134

CHAPTER 7
STUDIES ON CORROSION RESISTANCE OF
STAINLESS STEEL CLADDINGS

7.1

INTRODUCTION
Corrosion is the destructive result of chemical or electrochemical

reactions between a metal or metal alloy and its surroundings. The nature of
this reaction depends not only on the chemistry of the system but also on the
structure of the metal. The grain boundaries, which are imperfect and high
energy regions, generally weaken the corrosion resistance of materials due to
the depletion of corrosion resistance alloying elements on the grain
boundaries.
There are several test methods for determining the Pitting and Inter
Granular Corrosion (IGC) of stainless steel claddings. The weight loss acid
test in which the Pitting and IGC rates are determined by measuring the
weight loss of the sample as per ASTM G-48-practice-A and ASTM A-262practice-C respectively for the stainless steel cladding. Another test method of
measuring the degree of sensitization to intergranular corrosion involves
electrochemical reactivation of the samples as defined in ASTM G-108. This
reactivation process is called Electrochemical Potentiokinetic Reactivation
(EPR) and has been developed in to two types: Single loop (SLEPR) and
Double loop (DLEPR). The SLEPR test is usually accounted to detect the
susceptibility of the cladding towards pitting corrosion resistance and the

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DLEPR test is usually accounted to detect the susceptibility of the cladding

towards IGC resistance.
7.2

PLAN OF INVESTIGATION
The investigations are carried out in the following sequence:
1.

Conducting weight loss tests namely Total immersion ferric

chloride test and the Boiling nitric acid or Hueys test for
detecting the susceptibility of Pitting and Intergranular
corrosion

attack

in

stainless

steel

claddings

as

per

ASTM G-48 / Practice-A and ASTM A-262 / Practice-C

respectively, for the as cladded and liquid nitrided specimens.
2.

Conducting the Single Loop (SLEPR) and Double Loop

(DLEPR) tests to detect the susceptibility of Pitting and IGC
attack in stainless steel claddings as per ASTM G-5 and
ASTM G-108 respectively, for the as cladded and nitrided
specimens.

3.

Results and discussions.

7.3

WEIGHT LOSS TESTS

7.3.1

TOTAL IMMERSION FERRIC CHLORIDE TEST AS PER

ASTM G-48

7.3.1.1

Preparation of the test specimen and test solution

Four test specimens were prepared from overlay plates cladded at

low (4.10 KJ/mm), high (6.81 KJ/mm), optimum (4.61 KJ/mm) heat input
condition as well as at optimum dilution (4.61 KJ/mm) and liquidnitrided
condition for conducting the test. The top surface of the specimens were
ground flat to facilitate maximum surface exposure to the corrosive test
solution. The test solution was prepared by adding 100 gm of Ferric Chloride

136

(Fecl3) to 900 ml of distilled water (6% Fecl3 by wt) as per ASTM standards.
The solution was considered appropriate because, the effect of Fecl3 was more
pronounced and also aggressive in the environments that could formulate
pitting corrosion.
7.3.1.2

Experimental procedure
The total immersion ferric chloride test was conducted as per ASTM

standards to detect the susceptibility of pitting corrosion attack in austenitic

stainless steel. Samples of size 3.7 x 1.9 x 0.5 cm3 with a surface area of
19.66 cm2 were cut from the specimens weld cladded with different heat
inputs and at optimum condition. They were polished with 120 grit abrasive
paper, washed and dried by dipping in acetone. After taking the initial
weighed of the sample in a calibrated digital balance it was placed in a glass
cradle having holes and kept inside an Erlenmeyer flask fitted with a
condenser which dissipated the heat developed during the test period.
The flask was filled with 100 ml (5ml/cm2) of the test solution to
cover the entire specimen surface. Cooling water was passed through the
condenser for dissipating the heat generated and the flask is electrically heated
and maintained at 40C thereby keeping the test solution boiling throughout
the test period. The test period was of 72 hours duration and after the end of
the test period the specimen was rinsed with water and scrubbed with a nylon
brush under running water to remove any adhering corrosion products. Then
the specimen was dried by dipping in acetone and weighed in a calibrated
digital balance. The difference in weight is recorded for estimating the
corrosion rate.

