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Microstructural study and electrochemical

behavior of low alloy steel weldment

Article in Materials and Design · June 2010

DOI: 10.1016/j.matdes.2010.01.025

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 Materials and Design 31 (2010) 3051–3055

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Materials and Design

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Short Communication

Microstructural study and electrochemical behavior of low alloy steel weldment

K.M. Deen a,*, R. Ahmad a, I.H. Khan b, Z. Farahat c
a
Department of Metallurgy & Materials Engineering, University of the Punjab, Lahore 54590, Pakistan
b
Institute of Chemical Engineering & Technology, University of the Punjab, Lahore 54590, Pakistan
c
Department of Process Engineering & Applied Science, Dalhousie University, Halifax, Nova Scotia, Canada B3J 2X4

a r t i c l e i n f o a b s t r a c t

Article history: Submerged arc welding (SAW) was applied to SA516 (Grade 70) pressure vessel and boiler steel. The
Received 31 October 2009 microstructural and electrochemical corrosion study of base metal (BM), weld zone (WZ) and heat
Accepted 15 January 2010 affected zone (HAZ) was carried out to understand the effect of welding cycle by optical microscopy,
Available online 18 January 2010
X-ray diffraction (XRD), potentiodynamic polarization and linear polarization resistance (LPR) method
to correlate corrosion kinetic parameters with microstructural changes in tap water and 0.5% (w/v) NaCl
solution under plain and aeration conditions at room temperature. From microstructural study, the mor-
phology of ferrite in WZ and HAZ showed different electrochemical behavior and corrosion rate than that
of BM.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction was simulated by potentiodynamic polarization and linear polari-

The weld metal metallurgy for low alloy steel differs signifi-
cantly from the base metal metallurgy in several aspects. During
welding thermal cycle heating and cooling rates of weld are much
faster than those of steel base metal. Thus metallurgical transfor-
mations across the weld and heat affected zone vary, thereby their
microstructures and morphologies become important. The micro-
structures that develop during welding thermal cycle are depen-
dent on energy input, preheat, metal thickness (heat sink affect),
weld bead size, and reheating effects due to multipass weld. As a
result of different chemical compositions and inclusions (oxide
and sulphides) weld metal microstructures significantly differs
from those of the HAZ and base metal; corrosion behavior can also
change [1,2]. Therefore, welding process has a significant influence
on corrosion resistance and mechanical properties as result of met-
allurgical changes involved [3].
The electrochemical potential gradient is developed in adjacent
sites of a weld metal because of these microstructural changes;
therefore research work was directed towards the study of corro-
sion behavior of welded microstructures. The presence of chloride
impurities which are acidic or become acidic when heated can
cause corrosion [4–6]. In the present study the corrosion behavior
of low alloy steel weldment was investigated to evaluate the affect
of aeration and salinity of water at different weldment regions. The
results were correlated with microstructural changes that formed
during welding thermal cycle and their corrosion performance
zation resistance technique (LPR).
2. Experimental procedure
2.1. Base metal and welding process
Low carbon steel ASTM A516 (Grade 70) was used as base me-
tal. Two plates were welded by submerge arc welding using AWS
codes and standards. Designated filler metal (EM12K) was selected
and weld was deposited under the covering flux (F7P6-EM12K),
insuring full weld penetration, proper shape and contour.
2.2. Sample preparation for metallography
The three specimens from each BM, HAZ and WZ, were cut and
their top surfaces were selected to determine microstructural
changes. These specimens were first ground with 220, 320, 400
and 600 grit silicon carbide papers respectively followed by wheel
polishing with diamond paste, and etched in 2% Nital for 15 s.
2.3. XRD analysis
The specimens were subjected to qualitative phase analyses by
XRD. The diffraction patterns were obtained with the help of Joel
X-ray diffractometer using Ni filtered Cu Ka radiations.
2.4. Specimen preparation for corrosion testing

* Corresponding author. Tel.: +92 42 9232256; fax: +92 42 9231159. The weldment was macroetched to identify HAZ and WZ accord-
E-mail address: kashif_mairaj83@yahoo.com (K.M. Deen). ing to ASTM E340-00 (standard test method for macro-etching

