International J ournal of Advanced Mechatronics and Robotics (IJ AMR)

Vol. 3, No. 2, July-December 2011; pp. 85-95; International Science Press, ISSN: 0975-6108
Hot-corrosion Resistance of Alloy and
Composite Coatings: A Review
Harkulvinder Singh
1*
, Sukhpal Singh Chatha
1
,
Hazoor Singh Sidhu
1
& Kovid Sharma
1
1
Yadavindra College of Engineering, Punjabi University Guru Kashi Campus,
Talwandi Sabo, Punjab, India-151302, (
*
Corresponding Author: harkulvinder84@gmail.com)
(E-mail: Sukhpal_chatha@yahoo.com), (hazoors@yahoo.com), (kovids@yahoo.com)
ABSTRACT
Hot corrosion is a serious problem in boilers, gas turbines, internal combustion engines, and industrial
waste incinerators. It consumes the materials at an unpredictably rapid rate. Alloys used at high
temperature should possess good mechanical properties, corrosion and oxidation resistance. Thermal
spray technology encompasses a group of coating processes that provide functional surfaces to
protect or improve the performance of a substrate or component. Many types and forms of materials
can be thermal sprayed, Which provide protection from corrosion, wear, and abrasion and for a
variety of other applications. The use of protective coatings has been an answer to remedy the lack
of high temperature surface stability of metals and alloys in harsh environments. This study is done
with the aim of putting together the performance capabilities and applications of alloy and composite
coatings.
Keywords: Hot corrosion, Alloys, Composites, Coating.
1. INTRODUCTION
Coatings and surface modification technologies allow the engineer to improve the
performance, extend the life, and enhance the appearance of materials used for engineering
components. These technologies have been developed because the interactions of
manufactured components with other components, liquid, and/or gaseous environments
can result in component degradation and failure (Davis J. R., 2004). Metals and alloys
sometimes experience accelerated oxidation when their surfaces are covered with a thin
film of fused salt in an oxidizing gas atmosphere at elevated temperatures. This is known as
high temperature or hot corrosion where a porous nonprotective oxide scale is formed at
the surfaces and sulphides in the substrate (Singh H et al, 2007).
Hot corrosion is an accelerated form of oxidation that occurs at higher temperature in
the presence of salt contaminants such as Na
2
SO
4
, NaCl,V
2
O
5
that combine to form molten
deposits, which damage the protective oxide layer (N. eliaz et al, 2002). Hot corrosion is a
serious problem in boilers, gas turbines, internal combustion engines, and industrial waste
86 International Journal of Advanced Mechatronics and Robotics
incinerators. As a consequence the load-carrying abilities of the components are reduced
(Sidhu T. S. et al, 2006). In combustion products of fuel oil, sulfur is typically present as
Na
2
SO
4
, which occurs when the metals are heated in the temperature range of 700-900C,
in the presence of sulfate deposits. Vanadium as an impurity in fuel oil causes serious
corrosion problems because of the formation of V
2
O
5
(Ismail and Anees, 2004). Protective
coatings on superalloys encounter two types of high temperature corrosion degradation i.e
High temperature hot corrosion (HTHC) and Low temperature hot corrosion (LTHC). High
temperature hot corrosion (HTHC) also designated as Type 1, occurs at temperatures in the
800 to 950C range. It is caused by molten salt deposition on the coating surface. The
primarily active constituent of this salt is sodium sulphate Na
2
SO
4
. Low temperature hot
corrosion (LTHC), also known as Type 2, occurs in the 650-750C range. The low temperature
hot corrosion mechanism involves acidic fluxing of protective oxides by sulphur trioxide
(SO
3
) dissolved in molten sulphates (Bala N. et al, 2010).
1.1. Coating
Hot components of gas turbines and energy systems operating in aggressive environments
are subjected to a number of modes of attacks which include oxidation, sulphidising,
carburizing, chlorination, erosion and hot corrosion induced by molten salts. The use of
protective coatings has been an answer to remedy the lack of high temperature surface
stability of metals and alloys in harsh environments (Bhatia R. et al, 2010). Thermal spray
coatings can be applied to overcome the steam oxidation problem since it alters the surface
without affecting the bulk material properties. Thermal spray coating of FeAl, FeCrAl and
NiAl powders on 9Cr-1Mo steel was attempted to improve the steam oxidation resistance
for boiler applications (Sundararajan T. et al, 2003).