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7.3.2

BOILING NITRIC ACID TEST (HUEYS TEST) AS PER

ASTM A-262-C
The boiling nitric acid or Hueys test is used for detecting the

susceptibility of stainless steel cladding towards intergranular corrosion attack

and conducted as per ASTM A-262-Practice-C. It is conducted for detecting
the susceptibility of intergranular corrosion attack in stainless steel claddings.
This procedure can also be used to check the effectiveness of the stabilising
elements and the effect of carbon content in reducing the susceptibility to
intergranular corrosion attack in Cr-Ni stainless steel.
7.3.2.1

Preparation of the test specimen and test solution

The entire lateral surfaces of the four prepared test specimens were

finely grinded to facilitate better surface exposure to the corrosive test

solution. A 65 % by weight nitric acid solution was prepared by adding
distilled water to concentrated nitric acid (HNO3) of reagent grade with
specific gravity 1.42 at the rate of 108 ml of distilled water per litre of
concentrated nitric acid as per ASTM standards. The solution was considered
appropriate because of the effect of HNO3 being more pronounced and
aggressive in the environments that could formulate intergranular corrosion..
7.3.2.2

Experimental procedure
Intergranular attack in nitric acid is associated with the intergranular

precipitation of chromium carbides. The specimen was polished with 120 grit
abrasive paper and weighed initially. It was placed in a glass cradle is
presented in Figure 7.1 (a) and kept inside the Erlenmeyer flask fitted with an
Allihn condenser with four bulbs as presented in Figure 7.1 (b) to dissipate
the heat developed during boiling of the acid.

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(a)
Figure 7.1

(b)

Hueys test setup showing: (a) the glass cradle and

(b) Erlenmeyer flask fitted with an Allihn condenser

The flask was filled with sufficient quantity of the test solution to
cover the specimen and to provide a volume of 20 ml/cm2 of the specimen
surface. Cooling water was passed through the condenser for dissipating the
heat generated and the flask is electrically heated and maintained at 60C
thereby keeping the test solution boiling throughout the test period. The test
period was of 48 hours duration and after the end of each test period the
specimen was rinsed with water and scrubbed with a nylon brush under
running water to remove any adhering corrosion products. Then the specimen
was dried by dipping in acetone and weighed in an analytical balance. The
difference in weight is recorded for estimating the corrosion rate. This test
procedure was repeated for five consecutive boiling periods with duration of
48 hours for each period for every specimen. Fresh test solution was used
every time during the entire testing period.

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7.4

SINGLE LOOP EPR TEST AS PER ASTM G-5

7.4.1

Preparation of the test specimen and test solution

Four already prepared cladded test specimens were used for

conducting EPR tests. Figure 7.2 shows the surface of these specimens (I)
before and (II) after the EPR test.

(I)
Figure 7.2

(II)

Specimen with: (a) low heat input, 4.10 KJ/mm (b) high
heat input, 6.81 KJ/mm (c) optimum heat input, 4.61
KJ/mm and (d) optimum (4.61 KJ/mm) and liquid nitrided
condition, (I) before and (II) after Single loop EPR test

The top surface of the specimen was ground flat to facilitate 1 cm2
of the surface was exposed to the corrosive test solution. It was first polished
by a 600 grit SiC paper and further wet polished with 1 m alumina slurry on
a micro cloth mounted polishing wheel to a surface roughness of 6 m as per
ASTM E13 standards. Then they were washed with distilled water and dried
in a stream of cool air before immersing them in to the corrosive test solution.
The corrosion medium for the present investigation has been selected based
on the basis of corrosion environments as cited in the available literatures.

140

A 3.56 % sodium chloride (NaCl) solution was prepared by dissolving 34 g of

sodium chloride in 920 ml of deionised water.
7.4.2

Experimental procedure
The potentiodynamic polarisation test was conducted to predict the

pitting corrosion resistance of the specimens cladded at various heat input

conditions as per the ASTM G-5 standard. The schematic and experimental
set up of ACM Gill 5500 potentiostat instrument with a flat cell in three
electrode configuration is shown Figure 7.3 (a) and (b).

