BIRLA INSTITUTE OF TECHNOLOGY AND

SCIENCE PILANI
PRACTICE SCHOOL I

KUDANKULAM NUCLEAR POWER

PROJECT
STUDY PROJECT REPORT
ON
CORROSION OF STAINLESS STEEL IN THE
PRESENCE OF SULPHURIC ACID
SIDDHARTH PANDEY [2013A1PS742P PILANI CAMPUS]
SARVESH SHUKLA []

INDEX
I.
II.
III.
IV.
V.
VI.

Index
Acknowledgement
Introduction
Basics of Corrosion
Behaviour of stainless steel
Sulphuric acid handling system in
Kudankulam Nuclear Power Plant
VII. Proposed suggestions
VIII. Conclusion
IX. Bibliography

ACKNOWLEDGEMENT
We(Siddharth and Sarvesh) would like to take this
opportunity to thank the Senior Staff at Kudankulam
Nuclear Power Project, NPCIL because they have
granted us the chance to learn directly at the
industrial scale by visiting this safe and secure facility.
Secondly, we would like to thank the Mrs. Lakshmi and
Mr. Shashikanth for continuously guiding us, orienting
us with the functionalities, operation and maintenance
of the plant. They also arranged an excellent
orientation program for the students of BITS-PILANI
along with various project opportunities.
This study report on the Corrosion of stainless
steel in the presence of sulphuric acid was allotted to
us by our mentor in Kudankulam nuclear power
project, Mr. Naveen Balla. It is with his insight and
systematic guidance that we have been able to compile
this report for the above stated topic.
Lastly, we would like to show appreciation towards
our institute, Birla Institute of Technology and Science,
Pilani and its Practice School Division for directing us
towards industrial exposure and helping us tackle real
problems in our fields of interest as part of the
Practice School I program. Also, all our work has been
completed under the guidance and supervision of our

Practice School Professor, Dr. Micheal Alphonse,

whose help has been without doubt, irreplaceable in
our experience of the Practice School.

INTRODUCTION
Sulphuric acid is a chemical that is used in various
industrial processes, including ones in Nuclear Power
plants and specifically at Kudankulam Nuclear Power
Project. It is produced from sulphur dioxide, which
may be generated by burning sulphur, it may be a byproduct of a metallurgical smelting process, or it may
be produced by thermal decomposition (regeneration)
of spent acid. The sulphur dioxide is reacted with
oxygen over a catalyst at ~420 to 625C to form
Sulphur trioxide. The latter gas then reacts with water
in the absorbing towers to form sulphuric acid. This
process is exothermic and the acid can reach
temperatures as high as 180 to 200C. Most of this
energy is recovered by a range of means to minimize
energy consumption. Usually the acid is then cooled
from around 100C to close to ambient for storage.
This process is used in many plants for the production
of sulphuric acid, and subsequently its storage.

In a nuclear power plant, handling of this

corrosive sulphuric acid requires well designed piping
systems inclusive of special valves, storage tanks and
mixers. Each of these components requires specific
materials to lengthen their lives to reverse the effects
of their continuous contact with sulphuric acid. The
most commonly used material for this is stainless steel,
a class of steel with slightly varying compositions
manufactured to withstand oxidation or reduction
reactions with ions in the passing reagents. There are
hundreds of grades and sub grades in the stainless
steel family, each designed for a special application.
Chromium is the magic element that transforms iron
into stainless steel. Stainless steel must contain at
least 10.5% chromium to provide adequate resistance
to rusting, and the more chromium the alloy contains,
the better the corrosion resistance becomes. There is,
however an upper limit to the amount of chromium the
iron can hold. Therefore additional alloying elements
are necessary to develop corrosion resistance to
specific medias.
Thus in this report, a study on the usage of
stainless steel is made, along with some other
substitute materials, and their specific compositions
and usage. This report also studies the phenomenon of
corrosion extensively.