0261-3069/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.matdes.2010.01.025
3052 K.M. Deen et al. / Materials and Design 31 (2010) 3051–3055

metals and alloys). Top surface of specimens including HAZ and WZ
was selected for corrosion analysis. Glass tube encased copper wire
was soldered at the back of each specimen and cold mounted in
epoxy resin keeping one zone exposed at a time, under consider-
ation. The exposed metal surface (1.6 cm2) from each zone was
ground separately with silicon carbide paper up to 400 grit, washed
with distill water and rinsed in acetone before electrochemical
testing.
the allotrimorphic ferrite (a) as the grain boundary ferrite, wedge
shape secondary widmanstatten ferrite (aw) originated from these
allotrimorphs and lath like arrangement of acicular ferrite (aa) that
was a characteristic microstructure of upper bainite inside the
grain. The aw was formed by para-equilibrium transformation of
austenite grain surface, the detailed microstructure is given in
Fig. 2, it may be visualized as consisting of two mutually accommo-
dating plates with characteristic thin wedge morphology of aw. The

2.5. Electrochemical measurements

The electrochemical technique: potentiodynamic polarization

was used to determine the corrosion kinetic parameters of the
specimens in plain/aerated tap water containing 15 ppm chloride
(Cl), and 269 ppm total dissolved solids (TDS) at 25 °C and also
in 0.5% NaCl solution prepared in same water. The polarization
resistance Rp of the tested samples in aerated condition was also
measured by linear polarization resistance (LPR) method because
of the diffusion controlled corrosion mechanism which made the
potentiodynamic polarization technique incapable to determine
actual corrosion rate. The tests were conducted in an electrochem-
ical cell in which calomel electrode was used as reference electrode
and graphite rod as counter electrode. The cell was coupled with
Gamry Potentiostat version PC/750. For electrochemical measure-
ments the aeration condition was developed by air saturation of
the electrolyte and the air purging was maintained during the
experiment. The potentiodynamic curves were obtained with a
Fig. 1. Base metal microstructure showing polygonal ferrite (white), pearlite
scan rate of 1 mV/s in the range of 250–250 mV vs. OCP (open cir-
(black), 400 (2% Nital).
cuit potential). Before the starting of electrochemical measure-
ments, the OCP was monitored within initial 10 s period.

3. Results and discussion

3.1. Composition and welding parameters

The chemical composition of base metal, filler metal, WZ and

welding parameters are given in Tables 1 and 2 respectively.

3.2. As welded microstructures

Submerge arc weld metal microstructures generally are com-

posed of a complex mixture of microstructural constituents. Weld
deposit properties depend much on the relative proportions and
morphologies of these constituents that are formed during welding
process [7]. Optical micrographs of BM, submerged arc WZ and
HAZ were studied. The BM microstructure consisted of equiaxed
polygonal ferrite (white phase) and pearlite (black phase) grains
as shown in Fig. 1. In WZ the microstructural analysis indicated

Table 1
Chemical Composition of base metal, filler metal, and weld metal.

Composition C Mn Si S P Fe
(wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%)
Base metal 0.188 1.115 0.352 0.001 0.014 Balance
Filler metal 0.08 1.48 0.47 0.011 0.012 Balance
Weld metal 0.08 1.73 0.75 0.0079 0.012 Balance
Fig. 2. Weld zone microstructure (etched 2% Nital).

Table 2
Welding process parameters for submerge arc welding.