(a)

(b)
Figure 7.3

EPR test set up showing: (a) Schematic diagram and

(b) Experimental set up

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The cell consists of a glass cylinder clamped horizontally between

two end plates housing the working electrode, WE (AISI 316 L stainless steel
cladded surface) and the auxiliary electrode, AE, (platinum gauze). A
saturated calomel electrode (SCE) using 0.1 M KCl was used as the reference
electrode (RE). The cell was filled with 250 ml of test solution and all the
tests were conducted at room temperature, 30 2 C. All the three electrodes
are connected to corrosion measuring instrument through the leads provided
in the flat cell. Polarisation test was commenced by measuring the rest
potential after the samples were immersed for 50 minutes in non deaerated
chloride solution to allow for rest potential to settle. The potential was
anodically scanned at a rate of 60 mVmin-1 from - 400 mV to + 500 mV. The
current density was measured continuously using the data acquisition
software provided with the instrument.
7.5

DOUBLE LOOP EPR TEST AS PER ASTM G-108

Four already prepared test specimens cladded were used to conduct

the test. The double loop EPR test was done according to ASTM G-108
standard and the recommendations made by Majidi and Streicher (1984). The
standard solution was modified to suit the austenitic stainless steel and
consisted of 2M H2SO4 + 0.5MNaCl + 0.01MKSCN at 30 1 C and a scan
rate of 15 V/h. The test was performed by running the sample from a potential
lower than Ecorr in the cathodic region. The potential is scanned in the anodic
direction from Ecorr to a point of 0.250 V in the middle of the passive region.
The scanning direction is then reversed and the potential is reduced back to
the cathodic region. Two loops are generated, an anodic loop and a
reactivation loop. The peak activation current (Ia) and the peak reactivation
current (Ir) were measured during the forward and backward scans,
respectively. The degree of sensitization was measured as the ratio of peak
activation current to the maximum current densities generated in the double
loop test (Majidi and Streicher, 1984).

142

7.6

RESULTS AND DISCUSSION

7.6.1

Weight loss tests

7.6.1.1

Total immersion ferric acid test

The corrosion rate was measured by determining the weight loss of

the specimen after the test period and the weight loss was calculated for each
specimen. The corrosion rate was calculated by using the relation,
Corrosion rate = 7290 x W / A t, mm/month,
where W= the total weight loss of the specimen in grams,
A= the area of the specimen exposed in cm2,
= the density of the overlay material in grams / cm3 and
t= the time of exposure in hours.
The corrosion rate was calculated for each test period and the
average corrosion rate was referred against the ASTM acceptance limits for
all the four specimens cladded at different heat input conditions. The results
of the Total immersion ferric chloride test are presented in Table 7.1.

143

Table 7.1

No

Results of total immersion ferric chloride test

Initial
weight
of the
specimen,
gm

Final weight
of the
specimen,
gm

Difference
in weight,
gm

Corrosion
rate,
mm/month

ASTM
acceptance
limit,
mm / month

Cladded at low
heat input
(4.10 KJ / mm)

30.8201

30.8111

0.009

0.0447

0.10 0.12

Cladded at high
heat input
(6.81 KJ / mm)

30.8112

30.7952

0.016

0.1142

0.10 0.12

30.8224

30.7994

0.023

0.0982

0.10 0.12

30.8212

30.8102

0.011

0.0459

0.10 0.12

Thermal history
of the specimen

Cladded at
optimum heat
input
(4.61 KJ / mm)
Cladded at
optimum heat
input
(4.61 KJ / mm)
and liquid
nitrided
condition

From Table 7.1 it is found that cladding produced at low heat input
and optimum conditions are having lower corrosion rates than that of other
claddings in ferric chloride solution.
7.6.1.2

Boiling nitric acid test (Hueys test)

The results of the Hueys test are presented in Table 7.2.

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Table 7.2 Results of Hueys test

No

Description
of the specimen

Total
corrosion
Total weight
rate,
loss , gms
mm / month

Average
corrosion
rate, mm /
month

ASTM
acceptance
limit,
mm /
month

Cladded at low heat

input (4.10 KJ / mm)

0.5497

0.4101

0.0921

0.14 0.16

Cladded at high heat

input (6.81 KJ / mm)

0.8855

0.5623

0.1182

0.14 0.16

0.9104

0.5912

0.1125

0.14 0.16

0.5738

0.4902

0.0881

0.14 0.16

Cladded at optimum
heat input (4.61 KJ /
mm)
Cladded at optimum
heat input (4.61 KJ /
mm) and liquid
nitrided condition

It is observed that the corrosion rate in boiling nitric acid of nitrided

claddings produced at optimum dilution condition is lower compared with all
other claddings. Also it is evident from tables that corrosion rate increases
with the increase in heat input which may be attributed to increased dilution.
The scanning electron micrograph (SEM) of the nitrided cladding
produced at optimum heat input condition (4.61 KJ/mm) and at high heat
input (6.81 KJ/mm) condition after Hueys test are shown in Figure 7.4. A
stepped type microstructure is noticed for the nitrided specimen cladded at
optimum heat input condition. This is because of the reason that the lower
heat input promoted faster cooling rates thereby forming finer grains with
stepped structures. Finer grains with stepped structures possess excellent
corrosion resistance and tensile properties combined with good bonding
strength between adjacent grains (Aydogdu and Aydinol 2006, Mirko Gojic et
al 2008). This in turn promotes excellent ductility and toughness of the
cladding which will widen their potential applications.

