GTM-SU-718 in Molten Salt Environments

GTM-SU-718 in molten salt environments
A thesis submitted in partial fulfillment of

the requirements for the award of the degree of
Master of Technology
In
Industrial Metallurgy
By
Manoj Kumar
(Roll No-145514)
Supervisor
Dr. M. K. Mohan
Professor of Metallurgical & Materials
Engineering
DEPARTMENT OF METALLURGICAL AND MATERIALS

ENGINEERING
NATIONAL INSTITUTE OF TECHNOLOGY, WARANGAL
506004
June 2016
APPROVAL SHEET
This dissertation entitled Study of hot corrosion behavior of nickel based superalloy
GTM-SU-718 in molten salt environments by Manoj Kumar, Roll No: 145514, approved
for the degree of Master of Technology in Industrial Metallurgy from National Institute of
Technology, Warangal.
Examiners
Supervisors
Chairman
Date:
Place:
i
DECLARATION
Study of hot corrosion behavior
of nickel based superalloy GTM-SU-718 in molten salt environments
results of the investigations and research work carried out by me in the Department of
Metallurgical and Materials Engineering, National Institute of Technology, Warangal and the
same has not been submitted elsewhere either in part or in full for any degree or diploma
Waranagal Manoj Kumar
Date: Reg. No.: MM14128
iii
ACKNOWLEDGEMET
I express my deep sense of gratitude to Prof. M. K. Mohan, Professor of Metallurgical and

Materials engineering, National Institute of Technology (N.I.T), Warangal for his guidance and
invaluable cooperation in the course of my thesis. The important discussions I had with him
during my experimental work gave me the strength to complete my thesis on time. These
discussions were very important in understanding the subject.
I am very thankful to Prof. B. V. Appa Rao, Professor of Chemistry, National Institute of

Technology (N.I.T), Warangal for making me understand the subject. He was instrumental in
conceptualizing and his support was available in all stages. His availability at all times made the
experiments very easy and quick.
My regards are due to Dr. N. Narasaiah, Associate Professor, HOD, Metallurgical and Materials
Engineering, NIT Warangal for providing me this opportunity to perform my experiments.
I would like to thank Mr. Vimal Kumar, PhD scholar, Department of Chemistry for his
willingness to help and support at all the stages of my thesis work. I would also like to thank
Kaushik Devulapally, (B.Tech final year) for helping me during my experiments.
I would like to thank entire staff member of the Department of Metallurgical and Materials
Engineering NIT, Warangal for their help and support.
I am very thankful to my family members for bestowing their blessings and support.
Manoj Kumar
iv
ABSTRACT
The hot corrosion behavior of the Ni based superalloy GTM-SU-718 in different molten
environments has been studied by electrochemical impedance spectroscopy at 900 C. The
electrochemical impedance spectra in molten Na2SO4 consisted of a depressed semicircle at high
frequency and a linear plot at low frequency indicating a diffusion controlled reaction. Whereas,
the impedance spectra in molten NaCl consists of only depressed semicircle. In case of
moltenV2O5, the impedance spectrum was neither a perfect semicircle nor a depressed
semicircle. Impedance spectroscopy for different salt mixtures, binary and ternary system, has
also been carried out. Equivalent circuits representing the corrosion of the alloy in all the
corrosive environments are proposed to fit the impedance spectra.
v
CONTENTS Page No.
Approval sheet i
Certificate ii
Declaration iii
Acknowledgement iv
Abstract v
Contents vi
List of figures viii
List of tables xi
CHAPTER 1 INTRODUCTION
1.1 Definition of corrosion and cause of corrosion of

Metals and alloys 1
1.2 Hot Corrosion 2
1.3 Cost of corrosion 4
1.4 Review of literature on hot corrosion behavior of Nickel

based superalloys 5
1.5 Need of the present study 10
1.6 Objectives of the present study 10
Chapter 2 MATERIALS AND METHODS
2.1 Preparation of GTM-SU-718 alloy specimen s 11
2.2 Materials and chemicals used 11
2.3 Furnace used in the present study 12
vi
2.4 Electrochemical impedance spectroscopy (EIS) 13
2.5 X-Ray Diffractometry (XRD) studies 15
2.6 Scanning Electron Microscopic (SEM) studies 15
CHAPTER 3 RESULTS AND DISCUSSION
3.1 Analysis of the results of corrosion behavior of the
alloy GTM-SU-718 in molten sodium sulphate 16
alloy GTM-SU-718 in molten sodium chloride 20
alloy GTM-SU-718 in molten 95% Sodium Sulfate +
5% Sodium Chloride 23
10% Sodium Chloride 26
alloy GTM-SU-718 in molten vanadium pentoxide 29
5% vanadium pentoxide 33
alloy GTM-SU-718 in molten 90% Sodium Sulfate
vii
+ 5% Sodium Chloride + 5% Vanadium Oxide 36
3.8 Comparison of Rct and Cdl data in different
Environments 38
3.9 Conclusions 39
References 41
viii
List of Figures Page No
Fig. 2.1 Design of the cell used for electrochemical impedance studies 14
Fig.3.1. Nyquist plot for the alloy GTM-SU-718 immersed in molten
Na2SO4 16
Fig.3.2. Bode plots for the alloy GTM-SU-718 immersed in molten
Na2SO4 17
Fig.3.3. SEM image of polished alloy GTM-SU-718 18
Fig.3.4. SEM image of corroded alloy GTM-SU-718 in molten
Na2SO4 18
Fig.3.5. XRD pattern of corroded alloy GTM-SU-718 in molten
Na2SO4 19
Fig.3.6. Nyquist plot for the alloy GTM-SU-718 immersed in
molten NaCl 20
Fig.3.7. Bode plots for the alloy GTM-SU-718 immersed in
molten NaCl 21
sodium chloride 22
Fig.3.9. XRD pattern of the corroded alloy GTM-SU-718 in molten
sodium chloride 22
95% Na2SO4+ 5% NaCl 24
95% Na2SO4+ 5% NaCl 24
95% Na2SO4+ 5% NaCl 25
95% Na2SO4+ 5% NaCl 26
90% Na2SO4+ 10% NaCl 27
90% Na2SO4+ 10% NaCl 27
ix
90% Na2SO4 and 10 % NaCl 28
V2O5 30
V2O5 30
Fig.3.19. SEM image of corroded alloy GTM-SU-718 in molten V2O5 31
Fig.3.20. XRD pattern of the surface of the corroded alloy GTM-SU-718 in
molten V2O5 32
(95% Na2SO4+ 5 % V2O5) 33
(95% Na2SO4+ 5 % V2O5) 34
95 % Na2SO4 + 5% V2O5 34
(95 % Na2SO4 + 5% V2O5) 35
(90% Na2SO4+ 5% NaCl+ 5% V2O5) 36
(90% Na2SO4+ 5% NaCl+ 5% V2O5) 37
Fig.3.27 SEM image of corroded alloy GTM-SU-718 in molten
90 % Na2SO4+ 5% NaCl + 5% V2O5 37
Fig.3.28 XRD pattern of the corroded alloy GTM-SU-718 in molten
(90 % Na2SO4+ 5% NaCl + 5% V2O5) 38
x
List of Tables
Table 2.1 The chemical composition of Alloy GTM-SU-718 12
Table 2.2 Different corrosive environments 12
Table 3.1 Comparison of impedance parameter

in different corrosive environment 39
xi
Chapter - 1
Introduction
1.1. Definition of corrosion and cause of corrosion of metals and