Most high temperature alloys are iron, nickel or cobalt-base because these elements
have high melting point. Unfortunately, their oxides are not protective enough in the
combustion environment of a fossil-fuel power plant at temperatures above 550C.
Nevertheless, addition of other elements to establish more protective oxides such as Cr
2
O
3
,
Al
2
O
3
, or SiO
2
has improved their corrosion resistance (Calderon J. P. et al, 1997). Overlay
coatings include a family of corrosion resistant alloys specially designed for high temperature
surface protection. They referred to as M-Cr-Al-Y coatings, where m is alloy base metal
(Ni, Co or combination of two). The high resistance of high chromium, Nickle chromium
alloys to high temperature oxidation and corrosion makes them widely used as thermally
sprayed coating in fossil fuel-fired boilers, waste incineration boilers and electric furnaces
(Parkash S., et al, 2005). Cr and Al are added in Fe and Ni-based superalloys to enhance the
oxidation resistance (Chawla V., et al, 2009). Cr
3
C
2
-NiCr and NiCrBSi coatings obtained
by thermal spraying show good tribological properties in severe working conditions such
as at high temperatures or in aggressive environment applications. These coatings maintain
their high wear and corrosion resistance up to 1253 K and are used to improve the
performance life of the components working at elevated temperatures (Sidhu T. S. et al,
2007). The corrosion resistance of the Ni-based coating founded higher than that of the
Hot-corrosion Resistance of Alloy and Composite Coatings: A Review 87
stainless steel substrate material due to the passive film forming effect of Cr. The hot corrosion
behavior of NiCrBSi coatings resistance imparted by NiCrBSi coatings may be attributed
to the formation of oxides of silicon, chromium, nickel and spinels of nickel and chromium
in the molten salt environment at high temperature. (Karagz M. et al, 2011).
1.2. Thermal Spray Process
Thermal spraying is a group of processes in which metallic materials are deposited in a
molten or semi molten conditions to form a coating (Lal et al., 2010). Thermal spraying
gun produced heat using combustion of gases or electric arc. As the material is heated they
change to plastic or semi-molten state and accelerated towards the substrate. A confined
stream of particles strikes on substrate, flattens and forms thin splats that conform and
adhere to irregularities of prepared surface and to each other. As the sprayed particles
impinge upon substrate they cooled down and produce lamellar microstructure as shown in
Figure 1 (AWS, 1997).
Figure 1: Basic Principle of Thermal Spray Coating & Coating Microstructure
(Steffens H.D and Davis J.R, 1996, 2004).
88 International Journal of Advanced Mechatronics and Robotics
Alloy and composite Coatings can be deposited by electric arc spray, physical vapour
deposition, detonation spraying, flame spray, vacuum plasma spray, low pressure plasma
spray, high velocity oxy fuel by sputtering or by evaporation. Coatings serve more than one
functions For high temperature oxidation resistance, a coating should (a) resist oxygen and
metal ion diffusion, (b) have a low vapour pressure at the operating temperature, (c) have a
melting point above the operating temperature, (d) have low reactivity with the substrate,
and (e) have low reactivity with the high temperature environment (Datta S et al, 2005).
2. STUDIES ON COATINGS
Villafane et al, 1997 observed that when the specimens of SA213 grade T-22, SA213
austenitic grade TP347H were coated with actual ash collected from the super heater of a
power plant and passed through a simulated flue gas (oxygen and 0.25 v/o SO
2
+ 3.6 v/o O
2
,
balance N
2
). The results of x rays diffraction shows the corrosiveness of the deposits varied
with the atmosphere. It is also observed that the TP347H austenitic stainless steel had the
best performance, as expected, and the T22 ferritic steel had the worst when coated with
silicon or chromium.
Caldern F. A. et al, 2011. deposited metallic coating ( NiCrFeNbMoTiAl) on SA
213-T22 alloy steel substrates with thermal projection with non-transferred arc plasma
(APS) process. These coated test pieces were subject to corrosive attack in saline mixtures
of 80wt. %V
2
O
5
20wt. % Na
2
SO
4
and 80wt.% V
2
O
5
20wt. % K
2
SO
4
at a temperature of
700C. The results of linear polarization resistance (LPR), electrochemical techniques, and
electrochemical impedance spectroscopy (EIS) reveals that corrosive attack became more
severe when exposed to corrosion by molten salts in a mixture composed by 80%V
2
O
5

20%Na
2
SO
4
decreasing the thickness of the sprayed layer in a larger proportion than when
exposed to 80% V
2
O
5
20% K
2
SO
4
. Calderon J. P. et al, 1997 used plain carbon steel with
bond coat of Ni20Cr and uncoated 304 stainless steel as substrates and Fe75Si alloy coating
deposited on bond coat . The substrates were installed in the high-temperature, fireside,
corrosion zone of a steam generator for 13 months. Boiler burned heavy fuel oil with high
contents of vanadium. The results of SEM/EDAX shows that the uncoated 304 stainless
steel were destroyed almost completely by corrosion, whereas the carbon steel coated did
not suffer a significant attack, showing that the performance of the thermal spray coating
was outstanding and that the coating was not attacked by vanadium salts of the molten slag.