BASICS OF CORROSION

 What is corrosion?
Technically, corrosion is the tendency of any
metal to return to its most stable thermodynamic state.
Namely, that is the state with the most negative free
energy of formation. More simply stated, it is a
chemical reaction of the metal with the environment to
form an oxide, carbonate, sulfate, or other stable
compound. In most cases, using a different alloy,
material, proper coating, or impressed current can
prevent corrosion problems. When a metal part fails in
service, it is essential to determine the cause of the
failure so that the replacement part can be
manufactured from the proper alloy to prevent future
failure. Many times a failed part is replaced with the
same alloy.
Corrosion can be broadly classified in two forms:
(1) chemical dissolution of the metal and
(2) galvanic, or electrically driven.
Abrasion, fretting and erosion sometimes are classified
as corrosion mechanisms, but technically they are a
mechanical metal removal process as compared to a
chemical removal process. Chemical reaction may
accompany the mechanical removal process to speed
up the dissolution, but the chemical reaction will fit
into the two basic forms. Some authorities list other
types of corrosion, but the other types generally are
modifications of one of the existing corrosion forms. A
correct alloy choice for one type of corrosion
mechanism may be entirely the wrong choice for
another. Therefore, a proper diagnosis of the failure is

essential to make the correct material choice. Within

these two basic classifications there are five types of
corrosion:
1.General or uniform corrosion
Uniform corrosion occurs over large areas of the metal
surface. This is the most common form of corrosion
with steel and copper. It is the easiest form of
corrosion to measure, and service lifetime is easy to
calculate. This is the only form of corrosion that may
be accurately calculated for lifetime before failure and
the only corrosion mechanism in which increased
section thickness gives longer life. This type of
corrosion is measured by corrosion rate, usually
reported as mpy (mils per year), mm/y (millimeters per
year), ipm (inches per month), or mg/sdm/yr
(milligrams per square decimeter per year). This type
of corrosion may be minimized in the active metals by
painting the surface, and unexpected failures can be
avoided by periodic inspections. Acid cleaning of
metals is an exaggerated example of general corrosion.
Every time a copper or carbon steel surface is acid
cleaned, the metal walls are thinned due to uniform
corrosion. Stainless steel is subject to general
corrosion in many acids and some salt solutions. They
are not subject to general corrosion in water;
therefore, no data is available.
Uniform corrosion can be reduced or even prevented
by proper selection of materials that are resistant to
the corrosive environment. Certain elements make the
alloy more resistant to different media. For example,
high chromium content imparts oxidation resistance.

Therefore, look for high chromium for use with nitric

acid, the higher the better. High chromium is useful for
high temperature oxidation resistance; so, any
stainless steel is better than carbon steel in elevated
temperature applications. High copper content in
stainless steel imparts resistance to sulphuric acid.
High nickel content gives resistance to reducing acids
and produces a tightly adhering oxide film in high
temperature oxidation.

2. Inter granular corrosion

All metals are composed of small grains that are
normally oriented in a random fashion. These grains
are each composed of orderly arrays of atoms with the
same spacing between the atoms in every grain.
Because of the random orientation of the grains, there
is a mismatch between the atomic layers where the
grains meet. This mismatch is called a "grain
boundary." In a typical stainless steel product, there
are about 1,000 grain boundaries that intersect a oneinch (25 mm) line drawn on the surface.
Grain boundaries are regions of high-energy
concentration. Therefore, chemical or metallurgical
reactions usually occur at grain boundaries before they
occur within the grains. The most common reaction is
formation of chromium carbide in the heat-affected
zone (HAZ) during welding. These carbides, formed
along the grain boundaries, are called "sensitization."
Because the carbides require more chromium than is
locally available, the carbon pulls chromium from the