alloys
ial because of reaction
with its environment [1].
to its interaction with its environment [2]. Generally, all environments are corrosive in nature to
different extent. These may include moisture, air, salt, different chemicals etc. The deleterious
effect of corrosion has made it mandatory to study and find new methods to increase the
resistance towards corrosion.
To better understand the cause of corrosion, it is very essential to understand the

thermodynamics involved in it. It helps in understanding whether a particular reaction will take
reversible potential. According to the relation, all processes that occur spontaneously in nature
have Gibbs free energy change negative [2].The negative change implies that the products are
more stable than reactants.
-nFE (1)
Where,
n=number of electrons transferred in the reaction
E=Potential difference across the interface
The equation (1) relates the amount of energy required to move a charge of nF through a
potential difference of E. If a reaction is accompanied by negative free energy change, that
reaction is said to occur spontaneously. Essentially this is the cause of corrosion of any metal or
alloy as corrosion involves a chemical reaction (oxidation).
1.2 Hot corrosion
tempe
phenomenon of hot corrosion is the accelerated oxidation in a high temperature gaseous
environment of a material whose surface is coated by a thin fused salt film [4]. Hot corrosion
usually takes place in furnaces, gas turbines, diesel engines, and power plants etc, which come
into contact with hot gases containing certain contaminants. For example, the fuel may contain
vanadium compounds or sulfates which are highly corrosive.
In the present study, gas turbine materials are taken into consideration. Efficiency is the
prime requirement of any machine and it is true for gas turbines used in marine engines. The
turbines operate in highly aggressive conditions, which include high temperature and highly
corrosive surrounding environment consisting of sulfur, vanadium and sodium from fuel and
various halides present in sea environment. It is well known and accepted that corrosion rate
significantly increases at high temperature [5].In gas turbines, used in marine gas engines, sulfur
from the fuel reacts with sodium chloride from the air and forms sodium sulfate. The sulfate then
deposits on the hot sections like the rotor blades, which in turn results in accelerated oxidation
attack.
According to Guraappa et al. [5], the efficiency does not only depend on design but also
on selection of appropriate materials. The requirements include strength of material at high
temperature and its resistance to corrosion at high temperature. The mechanical properties are
also very much affected during service life due to hot corrosion attack, which ultimately leads to
the reduction in lifetime of turbines. Therefore, while selecting a material for turbines, one
should think of strength and corrosion resistance of the material at the required high temperature
of its use.
The factors which affect hot corrosion are [6] as follows
(1) Temperature (2) Alloy composition (3) Thickness of the deposit (4) Severity of environment
(5) Composition of deposits
Hot corrosion is categorized into two parts [4]
1.2.1 Type I hot corrosion

The High Temperature Hot Corrosion (HTHC) is observed at above the melting temperature of
pure sodium sulfate (884 ), where the condensed salt film is clearly liquid [4].HTHC is
observed mainly within the temperature range of 850-950 [7]. Condensation of the fused salt
initiates the corrosion process. The most common attacking salt in HTHC is Na2SO4 because of
its high thermodynamic stability. The common source of sodium is the sea environment because
sea salts contain NaCl and Na2SO4. Other sources include atmospheric pollutants and the fuels
used. There is hardly any metallic component which when coated with Na2SO4 does not form
sulfides. The sulfide penetrates through the protective oxide film and causes sulfidation in the
alloy [7].
The rate of attack is accelerated when Na2SO4 reacts with impurities like chloride,
vanadium, phosphorous, lead etc. This acceleration may be due to the formation of mixtures
having low melting temperature. For example, melting point of Na2SO4 (884 ) can be reduced
to 620 by mixing it with NaCl because it forms eutectic mixture
This means that the precipitation of the oxide particles

within the salt film could cause continuous dissolution of the oxide at the oxide/salt interface.
1.2.2 Type II hot corrosion
It is also known as Low Temperature Hot Corrosion (LTHC), and is observed in the temperature
range of 650-800 [7]. LTHC occurs below the 884 melting temperature of pure Na2SO4
[4].Usually this type of hot corrosion results in microstructure exhibiting pitting attack and very
less diffusion of sulfides unlike in HTHC. The localized nature of attack may be due to salt
entrapment in crevices.
1.2.2 Mechanism of hot corrosion
There are many different mechanisms proposed for the accelerated rate of hot corrosion. Two
most common mechanisms include:
(i) Sulfidation mechanism
(ii) Salt fluxing mechanism
J. A. Goebel et al. [8], suggested that the alloys containing Mo, V, W may result in self
sustaining oxidation. The resulted accelerated oxidation may be due to the fact that, the solution
of the oxides of these elements (Mo, V, W) decreases the oxide ion activity of the molten salt
when mixed with Na2SO4.The reduction in oxide ion activity results in the formation of melts
which act as acidic fluxes for the oxide scales. They also suggested that the diffusion of sulphate
from Na2SO4 into the alloy results in basic fluxing and concluded that the formation of sulphides
is a sufficient parameter to cause high rate of oxidation during basic fluxing.
N. Eliaz [7], discussed the effect of vanadium on high temperature hot corrosion (HTHC)
and concluded that accelerated dissolution of protective Cr2O3 and Al2O3 scales occurs because
V2O5 is a strong acidic oxide.
J. A. Goebel et al. [8], conducted experiments on pure nickel in Na2SO4 environment and
suggested that the reaction was not self sustaining because of the fact that the activity of oxide
ions required for reaction with NiO is developed only at the beginning of oxidation.
1.3 Cost of corrosion

According to the latest report by Federation of Indian Chambers of Commerce and Industry
(FICCI) and National Association for Corrosion Engineers (NACE), corrosion costs 4.2 % of
. These expenditures may include cost of corrosion of bridges, oil, gas pipe lines,
automobiles etc. The losses can be direct or indirect. Direct losses may include failure of the
component, use of inhibitors etc. Indirect losses may be complete shutdown of industry, severe
damage of equipments etc.
1.4 Review of literature on hot corrosion behavior of nickel based superalloys

Naing-Naing Aung et al. [3] carried out their work on nickel based superalloys in the
presence of synthetic flue gas and synthetic coal ash at high temperature. The surface
examination revealed that the alloy has undergone pitting attack and there were three different
layers from the top of the alloy, namely, the continuous Cr2O3 layer, the layer containing Ni-Al
phase, Ni-Ti intermetallics. According to them, formation of Cr2O3 sets the favorable condition
for hot corrosion diffusion of sulfur and oxygen was the major reason behind corrosion. They
finally concluded that the alloy suffered hot corrosion with deep corrosion effected zone (> 50
m) after 123 hours.
Gurrappa et al. [5] performed experiments on nickel based superalloys and suggested that
all superalloys are highly susceptible to hot corrosion. Type I (900 ) hot corrosion is far more
severe than type II (700 ) hot corrosion. Corrosion products consist of sulfides and oxides of
nickel and alloying elements of superalloys like Co, Cr, W, Ta etc. They concluded that the
presence of tungsten in superalloy, to enhance the high temperature strength, forms acidic
tungsten oxide (WO3) due to which fluxing of protective oxide scales such as alumina and
chromium oxide takes place very easily. It was concluded that the hot corrosion of superalloy is
an electrochemical process.
I. Gurrappa, [6] has investigated high temperature corrosion of nickel based superalloys
in Na2SO4 and NaCl environments at 900 and concluded that for CM 247 LC alloy corrosion
rate is negligible in pure sodium sulfate and appreciable in chloride containing environment.
Corrosion rate was proportional to temperature in both the environments. The corrosion rate was
highly dependent on the amount of NaCl mixed with Na2SO4, He finally suggested that hot
corrosion of CM 247 LC alloy is electrochemical in nature.
Goebel et al. [8] carried out experiments on Na2SO4 induced corrosion and concluded
that oxidation occurs as a result of formation of liquid flux based on Na2So4 which is responsible
for dissolving protective oxide scales. They suggested that the sulphate ion activity of Na2SO4 is
responsible for oxidation of alloy elements like Mo, W, and V. The important conclusion was
that chromium is effective in retarding oxidation since CrO3 forms protective film.
Zeng et al. [9] systematically carried out experiments on M38G superalloy at 900 and
concluded that corrosion of superalloy consisted of two capacitive loops in relation to the
formation of protective scale. Corrosion of the alloy in the initial stage was controlled by the
diffusion of oxidant in the bulk metal. Corrosion of the alloy was controlled by the ionic
diffusion into the scale.
Nishikata et al. [10] conducted electrochemical monitoring of nickel based superalloys in