Cr
3
C
2
-NiCr coating was deposited on SAE-347H boiler steel by HVOF spray process and
investigated at 700C for 50 cycles in Na
2
SO
4
-Fe
2
(SO
4
) molten salt, as well as air
environments by Kaur Met al, 2009. The results of HVOF spray Cr
3
C
2
-NiCr coating was
found to be successful in maintaining its adherence in both the environments. The formation
of chromium rich oxide scale might have contributed for the better hot corrosion/oxidation
resistance in the coated steel.
Parkash S. et al, 2005. deposited NiCrAlY, Ni20Cr, Ni
3
Al and Stellite metallic coatings
with plasma spray technology on Ni based Superni-718 substrate. NiCrAlY was used as
bond coat in all coatings. Hot corrosion studies were performed on 900C under cyclic
Hot-corrosion Resistance of Alloy and Composite Coatings: A Review 89
conditions. The results of SEM/EDAX and EPMA techniques reveals that NiCrAlY provides
best protection to the base alloy due to oxides of Ni, Al and NiCr2O4 spinal in the scales.
Hot corrosion resistance of Ni3Al coating is less as compared to NiCrAlY and Ni-20Cr but
it performs better than the satellite-6 coating. Sidhu H. S. et al, 2010. formulated NiCr and
Stellite-6 coatings on ASTM-SA-210 Grade A1, ASTM-SA213 T-11 and ASTM-SA213-T-
22 boiler tube steels by HVOF technique using LPG as fuel gas. These coatings have been
examined for characterization by metallography, SEM/EDAX and XRD techniques for
describe the transformations that take place during HVOF spraying. The results of Stellite-
6 coating were better than NiCr coatings for low value of porosity and surface roughness.
Microhardness of the Stellite-6 coating has higher hardness as compared to the NiCr coating,
although both coatings have high hardness values compared to the substrate steels. Sidhu
B.S. et al, 2005. were used Low carbon steel ASTM-SA210-Grade-A1, ASTMSA213
T-11, and 2 ASTM-SA213-T- 22 steels as substrate material and Ni-20Cr-10Al-1Y bond
coat applied on these specimens and Ni-20Cr coating deposited by plasma spraying. The
samples were exposed to the combustion gases for atotal of 10 cycles, each consisting of a
100 h exposure followed by 1 h cooling at ambient conditions. The possible mechanism of
attack for this coating is shown in Figure 2. XRD,SEM/EDAX Analysis shows top-most
scale is rich in nickel, and then a chromium rich layer lying just above the bond coat is
followed by an intermediate layer where nickel and chromium are coexisting, which confirms
the formation of spinel. The continuous thin band of chromium lying at the bond coat-
substrate interface blocks the transport of species to the substrate, which contributes to the
protection of the base steels.
Figure 2: Mechanism of Attack of Oxidation (Sidhu B.S. et al, 2005).
90 International Journal of Advanced Mechatronics and Robotics
The uncoated T22 steel showed better resistance to hot corrosion in boiler environment
as compared with T11 and GrA1 bare steels. All the plasma sprayed steels have shown
better degradation resistance than uncoated steels. Mohsen et al, 2007. Investigated
Ni based inconel 738 material and Amdry962 (Ni-22Cr-10Al-1Y) as bond coat and
Metco204YSZ (ZrO
2
-8%Y
2
O
3
) coating that deposited by plasma spray technique on the
substrate. Hot corrosion studies were performed on 1100C under cyclic conditions for
22, 24 and 100 hours. The results of SEM/EDAX and EPMA techniques reveal that
horizontal cracks as shown in Figure 3 and spallation of YSZ layer are due to formation of
monoclinic ZrO
2
and YVO
4
crystals.
Figure 3: SEMImage Showing the Cross-section of the Coating after Hot Corrosion Test
(Mohsen et al, 2007).