145

Figure 7.4

SEM photomicrograph of nitrided claddings produced

at optimum heat input (4.61 KJ/mm) condition after
Hueys test showing a stepped structure, X500

The stepped type microstructure is presented at a higher

magnification for clearly visualising the corrosion debris after the Hueys test,
in Figure 7.5.

Figure 7.5

SEM photomicrograph of nitrided cladding produced at

optimum heat input (4.61 KJ/mm) condition after Hueys
test showing a stepped structure, X2000

146

A ditched type microstructure noticed in the specimen cladded at

high heat input (6.81 KJ/mm) condition after Hueys test is shown in Figure
7.6.

Figure 7.6

SEM photomicrograph of high heat input specimen

(6.81 KJ/mm) after Hueys test showing a ditched
structure, X500

The slower cooling rates of the cladding due to higher heat input
promoted a coarser grain structure which does not have the normal
mechanical and metallurgical properties. Also, the slower cooling rates
promoted the formation of coarser grains with ditched structure. Their
bonding strength may not be evenly distributed due to the formation of
coarser grains with a lathy morphology (Arikan and Doruk 2008). The SEM
images reveal that the ditched type microstructure are highly prone to the
intergranular corrosion attack or sensitization than the stepped type structure.
The ditched type microstructure is presented at a higher
magnification for clearly visualising the corrosion debris after the Hueys teat,
in Figure 7.7.

147

Figure 7.7

7.6.2

SEM photomicrograph of high heat input specimen (6.81

KJ/mm) after Hueys test showing a ditched structure,
X2000

Single Loop EPR test as per ASTM G-5

Graphs were plotted keeping current density in logarithmic scale

along X-axis and potential along Y-axis using the analysis software. Typical
potentiodynamic anodic polarization curves of the specimens cladded at
corresponding conditions are shown in Figure 7.8 7.11. For each specimen,
the test was repeated twice in different areas and the average value was
recorded for the analysis. The current density was measured continuously
using commercial data acquisition software provided with the instrument.
Corrosion behaviour was investigated using potentiodynamic polarisation
measurements in 3.5 wt. % NaCl.

148

Figure 7.8

Single Loop EPR curve for a specimen cladded at low

heat input (4.10 KJ/mm) condition

Figure 7.9

Single Loop EPR curve for a specimen cladded at high

heat input (6.81 KJ/mm) condition

149

Figure 7.10

Single Loop EPR curve for a specimen cladded at

optimum heat input (4.61 KJ/mm) condition

Figure 7.11

Single Loop EPR curve for a specimen nitrided and

cladded at optimum heat input (4.61 KJ/mm) condition

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The rest potential (the potential at which the current becomes zero)
and the pitting potential are considered as a measure of the material
dissolution from the surface being tested. It has been referred that the passive
film on the surface was destroyed progressively with time and as a result
more and more of the metal (which is active) is exposed in the electrolyte.
The results are presented in Table 7.3. All potentials are vs. saturated calomel
electrode.
Table 7.3 Results of Single Loop EPR test

Sample
description

Corrosion
current
density,
(Icorr)
A cm-2

Rest
Potential,
mV

Pitting
Potential,
mV

-180

+410

7.2X10 -6

0.00202

0.07945

-120

+280

6.1X10 -6

0.04889

0.93534

-240

+ 260

8.3X10 -5

0.02378

1.92301

-120

+395

9.1X10 -6

0.00341

0.13413

Corrosion Corrosion
rate,
rate,
mils/yr
mm/year

Low heat
input of
4.10 KJ/mm
High heat
input of
6.81 KJ/mm
Optimum
heat input
4.61 KJ/mm
Optimum
heat input
4.61 KJ/mm
and nitrided

Prasad Rao et al (1986-a) investigated the pitting potential for

AISI 316L stainless steel claddings in 3.5% NaCl aqueous solution at a
controlled temperature of 30 2C were between -120 to +430 mV.
Pulino-Sagradi et al (1997) observed the same between -130 to +420 mV.