molten salts and concluded that polarization resistance method is useful for assessing the
corrosion resistance of alloys in molten salts. They found that corrosion resistance of nickel was
improved by alloying with chromium or molybdenum. The corrosion rate in molten chloride is
controlled by the partial cathodic reduction of impurities in the melts.
C. Cuevas-Arteaga et al. [11] have carried out investigation on alloy 800 Fe- 32%, Ni-
21%, Cr-0.3%, Al-0.4 %, Ti-0.04%, C-rest) in the presence of sulfates and vandate mixtures at
700 and 900 and suggested that the alloy suffered from localized corrosion when exposed
to high sulfate content and more generalized corrosion when exposed to high vandate content
and the rate of attack was proportional to temperature.
Cecilia Cuevas-Arteaga [12] performed experiment on alloy AISI-309 (0.2 C, 0.75 Si, 2.0
Mn, 23.0 Cr, 13.5 Ni, Bal Fe) exposed to a mixture of sodium sulfate and vanadium oxide at 700
by using polarization curves and weight-loss methods. He concluded that the alloy has
undergone three stages of corrosion namely uniform corrosion, the rupture and recovery of
passive film and intergranular corrosion. He also suggested that during first stage, chromium and
iron oxide layers were dissolved swiftly. A layer of nickel oxide under chromium oxide was
observed in the second stage. In the third stage sulfidation was observed which resulted in the
formation of nickel and iron sulfides.
C.L. Zeng et al. [13] performed Electrochemical Impedance Spectroscopy (EIS) studies
on B-1900 alloy at 800 in the presence of solid Na2SO4 and molten 25 wt% NaCl-75 wt%
Na2SO4 film. They concluded that the corrosion behavior in both the environments are similar
i.e. they are composed of a single capacitive loop. The only difference was that the rate of
corrosion was faster in molten environment as compared to solid environment. They have
indicated that EIS is a helpful technique to monitor solid/liquid induced corrosion.
C. Cuevas-Arteage et al. [14] carried out experiments on HK-40m alloy by polarization

and weight-loss methods with the environment of 80 mol% V2O5-20 mol% Na2SO4 at different
temperatures. Higher rate of corrosion was observed with polarization method as compared to
weight loss method. The interpretation for the observed difference is that V2O5 behaves as a
semiconductor oxide and it may not be purely electrochemical process. They concluded that the
polarization technique is important and powerful tool for measuring corrosion rate when the
charge transfer is controlling step and may produce errors when salt behaves as semiconductor
compound.
C. Cuevas-Arteaga et al. [15] have carried out experiments with the alloy 800 (Fe- 32%,
Ni-21%, Cr-0.3%, Al-0.4 %, Ti-0.04%, C-rest) at 700 and 900 with Na2SO4 and V2O5
mixtures by using polarization methods and weight-loss methods. They noted that at 700 the
corrosion rate was higher with weight loss method as compared with the polarization method and
explained that at 700 diffusion of species is controlling step and not the charge transfer. At
900 corrosion process was under mixed control i.e. charge transfer and diffusion. Important
conclusion is that electrochemical methods may induce errors when molten salt changes from an
ionic to electronic conductor.
G. Gao et al. [16] successfully performed experiments on Ni-1% Co alloy using

electrochemical impedance methods in the environments namely Na2SO4 or a mixture of
Na2SO4-10% NaCl. They concluded that propagation of corrosion in molten salt environment
can be studied and evaluated by electrochemical methods.
Naing-Naing Aung et al. [17] performed experiments on hot corrosion of Inconel 740
alloy to study the effect of SO2 in flue gas on coal ash thin film corrosion. They mentioned that
the rate of corrosion was similar with or without the presence of coal ash in the initiation stage of
corrosion. They also mentioned that the metal loss was doubled with an increase in SO2 content
by 1% when the study was carried out for an exposure period of 123 hours.
E. Mohammad Zohrani et al. [18] conducted experiments on Inconel 625 superalloy in

PbSO4-Pb3O4-PbCl2-Fe2O3-ZnO environment at the temperatures of 600 700 and 800
.They stated that an anodic film was formed on the surface of the alloy which greatly enhanced
the rate of corrosion of alloy. They mentioned general surface corrosion, intergranular corrosion
network of distributed pores, and formation of voids as the different modes of attack. The
Ni(Cr2O4) and Cr2O3 are protective oxide layers at ambient temperature but get disappeared
when exposed to salt medium at 600 ,700 and 800 . The result infers that corrosion
resistance of the alloy is less in molten salt environment.
C. Cuevas-Arteaga [19] conducted experiment on HK-40m alloy in high sulfate (80