Bala Net al, 2009 examined SA 516 (Grade 70) uncoated and SA 516 (Grade 70) steels
Ni-20Cr coated by Cold spray process .Cyclic corrosion was performed in molten salt
(Na
2
SO
4
-60%V
2
O
5
) at 900C for 50 cycles. The results of XRD,SEM/EDAX shows cold
spray coating of Ni-20Cr alloy powder was found to be useful in developing hot corrosion
resistance in SA-516 steel in Na
2
SO
4
-60%V
2
O
5
environment at 900C due to Ni and Cr in
its oxide scale, which are reported to be protective oxides. The uncoated steel showed
substantial spallation of its oxide scale during hot corrosion. The Ni-20Cr coating was
found to be successful in retaining its continuous surface contact with the substrate steel.
Ramesh M.Ret al, 2010. examined HVOF process used to deposit NiCrFeSiB alloy powder
on boiler tube steels SA210 grade-A1, SA213-T11, and SA213-T22. Thermocyclic oxidation
test were performed in static air at 900C in silicon carbide tube furnace up to 50 cycles.
The results of SEM/EDAX and EPMA techniques reveal that the microstructure of coatings
has a dense and layered structure with porosity less than 0.5%. The superior performance
of NiCrFeSiB coating can be attributed to continuous and protective thin oxide scale of
Hot-corrosion Resistance of Alloy and Composite Coatings: A Review 91
amorphous SiO
2
and Cr
2
O
3
formed on the surface of the oxidized coatings. Sundararajan
T. et al, 2004. Investigated 80Ni-20Cr and 50Ni-50Cr coatings that deposited by HVOF
(High Velocity Oxy Fuel) process and APS (Air plasma spray) on 9Cr-1Mo steel substrate
respectively. Steam oxidation test was carried out at 650C for 100, 1000 and 3000 hours.
These coatings have been examined by metallography, SEM/EDAX and XRD techniques
that show HVOF coatings of both 80Ni-20Cr and 50Ni-50Cr yielded a good protection
till 750C by forming Cr oxide as protective layer as compared to APS. Aalamialeagha
M.E. et al, 2003. Reveals that when Ni-20%Cr alloy gas and water atomized powders
sprayed BY Topgun HVOF with a gaseous propylene fuel and Met-Jet II HVOF system
with liquid fuel (kerosene) on mild steel substrates. The oxide, porosity and the amount
of melted material in the coatings were characterised using scanning electron microscopy
(SEM) and X-ray diffraction (XRD), whilst the corrosion resistance of the coatings was
evaluated by use of a salt spray chamber and potentiodynamic tests. The results observed
that greatest corrosion protection to the steel substrate is given by coatings produced
from gas atomized Ni-20%Cr powders when sprayed by the liquid fuelled Met Jet II
HVOF system Sidhu H.S et al, 2006 examined Cr
3
C
2
-NiCr, NiCr, WC-Co and Stellite-6
alloy coatings that were sprayed on ASTM SA213-T11 steel specimens using the HVOF
process, liquid petroleum gas was used as the fuel gas. Hot corrosion testing was done on
the specimens after exposure to molten salt at 900C under cyclic conditions. The testing
techniques shows that NiCr Coating to be most protective followed by the Cr
3
C
2
-NiCr
coating. WC-Co coating was least effective to protect the substrate steel. In this study it
is concluded that the formation of Cr
2
O
3
, NiO, NiCr
2
O
4
, and CoO in the coatings may
contribute to the development of a better hot-corrosion resistance. Sidhu H.S et al, 2006
Investigated The boiler tube steel, ASTM-SA210 grade A1 as substrate and Cr
2
O
3
NiCr,
WC12Co and stellite-6 alloy powder and Ni20Cr wire coating deposited by HVOF
process with oxygen and LPG as the fuel gases. Cyclic oxidation was performed in molten
salt (Na
2
SO
4
60% V
2
O
5
) for 50 cycles, The results of XRD, EDAX and EPMA analysis
shows the porosity of NiCr coating lies in the range of 13.5% that provided highest
resistance to hot corrosion.