151

Kamachimudali et al (2000) investigated the pitting potential between140 to

+450 mV. The results show that the pitting potential of the AISI 316L cladded
specimens in 3.5% NaCl aqueous solution at a controlled temperature of
30 2C lie between -120 to +410 mV for various heat inputs. The above
observations indicate that the values of pitting potentials obtained in the
present study are in agreement with the literature.
The optical and SEM micrographs of the nitrided cladding produced
at optimum heat input condition showing stepped structure with pits are
presented in Figure 7.12 and 7.13 respectively.

Figure 7.12

Optical micrograph of the nitrided cladding produced at

optimum heat input condition after Single Loop EPR test

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Figure 7.13

SEM micrograph of the nitrided cladding produced at

optimum heat input condition after Single Loop EPR test
The optical and SEM micrographs of the nitrided cladding produced

at high heat input condition showing ditched structure are presented in Figure
7.14 and 7.15 respectively.

Figure 7.14

Optical micrograph of the cladding produced at high

heat input condition after Single Loop EPR test

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Figure 7.15

SEM micrograph of the cladding produced at high

heat input condition after Single Loop EPR test
A step type microstructure with pits was noticed for the specimen

cladded with optimum heat input (4.61 KJ/mm) and nitrided condition and a
ditched type microstructure with pits was noticed for the specimen cladded
with high heat input (6.81 KJ/mm). Stepped type microstructure might have
formed due to the faster cooling of the cladding at low heat input conditions.
The ditched type microstructure might have formed due to the slow cooling of
the cladding produced during higher heat input condition. It is found that the
stepped type microstructure possesses comparatively better resistance to
pitting corrosion than the ditched type microstructure.
7.6.3

Double Loop EPR test as per ASTMG -108

Polarisation graphs were plotted keeping current density in

logarithmic scale along X-axis and potential along Y-axis using the analysis
software. Typical potentiodynamic anodic polarization curves of the
claddings produced at the specified heat input conditions are presented in
Figure 7.16 7.19.

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Figure 7.16

Double Loop EPR curve for a specimen cladded at low

heat input (4.10 KJ/mm) condition

Figure 7.17

Double Loop EPR curve for a specimen cladded at high

heat input (6.81 KJ/mm) condition

Figure 7.18

Double Loop EPR curve for a specimen cladded at

optimum heat input (4.61 KJ/mm) condition

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Figure 7.19

Double Loop EPR curve for a specimen nitrided and

cladded at optimum heat input (4.61 KJ/mm) condition

For each specimen, the test was repeated twice in different areas and
the average value was recorded for the analysis. The current density was
measured continuously using commercial data acquisition software provided
with the instrument. All potentials are vs. saturated calomel electrode. The
degree of sensitization was measured from the ratio of maximum current
densities generated in the double loop test (Majidi and Streicher 1984). The
results of the double loop EPR test is presented in Table 7.4.

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Table 7.4 Results of Double Loop EPR test

No

Description
Low heat
input of
4.10 KJ/mm
High heat
input of
6.81 KJ/mm
Optimum
heat input
4.61 KJ/mm
Optimum
heat input
4.61 KJ/mm
and nitrided

7.7

Activation
peak
potential,
Ea ,(mV)

Activation
peak
current
density,
Ia, (mA/cm2)

Reactivation
Reactivation Passivation
peak
peak current
current
potential,
density,
density,
Er,(mV)
2
Ipass ,(mA/cm2)
Ir,(mA/cm )

Degree of
sensitization
( Ir /Ia
x100) %

-201.59

16.2439

-196.26

0.0096

0.0266

0.0589

-214.66

24.1534

-218.19

0.8752

0.0338

3.6236

-194.27

26.7205

-227.99

0.0089

0.0253

0.0334

-212.78

23.1305

-267.33

0.0064

0.0014

0.0276

SUMMARY
From the weight loss test with ferric chloride it can be concluded

that the nitrided cladding deposited at optimum heat input condition possessed
better pitting corrosion resistance. In the Hueys test, the claddings deposited
at low and optimum heat input conditions possessed better resistance to IGC.
Also from the single loop EPR test an increase in pitting potential is noticed
in the cladding deposited with optimum heat input condition. The positive
value of pitting potential indicates that a stable film is formed over the surface
of the cladding which confirms that the material is more nobler with increased
pitting corrosion resistance. In the double loop EPR test the ratio of the degree
of sensitisation (Ir/Ia) was found to be very lower in the cladding deposited at

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optimum heat input condition, which reveal that the cladding possesses better
resistance to IGC.