area around the carbon. This leaves a low chromium

grain boundary zone and creates a new low chromium
alloy in that region. Now there is a mismatch in
galvanic potential between the base metal and the
grain boundary; so, galvanic corrosion begins. The
grain boundaries corrode, allowing the central grain
and the chromium carbides to drop out as if particles
of rusty sand.
3. Galvanic corrosion including pitting and
crevice corrosion
Galvanic corrosion occurs whenever two
electrically different metals are connected in a circuit
and are in an electrically conductive solution. This type
of corrosion requires three conditions: two metals that
differ in the galvanic or electromotive series, an
electrically conductive path between the metals and
both metals submerged in a conductive solution.
A variation of galvanic corrosion can occur with
passive film metals. If the alloy loses the passive film in
one spot, then it becomes active in that area. Now the
metal has both passive and active sites on the same
surface. This is the mechanism for pitting and crevice
corrosion. The following table is a list of materials and
their relative position in the galvanic series. This table
allows selection of metal pairs that are galvanically
compatible. In general, when an anode, for example
aluminum, is connected to a cathode or noble metal in
salt water, the anode will corrode and the cathode will
be unaffected.
Metal

Volt

Corresponding alloy

s
Magnesium
1.55
Aluminum
1.33
Zinc
0.76
Iron
0.44
Nickel
0.23
Hydrogen 0.00
Copper
+0.
34
Silver
Gold

+0.
80
+1.
36

Magnesium
Aluminum
Zinc
Steel, Iron, stainless steel(active),
alloy C(active)
Nickel (active), Alloy 600 (active),
Alloy B-2
Brass, copper, Monel, Nickel
(passive), alloy 600 (passive),
stainless steel (passive)
Silver
Gold

However, there is another factor called "area

relationship"; if the anode is very large, such as a
vessel wall, and the cathode is small like a bolt head,
the galvanic action is slight. But, if the anode is small
and the cathode is large, the anode will corrode very
rapidly.
Pitting corrosion is a form of galvanic corrosion
in which the chromium in the passive layer is dissolved
leaving only the corrosion prone iron. The voltage
difference between the passive and active layer on an
austenitic stainless steel is +0.78 volts. Acid chlorides
are the most common cause of pitting in stainless

steel. Chlorides react with chromium to form the very

soluble chromium chloride (CrCl3). Thus, chromium is
removed from the passive layer leaving only the active
iron. As the chromium is dissolved, the electrically
driven chlorides bore into the stainless steel creating a
spherical, smooth wall pit. The residual solution in the
pit is ferric chloride (FeCl3), which is very corrosive to
stainless steel. This is the reason ferric chloride is
used in so many of the corrosion tests for stainless
steel. When molybdenum and/or nitrogen is used as an
alloying element in stainless steel, the pitting
corrosion resistance improves. In an attempt to
quantify the effect of alloying elements, a relationship
of the various elements responsible for corrosion
resistance was developed. The resulting equation is
called the pitting resistance equivalent number, or
PREN.
PREN = %Cr + 3.3(%Mo) + 16(%N)
Three factors influence pitting corrosion: chloride
content, pH, and temperature. In general, the higher
the temperature, higher the chloride content and
lower the pH, greater is the probability of pitting. For
a given chloride content, a higher temperature and
lower pH encourage pitting. Conversely, a lower
temperature and a higher pH reduce pitting. The worst
conditions occur with acid chlorides, and less
dangerous conditions occur with alkaline or high pH
chlorides. Pitting can occur rapidly once it starts.
Crevice corrosion is another form of galvanic
corrosion, which occurs when the corroding metal is in
close contact with anything that makes a tight crevice.

Crevice corrosion is usually the first to occur and is

predictable as to when and where it will take place.
Like pitting, a conductive solution must be present;
and, the presence of chlorides makes the reaction
proceed at a fast rate. Crevice corrosion depends on
the environmental temperature, alloy content and
metallurgical category of the alloy. Also, there is a
relationship between the tightness of the crevice and
the onset time and severity of corrosion. There is a
"critical crevice corrosion temperature" (CCCT) below

which corrosion will not occur.