Welding process Filler metal Current Voltage (V) Travel speed Heat input
(mm/min) (kJ/mm)
Class Dia. (mm) Polarity Amp
SAW EM12K 3.2 DCEP 450–500 31–33 300–350 46.5
 K.M. Deen et al. / Materials and Design 31 (2010) 3051–3055 3053

aa was a phase, most commonly observed as austenite transforms sured at the start of polarization scan and its trend is demonstrated
during the cooling of low alloy steel weld deposits. The nature of aa in Fig. 4. The results obtained confirmed that under aerated condi-
in the weld metals was upper bainitic having needle like morphol- tion the potential was more noble (more positive) as compared to
ogy and this corresponds to mid temperature phase transformation plain, water and NaCl solution which indicates the formation of
[8–10]. The microstructure development in low carbon low alloy barrier oxide film at the surface.
steel weld can be well understood by continuous cooling transfor-
mation diagrams [11]. The XRD results are shown in Table 3. The d-
3.4. Electrochemical polarization study
values correspond to single phase a-Fe with lattice parameters
a = 2.8664 °A. It means that there was no second phase or the
3.4.1. Potentiodynamic polarization scans
amount of any second phase if present was below the detection
The potentiodynamic scans of samples in plain and aerated
limit. XRD results provided support to the microstructural
water and 0.5% NaCl are shown in Figs. 5 and 6 respectively. In aer-
investigation.
ated water and 0.5% NaCl the cathodic part of the polarization
But in HAZ very near to WZ the grains internal structure was re-
placed by aa and lower bainite with allotrimorphic ferrite (a) and
primary widmanstatten ferrite (aw) formed directly at the austen-
ite grain boundaries. The formation of acicular ferrite and lower
bainite within the grains as depicted in Fig. 3 was due to rapid
cooling of HAZ compared to WZ which was covered by flux powder
during welding.

3.3. Open circuit potential

The open circuit potential (OCP) of each sample in water and

0.5% NaCl solution under plain and aeration condition was mea-

Table 3
XRD results and analysis.

Specimen Peak # 2hX d-Value (hkl) Result

(XA) Fig. 4. Variation of open circuit potential (OCP) under different conditions.
As received WZ 1 44.5 2.0268 (1 1 0) Alpha-Iron (bcc)
and HAZ a = 2.8664 A°
2 65.10 1.4332 (2 0 0)
3 82.29 1.1702 (2 1 1)
Oxide layer formed 1 31.4 2.846 – Fe(CIO4)2(H2O)6
at the surface
2 45.1 2.009 –
3 74.95 1.266 –

Fig. 5. Potentiodynamic polarization scans in water under (a) plain, and (b) aerated
Fig. 3. Optical micrograph of ‘HAZ’ (etched 2% Nital). conditions.
3054 K.M. Deen et al. / Materials and Design 31 (2010) 3051–3055

Table 4
Potentiodynamic polarization scans parameters (water).

Water Eoc (mV) Ecorr Icorr (lA/ ba (mV/ bc (mV/ CR(Tafel)

(mV) cm2) decade) decade) (mpy)
Plain
BM 747.2 751.0 4.17 80.7 241.6 1.906
HAZ 741.1 752.0 3.61 85.0 194.0 1.648
WZ 719.4 717.0 7.79 92.4 397.8 3.559
– – – IL (lA/ – – –
cm2)
Aerated
BM 647.1 528.0 66.4 100.2 1.0E+18 –
HAZ 618.75 461.0 168 353.7 4.147E+06 –
WZ 570.3 502.0 75.8 337.9 668.0E+06 –

Table 5
Potentiodynamic polarization scans parameters (0.5% NaCl solution).

Solution Eoc Ecorr Icorr ba (mV/ bc (mV/ CR(Tafel)

0.5% NaCl (mV) (mV) (lA/cm2) decade) decade) (mpy)
Plain
BM 736.2 779.0 7.0 74.4 300 3.20
HAZ 720.9 746.0 5.12 63.5 188.6 2.337
WZ 720.7 719.0 20.8 65.2 353.6 5.946
– – – IL (lA/cm2) – – –
Aerated
BM 599.0 455.0 74.6 93.10 412.8 –
HAZ 664.0 557.0 108 91.7 1.0E+18 –
WZ 624.2 618.0 143 98.1 1.0E+4 –

Fig. 6. Potentiodynamic polarization scans in 0.5% NaCl solution under (a) plain,
and (b) aerated conditions.

