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Materials and Design 31 (2010) 30513055

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Materials and Design


journal homepage: www.elsevier.com/locate/matdes

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 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
b

a r t i c l e

i n f o

a b s t r a c t
Submerged arc welding (SAW) was applied to SA516 (Grade 70) pressure vessel and boiler steel. The microstructural and electrochemical corrosion study of base metal (BM), weld zone (WZ) and heat affected zone (HAZ) was carried out to understand the effect of welding cycle by optical microscopy, 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 morphology of ferrite in WZ and HAZ showed different electrochemical behavior and corrosion rate than that of BM. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 31 October 2009 Accepted 15 January 2010 Available online 18 January 2010

1. Introduction The weld metal metallurgy for low alloy steel differs signicantly 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 transformations across the weld and heat affected zone vary, thereby their microstructures and morphologies become important. The microstructures that develop during welding thermal cycle are dependent 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 signicantly differs from those of the HAZ and base metal; corrosion behavior can also change [1,2]. Therefore, welding process has a signicant inuence on corrosion resistance and mechanical properties as result of metallurgical 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 corrosion behavior of welded microstructures. The presence of chloride impurities which are acidic or become acidic when heated can cause corrosion [46]. 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

was simulated by potentiodynamic polarization and linear polarization resistance technique (LPR). 2. Experimental procedure 2.1. Base metal and welding process Low carbon steel ASTM A516 (Grade 70) was used as base metal. Two plates were welded by submerge arc welding using AWS codes and standards. Designated ller metal (EM12K) was selected and weld was deposited under the covering ux (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 rst 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 ltered Cu Ka radiations. 2.4. Specimen preparation for corrosion testing

* Corresponding author. Tel.: +92 42 9232256; fax: +92 42 9231159. E-mail address: kashif_mairaj83@yahoo.com (K.M. Deen). 0261-3069/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.matdes.2010.01.025

The weldment was macroetched to identify HAZ and WZ according to ASTM E340-00 (standard test method for macro-etching

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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 consideration. 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. 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 electrochemical 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 measurements 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 scan rate of 1 mV/s in the range of 250250 mV vs. OCP (open circuit potential). Before the starting of electrochemical measurements, 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, ller 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 composed 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

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 accommodating plates with characteristic thin wedge morphology of aw. The

Fig. 1. Base metal microstructure showing polygonal ferrite (white), pearlite (black), 400 (2% Nital).

Table 1 Chemical Composition of base metal, ller metal, and weld metal. Composition Base metal Filler metal Weld metal C (wt.%) 0.188 0.08 0.08 Mn (wt.%) 1.115 1.48 1.73 Si (wt.%) 0.352 0.47 0.75 S (wt.%) 0.001 0.011 0.0079 P (wt.%) 0.014 0.012 0.012 Fe (wt.%) Balance Balance Balance Fig. 2. Weld zone microstructure (etched 2% Nital).

Table 2 Welding process parameters for submerge arc welding. Welding process Filler metal Class SAW EM12K Dia. (mm) 3.2 Current Polarity DCEP Amp 450500 3133 Voltage (V) Travel speed (mm/min) 300350 Heat input (kJ/mm) 46.5

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aa was a phase, most commonly observed as austenite transforms during the cooling of low alloy steel weld deposits. The nature of aa
in the weld metals was upper bainitic having needle like morphology and this corresponds to mid temperature phase transformation [810]. The microstructure development in low carbon low alloy steel weld can be well understood by continuous cooling transformation diagrams [11]. The XRD results are shown in Table 3. The dvalues correspond to single phase a-Fe with lattice parameters a = 2.8664 A. It means that there was no second phase or the amount of any second phase if present was below the detection limit. XRD results provided support to the microstructural investigation. But in HAZ very near to WZ the grains internal structure was replaced by aa and lower bainite with allotrimorphic ferrite (a) and primary widmanstatten ferrite (aw) formed directly at the austenite 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 ux 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 meaTable 3 XRD results and analysis. Specimen As received WZ and HAZ Peak # 1 2 3 Oxide layer formed at the surface 1 2 3 2hX 44.5 65.10 82.29 31.4 45.1 74.95 d-Value (XA) 2.0268 1.4332 1.1702 2.846 2.009 1.266 (hkl) (1 1 0) (2 0 0) (2 1 1) Fe(CIO4)2(H2O)6 Result

sured at the start of polarization scan and its trend is demonstrated in Fig. 4. The results obtained conrmed that under aerated condition the potential was more noble (more positive) as compared to plain, water and NaCl solution which indicates the formation of barrier oxide lm at the surface. 3.4. Electrochemical polarization study 3.4.1. Potentiodynamic polarization scans The potentiodynamic scans of samples in plain and aerated water and 0.5% NaCl are shown in Figs. 5 and 6 respectively. In aerated water and 0.5% NaCl the cathodic part of the polarization

Fig. 4. Variation of open circuit potential (OCP) under different conditions. Alpha-Iron (bcc) a = 2.8664 A

Fig. 3. Optical micrograph of HAZ (etched 2% Nital).