SOURCE : www.stainless-steel-world.net reports

archive
The greater the difference between the CCCT
and the operating temperature, the greater the
probability that crevice corrosion will occur. This chart
is very useful in determining the effect of temperature
on corrosion by indicating the approximate
temperature at which pitting corrosion begins. The

effect of temperature on pitting corrosion is not as

clear as that for crevice corrosion, but by adding
approximately 100 F (60 C) to the CCCT, the
approximate temperature at which pitting starts can
be determined.
4. Stress corrosion cracking
Stress corrosion cracking (SCC) is one of the
most common and dangerous forms of corrosion.
Usually it is associated with other types of corrosion
that create a stress concentrator that leads to cracking
failure. Nickel containing stainless steel is especially
susceptible to chloride induced SCC. Stress corrosion
cracking (SCC) has three components: alloy
composition, environment and the presence of tensile
stress. All metals are susceptible to stress corrosion
cracking.

The stress component is more subtle. First the stress

must be tensile, and it must exceed the yield strength
of the component. This sounds simple enough, but any
time a component is bent or straightened, or when any
physical exertion is made to place the material into a
fixed shape, the yield strength is exceeded. Next,
matters can be complicated by stress multiplication
factors. If a pit or other sharp notch is present, the
residual stress is multiplied several times resulting in a
stress far in excess of the tensile yield strength. Thus,
SCC usually starts with pitting or crevice corrosion as
a precursor to forming a stress concentrator.
5. Microbiologically induced corrosion (MIC).
In some cases, the metabolic byproducts react
with the environmental solution to create a very

corrosive media. An example is the reaction of chlorine

in water with the manganese dioxide byproduct from
gallionella bacteria on the surface of the stainless
steel. This reaction generates hydrochloric acid, which
causes rapid pitting of many common grades of
stainless steel. One of the most common forms of MIC
is the metabolic byproduct of the sulfur-fixing bacteria
that produces sulfurous or sulfuric acid. These
bacteria cause rapid corrosion of the lower alloy
stainless steels, like Types 304L or 316L, resulting in
through wall crevice corrosion under the bacteria
colonies.

Many times, a metal starts to corrode by one

mechanism, for example pitting corrosion, and then
fails by a second mechanism, stress corrosion
cracking.

BEHAVIOUR OF STAINLESS STEEL

Common stainless steel compositions
Name
304
316
310
Alloy 20
Zeron
100
2507
S-23
S-25
S-SX
ZeCor

Fe
Bal
Bal
Bal
Bal
Bal

Cr
18
17
25
20
25

Ni
8
10
20
28
7

Mo
2
2.5
3.5

N
0.25

Cu
3.5
0.7

W
0.7

Si
0.6

Bal
Bal
Bal
Bal
Bal

25
18
18
18
14

7
18
18
18
15

3.5
1
1
1

0.25
-

2
2
1

0.6
5
5
5
6

Traditionally materials such as acid-brick lined steel

were used for vessels, and ductile irons, such as
Mondi or low alloy austenitic stainless steels such as
316 for piping, within a limited temperature and acid
concentration range. However, the development of
modern, high alloy stainless steels, with improved
resistance to hot concentrated acid has changed the
materials selection options. Table 1 shows the
composition of some stainless steels that are used with
sulphuric acid. 304 and 316 are the common austenitic
grades that are widely used by the chemical and
process industry. Alloy 310 is a high chromium, nickel
austenitic alloy that has superior acid corrosion
resistance compared with 304 and 316. ZERON100

and 2507 are superduplex stainless steels with an

approximate 50/50 austenite/ferrite phase balance.
This structure gives a much higher strength (~2
times) than that of the austenitic alloys and offers the
possibility of wall thickness savings for applications
involving high pressures and/or temperatures.
Saramet, Sandvik SX and ZeCor are all proprietary
austenitic stainless steels containing ~ 5% silicon,
which improves the corrosion resistance in hot strong
acid. Saramet comes in two variants, with slightly
different compositions. ZeCor is leaner in chromium
and nickel than the other two proprietary alloys but it
contains more silicon, an element known to promote
corrosion resistance in hot, strong acid. The naming
and compositions (within 0.05%) differ from country to
country and from company to company but it is the
core composition that matters here, neither the name
nor its origin.