curve, Figs. 5b and 6b, was attributed to limiting current density

(IL) which may be determined by diffusion controlled oxygen
reduction reaction for all BM, HAZ, and WZ. Since the solution
was saturated with air but the appearance of IL was due to the for-
mation of milky white oxide layer at the specimen surface as ob-
served during experimentation. This oxide layer formed, provide
barrier to oxygen reduction reaction hence occurring at constant
currents. It is also well known that oxide layers can play two
important but inverse roles on the oxygen reduction reaction. Basi-
cally it acted like a physical barrier against oxygen diffusion. There-
fore, it was expected that its quick formation could inhibit cathodic
Fig. 7. Variation of corrosion potential under different conditions.
process consequently reduce corrosion rate. On the other hand,
this oxide layers may also act as ideal surfaces for the oxygen
reduction due to the presence of active sites for electrochemical reason, the limiting current density cannot be assumed as the cor-
process [12]. The Zig-Zag trend in cathodic polarization curve rosion rate. On the other hand, polarization resistance values ob-
may be simulated to this behavior. It may also be deduced from tained from LPR method showed good agreement with calculated
polarization curves that the addition of 0.5% NaCl in water did corrosion rate [13].
not change the value of limiting current density IL significantly. The Polarization resistance RP values were obtained through LPR
The values of other parameters obtained from potentiodynamic method and the trend is shown in Fig. 8. The following equation
polarization scans and limiting current density in aerated water may be used to determine the value of Icorr and corrosion rate from
and 0.5% NaCl solution are given in Tables 4 and 5 respectively. polarization resistance Rp.
The large values for bc were further quantitative representation
 
of diffusion controlled oxygen reduction reaction. The variation ba ; bc 1
in corrosion potential Ecorr as shown in Fig. 7 also conformed that Icorr ¼  ð1Þ
2:303 ðba þ bc Þ Rp
the potential of weldment zones were nobler (less negative) under
aeration condition in both water and 0.5% NaCl solution than plain where, Rp is the DE/DI, ba is anodic Tafel slope, bc is the cathodic Ta-
condition. fel slope; obtained from Tafel line extrapolation.
The 0.5% NaCl solution, plain and aerated was found more cor-
3.4.2. Linear polarization resistance method rosive than water as indicated by high corrosion rates in Table 6.
The diffusion control mechanism in potentiodynamic polariza- The corrosion rate of BM was also high in water and NaCl solution
tion curves affected the calculation of the corrosion rate. For this as compared to HAZ and WZ under both conditions.
 K.M. Deen et al. / Materials and Design 31 (2010) 3051–3055 3055

inhibit the formation of uniform oxide layer by Fe + 1/2O2 +

H2O + 2e ? Fe(OH)2 and in the presence of excess oxygen,
Fe(OH)2 transforms into FeOOH [17,18].
The qualitative analysis of the surface after test in 0.5% NaCl
solution was carried out by X-ray diffraction method which
showed Fe(ClO4)2(H2O)6 type of oxide layer as tabulated in Table 3.
The lower polarization resistance Rp values obtained for aerated
solutions confirmed the behavior in polarization curves for the lim-
iting current density IL. The low values of Rp (Table 6) in aerated
0.5% NaCl solution and more active Ecorr and Rp values as depicted
in Figs. 7 and 8 were also in support of evaluated results.

4. Conclusion

The presence of acicular ferrite in WZ influences reduction reac-

tion in aerated water and NaCl solution. Therefore WZ was found
Fig. 8. Variation of polarization resistance under different conditions measured by least corrosion resistant than BM and HAZ, which was estimated
LPR method. from relatively more negative values of Eoc, Ecorr, low values of Rp
and higher IL under aerated conditions. This type of behavior was
due to non uniform oxide formation at the surface since needle like
Table 6 acicular ferrite structure provided low corrosion resistance than
LPR method; results. allotrimorphic and widmanstätten ferrite, the complete coverage
LPR method Icorr (lA/cm2) Rp (k X) CR(LPR) (mpy) of surface by oxide film was limited. It is also validated that aera-
tion and saline environments can effectively accelerate local weld
Aerated water
BM 41.95 0.6211 11.98
damage.
HAZ 38.68 0.6736 11.05
WZ 40.44 0.6448 11.19
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