mol% Na2SO4-20 mol% V2O5) and high vandate (80 mol% V2O5-20 mol% Na2SO4)
environments at 700 for 24 hours. He concluded that high vanadium environment dissolves
chromium oxide layer faster. The specimen exposed to high vanadium content suffered from
intergranular attack whereas the specimen exposed to high sulphate content had a mixed
corrosion process. He explained it by stating that intergranular corrosion in high vandate
environment was due to the fact that the mixture was very acidic, oxidizing and extremely
corrosive.
Tie-Bang Zhang et al. [20] carried out experiment on Ni-20 Cr-18 W superalloy in 75%
Na2SO4-25 % NaCl at 700 and 800 .They found that the alloy has undergone severe hot
corrosion and corrosion rate is higher at 800 as compared to 700 .They detected
Ni3S2,NiO,Cr2O3 as corrosion products at both the temperatures and NiCrO2 at 800 only. They
concluded that the microstructures of the corroded alloy consist of two layers, the outer layer
with coarse grain consisting of many pores and a compact inner layer with fine grains.
G. A. El-Awadi et al. [21] have performed experiments on Inconel 617 and Inconel 738
in NaCl and Na2SO4 environment at different exposure times of up to 100 hours. They observed
better oxidation resistance at 700 than at 800 and 900 . Internal oxidation was observed
at 900 when time of exposure was increased. Formation of Cr2O3, NiCr2O4 provided
resistance to corrosion at the exposure time of 5 hours and 10 hours. They concluded that
corrosion process is endothermic.
J. Brrennemaan et al. [22] conducted experiments to get oxidation behavior of GTD 111
Ni based superalloy at 900 C in an environment of electric air furnace for 1 hour to 452 hours.
They clarified that Al2O3 layer was discontinuous. Cr2O3 layer provided high protection against
oxidation. Nitrogen penetrates into oxide scales because of cracking and spalling of outer oxide
scales.
Chaur-Jeng Wnag and Jiann-Sheng Lin [23] performed experiment on MAR 247
superalloy with Na2SO4 coating at 1000 K, 1100 K and 1200 K for 4 hour-120 hours immersion
periods. They observed that presence of Na2SO4 accelerated oxidation of superalloy at all the
temperatures. Internal grain boundary attack was observed when the specimen was oxidized at
1200 K.
TZ. TZVETKOFF et al. [24] reviewed corrosion of nickel and its alloys in molten salt
electrolytes. They observed that Ni is one of the metals most resistant to corrosion. Higher oxide
of spinel and haematite, NiO were most common corrosion layers formed on nickel. Passivation
was common for Ni alloys in halide melts containing oxygen. They concluded that passive film
growth and dissolution were advanced in nitrate melts only.
C. S. Ni et al. [25] carried out EIS studies to understand the initial stage of corrosion of
310S alloy with thin film of molten (0.62 Li, 0.38 K)2 CO3 at 650 C in air. They observed that
there was a rapid decrease in the thickness of molten carbonate. Higher the thickness of the
molten salt, severe was the impact of lithiation process. When limited amount of slats are
present, diffusion becomes major.
Yiing Mei Wu and Robert A. Rapp [26] carried out EIS studies on hot corrosion of
preoxidized Ni by a thin-fused Na2SO4 film at 1200 K. They interpreted that EIS is an important
tool to understand reaction steps involved in hot corrosion. Three distinct modes of hot
corrosion, namely, passive, pseudo-passive and active, were observed.
Lu Yang et al. [27] performed experiment on corrosion behavior of Ni, Fe and Cr based
superalloys at 850 C in molten NaCl. They observed that in molten NaCl, corrosion rate is
maximum for Cr based superalloy and was minimum for Fe based superalloys. The corrosion
rate of Ni based superalloy was intermediate. Loss of Cr as alloying element was one of the
major reason of high corrosion rate. They noted down that corrosion layers of Ni based and Fe
based alloys give site for Cr2O3 adherence which reduces Cr diffusion to the surface and hence
inhibits mass transfer.
1.5 Need of the present study
Nickel based superalloys are potential materials to be used in marine gas turbines because
of their good electrical, thermal and corrosion resistance properties. Nevertheless, there are
several reports in the literature, which revealed the corrosion of even nickel based superalloys at
higher temperature. But very less information is found regarding hot corrosion behavior of
GTM-SU-718.Only gravimetric studies, SEM and XRD studies have been reported in the
literarature. Electrochemical impedance studies were not reported. In the present study an
attempt has been made to investigate the hot corrosion behavior of the stated alloy in different
corrosive environments by electrochemical impedance studies.
1.6 Objectives of the present study
1. To study the hot corrosion behavior of GTM-SU-718 superalloy in different molten salts
by electrochemical impedance spectroscopy and surface analytical techniques.
2. To develop suitable mechanisms for hot corrosion of the superalloy in different corrosive
environments.
3. To develop comprehensive experimental methodology to evaluate the hot corrosion of
superalloys.
Chapter 2
Materials and Methods
2.1 Preparation of GTM-SU-718 alloy specimen
Specimens of dimensions 2.0 X 1.0 X 0.5 cm were prepared using electric discharge
machining (EDM). The surface of these specimens was ground to 600 m finish. To suspend the
specimen in the crucible, with the help of platinum wire, a hole was drilled using carbide tipped
drill bit. The surface of the specimen was washed with distilled water, degreased with acetone
and dried by blowing hot air for 5 minutes. The specimens were then used in the study of
electrochemical impedance studies, SEM studies and XRD studies in different molten salt
environments.
For the EIS studies at 900 , 1 cm2 area of the sample was exposed to different
environments and was kept in muffle furnace. For EIS studies, electrochemical workstation,
Parstat 4000, was used. To give electrical connections from the alloy to the terminals in
workstation, platinum wire of thickness 0.5 mm was used. Platinum wire was used as it is inert
and can withstand the temperature of 900 inside the furnace. Outside the furnace the platinum
wires were connected to copper wires which were finally connected to the terminals of the
electrochemical workstation. After the completion of the experiment, the specimens were taken
out from the furnace and allowed to cool at room temperature. After the specimens attained room
temperature, they were washed with distilled water.
The corroded alloy sample was then taken for X-Ray Diffractometry (XRD), Scanning
Electron Microscopy (SEM), to analyze the corrosion products and the surface morphological
properties respectively.
2.2 Materials and chemicals used

The material used in the present study is GTM-SU-718.A few samples of alloy GTM-SU-718
were procured from the Department of Mechanical Engineering of NIT Warangal, which
procured the material from MIshra DHAtu Nigam Limited (MIDHANI), Hyderabad. All the
chemicals used in the present study were of Analytical Reagent (A.R) grade.
The composition of the selected superalloy for the present investigation is presented in table 2.1.
Table 2.1 The chemical composition of Alloy GTM-SU-718
Alloy Ni Cr Fe Nb Mo Ti Co
Weight % 54 18 18 5 3 1 < 0.05
Seven different corrosive environments were prepared using different weight percentages of
chemicals and are stated as below:
Table 2.2 Different corrosive environments
S.No. Corrosive Environment

Molten Na2SO4
1.
2. Molten NaCl
3. Molten(95% Na2SO4+ 5% NaCl)
4. Molten(90%Na2SO4+ 10% NaCl)
5. Molten (95% Na2SO4+ 5% V2O5)
6. Molten (90% Na2SO4+5% NaCl+5% V2O5)
7. Molten V2O5
2.3 Furnace used in the present study

Generally, there are four types of furnaces used in the laboratories:
1) Muffle furnace
2) Tube furnace
3) Ashing furnace
4) Melting furnace
In the present study muffle furnace with a temperature range of 1600 C + 5 C was used. The
furnace is based on heating by electrical resistance.
2.4 Electrochemical impedance spectroscopy (EIS)
For EIS studies, two electrode assembly was used. The alloy specimen of size 2.0 cm X
1.0 cm X 0.5 cm was cut by wire electric discharge machining (EDM) and was ground to a
surface finish of 600 m by using silicon carbide paper. A hole was drilled in the specimen to
give electrical connection. A platinum wire was used to connect the specimen inside the furnace
and a copper wire was connected to the platinum wire outside the furnace. The copper wire was
connected to the terminals of the electrochemical workstation. The same alloy was used as the
reference electrode in the impedance studies. Similar studies using the same alloy as working
electrode and reference electrode were reported in the literature (3, 9, 11, and 13).It may be noted
that the electrode is not polarized during the impedance studies. The EIS studies were carried out
by using electrochemical workstation, model PARSTAT 4000 and the experimental data were
analyzed by using the software VersaStudio.
The alloy specimen was placed in an alumina crucible and was filled with desired
chemical/chemical mixtures of 50 grams by weight. The furnace was allowed to attain a
temperature of 900 . Impedance plots were recorded after 60 minutes of immersion of the
electrodes in the molten electrolyte (corrosion environment) at 900 +5
+ 5 mV. Nyquist and bode plots provided valuable information

regarding the corrosion resistance behavior of the alloy sample which will be discussed in
chapter 3.
The same procedure was repeated for each corrosive environment and the experimental
data were recorded and discussed later on under discussion part of this thesis.
Design of the cell used in the electrochemical impedance studies
A design of the cell for electrochemical impedance studies of super alloys in molten
electrolytes has been made, which is shown in fig. 2.1. The design consists of an alumina
crucible which can sustain a temperature of around 1500 . This alumina crucible is to be filled
with desired electrolyte. The samples were suspended in to this crucible using platinum wire
(used because of high temperature requirement). To give stability to specimen, samples were
inserted in to a cylinder, both sides open, and were filled with high temperature ceramic paste.
Fig. 2.1 Design of the cell used for electrochemical impedance studies
2.5 X-Ray Diffractometry (XRD) studies
The corrosion products formed during corrosion on the surface of alloy have been
analyzed by powder XRD technique (Make: PANalytical, Model-
HighScore plus software with JCPDS-2013 database.
The corroded sample was washed with flowing water so that the salt deposits were removed. It
was again cleaned with ethanol and then dried in hot air. The sample was scanned between 15
and115
2.6 Scanning Electron Microscopic (SEM) studies
The surface morphology of the corroded sample was examined by Scanning Electron
Microscope (Make: TESCAN, Model: VEGA3LMV). The SEM images were recorded at a
magnification of 3000X for all the corrosive environments.
CHAPTER 3
Result and Discussion
3.1 Analysis of the results of corrosion behavior of the alloy GTM-
SU-718 in molten sodium sulphate
Results of EIS Studies