Figure 1 shows the iso-corrosion curves for some

common alloys in sulphuric acid. It can be seen that
the superduplex alloys are superior to 316L. ZERON
100 is also superior to 2507, which is believed to be
due to the deliberate additions of tungsten and copper
to ZERON 100. Alloy 20 is commonly used in sulphuric
acid and from about 50% to 90% acid it is superior to
ZERON 100. However, in strong acid (>90%) ZERON
100 shows a marked increase in corrosion resistance
compared with 2507 and alloy 20.

Figure 2 compares the iso-corrosion curves for

the three proprietary alloys containing silicon and
ZERON 100. There are clearly differences between the
alloys, with the silicon-containing alloys showing
improved corrosion resistance in more dilute acid.
Figure 3 shows the iso-corrosion curves for 304, 310
and Saramet 23 in very strong acid 1,2. It can be seen
that there is an increase in the corrosion resistance of
both 310 and Saramet in the temperature range 180
to 200C. It is assumed that SX and ZeCor show

similar behaviour. This means that these alloys can be

used in the higher temperature parts of acid plants.

Figure 4 shows the corrosion rate of some

stainless steels in strong sulphuric acid at 110C taken
from the manufacturers published data. It can be seen
that the corrosion resistance of Saramet 23 decreases
with increasing acid concentration unlike the other
alloys. At acid concentrations greater than 100% there
is excess sulphur trioxide and the mixture is then
known as oleum. This is known to be more corrosive to
alloys like Saramet than to ZERON 100 and alloy 310.

Although there is no publicly available data on

310 stainless in very strong acid, there is a single data
point. At an acid concentration of 99% and a
temperature of 110C, the corrosion rate of 310 was
0.1mm/y1. This shows the improved resistance of
ZERON 100 over 310 stainless at this temperature
(Figure 4). ZERON 100 also has similar corrosion
resistance to ZeCor and Sandvik SX in stronger acid,
>97 wt%. In commercial acid plants there is usually a
small quantity of iron present (typically 5ppm) and this
can affect the corrosion rate of some alloys.

Figure 5 shows the effect of 5ppm of iron on the

corrosion rate of ZERON 100 at 110C. It can be seen
that, within experimental error, there was no
significant effect of iron on corrosion.

Effect of velocity of flow

Because stainless steels are often active (as
opposed to passive) in hot, concentrated sulphuric
acid, the corrosion rate is a function of velocity. It is
commonly recommended that alloys such as 316 and
310 be restricted to a maximum flow velocity of

1.5m/sec 2. Velocity tests have been conducted in

aerated 95 wt% sulphuric acid at 70C using rotating
cylindrical samples.
The corrosion rate of ZERON 100 was high for
the first two or three days. Thereafter the corrosion
rate was less than 0.1mm/year. The high initial rate of
corrosion was associated with the formation of a thin
black film on the metal surface. The film appears to
confer corrosion resistance as shown by the
subsequent low metal loss rate. These results show
that ZERON 100 can be used at higher temperatures
and velocities than 316L in strong sulphuric acid. Tests
in stronger acid showed even lower corrosion rates.
Silicon additions tend to remove the velocity sensitivity
of stainless steels to corrosion in hot, strong sulphuric
acid. Sandvik reported extremely low corrosion rates
(<0.01mm/y) for SX in 96% acid at 70C and 25m/sec
in the alloy data sheet. They obtained a similar
corrosion rate in 98.5% acid at 115C and 10m/sec
flow velocity. Saramet 35 showed similar very low
corrosion rates in 98.5% acid at 120C at 9 and 25 m/s
velocity4. Although there is no data published for
ZeCor at high velocities, it is presumed that it is also
superior to the 304 and 316 grades(most commonly
used grades of stainless steels).
After conducting multiple tests on most samples,
it was found that since sulphuric acid density increases
sharply with concentration along with its viscosity, it is
advisable for plant designers to maintain a low velocity
in acid piping systems to prevent the corrosion of the
passive layer that protects the inner lying steel. A low

temperature field further aids the longevity of the

piping systems.