Fig. 5. Potentiodynamic polarization scans in water under (a) plain, and (b) aerated conditions.

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K.M. Deen et al. / Materials and Design 31 (2010) 30513055 Table 4 Potentiodynamic polarization scans parameters (water). Water Plain BM HAZ WZ Eoc (mV) Ecorr (mV) 751.0 752.0 717.0 Icorr (lA/ cm2) 4.17 3.61 7.79 IL (lA/ cm2) 66.4 168 75.8 ba (mV/ decade) 80.7 85.0 92.4 bc (mV/ decade) 241.6 194.0 397.8 CR(Tafel) (mpy) 1.906 1.648 3.559

747.2 741.1 719.4

Aerated BM 647.1 HAZ 618.75 WZ 570.3

528.0 461.0 502.0

100.2 353.7 337.9

1.0E+18 4.147E+06 668.0E+06

Table 5 Potentiodynamic polarization scans parameters (0.5% NaCl solution). Solution 0.5% NaCl Plain BM HAZ WZ Aerated BM HAZ WZ Eoc (mV) 736.2 720.9 720.7 599.0 664.0 624.2 Ecorr (mV) 779.0 746.0 719.0 455.0 557.0 618.0 Icorr (lA/cm2) 7.0 5.12 20.8 IL (lA/cm2) 74.6 108 143 ba (mV/ decade) 74.4 63.5 65.2 93.10 91.7 98.1 bc (mV/ decade) 300 188.6 353.6 412.8 1.0E+18 1.0E+4 CR(Tafel) (mpy) 3.20 2.337 5.946

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 formation of milky white oxide layer at the specimen surface as observed 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. Basically it acted like a physical barrier against oxygen diffusion. Therefore, it was expected that its quick formation could inhibit cathodic 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 process [12]. The Zig-Zag trend in cathodic polarization curve may be simulated to this behavior. It may also be deduced from polarization curves that the addition of 0.5% NaCl in water did not change the value of limiting current density IL signicantly. The values of other parameters obtained from potentiodynamic polarization scans and limiting current density in aerated water and 0.5% NaCl solution are given in Tables 4 and 5 respectively. The large values for bc were further quantitative representation of diffusion controlled oxygen reduction reaction. The variation in corrosion potential Ecorr as shown in Fig. 7 also conformed that the potential of weldment zones were nobler (less negative) under aeration condition in both water and 0.5% NaCl solution than plain condition. 3.4.2. Linear polarization resistance method The diffusion control mechanism in potentiodynamic polarization curves affected the calculation of the corrosion rate. For this

Fig. 7. Variation of corrosion potential under different conditions.

reason, the limiting current density cannot be assumed as the corrosion rate. On the other hand, polarization resistance values obtained from LPR method showed good agreement with calculated corrosion rate [13]. The Polarization resistance RP values were obtained through LPR method and the trend is shown in Fig. 8. The following equation may be used to determine the value of Icorr and corrosion rate from polarization resistance Rp.

Icorr

  ba ; bc 1 2:303 ba bc Rp

where, Rp is the DE/DI, ba is anodic Tafel slope, bc is the cathodic Tafel slope; obtained from Tafel line extrapolation. The 0.5% NaCl solution, plain and aerated was found more corrosive than water as indicated by high corrosion rates in Table 6. The corrosion rate of BM was also high in water and NaCl solution as compared to HAZ and WZ under both conditions.