Fig.3.1 shows the Nyquist plot for the alloy, GTM-SU-718, immersed in molten Na2SO4
(Temp: 900 oC, immersion period 1 hr).This plot is characterized by a depressed semicircle in
the high frequency region and a linear plot in the mid and low frequency region, which is
characteristic of Warburg behavior.
Fig.3.1. Nyquist plot for the alloy GTM-SU-718 immersed in molten Na2SO4
(Temp: 900oC, immersion period 1 hr).
Fig.3.2 presents the total impedance vs. frequency Bode plot and the phase angle vs.
frequency Bode plot. This plot consist of three segments namely, the electrolyte resistance in the
high frequency region, charge transfer resistance in the mid frequency region and diffusion
impedance in the low frequency region. It may be noted that the phase angle maximum is only
about 7 degrees as is evident in the phase angle vs. frequency Bode plot. Thus both the Nyquist
plot and the Bode plot show some characteristic features of the corrosion behavior of the alloy
GTM-SU-718 in molten Na2SO4 environment at a temp of 900 oC at an immersion period of 1
hour. The values of charge transfer resistance (Rct) and double layer capacitance (Cdl) at the
interface between the alloy and molten Na2SO4 are evaluated by fitting the experimental data
with the appropriate equivalent circuit as shown above and the data are presented in table 3.1
later in this report.
Fig.3.2. Bode plots for the alloy GTM-SU-718 immersed in molten Na2SO4
Similar equivalent circuit model was used by C. L. Zeng and J. LI [9] in their studies on
M38G superalloy in (0.9 Na, 0.1 K) SO4 environment at 900 oC .The authors interpreted that the
protective scale may be considered as an oxide capacitor. The model represented initial diffusion
controlled reaction.
G. Gao et al. [16] conducted EIS studies on Ni-1% Co alloy in Na2SO4 melt at 900 oC.
They showed that Nyquist plot consists of a concentration of points in a small region, which
2
and charge transfer resistance (Rct) of less
2
.
It may be noted that in case of the alloy GTM-SU-718 in molten Na2SO4 at 900 oC
(present study) Rct 2
is obtained. This result infers that the alloy GTM-SU-718
has more corrosion resistance than Ni-1% Co.
Naing Naing Aung and Xingbo Liu [3] carried out experiments on Ni based superalloys
(Ni-49.45%, Cr-24.67%, Fe-0.62% ,Co-19.98%, Mo-0.5% ,Nb-1.47% ,Al-1.23% ,Mn-0.3% ,Ti-
1.23% ,Si-0.29%) in the presence of sulfur dioxide and synthetic coal gas. From the impedance
spectra they interpreted that the impedance spectra were similar during initiation and propagation
stages of corrosion. The impedance spectra consisted of depressed semicircle at high frequency
and a line at low frequency. They concluded that overall corrosion could be controlled by the
diffusion of oxidants in the melts.
3.1.2 Results of SEM
Fig.3.3 and 3.4 show the scanning electron micrographs of the alloy before and after
immersion in molten sodium sulfate at 3000X magnification. The scanning electron micrographs
of the alloy specimens immersed in molten sodium sulfate for one hour clearly establish that the
alloy has undergone corrosion. The corrosion product is seen on the alloy surface.
Fig.3.3. SEM image of polished alloy GTM-SU-718 at 3000X magnification.
Fig.3.4. SEM image of corroded alloy GTM-SU-718 in molten Na2SO4 at 3000X magnification.
Naing Naing Aung and Xingbo Liu [3] carried out experiments on Ni based superalloys
(Ni-49.45%, Cr-24.67%, Fe- 0.62% ,Co-19.98% ,Mo-0.5% ,Nb-1.47% ,Al-1.23%, Mn-0.3% ,Ti-
1.23% ,Si-0.29%) in the presence of sulfur dioxide and synthetic coal gas. SEM revealed that the
alloy has undergone localized pitting attack. There were three different layers. They suggested
that favorable condition for initiation of hot corrosion was formation of Cr2O3.After some
exposure time pitting propagated internally along the grain boundary.
3.1.3 Results of XRD
The XRD pattern for the alloy GTM-SU-718 in molten Na2SO4 is shown in Fig.3.5. It is
seen that there is presence of NiFe2O4 601).
Fig.3.5. XRD pattern of corroded alloy GTM-SU-718 in molten Na2SO4

(Temp: 900 oC, immersion period 1 hr).
Mechanism of corrosion
Robert A. Rapp [4] suggested that sulfidation occurs when the metal is in contact with
Na2SO4 and when a pore or crack occurs in the protective oxide film. The protective oxide
continues to dissolve at the oxide/salt interface. They suggested a criterion that the gradient in
the solubility of the protective oxide in the salt film is negative at the oxide/salt interface.
J. A. Goebel et al. [8] explained that the alloys which contain Mo, W, or V result in self
sustaining oxidation because oxides of these elements with Na2SO4 decrease the oxide ion
activity of the molten salts which produce melts that are acidic fluxes to oxide scales.
In the present case the oxide film consisting of NiFe2O4 interacts with SO42- which
reaches the surface of the alloy through diffusion. Thus, there are two interfaces, namely 1) the
superalloy/oxide interface and 2) the oxide film /Na2SO4 interface. The XRD pattern of the alloy
surface after immersion in molten Na2SO4 reveals the presence of NiFe2O4, which means a
combination of NiO and Fe2O3. The oxide is not at all protective and hence the superalloy
continues to undergo corrosion in molten Na2SO4.Thus, the corrosion resistance of the alloy is
less as evident by a low charge transfer resistance (Rct 2
. SEM also reveals the
corrosion product on the alloy surface.