Sidhu H.S et al, 2006 used Low carbon steel ASTM-SA210 grade A1, 1Cr0.5Mo
steel ASTM-SA213-(T11) and 2.25Cr1Mo steel ASTM-SA213-(T22) as substrate and
WC12%Co, Cr
3
C
2
25% NiCr powder coating were deposited by HVOF thermal spraying
process with LPG as fuel gas in the thickness range of 350380m.Characterization were
done in order to achieve microstructure of coatings. SEM/EDAX and XRD techniques
show that WCCo coatings have slightly higher hardness and porosity as compared to the
Cr
3
C
2
-NiCr coatings that is desired for hot corrosion. Kamal S. et al, 2010 formulated
NiCrAlY + 0.4 wt.% CeO
2
coatings with D-gun process on Nickel- and Iron based
superalloys superni 75, superni 718, and superfer 800H specimens .Hot corrosion studies
were performed in a molten salt (40% Na
2
SO
4
-60% V
2
O
5
) for 100 cycles at 900C under
cyclic conditions. The proposed hot corrosion mechanism of the NiCrAlY + 0.4 wt.%CeO
2
coated superalloy superfer shown in Figure 4.
92 International Journal of Advanced Mechatronics and Robotics
The SEM/EDAX, XRD results reveals that bare and coated Fe-based superfer 800H
superalloy showed least and highest resistance to the hot corrosion, respectively. D-gun-
sprayed NiCrAlY + 0.4 wt.% CeO
2
coating found to be effective in imparting hot corrosion
resistance to superfer 800H in the molten salt environment Pint B. A. et al, 2001 investigated
Fe-9Cr-1Mo (ferritic alloy),and an austenitic stainless steel, 304L as substrate material and
iron-aluminide coating were deposited by Chemical vapor deposited (CVD). High
temperature cyclic oxidation testing in air with 10 0.5vol.%H
2
O was done in an automated
test rig with a cycle consisting of 1h at 800C temperature and 10min cooling at room
temperature. The XRD, SEM/EDAX results show that CVD aluminized coatings have
excellent resistance to environments containing water vapor but do not appear to have
sufficient Al for long-term resistance to low oxygen, high sulfur environments. The high
coefficient of thermal expansion of 304L may be more compatible with Fe
3
Al coatings
while the ferritic substrates should avoid the intermetallic phase formation Lasota B. S.
et al, 2005 examined composite coatings FeAl- FexAly strengthened by a fine dispersive
Al
2
O
3
were thermally sprayed by HVOF process. The cyclic corrosion behavior of coatings
with FeAl intermetallic matrix was investigated in N
2
+ 9% O
2
+ 0,2% HCl +0,08% SO
2
aggressive gases at 600C for exposure times of up to 500 hours. Model of the corrosion
mechanism of intermetallic coatings in aggressive gas.
Mixture is shown in Figure 5.
One portion of intermetallic coatings was sealed with an inorganic phosphate seal. The
results of SEM/EDAX, XRD show that an adherent alumina scale and iron oxide layers
were formed on all studied coatings. A stable Al
2
O
3
phase on the surface of the studied
Figure 4: Schematic Diagram Showing Proposed Hot Corrosion Mechanism of the NiCrAlY + 0.4
wt.%CeO
2
Coated Superalloy Superfer 800H at 900 C in Na
2
SO
4
+ 60% V
2
O
5
after 100 Cycles
(Kamal S. et al, 2010).
Hot-corrosion Resistance of Alloy and Composite Coatings: A Review 93
coatings ensure high oxidation resistance. All the results confirm good heat proofness of
HVOF sprayed coatings with an intermetallic FeAl matrix.
3. CONCLUSION
Degradation of metals is a severe problem in the industrial applications. It is not possible for
single material to have different properties to meet the demand of todays industries. So alloy
and composite materials is required to provide the necessary mechanical properties and
protective surface layer which immune the substrate surface from hot corrosion, wear and
erosion also. The formation of chromium rich oxide scale might have contributed for the
better hot corrosion/oxidation resistance in the coated steel. NiCrAlY provides best protection
to the base alloy due to oxides of Ni , Al and NiCr
2
O
4
spinal in the scales. Alloy and composite
coatings has high hardness and low value of porosity as compared to substrate steel that is
desirable in hot corrosion resistance. In order to improve the corrosion resistance of coatings,
post-treatments are often used to eliminate the inherent defects in the ceramic coatings, such
as liquid metal impregnation, Sealing treatment .sealing is to close or fill open structural
defects connecting to the surface and make the sealants penetrate into the coating as deep as
possible. Sealing treatment is an effective method to improve the corrosion resistance of
porous materials. Therefore high temperature oxidation and hot corrosion behaviour of alloy
and composite coatings need to be further investigated to understand the behaviour and
performance of these coatings at higher temperature in different corrosive environment.
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