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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 conrmed the behavior in polarization curves for the limiting 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 inuences reduction reaction in aerated water and NaCl solution. Therefore WZ was found least corrosion resistant than BM and HAZ, which was estimated 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 acicular ferrite structure provided low corrosion resistance than allotrimorphic and widmansttten ferrite, the complete coverage of surface by oxide lm was limited. It is also validated that aeration and saline environments can effectively accelerate local weld damage. References
[1] Trindade Filho VB, Guimaraes AS, Payao Filho Jda C. Normalizing heat treatment effect on low alloy steel weld metals. J Braz Soc Mech Sci Eng 2004;XXVI(1):626. [2] Bond, S. Corrosion of carbon steel weldments. Corrosion: fundamentals, testing and protection, vol. 13A. ASM Handbook. ASM International; 2003. [3] Ahmad Zaki. Principles of corrosion engineering and corrosion control. 1st ed. Elsevier Ltd.; 2006. [4] O Brien, RL. Welding processes. Welding handbook. 8th ed., vol. 2. Miami (FL): AWS; 1995. [5] Gooch TG. The effect of welding on corrosion. Process Industry Corrosion, NACE Publication; 1982. p. 73955. [6] Natarajan S, Kumaresh Babu SP. Corrosion and its inhibition in SA213-T 22 TIG weldments used in power plants under neural and alkaline environments. J Mater Sci Eng 2006;A432:4751. [7] Olson David LeRoy. Welding, brazing, and soldering. Submerge arc welding, ASM metal handbook. 9th ed., vol. 6. Metal Park (OH): ASM International; 1983. [8] Kumar Ravindra, Tewari VK, Prakash Satya. J Alloy Compd 2009;19196. doi:10.1016/j.jallcom.2008.a2.110. [9] Bhadeshia HKDH, Svensson L-E. In: Cerjak H, Easterling KE, editors. Mathematical modelling of weld phenomena. London: Institute of Materials; 1993. [10] Juan Wang, Yajiang Li. Bull Mater Sci 2003;26(3):2959. [11] Kuo Sindo. Welding metallurgy. 2nd ed. John Wiley & Sons, Inc.; 2003. [12] Strattmann M, Muller J. The mechanism of the oxygen reduction on rust covered metal substrates. Corros Sci 1994;36(2):32759. [13] Klapper Helmuth Sarmiento, Laverde Dionisio, Vasquez Custodio. Evaluation of the corrosion of UNS G10200 steel in aerated brines under hydrodynamic conditions. Corros Sci 2008;50:271823. [14] Kumaresh Babu SP, Natarajan S. Inuence of heat input on high temperature weldment corrosion in submerged arc welded power plant carbon steel. J Mater Des 2008;29:103642. [15] Huang Her-Hsiung, Tsai Wen-TA, Lee Ju-Tung. The inuence of microstructure and composition on the electrochemical behavior of A516 steel weldment. J Corros Sci 1994;36(6):102738. [16] Farrar RA, Taylor LG, Harrison EM. Met Technol 1979;6. [17] Bayliss DA, Deacon DH. Steelwork and corrosion control. 2nd ed. Spon Press; 2002. [18] Kumaresh Babu SP, Natarajan S. In: Proceedings of international conference, inuence of heat input on corrosion behavior of FCA weldment in power plant carbon steel, corrosion, Chennai, NACE; 2005.

Fig. 8. Variation of polarization resistance under different conditions measured by LPR method.

Table 6 LPR method; results. LPR method Aerated water BM HAZ WZ Aerated 0.5% NaCl BM HAZ WZ Icorr (lA/cm2) 41.95 38.68 40.44 193.0 121.6 131.4 Rp (k X) 0.6211 0.6736 0.6448 0.1350 0.2142 0.1986 CR(LPR) (mpy) 11.98 11.05 11.19 55.13 34.73 36.38

3.5. Microstructural affect on corrosion behavior From microstructure of BM as shown in Fig. 1 greater amount of equiaxed polygonal ferrite grains corresponded to this high corrosion rate. In plain water and NaCl solution, the acicular ferrite morphology presented less exposure area to the corrosive medium than other form of ferrite. The presence of bainite in HAZ also favors low corrosion damage. That is why lower corrosion currents were registered by WZ and HAZ [14]. The WZ and HAZ showed less corrosion rates as compared to BM in both plain water and NaCl solution which indicated that SAW process benecial to carbon steel. The effect of microstructural difference between allotrimorphic ferrite and acicular ferrite on the corrosion behavior of weld metal is not well established. While increasing the volume fraction ratio of allotrimorphic ferrite to acicular ferrite in weld metal results in an increase corrosion resistance of carbon steel weld metal in acidic saline solution [15]. The lower polarization resistance of WZ having low allotrimorphic ferrite contents indicates that higher volume fraction of acicular ferrite is less corrosion resistant than allotrimorphic ferrite in aerated water and NaCl solution. In WZ a higher volume fraction of acicular ferrite, associated with higher dislocation density [16], accelerates localized oxygen reduction reaction rate, the results under deaerated condition are already explained by Her-Hsiung Huang et al [15]. During electrochemical reaction, the higher limiting current density IL and corrosion rate under aerated condition was due to acicular ferrite which may

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