SU-718 in molten sodium chloride
3.2.1 Results of EIS studies
Fig.3.6 shows the Nyquist plot for the alloy, GTM-SU-718, immersed in molten NaCl
(Temp: 900 oC, immersion period 1 hr). As it can be observed that the Nyquist plot for NaCl
consists of only depressed semicircle without linear segment. The nature of the Nyquist plot is
different from that observed in the case of molten Na2SO4.This Nyquist plot is fitting well with
the simple Randles circuit, as shown in the figure below.
Fig.3.6. Nyquist plot for the alloy GTM-SU-718 immersed in molten NaCl
The corresponding Bode plots are shown in Figure 3.7.
Fig.3.7. Bode plots for the alloy GTM-SU-718 immersed in molten NaCl
It is seen from the Bode plot that the charge transfer region (mid frequency linear region)
is higher in the case of molten NaCl than in the molten Na2SO4.It may also be noted that the
phase angle maximum is around 32 degrees which is higher than in the case of molten
Na2SO4.The phase angle vs. frequency Bode plot is also characterized with a broader maximum
than in the case of Na2SO4.Thus both the Nyquist and the Bode plots for GTM-SU-718 alloy in
molten NaCl are different from those of Na2SO4.The Rct and the Cdl values are evaluated from
the best fit of the data using the software and listed in table 3.1.
Fig.3.8 shows the scanning electron micrograph of the alloy after immersion in molten
sodium chloride at 3000X magnification. The scanning electron micrograph clearly establishes
that the alloy has undergone corrosion. The corrosion product is seen on the alloy surface.
Fig.3.8. SEM image of corroded alloy GTM-SU-718 in molten sodium chloride
at 3000X magnification.
Fig.3.9 shows the XRD patterns of the corroded alloy specimen in molten sodium
chloride. It is inferred that there is presence of NiCl2
NiCr2O4 o
, 35.279).
Fig.3.9. XRD pattern of the corroded alloy GTM-SU-718 in molten sodium chloride
For an immersion period of 1 hour in NaCl at 900 oC, the XRD pattern shows the
presence of NiCl2, NiO and Cr2O3. Presence of Cr2O3 increases the corrosion resistance of the
alloy as it is protective in nature. It should be noted that the corrosion product formed are only
for an immersion period of one hour. If we increase the immersion period, there is a possibility
of formation of more NiCl2 in place of NiO and Cr2O3. The Rct 2
, which is
2
as in molten Na2SO4.The presence of Cr2O3 may be one of the
reasons of higher Rct value.

SU-718 in molten 95% Sodium Sulfate + 5% Sodium Chloride
3.3.1 Results of impedance studies
Nyquist plot for the alloy GTM-SU-718 immersed in molten 95% Na2SO4+ 5% NaCl
(Temp: 900oC, immersion period 1 hr) is presented in Fig.3.10. It is evident that the nature of
this plot is different from that of molten Na2SO4 (100%) and also different from that of molten
NaCl (100%). Nevertheless, the experimental data fitted well with the equivalent circuit which
fitted the experimental data of molten Na2SO4 (100%).The linear segment in the low frequency
region, indicates Warburg behavior, is clearly seen in this plot.
Fig.3.10. Nyquist plot for the alloy GTM-SU-718 immersed in molten 95% Na2SO4+ 5% NaCl
Fig.3.11. Bode plots for the alloy GTM-SU-718 immersed in molten 95% Na2SO4+ 5% NaCl
The Bode plots for the alloy GTM-SU-718, immersed in molten 95% Na2SO4+ 5% NaCl
(Temp: 900oC, immersion period 1 hr) are shown in Fig.3.11. It can be seen from these plots that
the maximum phase angle is around 29 degrees. It is broader in comparison to Na2SO4 and less
broad in comparison to NaCl. The Rct and Cdl values are calculated from the best fit and
tabulated in table 3.1.
Fig.3.12 represents the SEM image of corroded alloy GTM-SU-718 immersed in molten
95% Na2SO4 and 5% NaCl for the immersion time of one hour. The image clearly indicates that
the alloy has undergone corrosion and the corrosion product is visible on the surface.
Fig.3.12. SEM image of corroded alloy GTM-SU-718 in molten 95% Na2SO4+ 5% NaCl
The XRD pattern for the alloy GTM-SU-718 in molten 95% Na2SO4 and 5% NaCl is
shown below in Fig.3.13.The pattern clearly indicates the presence of FeNi2O4 (peak intensity at
2
NiO4
Fig.3.13. XRD pattern of the corroded alloy GTM-SU-718 in molten 95% Na2SO4+ 5% NaCl
In the present case the XRD pattern of the alloy GTM-SU-718 immersed in molten 95%
Na2SO4+ 5% NaCl at 900 oC, shows the presence of FeNi2O4 and Fe2NiO4.The corrosion
products are quite similar to that of the corrosion products obtained in pure Na2SO4. The Rct
2
which is higher than that in the case of Na2SO4 (Rct =
2
) and much lower than that of pure NaCl (Rct=27.57). This may be because in the
present case there is no Cr2O3 in the surface film.

SU-718 in molten 90% Sodium Sulfate + 10% Sodium Chloride
Nyquist plot for the alloy GTM-SU-718 immersed in molten 90% Na2SO4 + 10% NaCl
(Temp: 900 oC, immersion period 1 hr) is shown in Fig. 3.14. It is clear that the nature of this
plot is also similar to that of the corresponding plot of molten 95% Na2SO4
+ 5% NaCl.
Fig.3.14. Nyquist plot for the alloy GTM-SU-718 immersed in molten 90% Na2SO4+ 10% NaCl
Fig.3.15. Bode plots for the alloy GTM-SU-718 immersed in molten 90% Na2SO4+ 10% NaCl
It can be observed from the Bode plots (Fig.3.15) that the maximum phase angle is
around 35 degrees. It can also be seen that the phase angle vs. frequency plot has a broad
maximum and the total impedance vs. frequency plot is linear in a large mid frequency region,
which corresponds to charge transfer. The Rct and Cdl values are calculated and tabulated in table
3.1.Though there is a resemblance in the nature of both the Nyquist and the Bode plots by
increasing NaCl from 5% to 10 % and simultaneously decreasing Na2SO4 from 95 % to 90 % in
the binary mixture. Nevertheless, the Rct and Cdl values are different from each other in the two
binary compositions.
G. Gao et al. [16] conducted experiment on alloy 800 (Fe- 32%, Ni-21%, Cr-0.3%, Al-
0.4 %, Ti-0.04%, C-rest) in 90% Na2SO4 + 10% NaCl mixtures for an immersion period of 30
minute to 7 hour. They concluded that the Nyquist plot showed diffusion controlled corrosion
reaction which is represented by Warburg.
It may be noted that in case of the alloy GTM-SU-718 in molten 90% Na2SO4 + 10 %
NaCl at 900 oC (present study), Nyquist plot consists of a straight line showing Warburg
resistance which represents a diffusion controlled corrosion.
Fig.3.16 represents the SEM image of corroded alloy GTM-SU-718 immersed in

molten 90% Na2SO4 and 10% NaCl for the immersion time of one hour. The image clearly
indicates that the alloy has undergone corrosion and the corrosion product is visible on the
surface.
Fig.3.16. SEM image of corroded alloy GTM-SU-718 in molten 90% Na2SO4 and 10 % NaCl
I Guruappa [6] performed experiment on CM 247 LC alloy in a mixture of 90 % Na 2SO4

+ 10 % NaCl at 900 oC and concluded that the alloy surface was heavily pitted and the degree of
pitting was proportional to immersion time. The XRD analysis showed the presence of a number
of corrosion products because the alloy consists of many alloying elements. The corrosion
products included Al2O3, Ni7S6, NiO among others.
Same XRD results are predicted as in the case of 95% Na2SO4 + 5% NaCl. The quantity
of NaCl has been increased from 5 wt. % to 10 wt% and all other parameters are constant.
I. Guruappa [6] has explained that the presence of refractory elements like Mo, W, V etc.
react with sulphate ions of Na2SO4 and prevent basic fluxing reaction. He suggested that the
presence of NaCl increases the rate of corrosion. Chlorides can result in breakdown of the
normally protective surface oxide scales. The presence of NaCl results in spalling of protective
oxide scales which is not the case with pure Na2SO4. He explained that Cr, Ti react with chloride
and form chromium chloride, titanium chloride along the Cr2O3, TiO2 grains which ultimately
weakens the mechanical stability of scale. For the present case, mechanism of corrosion is
similar to that of the 95 % Na2SO4 + 5 % NaCl (section 3.3)

