °C under cyclic conditions. The authors used the air
plasma spraying method to deposit coating powders. The uncoated steel
suffered severe corrosion and spallation due to the formation of oxides
of iron. Zirconium yttrium coatings mixed with carbon nanotubes
indicated an increase in corrosion resistance in the selected
environment. The increase in corrosion resistance was attributed to the
uniform dispersion of carbon nanotubes in the coating matrix and th e
formation of zirconium oxide in the scale.
 Wang et al. [32] developed the detonation gun spraying separator
device and examined its influence on WC-Co coating performance. The
findings revealed that the separation system improved the properties of
D-gun sprayed WC–Co coatings. Furthermore, the researchers have
concluded that the porosity of the coatings had been reduced but
porosity was not completely prevented.
The effectiveness of Ni3Al and TiO2 coatings on boiler steel T-91 at
900 °C was investigated by Singh et al. [33]. The HVOF method was
used to coat the specifics. Following coating, the specimens were
exposed for 50 cycles to a molten salt environment of Na2SO4-60%
V2O5 at 900 °C. The cycles were made up of a 20-minute cooling period
after a 1-hour heating period. The behaviour of coatings and rate of
corrosion were observed during an experiment using the thermo
gravimetric method, X-ray Diffraction XRD, and SEM/EDS techniques.
According to the XRD test findings, the predominant phases were
Fe2O3, Cr2O3, and Fe3O4. Singh et al. [33] examined the efficacy of
Ni3Al and TiO2 coatings on boiler steel T-91 at 900 °C. The
specifications were coated using the HVOF procedure. Following
coating, the specimens were subjected for 50 cycles to a Na2SO4-60%
V2O5 molten salt environment at 900 °C. The cycles consisted of a 20-
minute cooling interval followed by an hour of heating. Using the
thermo gravimetric method, X-ray Diffraction XRD, and SEM/EDS
methods, an experiment was conducted to evaluate the behaviour of
coatings and the rate of corrosion. The results of the XRD test revealed
that Fe2O3, Cr2O3, and Fe3O4 were the predominant phases.
On carbon steel tube (St35.8, DIN 17175-79, dimension 38/5.5 mm),
Oksa et al. [34] investigated the corrosion effects of two thermally
sprayed HVOF coatings, Fe-27Cr-11Ni-4Mo and Fe-19Cr-9W-7N b-
4Mo. The coatings in this investigation have been subjected to boiler
conditions for a period of two years. In the coating's 20 lm outer layer,
coating Fe-19Cr showed some minor corrosion. Low porosity and some
perpendicular cracks in the covering allowed corrosion to spread to the
surface. The Fe-27Cr HVOF coating demonstrated significant resistance
to corrosion under the conditions, according to the scientists' conclusion.
The hot corrosion behaviour of iron-based superalloys covered with
Cr3C2-NiCr coatings was assessed by Kamal et al. [35]. The specimens
were subjected to the corrosive effects of Na2SO4 at 900 °C for 100
cycles. The detonation gun spraying method was used to create the
coating. Thermogravimetric methods, XRD, SEM, and FE-SEM/EDAX
were used to evaluate the hot corrosion behaviour of
uncoated and coated specimens in a molten salt environment. The
Cr3C2-NiCr coating demonstrated improved resistance to heat
corrosion. However, compared to Superni 75 and Superni 718, super
alloy 800H was more resistant to heat corrosion. By using the D-gun
spraying method to create the Cr3C2-NiCr coating, the pores were
reduced, resulting in flat splat structures and uniform fine grains.
The behaviour of the Cr3C2-NiCr coating resistance on T-22 steel in
corrosive environments was examined by Kaur et al. [36]. The base
material was coated using the D spray technique. Coated and uncoated
specimens were subjected to 15 cycles, each cycle consisting of a 100-
hour boiler environment exposure at a temperature of 700 °C and a 1-
hour cooling period at room temperature. The weight change
methodology, the XRD technique, the SEM/EDS method, and cross-
sectional analysis were used to get the results. Uncoated specimens were
found to exhibit scale spalling as well as an increase in weight, whereas
coated specimens exhibited no change in weight growth and no
spallation.
In an actual boiler developing at 900 °C with cyclic thermal loading,
Goyal et al. [37] examined the hot corrosion behaviour of carbon
nanotube-enhanced chromium oxide composite coatings. The coatings
were applied using the high-velocity oxy-fuel technique, with the CNT
concentration ranging from 1 to 8 wt%. By filling up gaps, fissures, and
tiny holes in the coating microstructure, the scientists discovered that
carbon nanotubes worked as a physical barrier against the species that
cause corrosion. Throughout the trial, the coatings developed
protective oxide scales and had less weight increase. Increased CNT
content in the coating matrix was associated with a decrease in hot
corrosion rates.
By using the detonation gun spray coating (D-Gun) procedure, Singh et
al. [38] applied Ni-Cr and Cr3C2-NiCr coatings to T11 and P91 boiler
steels and examined how they responded to heat corrosion in a real boiler
environment. The researchers found that among all specimens, uncoated
boiler steel specimens lost the most weight. In a real boiler setting, the
Cr3C2-NiCr coating performed better than the Ni-Cr coating due to the
creation of Cr2C3, Cr3O2, Ni3Fe, and Cr3Ni2.