SU-718 in molten vanadium pentoxide
The Nyquist and Bode plots for V2O5 are presented in Figs.3.17 and 3.18 respectively.
Nyquist plot pressed semicircle as usually
observed in case of the other four systems reported above. Even the fitting is not good. One
possible explanation could be that V2O5 is not an ionic conductor.
Fig.3.17. Nyquist plot for the alloy GTM-SU-718 immersed in molten V2O5
Fig.3.18. Bode plots for the alloy GTM-SU-718 immersed in molten V2O5
Even the Bode plots also exhibit quite a different nature from the other four systems
reported above. Nevertheless, in order to provide an idea, the Rct and Cdl are calculated and listed
in table 3.1.
C. Cuevas-Arteaga et al. [15], conducted experiments on alloy 800 (Fe- 32%, Ni-21%,
Cr-0.3%, Al-0.4 %, Ti-0.04%, C-rest) at 700 oC and 900 oC in a mixture of Na2SO4 and
V2O5.They suggested that electrochemical methods are useful only when corrosion rate is
controlled by electrochemical reaction but may induce error when salt changes from an ionic to
electronic conductor. They explained that molten salts are ionic conductors but when dissolution
of the metal or metal oxide occurs, the molten salt becomes an electronic conductor.
The above explanation may be one of the reasons of improper Nyquist and Bode plots
because V2O5 is not an ionic conductor.
The scanning electron micrographs obtained for the alloy GTM-SU-718 in molten V2O5 is
shown in Fig.3.19.These images clearly show that the specimen has undergone severe corrosion.
Fig.3.19. SEM image of corroded alloy GTM-SU-718 in molten V2O5

Guruappa et al. [5] performed experiment on GTM-SU-718 superalloy in marine gas

turbine engine conditions at 700 oC and 900 oC. SEM revealed that the surface of the superalloy
has undergone severe corrosion. EDS showed that the products of corrosion contained sulphides
and oxides of Ni and other superalloys. They observed extensive diffusion of sulfur, oxygen,
sodium in corrosion products.
Fig.3.20 shows the XRD analysis of GTM-SU-718 in molten V2O5, immersion time
1hr.The analysis reveals the pres
Fig.3.20. XRD pattern of the surface of the corroded alloy GTM-SU-718 in molten V2O5
(immersion time 1hr).
Mechanism of Corrosion
The authors I. Guruappa et al. [5] suggested that molten V2O5 is acidic in nature and it
causes fluxing of protective oxide scales. This type of acidic fluxing is self sustaining because
there is always presence of molten V2O5. It causes faster degradation.
In the present investigation the alloy GTM-SU-718 does not contain vanadium as
alloying element but the environment is purely of vanadium oxide. The analysis of the XRD
pattern for the alloy GTM-SU-718 immersed in V2O5 at 900 oC for 1 hour reveals NiCl2, V2O5
and FeO as corrosion products. As none of the oxides is protective in nature, the alloy is very
susceptible to corrosion, as is evident from the Rct 2
. As V2O5 is acidic in
nature it causes acidic fluxing of protective oxide scales, which increase the corrosion rate.
Analysis of the results of corrosion behavior of the alloy GTM-
SU-718 in molten 95% Sodium Sulfate + 5% vanadium
pentoxide
The Nyquist plot (Fig.3.21) for the (95% Na2SO4+ 5 % V2O5) is far different from that of
molten Na2SO4 (100%). The linear segment exists in a very large frequency region. Even with
the addition of just 5% V2O5 only, there is so much differnce in the nature of Nyquist plot
exhibiting Warburg behavior associated with diffusion.
Fig.3.21. Nyquist plot for the alloy GTM-SU-718 immersed in molten (95% Na2SO4+ 5 % V2O5)
The phase angle maximum is around 36 degrees in Bode plot (Fig.3.22).The total
impedance vs. frequency plot is also different from that of molten Na2SO4 (100%).The Rct and
Cdl Values are noted in table 3.1 and these values are changed by the addition of just 5% V2O5.
C. Cuevas-Arteaga et al. [11] carried out experiment on alloy 800 (Fe- 32%, Ni-21%, Cr-
0.3%, Al-0.4 %, Ti-0.04%, C-rest) which was exposed to 80% Na2SO4 + 20 % V2O5
environment at 700 oC and 900 oC. A chromium oxide layer was reported on the surface of alloy.
They quoted that under certain high temperature conditions, nickel exposed to different sodium
sulfate-vandate concentration mixtures reacts to form nickel oxides that produces nickel
orthovandate (Ni3(VO4)2) which is a protective compound.
Fig.3.22. Bode plots for the alloy GTM-SU-718 immersed in molten (95% Na2SO4+ 5 % V2O5)
Surface morphology of the corroded sample was obtained with the help of Scanning
Electron Microscope (SEM). Fig.3.23 shows the scanning electron micrograph of the alloy
GTM-SU-718 in molten 95 % Na2SO4 + 5% V2O5 at 3000X magnification. This clearly reveals
the presence of corrosion products.
Fig.3.23. SEM image of corroded alloy GTM-SU-718 in molten 95 % Na2SO4 + 5% V2O5 at

3000X magnification.
C. Cuevas-Arteage et al [11] carried out experiment on alloy 800 (Fe- 32%, Ni-21%, Cr-
0.3%, Al-0.4 %, Ti-0.04%, C-rest) exposed to 80 % Na2SO4 + 20 % V2O5 at 700 oC and 900 oC.
They observed that the presence of more Na2SO4 as compared to V2O5 resulted in pitting
corrosion. A discontinuous layer was present at the interface between the metal surface and
corrosion products, which revealed possible path for corrosion species.
The XRD analysis (Fig.3.24) of the alloy GTM-SU-718 in molten (95 % Na2SO4 + 5%
V2O5 o
) and nickel
undergone corrosion
Fig.3.24. XRD pattern of the corroded alloy GTM-SU-718 in molten (95 % Na2SO4 + 5% V2O5)
(immersion time 1hr).
XRD analysis for the alloy GTM-SU-718 in molten 95% Na2SO4 + 5% V2O5
environment at 900 oC shows the presence of V16O3 and NiO. The obtained Rct value for the
2
which is higher than pure molten V2O5 2
). As
major constituent of the mixture is Na2SO4, the expected behavior of corrosion should be similar
to pure Na2SO4. But, the presence of V2O5 may be causing acidic fluxing of protective oxide
scales. The XRD analysis also shows the similarity in corrosion products with that in case of
pure Na2SO4. Both the environments i.e. present environment and Na2SO4, have NiO layer
which is not at all protective in nature. It should be noted that all results shown are for an
immersion period of 1 hour at 900 oC.
Analysis of the results of corrosion behavior of the alloy GTM-