In a 700 °C simulated molten salt environment, Singh et al. [39] studied
the hot corrosion behaviour of various Cr3C2-NiCr coatings on boiler
tube steel. With the use of elemental compositional analysis and X-ray
diffraction, the microstructures of corroded specimens were studied. In
comparison to 20Cr3C2-80NiCr, 100NiCr, and 35Cr3C2-65NiCr, they
discovered that 10Cr3C2-90NiCr and its coating offered the strongest
resistance against corrosion. Corrosion resistance was achieved via a
layer of chromium carbide forming on the coated surface.
Rehman et al. [40] produced the Trib-alloy T-900 wear-resistance coating
alloy that has been mechanically alloyed with aluminium and yttrium. At
900 °C, the researchers looked at how modified and unaltered alloys
behaved during hot corrosion. According to experimental findings,
coatings treated with yttrium and aluminium displayed the best hot
corrosion resistance. The creation of molybdenum oxide, the breakdown
of less stable NiO in the salt, and the subsequent generation of sulphide
was observed to cause significant hot corrosion attack on unaltered
coatings. Al2O3 and Cr2O3 layers were formed thanks to the Yttrium
addition's selective oxidation of Al and Cr. The oxide layer served as a
defence against the onslaught from the molten salt. Rehman et al. [40]
produced the Trib-alloy T-900 wear-resistance coating alloy that has
been mechanically alloyed with aluminium and yttrium. At 900 °C, the
researchers looked at how modified and unaltered alloys behaved during
hot corrosion. According to experimental findings, coatings treated with
yttrium and aluminium displayed the best hot corrosion resistance. The
creation of molybdenum oxide, the breakdown of less stable NiO in the
salt, and the subsequent generation of sulphide was observed to cause
significant hot corrosion attack on unaltered coatings. Al2O3 and Cr2O3
layers were formed thanks to the Yttrium addition's selective oxidation
of Al and Cr. The oxide layer served as a defence against the onslaught
from the molten salt.
In a molten salt V2O5 + 45 wt% Na2SO4 environment at 900 °C, Kadhim
et al. [41] investigated the hot corrosion behaviour of partially stabilised
zirconia alumina composite (YPSZ/ Al2O3) coating on stainless steel
316L specimens. The findings showed that YSZ/Al2O3 composite
coatings had superior hot corrosion resistance than traditional YSZ
sprayed coatings. The destabilisation of yttria from the zirconia yttria
coatings was blamed for the degradation of YSZ. Al2O3 was used to
cover the gaps and cracks in the YSZ coating for the composite coating,
which decreased porosity and increased corrosion resistance.
Recently, several researchers have combined nanomaterials with
coatings made of nanocrystalline metal matrices, including alumina,
titanium dioxide, and silicon carbide [37–46]. Corrosion resistance
increased with the inclusion of nanoparticles. SiC nanoparticles have
been combined with Ni, Ni-W, or Ni-Co alloys by researchers, and they
have seen an increase in corrosion resistance as a result [43–44,47–48].
SiC nanoparticles act as inert physical barriers to the initiation and
development of defect corrosion as well as due to the modification of
the nickel layer's microstructure. [43–44,47–48]. Al2O3 nanoparticles
were incorporated into nickel coatings and this nanocoating was
deposited on steel and subsequently was tested for corrosion resistance
in molten salt solution. The authors found that Al2O3 acted as aninsulator
on the composite surface, where a slightly better resistivity was found
in the NaCl solution [51]. The Al2O3 nanoparticles were able to refine
the nickel grains which had blocked the penetration of corrosive
elements [50].
Due to their higher mechanical qualities and improved wear and
corrosion resistance, metal nitride films are frequently utilised as
protective coatings [47-50,52]. Because they don't deteriorate into porous
oxides at the film surface when employed in high-temperature
 applications, these coatings offer the advantage of working at high
temperatures (over 700oC) [53]. It is well known that Cr and Ni-based
coatings offer great wear resistance [55] and oxidation resistance up to
900 °C [53,54]. Due to a decrease in linked porosity, a reduction in
coating roughness, and an increase in coating density, a multilayer
structure based on Cr and Ni offers greater corrosion resistance [56]. It
should be mentioned that Cr-based nitride coatings are superior to Ti-
based nitrides in terms of strength and oxidation resistance, making
them more appropriate for use in high-temperature applications.
B.
Conclusions:
The following results are reached after reviewing previous research works
on the high-temperature corrosion behaviour of thermal spray coatings:
• Thermal power plants are dealing with a severe issue with hot
corrosion of boiler steels under high-temperature working
conditions.
• According to a review of the literature, several researchers have
created various types of coatings using thermal spraying
techniques to improve the hot corrosion resistance of boiler steels.
• To boost corrosion resistance, researchers created hard coatings
using thermal spray methods, HVOF techniques, air plasma spray
techniques, cold spraying, and D-gun spray techniques.
• Since thermal spray coatings are porosity in nature and feature
numerous local microcracks or through pores, it is impossible to
generate defect-free coatings, even when using cutting-edge and
advanced coating systems.
• The hardness of the coatings is also lowered as a result of the
fractures and porosities. These porosities/voids allow the
corrosive elements to attack the substrate alloy. The coating's
hardness reduces and surface roughness rises as a result of its
high porosity. It is the main reason why thermal spray coatings
fail.
• To boost the hot corrosion resistance of boiler steels at high
operating temperatures, additional study is needed to minimize
the porosity of coatings and to raise their hardness.
Declaration of Competing Interest:
The authors declare that they have no known competing
financial interests or personal relationships that could have appeared
to influence the work reported in this paper.
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