SU-718 in molten 90% Sodium Sulfate + 5% Sodium Chloride +
5% Vanadium Oxide
The Nyquist and Bode plots of the ternary system (90% Na2SO4+ 5% NaCl+ 5% V2O5) are
shown in Figs.3.25 and 3.26 respectively.These figures indicate that there is role of all the three
salts namely Na2SO4, NaCl and V2O5 on the behavior of the alloy in the ternary system.
Neverthless, the experimental data fitted well with the equivalent circuit, corresponding to that of
molten Na2SO4 (100%) shown in Fig.3.1 above.
Fig.3.25. Nyquist plot for the alloy GTM-SU-718 immersed in molten (90% Na2SO4+
5% NaCl+ 5% V2O5) (Temp: 900oC, immersion period 1 hr).
Fig.3.26. Bode plots for the alloy GTM-SU-718 immersed in molten (90% Na2SO4+ 5% NaCl+
5% V2O5) (Temp: 900 oC, immersion period 1 hr).
The phase angle maximum is around 23 degrees and is shifted to low frequency
region.The corresponding Rct and Cdl values are given in table 3.1.
The scanning electron micrographs obtained for the alloy GTM-SU-718 in molten 90%
Na2SO4+ 5% NaCl+ 5% V2O5 is shown in Fig.3.27.These images clearly show that the
specimen has undergone severe corrosion and the image shows presence of corrosion products.
Fig.3.27 SEM image of corroded alloy GTM-SU-718 in molten 90 % Na2SO4+ 5% NaCl

+ 5% V2O5 (immersion time 1 hr) at 3000X magnification.
To exactly know the constituents of corrosion products, XRD analysis was used. Fig.3.28
shows the XRD pattern of the corroded alloy specimen in molten 90 % Na2SO4+ 5% NaCl + 5%
V2O5.The analysis shows the presence of vanadium Oxide (peaks of inten
Fig.3.28 XRD pattern of the corroded alloy GTM-SU-718 in molten (90 % Na2SO4+ 5% NaCl +
5% V2O5) (immersion time 1hr).
The XRD analysis of GTM-SU-718 in molten 90 % Na2SO4+ 5% NaCl + 5% shows the

presence of nickel oxide, vanadium oxide and chromium oxide layers. The R ct value of this
2
. It can be observed that the Rct value of molten 95% Na2SO4 + 5%
NaCl is 2
which is far higher than the present environment. It means that, addition of
5% of V2O5 has lowered the corrosion resistance of the superalloy. As V2O5 is not an ionic
conductor, the results may not be true because presence of V2O5 deviates the system from its
electrochemical nature.
3.8 Comparison of Rct and Cdl data in different environment

The Rct and Cdl data as obtained from the impedance studies for the alloy GTM-SU-718
in different corrosion environments (Temp: 900 oC, immersion period: 1 hr) are given in table
3.1. It is evident from the results that aggressiveness of the corrosive environments is in the order
Na2SO4 >V2O5 >NaCl, for this particular alloy GTM-SU-718.
In the case of binary systems the aggressive nature of the environment is in the order
(95% Na2SO4+ 5% V2O5) > (95% Na2SO4+ 5% NaCl) > (90%Na2SO4 + 10% NaCl).
Ternary system namely (90% Na2SO4+5% NaCl+5% V2O5) is more corrosive than any of
the binary systems.
Table 3.1 Comparison of impedance parameter in different corrosive environment
Corrosive Environment Temp. Immersion Rct Capacitance

(oC) time (min) ) 2 2
)
Molten Na2SO4 900 60 0.6926 231.9
Molten NaCl 900 60 27.57 2933
Molten(95% Na2SO4+ 5% NaCl) 900 60 14.34 621.8

Molten(90%Na2SO4+ 10% NaCl) 900 60 24.15 670.6
Molten (95% Na2SO4+ 5% V2O5) 900 60 7.573 785.3
Molten (90% Na2SO4+5% 900 60 7.168 815.6

NaCl+5% V2O5)
Molten V2O5 900 60 3.045 3.395
3.9 Conclusions
A study of hot corrosion behavior from the electrochemical impedance spectroscopy, together
with SEM and XRD analysis was performed for the GTM-SU-718 superalloy in different molten
salt environments at 900 C. The results indicated that
The aggressiveness of the corrosive environments is in the order Na2SO4 >V2O5 >NaCl,
for this particular alloy GTM-SU-718.
Aggressiveness for the binary systems is in the order (95% Na2SO4+ 5% V2O5) > (95%
Na2SO4+ 5% NaCl) > (90%Na2SO4 + 10% NaCl).
The ternary system % Na2SO4+5% NaCl+5% V2O5) is more corrosive than any of the
binary systems
Presence of V2O5 may induce errors during electrochemical methods because it is not an
ionic conductor
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GTM-SU-718 in Molten Salt Environments

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GTM-SU-718 in molten salt environments

A thesis submitted in partial fulfillment of

DEPARTMENT OF METALLURGICAL AND MATERIALS

NATIONAL INSTITUTE OF TECHNOLOGY, WARANGAL

Waranagal Manoj Kumar

Date: Reg. No.: MM14128

I express my deep sense of gratitude to Prof. M. K. Mohan, Professor of Metallurgical and

I am very thankful to Prof. B. V. Appa Rao, Professor of Chemistry, National Institute of

List of figures viii

1.1 Definition of corrosion and cause of corrosion of

1.2 Hot Corrosion 2

1.3 Cost of corrosion 4

1.4 Review of literature on hot corrosion behavior of Nickel

1.5 Need of the present study 10

1.6 Objectives of the present study 10

Chapter 2 MATERIALS AND METHODS

2.1 Preparation of GTM-SU-718 alloy specimen s 11

2.2 Materials and chemicals used 11

2.3 Furnace used in the present study 12

2.5 X-Ray Diffractometry (XRD) studies 15

2.6 Scanning Electron Microscopic (SEM) studies 15

CHAPTER 3 RESULTS AND DISCUSSION

3.1 Analysis of the results of corrosion behavior of the

alloy GTM-SU-718 in molten sodium sulphate 16

3.2 Analysis of the results of corrosion behavior of the

alloy GTM-SU-718 in molten sodium chloride 20

3.3 Analysis of the results of corrosion behavior of the

alloy GTM-SU-718 in molten 95% Sodium Sulfate +

3.4 Analysis of the results of corrosion behavior of the

alloy GTM-SU-718 in molten 90% Sodium Sulfate +

10% Sodium Chloride 26

3.5 Analysis of the results of corrosion behavior of the

alloy GTM-SU-718 in molten vanadium pentoxide 29

3.6 Analysis of the results of corrosion behavior of the

alloy GTM-SU-718 in molten 95% Sodium Sulfate +

3.7 Analysis of the results of corrosion behavior of the

alloy GTM-SU-718 in molten 90% Sodium Sulfate

3.8 Comparison of Rct and Cdl data in different

Table 2.1 The chemical composition of Alloy GTM-SU-718 12

Table 2.2 Different corrosive environments 12

Table 3.1 Comparison of impedance parameter

1.1. Definition of corrosion and cause of corrosion of metals and

To better understand the cause of corrosion, it is very essential to understand the

n=number of electrons transferred in the reaction

E=Potential difference across the interface

The factors which affect hot corrosion are [6] as follows

1.2.1 Type I hot corrosion

This means that the precipitation of the oxide particles

1.2.2 Type II hot corrosion

1.2.2 Mechanism of hot corrosion

(i) Sulfidation mechanism

(ii) Salt fluxing mechanism

1.3 Cost of corrosion

1.4 Review of literature on hot corrosion behavior of nickel based superalloys

Nishikata et al. [10] conducted electrochemical monitoring of nickel based superalloys in

C. Cuevas-Arteage et al. [14] carried out experiments on HK-40m alloy by polarization

G. Gao et al. [16] successfully performed experiments on Ni-1% Co alloy using

E. Mohammad Zohrani et al. [18] conducted experiments on Inconel 625 superalloy in